CN110233063A - Advanced electrolyte system and its purposes in energy accumulating device - Google Patents

Abstract

The present invention provides a kind of advanced electrolyte system and its purposes in energy accumulating device, it includes immersing in advanced electrolyte system and being arranged in the intracorporal energy storage unit of gas-tight seal shell, the unit is electrically coupled to positive contact and cathode contact part, wherein exporting electric energy within the temperature range of Cheng Yue -40 degrees Celsius to about 210 degrees Celsius of the ultracapacitor configurations.The present invention also provides its manufacture and purposes.

Description

Advanced electrolyte systems and their use in energy storage devices

This application is a divisional application of a Chinese patent application entitled "Advanced Electrolyte System and Its Use in Energy Storage Devices" with application number 201380022019.X. Patent application 201380022019.X was filed in February 2013 under the Patent Cooperation Treaty. The international application (PCT/US2013/027697) filed on March 25 is a national application that has entered the Chinese national phase.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims U.S. Provisional Patent Application No. 61/602,713, filed Feb. 24, 2012, entitled "Electrolytes for Ultracapacitors," and entitled "High Temperature Energy Storage" Device (High Temperature Energy Storage Device)" International Application No. PCT/US2012/045994, filed on July 19, 2012, entitled "Power Supply for Downhole Instruments," U.S. Application Serial No. 13/553,716 and the benefit of priority of U.S. Provisional Patent Application No. 61/724,775, entitled "Electrolytes for Ultracapacitors," filed November 9, 2012. These are incorporated herein by reference Each of the disclosures is incorporated herein.

technical field

The invention disclosed herein relates to energy storage cells, and in particular to advanced electrolyte systems for use in these energy storage cells, and related techniques for providing electric double layer capacitors that can operate at high temperatures.

Background technique

Energy storage units are ubiquitous in our society. While most people think of energy storage units simply as "batteries," other types of units should also be included in the scope. For example, recently, supercapacitors have attracted much attention due to their favorable properties. In short, many types of energy storage units are known and in use today.

Electric double layer capacitors, also known as "supercapacitors (supercapacitors, supercondenser, ultracapacitors", "pseudocapacitors" or "electrochemical electric double layer capacitors", are capacitors that exhibit significantly improved performance over conventional capacitors. One such parameter is energy density. In general, the energy density of supercapacitors is on the order of thousands of times higher than that of high-capacity electrolytic capacitors.

Capacitors are one of the key components in any electronic device and electronic system. General functions include supply voltage smoothing, support for energy sources, and filtering. A demand environment for implementing electronic devices and capacitors exists across multiple industries.

Consider, for example, industries with some applications that require electrical components to operate continuously at high temperatures (eg, temperatures in excess of 80 degrees Celsius), such as oil drilling, aerospace, aviation, military and automotive industries. This thermal exposure, along with various factors, causes the performance of the energy storage system to degrade at elevated temperatures and results in premature degradation of the energy storage unit. Durability and safety are key requirements in typical aerospace and defense applications. Examples are those applications where engines, turbofans, and control and sensing electronics are located near a rocket motor casing. Automotive applications such as small transmissions or embedded alternators/starters also require durability and long life at elevated temperatures.

Electronic components used in industrial environments must be physically robust while meeting performance requirements. One of the attendant challenges for designers and producers of supercapacitors is to obtain electrolytes that work well and reliably at high temperatures and electrolytes that work well and reliably at both high and low temperatures. Unfortunately, the desired properties of some electrolytes do not exhibit or persist at higher temperatures, and even those electrolytes that have achieved durability at high temperatures do not operate reliably at low temperatures. Thus, what is needed is an electrolyte for supercapacitors that performs well under the required conditions. Preferably, the electrolyte provides stable conductivity and low internal resistance and stable and high capacitance, and stable and low leakage current over a wide range of temperatures.

SUMMARY OF THE INVENTION

In one embodiment, an ultracapacitor is disclosed. The ultracapacitor includes an energy storage cell and an advanced electrolyte system (AES) within a hermetically sealed housing, the cell being electrically coupled to positive and negative contacts, wherein the ultracapacitor is configured to operate at a temperature of about -40 degrees Celsius to about 210 degrees Celsius Operates at temperatures in the temperature range of Celsius.

In another embodiment, a method for fabricating an ultracapacitor is provided. The method includes the steps of: disposing an energy storage unit including an energy storage medium within a housing; and filling the housing with an advanced electrolyte system (AES) such that the supercapacitor is fabricated at a temperature of about -40 degrees Celsius to about 210 degrees Celsius operating temperature range.

In yet another embodiment, a method of using a high temperature rechargeable energy storage device (HTRESD) is provided. The method includes the steps of: obtaining an HTRESD comprising an advanced electrolyte system (AES); and cycling the HTRESD by alternately charging and discharging the HTRESD at least twice while maintaining the voltage across the HTRESD such that the HTRESD exhibits 0.01 W/up to 150 kW The initial peak power density per liter enables the HTRESD to operate at ambient temperature at a temperature ranging from about -40 degrees Celsius to about 210 degrees Celsius.

In yet another embodiment, a method of using an ultracapacitor is provided. The method includes the steps of obtaining an ultracapacitor as described herein, wherein the ultracapacitor exhibits a flow rate of less than about 10 mA/cm when maintained at a substantially constant temperature in a range between about 100 degrees Celsius and about 150 degrees Celsius Volume leakage current (mA/cm3); and cycling the supercapacitor by alternately charging and discharging the supercapacitor at least twice while maintaining the voltage across the supercapacitor such that the supercapacitor is at about -40 degrees Celsius to about 210 A substantially constant temperature in the range between degrees Celsius exhibits an ESR increase of less than about 1000% after use for at least 1 hour when maintained at a substantially constant temperature.

In another embodiment, a method of providing a high temperature rechargeable energy storage device to a user is provided. The method includes the steps of selecting a high temperature rechargeable energy storage device (HTRESD) comprising an advanced electrolyte system (AES) that is exposed to temperatures ranging from about -40 degrees Celsius to about 210 degrees Celsius exhibit an initial peak power density of between 0.01 W/liter and 100 kW/liter and a durability of at least 1 hour at ambient temperature within; and deliver the storage device such that the HTRESD is provided to the user.

In yet another embodiment, a method of providing a high temperature rechargeable energy storage device to a user is provided. The method includes the steps of obtaining any ultracapacitor as described herein, the ultracapacitor exhibiting less than about 10 mA/cubic when maintained at a substantially constant temperature in a range between about -40 degrees Celsius and about 210 degrees Celsius centimeter volume leakage current (mA/cm 3 ); and deliver the storage device so that the HTRESD is provided to the user.

In yet another embodiment, an advanced electrolyte system (AES) is disclosed. The AES includes an ionic liquid containing at least one cation and at least one anion and exhibits a halide ion content of less than 1000 ppm and a water content of less than 100 ppm.

In yet another embodiment, an advanced electrolyte system (AES) is disclosed. The AES includes an ionic liquid containing at least one cation and at least one anion and at least one solvent and exhibits a halide ion content of less than 1000 ppm and a water content of less than 1000 ppm.

Description of drawings

The foregoing and other features and advantages of the present invention are apparent from the following detailed description, taken in conjunction with the accompanying drawings, which should not be considered limiting:

1 illustrates aspects of an exemplary ultracapacitor;

2 is a block diagram depicting a plurality of carbon nanotubes (CNTs) grown onto a substrate;

3 is a block diagram depicting the deposition of a current collector onto the CNTs of FIG. 3 to provide electrode elements;

Figure 4 is a block diagram depicting the addition of a transfer tape to the electrode element of Figure 3;

5 is a block diagram depicting electrode elements during the transfer process;

6 is a block diagram depicting electrode elements after transfer;

7 is a block diagram depicting an exemplary electrode fabricated from a plurality of electrode elements;

8 depicts an embodiment of the primary structure of cations that may be included in an exemplary supercapacitor;

Figures 9 and 10 provide comparative data for exemplary supercapacitors utilizing pristine and purified electrolytes, respectively;

FIG. 11 depicts an embodiment of a housing of an exemplary ultracapacitor;

FIG. 12 shows an embodiment of a storage cell of an exemplary supercapacitor;

Figure 13 depicts a barrier disposed on the interior of the body of the housing;

Figures 14A and 14B (collectively referred to herein as Figure 14) depict aspects of the cover of the housing;

15 depicts an assembly of ultracapacitors in accordance with the teachings herein;

Figures 16A and 16B (collectively referred to herein as Figure 16) are graphs depicting the performance of an embodiment of a supercapacitor without a barrier and a similar embodiment including a barrier, respectively;

Figure 17 depicts a barrier disposed around a storage unit as a wrap;

Figures 18A, 18B, and 18C (collectively referred to herein as Figure 18) depict an embodiment of a lid comprising a multi-layered material;

19 is a cross-sectional view of an electrode assembly including a glass-to-metal seal;

Figure 20 is a cross-sectional view of the electrode assembly of Figure 19 installed in the cover of Figure 18B;

Figure 21 depicts the arrangement of energy storage cells in the assembly;

Figures 22A, 22B, and 22C (collectively referred to herein as Figure 22) depict an embodiment of an assembled energy storage unit;

Figure 23 depicts the incorporation of polymer insulators into supercapacitors;

Figures 24A, 24B, and 24C (collectively referred to herein as Figure 24) depict aspects of a template for another embodiment of a lid for an energy storage device;

25 is a perspective view of an electrode assembly including a hemispherical material;

26 is a perspective view of a cover including the electrode assembly of FIG. 25 installed in the template of FIG. 24;

Figure 27 is a cross-sectional view of the cover of Figure 26;

Figure 28 depicts the coupling of the electrode assembly to the terminals of the storage cell;

Figure 29 is a transparent isometric view of an energy storage unit disposed within a cylindrical housing;

Figure 30 is a side view of a storage unit showing layers of one embodiment;

31 is an isometric view of a rolled up storage unit including reference marks for routing a plurality of leads;

Figure 32 is an isometric view of the storage unit of Figure 31 once deployed;

Figure 33 depicts a rolled-up storage cell containing multiple leads;

34 depicts Z-folds imparted to aligned leads (ie, terminals) coupled to storage cells;

Figures 35, 36, 37, 38 are graphs depicting the performance of exemplary ultracapacitors; and

39, 40, 41, 42, 43 are graphs depicting the performance of exemplary ultracapacitors at 210 degrees Celsius.

Figures 44A and 44B respectively depict entities with a novel electrolyte: 1-butyl-1-methylpiperidine Capacitance and ESR curves of supercapacitor performance of bis(trifluoromethylsulfonyl)imide at 150 degrees Celsius and 1.5 V.

Figures 45A and 45B respectively depict trihexyltetradecyl with a novel electrolyte entity Capacitance and ESR curves of supercapacitor performance of bis(trifluoromethylsulfonyl)imide at 150 degrees Celsius and 1.5 V.

46A and 46B are capacitance and ESR curves, respectively, depicting the performance of supercapacitors with the novel electrolyte entity butyltrimethylammonium bis(trifluoromethylsulfonyl)imide at 150 degrees Celsius and 1.5V.

47A and 47B are capacitance and ESR curves, respectively, depicting the performance of a supercapacitor with ionic liquids selected from ionic liquids used in the preparation of enhanced electrolyte combinations at 125 degrees Celsius and 1.5V.

Figures 48A and 48B are capacitance and ESR curves depicting the performance of a supercapacitor with 37.5% organic solvent-ionic liquid (same as in Figure 47) v/v at 125 degrees Celsius and 1.5V, respectively.

Figure 49 is an ESR curve depicting the performance of a supercapacitor with 37.5% organic solvent-ionic liquid (same as in Figure 47) v/v at -40 degrees Celsius and 1.5V.

Detailed ways

Various variables are described in this application, including but not limited to composition (eg, electrode materials, electrolytes, etc.), conditions (eg, temperature, degrees of freedom of various impurities at various levels), and performance characteristics (eg, post-cycle capacitance relative to initial capacitance, low leakage current, etc.). It should be understood that any combination of any of these variables may define embodiments of the invention. For example, embodiments of the invention are specific electrode materials, with specific dielectrics, at specific temperature ranges and with combinations of impurities less than a specific amount, operation with post-cycle capacitance, and specific values of leakage current (including these variables as much as possible) However, specific combinations may not be highlighted). Other combinations of articles, compositions, conditions and/or methods may also be specifically selected from among the variables listed herein to define other embodiments, as will be apparent to those skilled in the art.

The present invention, including advanced electrolyte systems and their uses, will be described with reference to the following definitions set forth below for convenience. Unless otherwise stated, the following terms are used herein as defined below:

I. Definitions

When introducing elements of the invention or its embodiments, when nouns are not modified by a quantifier, they are intended to include both the singular and the plural. Similarly, when the adjective "another" is used to modify an element, it is intended to include both the singular and the plural. The terms "comprising", "comprising" and "having" are meant to include additional elements other than the listed elements.

The terms "alkenyl" and "alkynyl" are art-recognized and refer to unsaturated aliphatic groups similar in length and possible substitution to the alkyl groups described below, but containing at least one double or triple bond, respectively group.

The term "alkyl" is art-recognized and can include saturated aliphatic groups, including straight chain alkyl groups, branched chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted rings Alkyl and cycloalkyl-substituted alkyl groups. In certain embodiments, a straight or branched chain alkyl group has about 20 or fewer carbon atoms in its backbone (eg, C ₁ -C ₂₀ for straight chain, C ₁ -C ₂₀ for branched chain). Likewise, a cycloalkyl group has about 3 to about 10 carbon atoms in its ring structure, or about 5, 6, or 7 carbons in its ring structure. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

As used herein, the terms "cladding", "cladding" and the like refer to the joining together of dissimilar metals. Cladding is often accomplished by extruding the two metals through a die and pressing or rolling sheets together under high pressure. Other methods such as laser cladding can be used. The result is a sheet of material composed of multiple layers, wherein the multiple layers of material are bonded together so that the material can work together as a single sheet (eg, formed into a single sheet of uniform material).

As a general rule, it is believed that a "contaminant" may be defined as any undesired material that would adversely affect the performance of the ultracapacitor 10 if introduced. It should also be noted that in general herein, contaminants can be evaluated in terms of concentrations, such as parts per million (ppm). Concentrations can be by weight, by volume, by weight of the sample, or by any other means as determined to be appropriate.

The term "cyano" is given its ordinary meaning in the art and refers to the group CN. The term " _sulfate " is given its ordinary meaning in the art and refers to the group SO2. The term "sulfonic acid" is given its ordinary meaning in the art, and refers to the group _SO3X , where X can be an electron pair, hydrogen, alkyl, or cycloalkyl. The term "carbonyl" is known in the art and refers to the group C=O.

In general, the term "electrode" refers to an electrical conductor used in contact with another material, often non-metal, in a device that can be incorporated into an electrical circuit. In general, the term "electrode" as used herein refers to the current collector 2 and additional components (eg, energy storage medium 1 ) that may accompany the current collector 2 to provide the desired functionality (eg, energy matching the current collector 2 ) storage medium 1 to provide energy storage and energy transfer).

"Energy density" is the square of the peak device voltage multiplied by one-half the capacitance of the device divided by the mass or volume of the device.

As discussed herein, "hermetic" refers to a seal whose properties (ie, leak rate) are defined in units of "atm-cubic centimeters per second," which means at ambient atmospheric pressure and 1 cubic centimeter per second of gas (eg, He) at temperature. This is equivalent to a representation in "standard He-cubic centimeters per second". Also, consider 1 atm-cubic centimeter/second equal to 1.01325 millibar-liter/second.

The terms "heteroalkenyl" and "heteroalkynyl" are known in the art and refer to compounds as described herein wherein one or more atoms are heteroatoms (eg, oxygen, nitrogen, sulfur, etc.) Alkenyl and alkynyl.

The term "heteroalkyl" is known in the art and refers to an alkyl group as described herein wherein one or more atoms are heteroatoms (eg, oxygen, nitrogen, sulfur, etc.). For example, an alkoxy group (eg, -OR) is a heteroalkyl group.

By convention, the terms "internal resistance" and "effective series resistance" and "ESR", terms known in the art to refer to the resistive aspect of a device, are used interchangeably herein.

As a convention, the term "leakage current" generally refers to the current drawn by a capacitor measured after a given period of time. This measurement is made while the capacitor terminals are held at a substantially fixed potential difference (terminal voltage). When evaluating leakage current, a typical time period is seventy-two (72) hours, although different time periods may be used. It should be noted that the leakage current of prior art capacitors generally increases as the volume and surface area of the energy storage medium increases with the increase in the internal surface area of the housing. In general, elevated leakage current is considered to be indicative of a progressively higher reaction rate in the ultracapacitor 10 . The performance requirements for leakage current are generally defined by the environmental conditions prevailing in a particular application. For example, for a supercapacitor 10 with a volume of 20 mL, the practical limit of leakage current can be reduced to less than 200 mA.

The "lifetime" of a capacitor is also generally defined by a particular application and is usually expressed as some percentage increase in leakage current or degradation of another parameter such as capacitance or internal resistance (as appropriate or decisive for a given application). For example, in one embodiment, the lifetime of a capacitor in automotive applications can be defined as the time for the leakage current to rise to 200% of its initial (begin of life, "BOL") value. In another embodiment, the lifetime of a capacitor in oil and gas applications can be defined as the time when any of the following phenomena occur: the capacitance drops to 50% of its BOL value; the internal resistance rises to 200% of its BOL value; The leakage current rises to 200% of its BOL value. As a convention, the terms "durability" and "reliability" of a device as used herein generally relate to the lifetime of the device as defined above.

The "operating temperature range" of a device generally relates to the range of temperatures within which a certain level of performance is maintained and is generally determined for a given application. For example, in one embodiment, an operating temperature range in the oil and gas field may be defined as a temperature range in which the resistance of a device is less than about 1000% of the resistance of the device at 30 degrees Celsius, and the capacitance is greater than About 10% of the capacitance at 30 degrees Celsius.

In some cases, the operating temperature range specification provides a lower limit for the effective temperature and the lifetime specification provides an upper limit for the effective temperature.

"Peak power density" is one quarter of the square of the peak device voltage divided by the effective series resistance of the device divided by the mass or volume of the device.

As referred to herein, the "volume leakage current" of an ultracapacitor 10 generally refers to the leakage current divided by the volume of the ultracapacitor 10, and may be expressed, for example, in units of mA per cubic centimeter. Similarly, the "volumetric capacitance" of an ultracapacitor 10 generally refers to the capacitance of the ultracapacitor 10 divided by the volume of the ultracapacitor 10, and may be expressed, for example, in units of F/cc. Furthermore, the "volume ESR" of an ultracapacitor 10 generally refers to the ESR of the ultracapacitor 10 multiplied by the volume of the ultracapacitor 10, and may be expressed, for example, in units of ohm-cubic centimeters.

As a general rule, it should be understood that the term "may" as used herein is understood to be optional; "comprising" is understood to not exclude other options (ie, steps, materials, components, components, etc.); "should" does not imply requirements, but only an accidental preference or preference according to circumstances. Other similar terms are used analogously in a generally conventional manner.

As discussed herein, terms such as "adjust," "configure," "configure," etc. may be considered to refer to the application of any of the techniques disclosed herein, as well as other similar techniques (as now known or later developed), to provide the intended result.

II. The capacitor of the present invention

Disclosed herein is to provide users with capacitors with improved performance over a wide temperature range. For example, capacitors of the present invention including the advanced electrolyte systems described herein are capable of operating at temperatures ranging from about as low as -40 degrees Celsius to as high as about 210 degrees Celsius.

In general, capacitors of the present invention include energy storage media suitable for providing a combination of high reliability, wide operating temperature range, high power density, and high energy density compared to prior art devices. The capacitor includes components configured to ensure operation within the stated temperature range, and includes an electrolyte 6 selected only from the advanced electrolyte systems described herein. The combination of construction, energy storage medium and advanced electrolyte system provides robust capacitors of the present invention capable of providing enhanced properties over existing capacitors under extreme conditions and with better performance and durability sexual operation.

Accordingly, the present invention provides a supercapacitor comprising: an energy storage cell and an advanced electrolyte system (AES) within a hermetically sealed housing, the cell being electrically coupled to positive and negative contacts, wherein the supercapacitor is The capacitors are configured to operate at temperatures ("operating temperatures") within the following temperature ranges: about -40 degrees Celsius to about 210 degrees Celsius; about -35 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 205 degrees Celsius; about -30 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 200 degrees Celsius; about -25 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 195 degrees Celsius; about -20 degrees Celsius to about 210 degrees Celsius; degrees; about -15 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 185 degrees Celsius; about -10 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 180 degrees Celsius; about -5 degrees Celsius to about 210 degrees Celsius; 40 degrees Celsius to about 175 degrees Celsius; about 0 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 170 degrees Celsius; about 5 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 165 degrees Celsius; -40 degrees Celsius to about 160 degrees Celsius; about 15 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 155 degrees Celsius; about 20 degrees Celsius to about 210 degrees Celsius; about -40 degrees Celsius to about 150 degrees Celsius.

In a specific embodiment, the AES includes a Novel Electrolyte Entity (NEE), eg, where the NEE is suitable for use in high temperature supercapacitors. In certain embodiments, the ultracapacitor is configured to operate at a temperature within a temperature range of about 80 degrees Celsius to about 210 degrees Celsius (eg, a temperature range of about 80 degrees Celsius to about 150 degrees Celsius).

In a particular embodiment, the AES includes a highly purified electrolyte, eg, where the highly purified electrolyte is suitable for use in high temperature supercapacitors. In certain embodiments, the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 210 degrees Celsius.

In a particular embodiment, the AES includes an enhanced electrolyte combination, eg, wherein the enhanced electrolyte combination is suitable for use in both high temperature and low temperature supercapacitors. In certain embodiments, the ultracapacitor is configured to operate at a temperature in a temperature range of about -40 degrees Celsius to about 150 degrees Celsius.

As such, and as described above, the advantages of existing electrolytes over known energy storage devices are selected from one or more of the following improvements: reduced overall resistance; increased long-term stability of resistance; increased overall capacitance; capacitance Improved long-term stability, increased energy density, improved voltage stability, reduced vapor pressure, wider temperature range performance of a single capacitor, improved temperature durability of a single capacitor, improved ease of manufacture, and improved cost-effectiveness.

In certain embodiments of the supercapacitor, the energy storage unit includes a positive electrode and a negative electrode.

In certain embodiments of the supercapacitor, at least one of the electrodes includes a carbonaceous energy storage medium, eg, wherein the carbonaceous energy storage medium includes carbon nanotubes. In certain embodiments, the carbonaceous energy storage medium may include at least one of activated carbon, carbon fibers, rayon, graphene, aerogels, carbon cloth, and carbon nanotubes.

In certain embodiments of the supercapacitor, each electrode includes a current collector.

In certain embodiments of the supercapacitor, the AES is purified to reduce impurity levels. In certain embodiments of the supercapacitor, the electrolyte contains less than about 1000 parts per million halide ions, eg, less than about 500 parts per million, eg, less than about 100 parts per million, For example, below about 50 parts per million. In certain embodiments, the halide ions in the electrolyte are selected from one or more halide ions selected from chloride, bromide, fluoride, and iodide. In certain embodiments, the total concentration of impurities in the electrolyte is less than about 1000 parts per million. In certain embodiments, the impurity is selected from one or more of bromoethane, chloroethane, 1-bromobutane, 1-chlorobutane, 1-methylimidazole, ethyl acetate, and dichloromethane kind.

In certain embodiments of the supercapacitor, the total concentration of metal species in the electrolyte is less than about 1000 parts per million. In certain embodiments, the metal species is selected from one or more metals selected from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb, and Zn. In another specific embodiment, the metal species is selected from one or more alloys of metals selected from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb, and Zn. In yet another specific embodiment, the metal species is selected from oxides of one or more metals selected from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb and Zn.

In certain embodiments of the ultracapacitor, the total water content in the electrolyte is less than about 500 parts per million, eg, less than about 100 parts per million, eg, less than about 50 parts per million, For example, below about 20 parts per million.

In certain embodiments of the supercapacitor, the housing includes a barrier disposed over a substantial portion of its interior surface. In certain embodiments, the barrier comprises at least one of polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE) one. In certain embodiments, the barrier includes a ceramic material. Barriers may also include materials that exhibit corrosion resistance, desirable dielectric properties, and low electrochemical reactivity. In certain embodiments of the barrier, the barrier includes multiple layers of material.

In certain embodiments of the supercapacitor, the housing comprises a multi-layer material, eg, wherein the multi-layer material comprises a first material coated on a second material. In certain embodiments, the multilayer material comprises at least one of steel, tantalum, and aluminum.

In certain embodiments of the supercapacitor, the housing includes at least one hemispherical seal.

In certain embodiments of the supercapacitor, the housing contains at least one glass-to-metal seal, eg, wherein a pin of the glass-to-metal seal provides one of the contacts. In certain embodiments, the glass-to-metal seal includes a feedthrough constructed of one of the following materials: iron-nickel-cobalt alloys, nickel-iron alloys, tantalum, molybdenum, niobium, tungsten, and some forms of stainless steel and titanium. In another specific embodiment, the glass-to-metal seal includes a body composed of at least one material selected from the group consisting of nickel, molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon, and tungsten , and its alloys.

In certain embodiments of the supercapacitor, the energy storage unit includes a separator to provide electrical isolation between the positive and negative electrodes, eg, wherein the separator comprises a separator selected from the group consisting of polyamide, polytetrafluoroethylene (PTFE), polyether Materials in ether ketone (PEEK), alumina (Al ₂ O ₃ ), fiberglass, fiberglass reinforced plastic, or any combination thereof. In certain embodiments, the separator is substantially free of moisture. In another specific embodiment, the separator comprises substantially hydrophobic.

In certain embodiments of the ultracapacitor, the hermetic seal exhibits a leak rate of no greater than about 5.0 x ^10-6 atm-cc/sec; eg, no greater than about 5.0 x ^10-7 atm-cc/sec seconds; eg, no greater than about 5.0 x ^10-8 atm-cc/sec; eg, no greater than about 5.0 x ^10-9 atm-cc/sec; eg, no greater than about 5.0 x ^10-10 atm-cc /second.

In certain embodiments of an ultracapacitor, at least one contact is configured to mate with another contact of another ultracapacitor.

In certain embodiments of the ultracapacitor, the memory cell includes a wrap disposed over its exterior, eg, wherein the wrap comprises one of PTFE and polyimide.

In certain embodiments of the ultracapacitor, the volumetric leakage current is less than about 10 amps/liter over the temperature range.

In certain embodiments of the ultracapacitor, the volumetric leakage current is less than about 10 amps/liter over a specified voltage range between about 0 volts to about 4 volts, eg, about 0 volts to about Between 3 volts, eg, between about 0 volts and about 2 volts, eg, between about 0 volts and about 1 volt. In certain embodiments of the ultracapacitor, the moisture level within the case is less than about 1000 parts per million (ppm), eg, less than about 500 parts per million (ppm), eg, less than about 350 parts per million (ppm) / parts per million (ppm).

In certain embodiments of the ultracapacitor, the moisture content in the electrodes of the ultracapacitor is less than about 1000 ppm, eg, less than about 500 ppm, eg, less than about 350 parts per million (ppm).

In certain embodiments of the ultracapacitor, the moisture content in the separator of the ultracapacitor is less than about 1000 ppm, eg, less than about 500 ppm, eg, less than about 160 parts per million (ppm).

In certain embodiments of the ultracapacitor, the chloride ion content is less than about 300 ppm for one of the components selected from the group consisting of electrodes, electrolytes, and separators.

In certain embodiments of the ultracapacitor, the volumetric leakage current (mA/cm3) of the ultracapacitor is less than about 10 mA/cm3 when maintained at a substantially constant temperature, eg, in certain embodiments, when maintained at a substantially constant temperature Below about 1 mA/cm3 at temperature.

In certain embodiments of the ultracapacitor, the volumetric leakage current of the ultracapacitor is greater than about 0.0001 mA/cm 3 when maintained at a substantially constant temperature.

In certain embodiments of the ultracapacitor, the volumetric capacitance of the ultracapacitor is between about 6 F/cc and about 1 F/cc; between about 10 F/cc and about 5 F/cc; or about 50 F/cc Between centimeters and about 8F/cc.

In certain embodiments of the ultracapacitor, the volumetric ESR of the ultracapacitor is between about 20 milliohm·cc and 200 milliohm·cc, between about 150 milliohm·cc and 2 ohm·cc, about Between 1.5 ohm·cc and 200 ohm·cc or about 150 ohm·cc and 2000 ohm·cc.

In certain embodiments of the ultracapacitor, the ultracapacitor exhibits a capacitance drop of less than about 90% while maintaining a substantially constant voltage and operating temperature. In certain embodiments, the ultracapacitor is maintained at a substantially constant voltage and operating temperature for at least 1 hour (eg, at least 10 hours; eg, at least 50 hours; eg, at least 100 hours; eg, at least 200 hours; eg, at least 300 hours) hours; eg, at least 400 hours; eg, at least 500 hours; eg, at least 1000 hours) exhibits a capacitance drop of less than about 90%.

In certain embodiments of the ultracapacitor, the ultracapacitor exhibits an increase in ESR of less than about 1000% when maintained at a substantially constant voltage and operating temperature for at least 1 hour, eg, at least 10 hours; eg, at least 50 hours; eg, at least 100 hours; eg, at least 200 hours; eg, at least 300 hours; eg, at least 400 hours; eg, at least 500 hours; eg, at least 1000 hours.

For example, as shown in FIG. 1, an exemplary embodiment of a capacitor is shown. In this case, the capacitor is "Supercapacitor 10". An exemplary ultracapacitor 10 is an electric double layer capacitor (EDLC). The ultracapacitor 10 may be implemented in several different form factors (ie, exhibit a certain appearance). Examples of potentially useful form factors include cylindrical cells, wheel-shaped or ring-shaped cells, flat prismatic cells or stacks of flattened prismatic cells including box-shaped cells, and flat prisms adapted to accommodate special geometries such as curved spaces unit. Cylindrical form factors may be most useful when incorporating cylindrical systems or systems mounted in cylindrical form factors or with cylindrical cavities. A wheel or ring cell form factor may be most useful when incorporating a ring system or a system mounted in a ring form factor or having a ring cavity. The flat prismatic element form factor may be most useful when incorporating rectangular systems or systems that are mounted in a rectangular form factor or have a rectangular cavity.

Although disclosed herein generally in the shape of a "jelly roll" application (ie, storage unit 12 configured as cylindrical housing 7), rolled storage unit 23 may take any desired shape. For example, the folding of the storage unit 12 may be performed to provide the rolled storage unit 23 as opposed to rolling the storage unit 12 . Other types of assemblies can be used. As one example, the storage unit 12 may be a flat unit, known as a coin, pouch, or prismatic unit. Thus, rolling is only one option for the assembly of rolled storage units 23 . Thus, although discussed herein in terms of "rolled storage unit 23", this is not a limitation. The term "rolled storage unit 23" may be considered to generally include a storage unit 12 that is packaged or packaged in any suitable form that is well suited to the given design of the housing 7.

Various shapes of supercapacitors 10 can be connected together. The various shapes may be connected using known techniques such as soldering contacted together, by using at least one mechanical connector, by arranging contacts in electrical contact with each other, and the like. The plurality of ultracapacitors 10 may be electrically connected in at least one of parallel and series.

For the purposes of the present invention, the volume of the ultracapacitor 10 may be about 0.05 milliliters to 7.5 liters.

There may be a variety of environments in which the ultracapacitor 10 is particularly useful. For example, in automotive applications, an ambient temperature of 105 degrees Celsius can be achieved (where the capacitor has a practical life of about 1 to 20 years). In some downhole applications such as geothermal drilling, ambient temperatures of 300 degrees Celsius or higher can be reached (where the capacitors have a practical life of about 1 hour to 10,000 hours).

The components of the ultracapacitor of the present invention will now be discussed in turn.

A. Advanced Electrolyte Systems of the Invention

The advanced electrolyte system of the present invention provides the electrolyte composition of the supercapacitor of the present invention and is labeled "Electrolyte 6" in FIG. 1 . Electrolyte 6 fills the void spaces in and between electrode 3 and separator 5 . In general, the advanced electrolyte systems of the present invention include unique electrolytes, purification-enhanced electrolytes, or combinations thereof, wherein electrolyte 6 is a species that dissociates into charged ions (eg, positively charged cations and negatively charged anions) (eg consisting of one or more salts or ionic liquids) and may include a solvent. In the advanced electrolyte systems of the present invention, such electrolyte compositions are selected based on enhancement of certain performance and durability characteristics, and may be combined with one or more solvents, the one or more A solvent dissolves the above substances to yield compositions with novel and useful electrochemical stability and properties.

The advanced electrolyte systems of the present invention provide supercapacitors of the present invention with advantages over existing energy storage devices (eg, energy storage devices comprising electrolytes not disclosed herein, or energy storage devices comprising electrolytes of insufficient purity) Unique and distinct advantages. These advantages include improvements in both performance and durability, such as one or more of the following: reduction in overall resistance; increased long-term stability of resistance (eg, increase in resistance of a material over time at a given temperature) increase in total capacitance; increase in long-term stability of capacitance (e.g., decrease in capacitance reduction over time for a capacitor at a given temperature); increase in energy density (e.g., by supplying higher voltages and/or by generating more higher capacitance); improved voltage stability, reduced vapor pressure, wider temperature range performance of a single capacitor (e.g. no significant reduction in capacitance and/or significant increase in ESR when switching between two temperatures, e.g. , no greater than 90% reduction in capacitance and/or greater than 1000% increase in ESR when transitioning from about +30°C to about -40°C), the temperature endurance of a single capacitor improves (eg, at a given temperature at a given temperature Less than 50% capacitance reduction after a given time and/or less than 100% ESR rise after a given time at a given temperature, and/or less than 10A/L after a given time at a given temperature leakage current, eg, less than 40% capacitance reduction and/or less than 75% ESR rise, and/or less than 5A/L leakage current; eg, less than 30% capacitance reduction and/or low 50% higher ESR, and/or less than 1 A/L leakage current), improved ease of manufacture (eg, by having reduced vapor pressure, resulting in better yields and/or filling capacitors with electrolytes) more efficient methods); and cost-effective improvements (eg, by filling void spaces with less expensive materials compared to other materials). For the sake of clarity, performance characteristics relate to properties that relate to the utility of a device for a given application, which is suitable for comparison of materials used for a similar given application; while durability relates to maintenance over time Properties related to the capabilities of the above properties. The above examples of performance and durability should be used to provide context for what is considered to be a "significant change in performance or durability" herein.

For the sake of clarity, and generally speaking, references to "electrolyte 6" included in the energy storage device of the present invention as used herein refers to the advanced electrolyte system of the present invention.

The properties of the AES or electrolyte 6 may be the result of improvements selected from: increased capacitance, reduced equivalent series resistance (ESR), high thermal stability, low glass transition temperature (Tg), improved viscosity, specific rhoepectic ) or thixotropic properties (eg temperature dependent properties) as well as high conductivity and good electrical properties over a wide temperature range. For example, the electrolyte 6 may have a high fluidity or, conversely, be substantially solid, so that the isolation of the electrodes 3 is ensured.

The advanced electrolyte systems of the present invention include: the novel electrolytes described herein for use in high temperature supercapacitors; highly purified electrolytes for use in high temperature supercapacitors; and suitable for use in temperatures ranging from -40 degrees Celsius to 210 degrees Celsius The enhanced electrolyte combination is used at all temperatures without significant degradation in performance or durability.

Although the disclosure presented herein should focus on applying the advanced electrolyte systems described herein to supercapacitors, these advanced electrolyte systems can be applied to any energy storage device.

i. Novel Electrolyte Entity (NEE)

In one embodiment, the advanced electrolyte systems (AES) of the present invention include certain novel electrolytes used in high temperature supercapacitors. In this regard, it has been found that maintaining purity and low moisture relates to the level of performance of the energy storage 10; and, the use of electrolytes comprising hydrophobic materials and electrolytes that have been found to exhibit higher purity and lower moisture content is beneficial for obtaining improvements performance. These electrolytes exhibit good performance characteristics at temperatures ranging from about 80 degrees Celsius to about 210 degrees Celsius, eg, about 80 degrees Celsius to about 200 degrees Celsius; eg, about 80 degrees Celsius to about 190 degrees Celsius; eg, about 80 degrees Celsius to about 180 degrees Celsius Celsius; for example, about 80 degrees Celsius to about 170 degrees Celsius; for example, about 80 degrees Celsius to about 160 degrees Celsius; for example, about 80 degrees Celsius to about 150 degrees Celsius, for example, about 85 degrees Celsius to about 145 degrees Celsius; Celsius; eg, about 95 degrees Celsius to about 135 degrees Celsius; eg, about 100 degrees Celsius to about 130 degrees Celsius; eg, about 105 degrees Celsius to about 125 degrees Celsius; eg, about 110 degrees Celsius to about 120 degrees Celsius.

Accordingly, novel electrolyte entities useful as advanced electrolyte systems (AES) include species comprising cations (eg, those shown in Figure 8 and described herein) and anions, or combinations of such species. In some embodiments, such species include nitrogen-containing cations, oxygen-containing cations, phosphorus-containing cations, and/or sulfur-containing cations, including heteroaryl cations and heterocyclyl cations. In one set of embodiments, the Advanced Electrolyte System (AES) comprises a compound comprising a compound selected from the group consisting of ammonium, imidazole azole piperidine Pyrazine Pyrazole Pyridazine Pyridine Pyrimidine Sulfonium, Thiazole triazole guanidine isoquinoline benzotriazole As well as cationic species of viologen type cations, any of the aforementioned cations may be substituted with the substituents described herein. In one embodiment, the novel electrolyte entity used in the advanced electrolyte system (AES) of the present invention comprises the cation shown in Figure 8, and is selected from the group consisting of tetrafluoroborate, bis(trifluoromethylsulfonyl)imide , any combination of anions of tetracyanoborate and triflate, the cations shown in Figure 8 are selected from piperidine and ammonium, where each branched group R _x (eg, R ₁ , R ₂ , R ₃ . . . R _x ) can be selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkyne group, halogen, amino, nitro, cyano, hydroxy, sulfate, sulfonic acid, and carbonyl, any of which are optionally substituted, and wherein at least two Rx are not H (ie, such that the R group's Selection and orientation resulted in the cationic species shown in Figure 8).

For example, given the combination of cations and anions described above, in certain embodiments, the AES may be selected from trihexyltetradecyl Bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpiperidine The group of bis(trifluoromethylsulfonyl)imide and butyltrimethylammonium bis(trifluoromethylsulfonyl)imide. Data supporting the enhanced performance characteristics over temperature as evidenced by time-varying capacitance and ESR measurements are provided in Figures 44A and 44B, 45A and 45B, and 46A and 46B, which demonstrate that High temperature practicality and long term durability.

In certain embodiments, AES is trihexyltetradecyl Bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the AES is 1-butyl-1-methylpiperidine Bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the AES is butyltrimethylammonium bis(trifluoromethylsulfonyl)imide.

In another embodiment, novel electrolyte entities useful in the advanced electrolyte systems (AES) of the present invention include the cations shown in Figure 8, and are selected from the group consisting of tetrafluoroborate, bis(trifluoromethylsulfonyl)idene Any combination of anions of amine, tetracyanoborate and triflate, the cation shown in Figure 8 is selected from imidazole and pyrrolidine wherein each branched chain group _{Rx (} eg, R1, R2, _R3 ... _{Rx )} can be selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, halogen , amino, nitro, cyano, hydroxy, sulfate, sulfonate, and carbonyl groups, any of which are optionally substituted, and wherein at least two R _x are not H (ie, such that the R group's Selection and orientation resulted in the cationic species shown in Figure 8). In a specific embodiment, the two _Rx that are not H are alkyl. Furthermore, the cations exhibit high thermal stability as well as high conductivity and exhibit good electrochemical performance over a wide temperature range.

For example, given the above combinations of cations and anions, in certain embodiments, the AES may be selected from 1-butyl-3-methylimidazole Tetrafluoroborate; 1-Butyl-3-methylimidazole Bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazole Tetrafluoroborate; 1-ethyl-3-methylimidazole Tetracyanoborate; 1-hexyl-3-methylimidazole Tetracyanoborate; 1-Butyl-1-methylpyrrolidine Bis(trifluoromethylsulfonyl)imide; 1-butyl-1-methylpyrrolidine Tris(pentafluoroethyl)trifluorophosphate; 1-butyl-1-methylpyrrolidine Tetracyanoborate and 1-butyl-3-methylimidazole Triflate.

In one embodiment, the AES is 1-butyl-3-methylimidazole Tetrafluoroborate.

In one embodiment, the AES is 1-butyl-3-methylimidazole Bis(trifluoromethylsulfonyl)imide.

In one embodiment, the AES is 1-ethyl-3-methylimidazole Tetrafluoroborate.

In one embodiment, the AES is 1-ethyl-3-methylimidazole Tetracyanoborate.

In one embodiment, the AES is 1-hexyl-3-methylimidazole Tetracyanoborate.

In one embodiment, the AES is 1-butyl-1-methylpyrrolidine Bis(trifluoromethylsulfonyl)imide.

In one embodiment, the AES is 1-butyl-1-methylpyrrolidine Tris(pentafluoroethyl)trifluorophosphate.

In one embodiment, the AES is 1-butyl-1-methylpyrrolidine Tetracyanoborate.

In one embodiment, the AES is 1-butyl-3-methylimidazole Triflate.

In another specific embodiment, one of the two Rx that _is not H is an alkyl group, eg, methyl, and the other is an alkyl group substituted with an alkoxy group. Furthermore, it has been found that cations having an N,O-acetal skeleton structure of the formula (1) in the molecule have high conductivity, and are included in these cations and have pyrrolidine The ammonium cations of the backbone and N,O-acetal groups are particularly conductive and soluble in organic solvents and support relatively high voltages. Thus, in one embodiment, the advanced electrolyte system includes a salt of the formula:

wherein R ₁ and R ₂ may be the same or different, and are both alkyl groups, and X- is an anion. In some embodiments, R ₁ is a straight or branched chain alkyl group having 1 to 4 carbon atoms, R ₂ is methyl or ethyl, and X ^— is a cyanoborate-containing anion 11. _In certain embodiments ^, X- includes [B(CN)] ₄ and R2 is one of methyl and ethyl. _In another specific embodiment, _both R1 and R2 are methyl. Additionally, in one embodiment, suitable cyanoborate anions 11,X- for the advanced electrolyte systems of the present invention include [B(CN)4] ^- or [BFn(CN)4 ^-n]- _, ^where n= 0, 1, 2 or 3.

Examples of cations of the AES of the present invention comprising the novel electrolyte entity of formula (1) and consisting of quaternary ammonium cations shown in formula (I) and cyanoborate anions are selected from N-methyl-N-methoxymethyl pyrrolidine (N-Methoxymethyl-N-methylpyrrolidine ), N-ethyl-N-methoxymethylpyrrolidine N-Methoxymethyl-N-n-propylpyrrolidine N-Methoxymethyl-N-isopropylpyrrolidine N-n-Butyl-N-methoxymethylpyrrolidine N-isobutyl-N-methoxymethylpyrrolidine N-tert-Butyl-N-methoxymethylpyrrolidine N-Ethoxymethyl-N-methylpyrrolidine N-Ethyl-N-ethoxymethylpyrrolidine (N-Ethoxymethyl-N-ethylpyrrolidine ), N-ethoxymethyl-N-n-propylpyrrolidine N-Ethoxymethyl-N-isopropylpyrrolidine N-n-Butyl-N-ethoxymethylpyrrolidine N-isobutyl-N-ethoxymethylpyrrolidine and N-tert-butyl-N-ethoxymethylpyrrolidine Other examples include N-methyl-N-methoxymethylpyrrolidine (N-Methoxymethyl-N-methylpyrrolidine ), N-ethyl-N-methoxymethylpyrrolidine and N-ethoxymethyl-N-methylpyrrolidine

Further examples of cations of formula (1) combined with further anions may be selected from N-methyl-N-methoxymethylpyrrolidine Tetracyanoborate (N-methoxymethyl-N-methylpyrrolidine tetracyanoborate), N-ethyl-N-methoxymethylpyrrolidine Tetracyanoborate, N-ethoxymethyl-N-methylpyrrolidine Tetracyanoborate, N-methyl-N-methoxymethylpyrrolidine Bistrifluoromethanesulfonylimide, (N-methoxymethyl-N-methylpyrrolidine bistrifluoromethanesulfonylimide), N-ethyl-N-methoxymethylpyrrolidine Bistrifluoromethanesulfonylimide, N-ethoxymethyl-N-methylpyrrolidine Bistrifluoromethanesulfonylimide, N-methyl-N-methoxymethylpyrrolidine Triflate (N-methoxymethyl-N-methyl triflate).

In the case of use as an electrolyte, a quaternary ammonium salt can be used in admixture with a suitable organic solvent. Usable solvents include cyclic carbonates, chain carbonates, phosphoric acid esters, cyclic ethers, chain ethers, lactone compounds, chain esters, nitrile compounds, amide compounds, and sulfone compounds. Examples of such compounds are listed below, but the solvent used is not limited to these compounds.

Examples of the cyclic carbonate are ethylene carbonate, propylene carbonate, butylene carbonate and the like, among which propylene carbonate is preferred.

Examples of the chain carbonate are dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and the like, among which dimethyl carbonate and ethyl methyl carbonate are preferred.

Examples of phosphate esters are trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate and the like. Examples of cyclic ethers are tetrahydrofuran, 2-methyltetrahydrofuran, and the like. Examples of chain ethers are ethylene glycol dimethyl ether and the like. Examples of the lactone compound are γ-butyrolactone and the like. Examples of chain esters are methyl propionate, methyl acetate, ethyl acetate, methyl formate, and the like. Examples of the nitrile compound are acetonitrile and the like. Examples of the amide compound are dimethylformamide and the like. Examples of sulfone compounds are sulfolane, methyl sulfolane, and the like. In some embodiments, cyclic carbonates, chain carbonates, nitrile compounds, and sulfone compounds are particularly desired.

These solvents can be used alone, or at least two solvents can be used in admixture. Examples of preferred organic solvent mixtures are: mixtures of cyclic carbonates and chain carbonates, for example mixtures of ethylene carbonate and dimethyl carbonate, mixtures of ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and Mixtures of diethyl carbonate, mixtures of propylene carbonate and dimethyl carbonate, mixtures of propylene carbonate and ethyl methyl carbonate and mixtures of propylene carbonate and diethyl carbonate; mixtures of chain carbonates such as Mixtures of dimethyl carbonate and ethyl methyl carbonate; and mixtures of sulfolane compounds such as mixtures of sulfolane and methyl sulfolane. More preferred are mixtures of ethylene carbonate and ethyl methyl carbonate, mixtures of propylene carbonate and ethyl methyl carbonate, and mixtures of dimethyl carbonate and ethyl methyl carbonate.

In some embodiments, where the quaternary ammonium salts of the present invention are used as electrolytes, the electrolyte concentration is at least 0.1M, in some cases at least 0.5M and may be at least 1M. Concentrations below 0.1 M will result in low electrical conductivity, resulting in a compromised electrochemical device. In the case where the electrolyte is a liquid salt at room temperature, the upper limit concentration is the isolated concentration. In the case where the solution does not separate, the limiting concentration is 100%. When the salt is solid at room temperature, the limiting concentration is the concentration at which the solution is saturated with the salt.

In certain embodiments, the advanced electrolyte system (AES) may be blended with electrolytes other than those disclosed herein, so long as such a combination does not significantly affect the advantages achieved using the advanced electrolyte system, For example, changing performance or durability characteristics by more than 10%. Examples of electrolytes that may be suitable for blending with AES are alkali metal salts, quaternary ammonium salts, quaternary salt etc. When blended with the AES disclosed herein, these electrolytes can be used alone, or at least two of these electrolytes can be used in combination. Useful alkali metal salts include lithium, sodium and potassium salts. Examples of such lithium salts are lithium hexafluorophosphate, lithium fluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium sulfonimide, lithium methanesulfonyl, and the like, although this is not limiting. Examples of sodium salts that can be used are sodium hexafluorophosphate, sodium fluoroborate, sodium perchlorate, sodium triflate, sodium sulfonimide, sodium methanesulfonyl, and the like. Examples of potassium salts that can be used are potassium hexafluorophosphate, potassium fluoroborate, potassium perchlorate, potassium triflate, potassium sulfonimide, potassium methanesulfonyl, and the like, although these are not limiting.

Useful quaternary ammonium salts described above that can be used in combination (ie, do not significantly affect the advantages achieved using advanced electrolyte systems) include tetraalkylammonium salts, imidazoles salt, pyrazole salt, pyridine salt, triazole salt, pyridazine Salt, etc, this is not limiting. Examples of tetraalkylammonium salts that can be used are tetraethylammonium tetracyanoborate, tetramethylammonium tetracyanoborate, tetrapropylammonium tetracyanoborate, tetrabutylammonium tetracyanoborate , triethylmethylammonium tetracyanoborate, trimethylethylammonium tetracyanoborate, dimethyldiethylammonium tetracyanoborate, trimethylpropylammonium tetracyanoborate, Trimethylbutylammonium tetracyanoborate, dimethylethylpropylammonium tetracyanoborate, methylethylpropylbutylammonium tetracyanoborate, N,N-dimethylpyrrolidine Tetracyanoborate, N-ethyl-N-methylpyrrolidine Tetracyanoborate, N-methyl-N-propylpyrrolidine Tetracyanoborate, N-ethyl-N-propylpyrrolidine Tetracyanoborate, N,N-Dimethylpiperidine Tetracyanoborate, N-methyl-N-ethylpiperidine Tetracyanoborate, N-methyl-N-propylpiperidine Tetracyanoborate, N-ethyl-N-propylpiperidine Tetracyanoborate, N,N-Dimethylmorpholine Tetracyanoborate, N-methyl-N-ethylmorpholine Tetracyanoborate, N-methyl-N-propylmorpholine Tetracyanoborate, N-ethyl-N-propylmorpholine Tetracyanoborate and the like, however these examples are not limiting.

The imidazoles described above can be used in combination (ie, without significantly affecting the advantages achieved using advanced electrolyte systems) Examples of salts include 1,3-dimethylimidazole Tetracyanoborate, 1-ethyl-3-methylimidazole Tetracyanoborate, 1,3-diethylimidazole Tetracyanoborate, 1,2-Dimethyl-3-ethylimidazole Tetracyanoborate and 1,2-Dimethyl-3-propylimidazole Tetracyanoborate, but not limited to these. Pyrazole An example of a salt is 1,2-dimethylpyrazole Tetracyanoborate, 1-Methyl-2-ethylpyrazole Tetracyanoborate, 1-propyl-2-methylpyrazole Tetracyanoborate and 1-methyl-2-butylpyrazole Tetracyanoborate, but not limited to these. Pyridine An example of a salt is N-picoline Tetracyanoborate, N-ethylpyridine Tetracyanoborate, N-propylpyridine Tetracyanoborate and N-butylpyridine Tetracyanoborate, but not limited to these. triazole An example of a salt is 1-methyltriazole Tetracyanoborate, 1-ethyltriazole Tetracyanoborate, 1-propyltriazole Tetracyanoborate and 1-Butyltriazole Tetracyanoborate, but not limited to these. Pyridazine An example of a salt is 1-methylpyridazine Tetracyanoborate, 1-ethylpyridazine Tetracyanoborate, 1-propylpyridazine Tetracyanoborate and 1-butylpyridazine Tetracyanoborate, but not limited to these. season An example of a salt is tetraethyl Tetracyanoborate, Tetramethyl Tetracyanoborate, Tetrapropyl Tetracyanoborate, Tetrabutyl tetracyanoborate, triethylmethyl Tetracyanoborate, Trimethylethyl Tetracyanoborate, Dimethyldiethyl Tetracyanoborate, Trimethylpropyl Tetracyanoborate, Trimethylbutyl Tetracyanoborate, Dimethylethylpropyl Tetracyanoborate, methylethylpropylbutyl Tetracyanoborate, but not limited to these.

In certain embodiments, the novel electrolytes selected herein for advanced electrolyte systems can also be purified. Such purification can be performed using techniques known in the art or provided herein. This purification can further improve the properties of the novel electrolyte entities described herein.

ii. Highly purified electrolyte

In one embodiment, the advanced electrolyte systems of the present invention include certain highly purified electrolytes used in high temperature supercapacitors. In certain embodiments, the highly purified electrolytes that make up the AES of the present invention are those electrolytes described below and those novel electrolytes described above purified by the purification methods described herein. The purification methods provided herein result in impurity levels capable of providing advanced electrolyte systems with enhanced performance for use in high temperature applications (eg, high temperature supercapacitors), eg, at about 80 degrees Celsius to about In the temperature range of 210 degrees Celsius, for example, about 80 degrees Celsius to about 200 degrees Celsius; for example, about 80 degrees Celsius to about 190 degrees Celsius; for example, about 80 degrees Celsius to about 180 degrees Celsius; for example, about 80 degrees Celsius to about 170 degrees Celsius; 80 degrees Celsius to about 160 degrees Celsius; for example, about 80 degrees Celsius to about 150 degrees Celsius; for example, about 85 degrees Celsius to about 145 degrees Celsius; for example, about 90 degrees Celsius to about 140 degrees Celsius; 100 degrees Celsius to about 130 degrees Celsius; eg, about 105 degrees Celsius to about 125 degrees Celsius; eg, about 110 degrees Celsius to about 120 degrees Celsius.

Obtaining the improved properties of the supercapacitor 10 has led to a need for a better electrolyte system than currently available. For example, it has been found that increasing the operating temperature range can be achieved by significantly reducing/removing impurities from certain forms of known electrolytes. Impurities of particular concern include water, halides (chloride, bromide, fluoride and iodide), free amines (ammonia), sulfate and metal cations (Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sr, Ti, Zn). The highly purified electrolyte product thus purified provides an electrolyte that is unexpectedly far superior to the unpurified electrolyte, and thus, is an advanced electrolyte system of the present invention.

In certain embodiments, the present invention provides purified mixtures of cations 9 and anions 11, and in some cases solvents, that can be used as AES of the present invention comprising less than about 5000 parts per million parts (ppm) chloride ions; less than about 1000 ppm fluoride ions; and/or less than about 1000 ppm water (e.g., less than about 2000 ppm chloride ions; less than about 200 ppm fluoride ions; and/or less than about 2000 ppm chloride ions; 200 ppm water, eg, less than about 1000 ppm chloride ion; less than about 100 ppm fluoride ion; and/or less than about 100 ppm water, eg, less than about 500 ppm chloride ion, less than about 50 ppm fluoride ion; and/or less than about 50 ppm water, for example, less than about 780 parts per million chloride ions; less than about 11 parts per million fluoride ions; and less than about 20 parts per million water .)

In general, the purification methods described herein are used to remove impurities from the electrolyte being purified. For example, in some embodiments, the total concentration of halide ions (chloride, bromide, fluoride, and iodide) can be reduced to less than about 1000 ppm. The total concentration of metal species (eg, Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb, Zn, including at least one of alloys and oxides thereof) can be reduced to less than about 1000ppm. In addition, impurities from solvents and precursors used in the synthesis process can be reduced to less than about 1000 ppm and can include, for example, bromoethane, chloroethane, 1-bromobutane, 1-chlorobutane, 1-methylmethane imidazole, ethyl acetate, dichloromethane, etc.

In some embodiments, the impurity content of the supercapacitor 10 is measured using ion selective electrodes and Karl Fischer titration methods that have been applied to the electrolyte 6 of the supercapacitor 10 . In certain embodiments, ultracapacitors 10 according to the teachings herein have been found to have a total halide ion content of less than about 200 ppm of halide ions (Cl ⁻ and F ⁻ ) and a water content of less than about 100 ppm.

Impurities can be measured using various techniques such as atomic absorption spectrometry (AAS), inductively coupled plasma mass spectrometry (ICPMS) or simplified solubilization and electrochemical sensing of trace heavy metal oxide particles. AAS is a spectroscopic analysis method for qualitatively and quantitatively determining chemical elements using absorption of optical radiation (light) by gaseous free atoms. This technique is used to determine the concentration of a specific element (analyte) in a sample to be analyzed. AAS can be used to determine over 70 different elements in solution or directly in solid samples. ICPMS is a mass spectrometry method that is highly sensitive and capable of determining concentrations of metals and several non-metals in the sub-10 ¹² (part-per-trillion) range. The technique is based on combining inductively coupled plasma as a method of generating ions (ionization) with mass spectrometry as a method of separating and detecting ions. ICPMS is also capable of monitoring the isotopic species of selected ions.

Additional techniques can be used to analyze impurities. Some of these techniques are particularly beneficial for analyzing impurities in solid samples. Ion chromatography (IC) can be used to determine trace levels of halide impurities in electrolyte 6 (eg, an ionic liquid). An advantage of ion chromatography is that the related halides can be measured in a single chromatographic analysis. A Dionex AS9-HC column using an eluent containing 20 mM NaOH and 10% (v/v) acetonitrile is an example of a device that can be used to quantify halides from ionic liquids. Another technique is X-ray fluorescence spectroscopy.

Halogen content in solid samples can be measured using an X-ray fluorescence (XRF) instrument. In this technique, the sample to be analyzed is placed in a sample cup, which is then placed in an analyzer that is irradiated with X-rays of a specific wavelength. Any halogen atom in the sample absorbs a portion of the X-rays and then reflects the radiation at wavelengths characteristic of a given halogen. A detector in the instrument then quantifies the amount of radiation coming back from the halogen atoms and measures the intensity of the radiation. By knowing the exposed surface area, the concentration of halogen in the sample can be determined. Another technique for assessing impurities in solid samples is pyrolysis.

The adsorption of impurities can be effectively measured by using pyrolysis and a microcoulometer. Microcoulometers are capable of testing the total chlorine content of almost any type of material. As an example, a small amount of sample (less than 10 mg) is injected or placed into a quartz burner tube where the temperature is from about 600 degrees Celsius to about 1000 degrees Celsius. Pure oxygen is passed through the quartz tube and any chlorine-containing components are completely burned. The resulting combustion products are purged into a titration cell where chloride ions are trapped in the electrolyte solution. The electrolyte solution contains silver ions, which immediately combine with any chloride ions and drop out of solution as insoluble silver chloride. The silver electrodes in the titration unit electrically displace the spent silver ions until the concentration of silver ions returns to the concentration before the titration started. By tracking the amount of current required to produce the desired amount of silver, the instrument was able to determine how much chlorine was present in the initial sample. The total amount of chlorine present divided by the weight of the sample gives the concentration of chlorine actually in the sample. Other techniques for assessing impurities can be used.

Surface features and water content in the electrode 3 can be detected, for example, by infrared spectroscopy techniques. The four main absorption bands at approximately 1130 cm ^-1 , 1560 cm ^-1 , 3250 cm ^-1 and 2300 cm ^-1 correspond to vC=O, vC=C, vO-H and vC-N in aryl groups, respectively. By measuring the intensities and peak positions, the surface impurities in the electrode 3 can be determined quantitatively.

Another technique for determining impurities in electrolyte 6 and supercapacitor 10 is Raman spectroscopy. This spectroscopic technique relies on inelastic or Raman scattering of monochromatic light, typically from lasers in the visible, near-infrared, or near-ultraviolet range. The laser interacts with molecular vibrations, phonons, or other excitations in the system, causing the energy of the laser photons to vary up and down. Therefore, this technique can be used to characterize the atoms and molecules in the supercapacitor 10 . Many variations of Raman spectroscopy are employed and may prove useful for characterizing the contents of supercapacitor 10 .

iii. Enhanced Electrolyte Combination

In one embodiment, the advanced electrolyte systems of the present invention include certain enhanced electrolyte combinations suitable for use at temperatures ranging from -40 degrees Celsius to 210 degrees Celsius without significant degradation in performance or durability Celsius; eg, -40 Celsius to 150 Celsius; eg, -30 Celsius to 150 Celsius; eg, -30 Celsius to 140 Celsius; eg, -20 Celsius to 140 Celsius; eg, -20 Celsius to 130 Celsius; eg, - 10 degrees Celsius to 130 degrees Celsius; e.g., -10 degrees Celsius to 120 degrees Celsius; e.g., 0 degrees Celsius to 120 degrees Celsius; e.g., 0 degrees Celsius to 110 degrees Celsius, for example, 0 degrees Celsius to 100 degrees Celsius; Celsius to 80 degrees Celsius; for example, 0 degrees Celsius to 70 degrees Celsius.

In general, a higher degree of durability at a given temperature can be consistent with a higher degree of voltage stability at lower temperatures. Thus, the development of high temperature durable AES utilizing enhanced electrolyte combinations often leads to concurrent development of high voltage but lower temperature AES such that these enhanced electrolyte combinations described herein can also be used at higher voltages , and thus a higher energy density, but a lower temperature.

In one embodiment, the present invention provides an enhanced electrolyte combination suitable for use in an energy storage unit (eg, a supercapacitor), the enhanced electrolyte combination comprising a novel electrolyte mixture selected from the group consisting of: An ionic liquid of a diionic liquid, an ionic liquid mixed with an organic solvent, and an ionic liquid mixed with a second ionic liquid and an organic solvent.

wherein each ionic liquid is selected from the following salts of any combination of cations and anions, wherein the cation is selected from: 1-butyl-3-methylimidazole 1-Ethyl-3-methylimidazole 1-hexyl-3-methylimidazole 1-Butyl-1-methylpiperidine Butyltrimethylammonium, 1-butyl-1-methylpyrrolidine trihexyltetradecyl and 1-butyl-3-methylimidazole and the anion is selected from the group consisting of: tetrafluoroborate, bis(trifluoromethylsulfonyl)imide, tetracyanoborate, and triflate; and

wherein the organic solvent is selected from linear sulfone (eg, ethyl isopropyl sulfone, ethyl isobutyl sulfone, ethyl methyl sulfone, methyl isopropyl sulfone, isopropyl isobutyl sulfone, isopropyl sec-butyl sulfone, butyl isopropyl sulfone, sulfone and dimethyl sulfone), linear carbonates (eg, ethylene carbonate, propylene carbonate, and dimethyl carbonate), and acetonitrile.

For example, given the above combinations of cations and anions, each ionic liquid can be selected from: 1-butyl-3-methylimidazole Tetrafluoroborate, 1-butyl-3-methylimidazole Bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazole Tetrafluoroborate, 1-ethyl-3-methylimidazole Tetracyanoborate, 1-hexyl-3-methylimidazole Tetracyanoborate, 1-butyl-1-methylpyrrolidine Bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidine Tris(pentafluoroethyl)trifluorophosphate, 1-butyl-1-methylpyrrolidine Tetracyanoborate, Trihexyltetradecyl Bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpiperidine Bis(trifluoromethylsulfonyl)imide, butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, and 1-butyl-3-methylimidazole Triflate.

In certain embodiments, the ionic liquid is 1-butyl-3-methylimidazole Tetrafluoroborate.

In certain embodiments, the ionic liquid is 1-butyl-3-methylimidazole Bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroborate.

In certain embodiments, the ionic liquid is 1-ethyl-3-methylimidazole Tetracyanoborate.

In certain embodiments, the ionic liquid is 1-hexyl-3-methylimidazole Tetracyanoborate.

In certain embodiments, the ionic liquid is 1-butyl-1-methylpyrrolidine Bis(trifluoromethylsulfonyl)imide.

In one embodiment, the ionic liquid is 1-butyl-1-methylpyrrolidine Tris(pentafluoroethyl)trifluorophosphate.

In certain embodiments, the ionic liquid is 1-butyl-1-methylpyrrolidine Tetracyanoborate.

In certain embodiments, the ionic liquid is trihexyltetradecyl Bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is 1-butyl-1-methylpiperidine Bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is butyltrimethylammonium bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is 1-butyl-3-methylimidazole Triflate.

In certain embodiments, the organic solvent is selected from the group consisting of ethyl isopropyl sulfone, ethyl isobutyl sulfone, ethyl methyl sulfone, methyl isopropyl sulfone, isopropyl isobutyl sulfone, isopropyl sec-butyl sulfone, butyl isobutyl sulfone sulfone, or dimethyl sulfone, straight chain sulfone.

In certain embodiments, the organic solvent is selected from the group consisting of polypropylene carbonate, propylene carbonate, dimethyl carbonate, ethylene carbonate.

In certain embodiments, the organic solvent is acetonitrile.

In certain embodiments, the enhanced electrolyte composition is an ionic liquid with an organic solvent, wherein the organic solvent is 55% to 90% by volume of the composition, eg, 37.5%.

In certain embodiments, the enhanced electrolyte composition is an ionic liquid with a second ionic liquid, wherein one ionic liquid is 5% to 90%, eg, 60%, by volume of the composition.

The enhanced electrolyte combination of the present invention provides a wider temperature range performance for a single capacitor (eg, no significant reduction in capacitance and/or significant increase in ESR when switching between two temperatures, eg, when switching from about +30 No greater than 90% capacitance reduction and/or greater than 1000% ESR increase when transitioning from °C to about -40°C), as well as improved temperature endurance of individual capacitors (e.g., less than after a given time at a given temperature 50% decrease in capacitance and/or less than 100% increase in ESR after a given time at a given temperature, and/or less than 10A/L leakage current after a given time at a given temperature; e.g. , below 40% capacitance reduction and/or below 75% ESR rise, and/or below 5A/L leakage current; eg, below 30% capacitance reduction and/or below 50% ESR rise, and/or leakage current below 1A/L). Figures 47A and 47B, Figures 48A and 48B, and Figure 49 show ionic liquids from the above ionic liquids at 125 degrees Celsius, 37.5% organic solvent-ionic liquid (same) v/v at 125 degrees Celsius and the same, respectively The behavior of the composition at -40 degrees Celsius.

Without wishing to be bound by theory, the above combination provides enhanced eutectic properties that affect the freezing point of advanced electrolyte systems to enable supercapacitors to operate within performance and durability standards at temperatures as low as -40 degrees Celsius .

As described above for the novel electrolytes of the present invention, in certain embodiments, advanced electrolyte systems (AES) may be blended with electrolytes, so long as such combinations do not significantly affect the advantages achieved using advanced electrolyte systems.

In certain embodiments, the enhanced electrolytes selected herein for advanced electrolyte systems may also be purified. Such purification can be performed using techniques known in the art or provided herein.

B. Electrodes

The EDLC includes at least one pair of electrodes 3 (wherein electrodes 3 may be referred to as negative electrode 3 and positive electrode 3 for purposes of reference herein only). When assembled into a supercapacitor 10, each electrode 3 exhibits an electric double layer at the electrolyte interface. In some embodiments, a plurality of electrodes 3 are included (eg, in some embodiments, at least two pairs of electrodes 3 are included). However, for discussion purposes only one pair of electrodes 3 is shown. As is customary herein, at least one of the electrodes 3 uses a carbon-based energy storage medium 1 (as discussed further herein) to provide energy storage. However, for the purposes of this discussion, it is generally assumed that each of the electrodes includes a carbon-based energy storage medium 1 .

i current collectors

Each of the electrodes 3 includes a respective current collector 2 (also referred to as a "charge collector"). In some embodiments, electrodes 3 are separated by separators 5 . In general, the separator 5 is a thin structural material (usually a sheet) used to separate the negative electrode 3 from the positive electrode 3 . Separator 5 can also be used to separate pairs of electrodes 3 . Note that in some embodiments, the carbon-based energy storage medium 1 may not be included on one or both of the electrodes 3 . That is, in some embodiments, the respective electrode 3 may consist of the current collector 2 only. The material used to provide the current collector 2 may be roughened, anodized, etc. to increase its surface area. In these embodiments, a separate current collector 2 may serve as electrode 3 . In this regard, however, the term "electrode 3" as used herein generally refers to the combination of energy storage medium 1 and current collector 2 (although this is not limiting for at least the foregoing reasons).

ii. Energy storage medium

In the exemplary supercapacitor 10, the energy storage medium 1 is formed from carbon nanotubes. The energy storage medium 1 may include other carbonaceous materials including, for example, activated carbon, carbon fibers, rayon, graphene, aerogels, carbon cloth, and various forms of carbon nanotubes. The activated carbon electrode can be manufactured by, for example, performing a first activation treatment on a carbon material obtained by carbonization of a carbon compound to produce a carbon-based material; manufacturing a formed body by adding a binder to the carbon-based material; carbonizing the formed body ; and finally by performing a second activation treatment on the carbonized former to manufacture an activated carbon electrode. Carbon fiber electrodes can be fabricated, for example, by using paper or cloth preforms of carbon fibers with high surface area.

In an exemplary method for making carbon nanotubes, an apparatus for producing aligned carbon-nanotube aggregates includes for synthesizing aligned carbon nanotubes on a substrate having a catalyst on its surface Device for tube aggregates. The apparatus includes: a forming unit that performs the forming step of making the environment around the catalyst a reducing gas environment and heating at least the catalyst or the reducing gas; and a growing unit that performs the forming step by making the environment around the catalyst a raw material gas environment and a growth step of synthesizing aligned carbon nanotube aggregates by heating at least a catalyst or a raw material gas; and a transfer unit that transfers at least the substrate from the formation unit to the growth unit. A variety of other methods and apparatus can be used to provide oriented carbon nanotube aggregates.

In some embodiments, the materials used to form the energy storage medium 1 may include materials other than pure carbon (and various forms of carbon that may currently exist or will be invented later). That is, various formulations of other materials may be included in the energy storage medium 1 . More specifically, and by way of non-limiting example, at least one binder material may be used in the energy storage medium 1, however, it is not suggested or required to add other materials (eg, binder materials). In general, however, the energy storage medium 1 is formed essentially of carbon, and thus may be referred to herein as "carbon-containing material", "carbon-containing layer", and other similar terms. In short, although formed primarily of carbon, the energy storage medium 1 may include carbon in any form (and any additives or impurities deemed appropriate or acceptable) to provide the desired functionality as the energy storage medium 1 .

In one set of embodiments, the carbonaceous material includes at least about 60% by mass elemental carbon, and in other embodiments, at least about 75%, 85%, 90%, 95%, or 98% by mass Elemental carbon.

Carbonaceous materials can include carbon in various forms, including carbon black, graphene, and the like. The carbonaceous material may include carbon particles (including nanoparticles, eg, nanotubes, nanorods, graphene sheets in sheet form) and/or be formed as cones, rods, balls (buckyballs), and the like.

Some embodiments of various formed carbonaceous materials suitable for use in the energy storage medium 1 are provided herein as examples. These embodiments provide robust energy storage and are well suited for use in electrode 3 . It should be noted that these examples are illustrative and not limited to embodiments of carbonaceous materials suitable for use in the energy storage medium 1 .

In certain embodiments, the porosity of the energy storage medium 1 of each electrode can be selected based on the size of each electrolyte to enhance the performance of the capacitor.

An exemplary method for complimenting a current collector 2 for an energy storage medium 1 to provide electrodes 3 is now provided. Referring now to FIG. 2, the substrate 14 is shown as a matrix of carbonaceous material in the form of carbon nanotube aggregates (CNTs). In the embodiment shown, the substrate 14 includes a substrate 17 having a thin layer of catalyst 18 disposed thereon.

In general, the substrate 14 is at least somewhat flexible (ie, the substrate 14 is not fragile) and is made of components that can withstand the environment in which the energy storage medium 1 (eg, CNTs) is deposited. For example, the substrate 14 may withstand a high temperature environment between about 400 degrees Celsius and about 1100 degrees Celsius. A variety of materials may be used for substrate 14 as deemed appropriate.

Referring now to FIG. 3 . Once the energy storage medium 1 (eg, CNTs) has been fabricated on the substrate 14, the current collector 2 can be provided thereon. In some embodiments, the current collector 2 is about 0.5 micrometers (μm) to about 25 micrometers (μm) thick. In some embodiments, the current collector 2 is about 20 micrometers (μm) to about 40 micrometers (μm) thick. The current collector 2 may represent a thin layer, eg a layer applied by chemical vapor deposition (CVD), sputtering, electron beam, thermal evaporation, or by another suitable technique. In general, the current collector 2 is selected for its properties such as conductivity, electrochemical inertness, and compatibility with the energy storage medium 1 (eg, CNTs). Some exemplary materials include aluminum, platinum, gold, tantalum, titanium, and may include other materials and various alloys.

Once the current collector 2 is disposed on the energy storage medium 1 (eg, CNTs), the electrode element 15 is realized. Each electrode element 15 may be used alone as electrode 3 or may be coupled to at least one other electrode element 15 to provide electrode 3 .

Once the current collector 2 has been manufactured according to the desired standard, post-processing can be undertaken. Exemplary post-treatments include heating and cooling the energy storage medium 1 (eg, CNTs) in a slightly oxidizing environment. After fabrication (and optional post-treatment), a transfer tool can be applied to the current collector 2 . Refer to Figure 4.

FIG. 4 shows the application of the transfer tool 13 to the current collector 2 . In this embodiment, the transfer tool 13 is a thermal release tape used in a "dry" transfer process. Exemplary thermal release tapes are manufactured by NITTO DENKO CORPORATION of Fremont, California and Osaka, Japan. A suitable transfer tape is sold as REVALPHA. The release tape is characterized by an adhesive tape that adheres strongly at room temperature and can be peeled off by heating. This tape, as well as other suitable embodiments of thermal release tapes, will be peeled at a predetermined temperature. Advantageously, the stripping tape does not leave chemically active residues on the electrode element 15 .

In another process called "wet" transfer, tapes designed for chemical peels can be used. Once applied, the tape is then removed by dipping the tape in a solvent. The solvent is designed to dissolve the adhesive.

In other embodiments, the transfer tool 13 employs a "pneumatic" method, such as by applying suction to the current collector 2 . Suction can be applied, for example, by slightly oversized paddles with a plurality of perforations for distributing the suction. In another embodiment, the suction is applied by a roller having a plurality of perforations for distributing the suction. The suction-driven embodiment provides both the advantages of electronic control and the advantage of economy since no consumables are used as part of the transfer process. Other embodiments of transfer tool 13 may be used.

Once the transfer tool 13 is temporarily coupled to the current collector 2, the electrode elements 15 are gently removed from the substrate 14 (see Figures 4 and 5). The removal generally involves stripping the energy storage medium 1 (eg, CNTs) from the substrate 14 starting from one edge of the substrate 14 and the energy storage medium 1 (eg, CNTs).

Then, the transfer tool 13 can be separated from the electrode element 15 (see Fig. 6). In some embodiments, transfer tool 13 is used to mount electrode element 15 . For example, the transfer tool 13 can be used to arrange the electrode elements 15 onto the separator 5 . Generally speaking, once removed from the substrate 14, the electrode elements 15 are ready for use.

In cases where a large electrode 3 is desired, a plurality of electrode elements 15 can be matched. Refer to Figure 7. As shown in FIG. 7 , the plurality of electrode elements 15 may be matched by, for example, coupling a coupling 52 with each electrode element 15 of the plurality of electrode elements 15 . The matched electrode elements 15 provide an embodiment of the electrode 3 .

In some embodiments, couplings 22 are coupled to each electrode element 15 at welds 21 . Each weld 21 may be configured as an ultrasonic weld 21 . Ultrasonic welding techniques have been found to be particularly well suited for providing each weld 21 . That is, in general, aggregates of energy storage medium 1 (eg, CNTs) are incompatible with welding, where only nominal current collectors such as those disclosed herein are used. Therefore, many techniques for connecting electrode elements 15 are destructive and damage said elements 15 . However, in other embodiments, other forms of coupling are used and the coupling 22 is not the weld 21 .

The coupling 22 may be in the form of foil, mesh, multiple wires, or other forms. In general, coupling 22 is selected for properties such as conductivity and electrochemical inertness. In some embodiments, coupling member 22 is made of the same material that is present in current collector 2 .

In some embodiments, coupling 22 is fabricated by removing the oxide layer thereon. The oxide can be removed, for example, by etching the coupling 22 before the solder 21 is provided. Etching can be accomplished, for example, with potassium hydroxide (KOH). Electrode 3 may be used in various embodiments of supercapacitor 10 . For example, the electrode 3 can be rolled up into a "jellyroll" type of energy storage.

c. isolator

The isolator 5 can be made of various materials. In some embodiments, separator 5 is nonwoven glass. Separator 5 may also be fabricated from fiberglass, ceramics, and fluoropolymers such as polytetrafluoroethylene commonly sold as TEFLON™ by DuPont Chemicals of Wilmington, DE (PTFE). For example, using nonwoven glass, the separator 5 may include main fibers and binder fibers, each binder fiber having a fiber diameter smaller than the fiber diameter of each main fiber and enabling the main fibers to bond together.

For the long life of the supercapacitor 10 and to ensure performance at high temperatures, the isolator 5 should have a reduced amount of impurities, and in particular a very limited amount of moisture contained therein. In particular, it has been found that a moisture limit of about 200 ppm is desirable to reduce chemical reactions and extend the life of the supercapacitor 10, as well as to provide good performance in high temperature applications. Some embodiments of materials used in isolator 5 include polyamide, polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), alumina ( _{Al2O3 )} , fiberglass, and glass reinforced plastic (GRP) .

In general, the materials used for the separator 5 are selected based on moisture content, porosity, melting point, impurity content, resulting electrical properties, thickness, cost, availability, and the like. In some embodiments, the separator 5 is formed of a hydrophobic material.

Therefore, methods can be employed to ensure that excess moisture is removed from each isolator 5 . Vacuum drying methods can be employed as well as other techniques. A selection of materials for isolator 5 is provided in Table 1 . Some relevant performance data are provided in Table 2.

Table 1

isolator material

Table 2

Isolator Performance Data

To collect the data of Table 2, two electrodes 3 based on carbonaceous materials are provided. The two electrodes 3 are placed opposite and facing each other. Each separator 5 is arranged between the electrodes 3 to prevent short circuits. The three parts are then wetted with electrolyte 6 and pressed together. The resulting supercapacitor 10 was encapsulated using two aluminum rods and a PTFE material as the outer structure.

The ESR first test and the ESR second test are performed one after the other in the same configuration. The second test was run 5 minutes after the first test, leaving time for the electrolyte 6 to penetrate further into the part.

In certain embodiments, the ultracapacitor 10 does not include the isolator 5 . For example, in specific embodiments, such as those in which the electrodes 3 are physically separated by the geometry of the structure, it is sufficient to have only the electrolyte 6 between the electrodes 3 . More specifically, and as an example of physical isolation, one such ultracapacitor 10 may include electrodes 3 disposed within the housing such that isolation is ensured on a continuous basis. A bench-top example would include an ultracapacitor 10 disposed in a beaker.

D. storage unit

Once assembled, electrodes 3 and separators 5 provide storage cells 12 . In general, the storage unit 12 is formed in one of a coiled or prismatic form and then enclosed in a cylindrical or prismatic housing 7 . Once the electrolyte 6 has been accommodated, the housing 7 can be hermetically sealed. In various embodiments, the package is hermetically sealed by techniques utilizing laser, ultrasonic, and/or welding techniques. In addition to providing solid physical protection for the storage unit 12 , the housing 7 is also configured with external contacts to provide electrical communication with the various terminals 8 within the housing 7 . Each terminal 8 in turn provides an electrical connection to the energy stored in the energy storage medium 1 , which electrical connection is typically achieved through electrical leads coupled to the energy storage medium 1 .

In general, the ultracapacitors 10 disclosed herein are capable of providing a hermetic seal with a leak rate of no greater than about 5.0×10 ⁻⁶ atm·cc ^/ sec, and may exhibit no greater than about 5.0×10 ⁻¹⁰ atm-cubic Leak rate in cm/sec. It is also believed that the performance of a successful hermetic seal is at the discretion of the user, designer or manufacturer, and that "hermetic" ultimately means a standard defined by the user, designer, manufacturer or other interested party.

Leak detection can be achieved, for example, by using a tracer gas. The use of a tracer gas such as helium for leak testing is advantageous because it is a dry, fast, accurate and non-destructive method. In one embodiment of the technique, the ultracapacitor 10 is placed in a helium environment. The ultracapacitor 10 is subjected to pressurized helium gas. The ultracapacitor 10 is then placed in a vacuum chamber connected to a detector capable of monitoring the presence of helium (eg, an atomic absorption cell). Using the known pressurization time, pressure and internal volume, the leakage rate of the ultracapacitor 10 can be determined.

In some embodiments, at least one lead (which may also be referred to herein as a "tab") is electrically coupled to the corresponding one of the current collectors 2 . Multiple leads (corresponding to the polarities of the supercapacitors 10 ) may be grouped together and coupled to respective terminals 8 . In turn, the terminals 8 may be coupled in electrical connections referred to as "contacts" (eg, the housing 7 and external electrodes (also conventionally referred to herein as "feed-throughs" or "pins"). pin)”) one). Refer to FIG. 28 and FIGS. 32 to 34 .

E. Shell

FIG. 11 depicts some aspects of an exemplary housing 7 . The housing 7 provides, among other things, structural and physical protection for the supercapacitor 10 . In this embodiment, the housing 7 comprises a body 20 of annular cylindrical shape and a complementary cover 24 . In this embodiment, cover 24 includes a central portion that has been removed and filled with electrical insulator 26 . The cover feedthrough 19 penetrates the electrical insulator 26 to provide the stored energy to the user. In addition, the housing also includes an internal barrier 30 .

While this embodiment depicts only one feedthrough 19 on cover 24, it should be appreciated that the configuration of housing 7 is not limited to the embodiments discussed herein. For example, cover 24 may include multiple feedthroughs 19 . In some embodiments, the body 20 includes a second similar cover 24 at the opposite end of the annular cylinder. Furthermore, it should also be appreciated that the housing 7 is not limited to embodiments of the body 20 having an annular cylindrical shape. For example, the housing 7 may be of a clamshell design, a prismatic design, a bag or any other design suitable to the needs of the designer, manufacturer or user.

Referring now to FIG. 12 , an exemplary energy storage unit 12 is shown. In this embodiment, the energy storage unit 12 is a "jelly roll" type of energy storage. In these embodiments, the energy storage material is rolled up into a tight package. A plurality of leads generally form each terminal 8 and provide electrical connection to the appropriate layers of the energy storage cell 12 . Generally, when assembled, each terminal 8 is electrically coupled to the housing 7 (eg, to each feedthrough 19 and/or directly to the housing 7). The energy storage unit 12 may take a variety of forms. There are typically at least two sets of multiple leads (eg, terminals 8 ), one set for each current collector 2 . For simplicity, only one of the terminals 8 is shown in FIGS. 12 , 15 and 17 .

Efficient sealing of the housing 7 is desired. That is, preventing the intrusion of the external environment (eg, air, moisture, etc.) helps maintain the purity of the components of the energy storage unit 12 . Furthermore, it prevents leakage of the electrolyte 6 from the energy storage unit 12 .

In this embodiment, the cover 24 is manufactured with an outer diameter designed to fit closely with the inner diameter of the body 20 . When assembled, the cover 24 may be welded into the body 20 to provide a hermetic seal for the user. Exemplary welding techniques include laser welding and TIG welding, and may include other forms of welding as deemed appropriate.

Common materials for housing 7 include stainless steel, aluminum, tantalum, titanium, nickel, copper, tin, various alloys, laminates, and the like. Structural materials such as some polymer based materials may be used in the housing 7 (generally in combination with at least some metallic components).

In some embodiments, the material used to construct the body 20 includes aluminum, which may include any type of aluminum or aluminum alloy deemed suitable by the designer or manufacturer (all of which are referred to broadly herein simply as "aluminum"). Various alloys, laminates, etc. may be disposed over (eg, cladding) the aluminum (the aluminum exposed to the interior of the body 20). The body and/or housing 7 may be supplemented with other materials (eg, structural materials or electrically insulating materials, such as some polymer-based materials). The material placed over the aluminium can likewise be chosen as the designer or manufacturer sees fit.

In some embodiments, multiple layers of material are used for interior components. For example, aluminum can be clad with stainless steel to provide multiple layers of material in at least one terminal 8 . In some of these embodiments, a portion of the aluminum may be removed to expose the stainless steel. The exposed stainless steel can then be used to attach the terminal 8 to the feedthrough 19 by using a simple welding method.

The use of cladding materials for internal components may require specific embodiments of cladding materials. For example, it may be beneficial to use a cladding material comprising aluminum (bottom layer), stainless steel and/or tantalum (intermediate layer) and aluminum (top layer) so that it limits the exposure of the stainless steel to the internal environment of the supercapacitor 10 . These embodiments can be improved by, for example, additional coating with a polymeric material (eg, PTFE).

Therefore, providing a housing 7 with a multilayer material provides an energy storage which exhibits a leakage current with a relatively low initial value compared to the prior art and which increases significantly more slowly over time . Significantly, the leakage current of the energy storage remains at a usable (ie, desirably low) level when the supercapacitor 10 is exposed to ambient temperatures at which prior art capacitors would exhibit excessive initial leakage current value and/or leakage current increases too quickly over time.

In addition, the ultracapacitor 10 may exhibit other benefits resulting from the reduced reaction between the housing 7 and the energy storage unit 12 . For example, the effective series resistance (ESR) of an energy storage may exhibit relatively low values over time. Furthermore, the undesired chemical reactions that occur in prior art capacitors often produce undesired results (eg, outgassing or bulging of the case 7 if the case is hermetically sealed). In both cases, this results in a compromise of the structural integrity of the housing 7 and/or the gas-tight seal of the energy storage. Ultimately, this can lead to leakage or catastrophic failure of prior art capacitors. These effects can be significantly reduced or eliminated by application of the disclosed barriers.

By using multiple layers of material (eg, cladding material), stainless steel can be incorporated into the housing 7 so that components with glass-to-metal seals can be used. The components may be welded to the stainless steel side of the cladding material using techniques such as laser or resistance welding, while the aluminum side of the cladding material may be welded to other aluminum components (eg, body 20).

In some embodiments, an insulating polymer may be used for the coated portion of the housing 7 . In this way, it can be ensured that components of the energy storage are only exposed to acceptable types of metals (eg, aluminum). Exemplary insulating polymers include PFA, FEP, TFE, and PTFE. Suitable polymers (or other materials) are limited only by the needs of the system designer or manufacturer and the properties of each material. Referring to FIG. 23 , a small amount of insulating material 39 is included to limit the exposure of electrolyte 6 to the stainless steel of sleeve 51 and feedthrough 19 . In this embodiment, the terminal 8 is coupled to the feedthrough 19 , eg by soldering, and then coated with an insulating material 39 .

iCase Cover

While this embodiment depicts only one feedthrough 19 on cover 24, it should be appreciated that the configuration of housing 7 is not limited to the embodiments discussed herein. For example, cover 24 may include multiple feedthroughs 19 . In some embodiments, the body 20 includes a second similar cover 24 at the opposite end of the annular cylinder. Furthermore, it should also be appreciated that the housing 7 is not limited to embodiments of the body 20 having an annular cylindrical shape. For example, the housing 7 may be of a clamshell design, a prismatic design, a pouch or any other design suitable to the needs of the designer, manufacturer or user.

Referring now to FIG. 18 , aspects of an embodiment of the blank 34 of the cover 24 are shown. In Figure 18A, blank 34 includes multiple layers of material. The first material layer 41 is aluminum. The second material layer 42 is stainless steel. In the embodiment of Figure 18, stainless steel is clad to aluminum, thereby providing a material that exhibits the desired combination of metallurgical properties. That is, in some embodiments provided herein, the aluminum is exposed to the interior of the energy storage unit (ie, the housing), while the stainless steel is exposed to the exterior. In this way, the advantageous electrical properties of aluminum are enjoyed while relying on the structural properties (and metallurgical properties, ie, weldability) of stainless steel for construction. The multilayer material may include additional layers as deemed appropriate.

As mentioned above, the first material layer 41 is clad on the second material layer 42 (or the first material layer 41 is clad with the second material layer 42). Still referring to FIG. 18A , in one embodiment, a sheet of flat material (as shown) is used to provide the blank 34 to produce the flat cover 24 . A portion of the second material layer 42 may be removed (eg, around the perimeter of the cover 24 ) to facilitate attachment of the cover 24 to the body 20 . In Figure 18B, another embodiment of the blank 34 is shown. In this embodiment, the blank 34 has a sheet of cladding material formed in a concave configuration. In Figure 18C, the blank 34 has a sheet of cladding material formed into a convex configuration. Cover 24 fabricated from various embodiments of blanks 34 (eg, those shown in FIG. 18 ) is configured to support body 20 welded to housing 7 . More specifically, the embodiment of FIG. 18B is adapted to fit within the inner diameter of the body 20 , while the embodiment of FIG. 18C is adapted to fit over the outer diameter of the body 20 . In a number of alternative embodiments, the layers of cover material in the sheet may be reversed.

Referring now to FIG. 19, an embodiment of an electrode assembly 50 is shown. Electrode assembly 50 is designed to fit within blank 34 and provide electrical communication from the energy storage medium to the user. Generally speaking, the electrode assembly 50 includes a sleeve 51 . The sleeve 51 surrounds the insulator 26 which in turn surrounds the feedthrough 19 . In this embodiment, the sleeve 51 is an annular cylinder with a flanged top.

To assemble the cover 24, perforations (not shown) are made in the blank 34. The perforations are sized to match the geometry of the electrode assembly 50 . Thus, the electrode assembly 50 is inserted into the perforation of the blank 34 . Once the electrode assembly 50 is inserted, the electrode assembly 50 can be attached to the blank 34 by techniques (eg, welding). The welding may be laser welding, which is welded around the circumference of the flange of the welding sleeve 51 . Referring to Fig. 20, the point 61 at which the welding is made is shown. In this embodiment, point 61 provides a relatively simple welding process for welding stainless steel to a suitable location for stainless steel. Accordingly, the teachings herein provide a location for securely welding electrode assembly 50 to blank 34 .

Materials used to construct sleeve 51 may include various types of metals or metal alloys. In general, the material for sleeve 51 is selected based on, for example, structural integrity and engageability (to blank 34). Exemplary materials for sleeve 51 include 304 stainless steel or 316 stainless steel. Materials used to construct feedthrough 19 may include various types of metals or metal alloys. In general, the material used for the feedthrough 19 is selected based on, for example, structural integrity and electrical conductivity. Exemplary materials for the electrodes include 446 stainless steel or 52 alloy.

In general, insulator 26 is bonded to sleeve 51 and feedthrough 19 by known techniques (ie, glass-to-metal bonding). Materials used to construct insulator 26 may include, but are not limited to, various types of glass, including high temperature glass, ceramic glass, or ceramic materials. In general, materials for insulators are selected based on, for example, structural integrity and electrical resistance (ie, electrical insulating properties).

The use of components that rely on glass-to-metal bonding (eg, the foregoing embodiments of electrode assembly 50 ) and the use of various welding techniques provide hermetic sealing of the energy storage. Other components may also be used to provide a hermetic seal. The term "hermetic seal" as used herein generally refers to a seal that exhibits a leak rate no greater than the leak rate as defined herein. However, it is believed that actual sealing efficiency can be performed better than this standard.

Additional or other techniques for coupling the electrode assembly 50 to the blank 34 include the use of a joint under the flange of the sleeve 51 (between the flange and the second material layer 42 ) when such techniques are deemed appropriate. mixture.

Referring now to FIG. 21 , the energy storage unit 12 is disposed within the body 20 . At least one terminal 8 is suitably coupled (eg, to the feedthrough 19 ), and the cover 24 mates with the body 20 to provide the ultracapacitor 10 .

Once assembled, the lid 24 and the body 20 can be sealed. Figure 22 depicts various embodiments of an assembled energy storage (in this case, ultracapacitor 10). In Figure 22A, a flat blank 34 (see Figure 18A) is used to produce a flat cover 24. Once the cover 24 is placed on the body 20 , the cover 24 and the body 20 are welded to produce the seal 62 . In this case, since the body 20 is an annular cylinder, welding is performed around the body 20 and the cover 24 to provide the seal 62 . In a second embodiment, as shown in FIG. 22B , a concave blank 34 (see FIG. 18B ) is used to create the concave cover 24 . Once the cover 24 is placed on the body 20 , the cover 24 and the body 20 are welded to produce the seal 62 . In a third embodiment, as shown in Figure 22C, a male blank 34 (see Figure 18C) is used to produce the male cap 24. Once the cover 24 is positioned on the body 20 , the cover 24 and the body 20 can be welded to produce the seal 62 .

When appropriate, the cladding material may be removed (by techniques such as machining or etching, etc.) to expose other metals in the multilayer material. Thus, in some embodiments, seal 62 may comprise an aluminum-aluminum weld. Aluminum-aluminum weldments may be supplemented with other fasteners as appropriate.

Other techniques may be used to seal the housing 7 . For example, laser welding, TIG welding, resistance welding, ultrasonic welding, and other forms of mechanical sealing may be used. However, it should be noted that, in general, conventional forms of mechanical seal alone are not sufficient to provide the robust hermetic seal provided in ultracapacitor 10 .

Referring now to FIG. 24, aspects of another embodiment of an assembled cover 24 are depicted. FIG. 24A depicts a template (ie, blank 34 ) for providing the body of cover 24 . The size of the template generally matches the housing 7 of the appropriate type of energy storage unit (eg, supercapacitor 10). Cover 24 may be formed by initially providing a template to form a template that includes domes 37 in the template (shown in Figure 24B); then perforating domes 37 to provide channels 32 (shown in Figure 24C). Of course, the blank 34 (eg, an annular stocker) may be pressed or otherwise fabricated so as to provide the aforementioned features at the same time.

In general and with regard to these embodiments, the lid may be formed of aluminum or an alloy thereof. However, the cover may be formed of any material deemed appropriate by the manufacturer, user, designer, etc. For example, the cover 24 may be made of steel and passivated (ie, coated with an inert paint) or prepared for the housing 7 by other methods.

Referring now to FIG. 25, another embodiment of an electrode assembly 50 is shown. In these embodiments, electrode assembly 50 includes feedthrough 19 and a hemispherical shaped material disposed around feedthrough 19 . The hemispherical shaped material acts as insulator 26 and is generally shaped to conform to dome 37 . The hemispherical insulator 26 may be made of any suitable material to provide a hermetic seal while resisting the chemical effects of the electrolyte 6 . Exemplary materials include PFA (perfluoroalkoxy resin), FEP (fluorinated ethylene propylene copolymer), PVF (polyvinyl fluoride), TFE (tetrafluoroethylene), CTFE (chlorotrifluoroethylene), PCTFE (polytrifluoroethylene) Fluorochloroethylene), ETFE (polyethylene tetrafluoroethylene), ECTFE (polyethylene-chlorotrifluoroethylene), PTFE (polytetrafluoroethylene), another fluoropolymer based material, and any others that can show similar Materials that characterize (to varying degrees) and provide satisfactory performance (eg, exhibit high resistance to dissolution, acid, etc., under conditions of high temperature, low cost, etc., among others).

Feedthrough 19 may be formed of aluminum or alloys thereof. However, the feedthrough 19 may be formed of any material deemed appropriate by the manufacturer, user, designer, or the like. For example, feedthrough 19 may be made of steel and passivated (ie, coated with an inert coating such as silicon) or prepared for use in electrode assembly 50 by other methods. Exemplary techniques for passivation include depositing a hydrogenated amorphous silicon coating on the surface of a substrate and effectively by exposing the substrate to a binder having at least one unsaturated hydrocarbon group under pressure and elevated temperature for a period of time length of time to functionalize the coated substrate. The hydrogenated amorphous silicon coating is deposited by exposing the substrate to silicon hydride gas under pressure and elevated temperature for an effective length of time.

The hemispherical insulator 26 may be sized relative to the dome 37 to achieve a snug fit (ie, a hermetic seal) when assembled into the cover 24 . The hemispherical insulator 26 need not be perfectly symmetrical or have classical hemispherical proportions. That is, the hemispherical insulator 26 is substantially hemispherical and may include, for example, fine-tuning of proportions, moderate flanges (eg, at the base), and other features as deemed appropriate. The hemispherical insulator 26 is generally formed of a uniform material, however, this is not a requirement. For example, hemispherical insulator 26 may include air or gas in a torus (not shown) filled therein to provide the desired expansion or compressibility.

As shown in FIG. 26, the electrode assembly 50 may be inserted into a template (ie, the formed blank 34) to provide one embodiment of the cover 24 that includes a hemispherical hermetic seal.

As shown in Figure 27, in many embodiments, retainer 43 may engage or otherwise mate with the bottom of cover 24 (ie, the portion of cover 24 that faces the interior of housing 7 and faces energy storage unit 12). Retainer 43 may be joined to cover 24 by various techniques such as aluminum welding (eg, laser, ultrasonic, etc.). Other techniques may be used for bonding, including, for example, stamping (ie, mechanical bonding) and brazing. Engagement may occur, for example, along the circumference of the retainer 43 . Generally speaking, at least one joint is provided to produce the desired seal 71 . At least one fastener (eg, a plurality of rivets) may be used to seal insulator 26 in retainer 43 .

In the embodiment of Figure 27, the cover 24 is of concave design (see Figure 18B). However, other designs can also be used. For example, a raised cover 24 (FIG. 18C) may be provided, and an upper cover 24 may also be used (a variation of the embodiment of FIG. 18C configured for installation as depicted in FIG. 22C).

Materials for the cover and feedthrough 19 may be selected taking into account the thermal expansion of the hemispherical insulator 26 . In addition, manufacturing techniques can also be designed to account for thermal expansion. For example, when assembling cover 24, a manufacturer may apply pressure to hemispherical insulator 26, thereby compressing hemispherical insulator 26 at least to some extent. In this manner, provision is made for the presence of at least some thermal expansion of the cover 24 without compromising the effectiveness of the hermetic seal.

To further illustrate the assembled ultracapacitor, reference is made to FIG. 28, wherein a cross-sectional view of the ultracapacitor 10 is provided. In this embodiment, the storage unit 12 is inserted into and contained in the body 20 . Each set of multiple leads are tied together and coupled to the housing 7 as one of the terminals 8 . In some embodiments, multiple leads are coupled to the bottom (inside) of the body 20 , thereby turning the body 20 into the negative contact 55 . Likewise, another set of multiple leads are tied together and coupled to feedthrough 19 to provide positive contact 56 . Electrical isolation between negative contact 55 and positive contact 56 is maintained by electrical insulator 26 . Generally, the coupling of the leads is accomplished by welding, such as at least one of laser and ultrasonic welding. Of course, other techniques may be used as deemed appropriate.

ii. Internal Barriers

Referring now to FIG. 13 , the housing 7 may include an internal barrier 30 . In some embodiments, barrier 30 is a coating. In this embodiment, the barrier 30 is formed of polytetrafluoroethylene (PTFE). Polytetrafluoroethylene (PTFE) exhibits various properties that make this composition well suited for barrier 30 . PTFE has a melting point of about 327 degrees Celsius, excellent dielectric properties, a coefficient of friction of about 0.05 to 0.10 (the third lowest of any known solid material), high corrosion resistance, and other beneficial properties. In general, the interior portion of the cover 24 may include a barrier 30 disposed thereon.

Other materials may also be used for barrier 30 . These other materials are formed from ceramics (any type of ceramic that may be suitable for the application and meet performance criteria), other polymers (preferably high temperature polymers), and the like. Exemplary other polymers include perfluoroalkoxy resins (PFA) and fluorinated ethylene propylene copolymers (FEP) and ethylene-tetrafluoroethylene copolymers (ETFE).

Barrier 30 may comprise any material or combination of materials that provides a reduction in electrochemical or other types of reactions between energy storage unit 12 and housing 7 or components of housing 7 . In some embodiments, the combination is embodied as a uniform dispersion of the different materials in a single layer. In further embodiments, the combination is embodied as different materials in multiple layers. Other combinations can be used. In short, the barrier 30 can be considered to be at least one of an electrical insulator and chemically inert (ie, exhibits low reactivity), and thus, significantly resists or prevents electrical interactions between the storage unit 12 and the housing 7 and at least one of chemical interactions. In some embodiments, the terms "low reactivity" and "low chemical reactivity" generally refer to chemical interaction rates below the level of interest of the parties involved.

In general, the interior of the housing 7 can accommodate the barrier 30 so as to cover all surfaces of the housing 7 exposed to the interior. At least one untreated region 31 may be included in the body 20 and on the outer surface 36 of the cover 24 (see Figure 14A). In some embodiments, untreated areas 31 (see FIG. 14B ) may be included to meet assembly requirements, such as areas to be sealed or joined (eg, by welding).

Barrier 30 may be applied to the interior portion using conventional techniques. For example, in the case of PTFE, the barrier 30 may be applied by painting or spraying the barrier 30 as a paint on the interior surface. A mask may be used as part of a method to ensure that the untreated area 31 retains the desired integrity. Briefly, the barrier 30 can be provided using a variety of techniques.

In an exemplary embodiment, the thickness of the barrier 30 is from about 3 mils to about 5 mils, and the material used for the barrier 30 is a PFA-based material. In this example, the surface for receiving the material making up the barrier 30 is prepared by sandblasting, for example, with alumina. Once the surface is cleaned, the material is applied first as a liquid and then as a powder. The material is cured by a heat treatment process. In some embodiments, the heating cycle is at a temperature of about 370 degrees Celsius for a duration of about 10 minutes to about 15 minutes. This results in continuous polishing of the barrier 30 that is substantially free of defects of pinhole size or smaller. FIG. 15 depicts the assembly of an embodiment of the ultracapacitor 10 in accordance with the teachings herein. In this embodiment, the ultracapacitor 10 includes: a body 20 including a barrier 30 disposed therein; a lid 24 having the barrier 30 disposed therein; and an energy storage unit 12 . During assembly, the cover 24 is placed over the body 20 . The first terminal 8 is electrically coupled to the cover feedthrough 19 while the second terminal 8 is electrically coupled to the housing 7 , typically at the bottom, side or on the cover 24 . In some embodiments, the second terminal 8 is coupled to another feedthrough 19 (eg, the opposite cover 24).

With the barrier 30 disposed on the interior surface of the casing 7, electrochemical and other reactions between the casing 7 and the electrolyte are greatly reduced or substantially eliminated. This is particularly evident at higher temperatures where the rates of chemical and other reactions generally increase.

Referring now to FIG. 16, the relative performance of the ultracapacitor 10 compared to other equivalent ultracapacitors is shown. In Figure 16A, the leakage current of a prior art embodiment of the supercapacitor 10 is shown. In Figure 16B, the leakage current of the equivalent supercapacitor 10 including the barrier 30 is shown. In Figure 16B, the supercapacitor 10 is electrically equivalent to the supercapacitor whose leakage current is shown in Figure 16A. In both cases, the housing 7 was stainless steel, the voltage applied to the cell was 1.75 volts, and the electrolyte was not purified. The temperature was kept constant at 150 degrees Celsius. In particular, the leakage current in FIG. 16B shows a low initial value and does not increase significantly over time, while the leakage current in FIG. 16A shows a relatively high initial value and increases significantly over time.

In general, the barrier 30 provides a suitable material of suitable thickness between the energy storage unit 12 and the housing 7 . Barrier 30 may comprise a homogeneous mixture, a heterogeneous mixture, and/or at least one layer of material. The barrier 30 may provide full coverage (ie, provide coverage of the interior surface area of the housing excluding the electrode contacts) or partial coverage. In some embodiments, barrier 30 is formed from multiple components. For example, consider the embodiment shown below and shown in FIG. 8 .

17, aspects of other embodiments are shown. In some embodiments, the energy storage unit 12 is disposed in an envelope 73 . That is, the energy storage unit 12 has a barrier 30 disposed thereon, packaged over it, or otherwise applied once assembled to isolate the energy storage unit 12 from the housing 7 . The encapsulant 73 can be applied well before the energy storage unit 12 is encapsulated in the housing 7 . Therefore, the use of the encapsulant 73 may present certain advantages, eg, for the manufacturer. (It should be noted that the encapsulant 73 is shown loosely disposed on the energy storage unit 12 for illustration purposes).

In some embodiments, the encapsulant 73 is used in conjunction with a coating, wherein the coating is disposed on at least a portion of the interior surface. For example, in one embodiment, the paint is provided only in areas inside the housing 7 where the encapsulant 73 may be at least partially damaged (eg, the protruding terminals 8). The encapsulant 73 forms an efficient barrier 30 together with the coating.

Thus, the incorporation of barrier 30 may provide an ultracapacitor exhibiting a lower initial value of leakage current and a substantially slower increase in leakage current over time than in the prior art. Significantly, the leakage current of supercapacitors remains at practical (ie, desirably low) levels when exposed to ambient temperatures at which prior art capacitors would exhibit excessively large initial leakage current values and /or the leakage current increases too rapidly over time.

Having thus described the embodiment of the barrier 30 and its many aspects, it should be appreciated that the ultracapacitor 10 may exhibit other benefits resulting from the reduced reaction between the housing 7 and the energy storage medium 1 . For example, the effective series resistance (ESR) of ultracapacitor 10 may exhibit relatively low values over time. Furthermore, undesired chemical reactions that occur in prior art capacitors often produce undesired effects such as outgassing, or bulging of the case where the case is hermetically sealed. In both cases, this results in compromise of the structural integrity of the case and/or the hermetic seal of the capacitor. Ultimately, this can lead to leakage or catastrophic failure of prior art capacitors. In some embodiments, these results can be significantly reduced or eliminated by the use of the disclosed barrier 30 .

It should be appreciated that the terms "barrier" and "coating" are not limited to the teachings herein. That is, any technique for applying a suitable material to the interior of housing 7, body 20 and/or cover 24 may be used. For example, in other embodiments, the barrier 30 is actually fabricated into or onto the material that makes up the housing body 20 , which is then machined or shaped as appropriate to form the various components of the housing 7 . When considering some of the many possible techniques for applying the barrier 30, the material may be applied by roll on, sputtering, sintering, lamination, printing, or by other methods as appropriate. In short, barrier 30 may be applied using any technique deemed appropriate by the manufacturer, designer, and/or user.

The material used in barrier 30 may be selected based on properties such as reactivity, dielectric value, melting point, adhesion to the material of housing 7, coefficient of friction, cost, and other such factors. Combinations of materials (eg, layered, mixed, or otherwise combined) can be used to provide the desired properties.

In some embodiments, the use of a reinforced casing 7 (eg, casing 7 with barrier 30 ) can limit degradation of electrolyte 6 . While the barrier 30 illustrates one technique for providing a reinforced shell 7, other techniques may be employed. For example, the use of a housing 7 made of aluminium is advantageous due to the electrochemical properties of aluminium in the presence of the electrolyte 6 . However, in view of the difficulties in the manufacture of aluminum, it has not been possible (so far) to construct an embodiment of the housing 7 using aluminum.

Additional embodiments of the housing 7 include those in which aluminum is present on all interior surfaces exposed to the electrolyte, while providing the user with the ability to weld and hermetically seal the housing. The improved performance of the ultracapacitor 10 may be achieved through reduced internal corrosion, reduced problems associated with the use of dissimilar metals in the conductive medium, and other reasons. Advantageously, the housing 7 utilizes prior art such available electrode inserts including glass-metal seals (and may include those fabricated from stainless steel, tantalum or other advantageous materials and compositions) and thus can be manufactured economically.

Although disclosed herein as suitable embodiments for the housing 7 of the supercapacitor 10, these embodiments (as with the barrier 30) may be used with any type of energy storage deemed suitable, and may include any types of available technologies. For example, other forms of energy storage may be used, including electrochemical cells, particularly lithium-based cells.

In general, materials exposed to the interior of housing 7 exhibit sufficiently low reactivity when exposed to electrolyte 6 (ie, the advanced electrolyte system of the present invention) and are thus merely illustrative of some embodiments and not limiting herein. 's teaching.

F. Factors in the general construction of capacitors

An important aspect to consider in the construction of ultracapacitor 10 is maintaining good chemical hygiene. To ensure the purity of the components, in many embodiments, the activated carbon, carbon fibers, rayon, carbon cloth and/or nanotubes that make up the energy storage medium 1 of the two electrodes 3 are dried in a vacuum environment at elevated temperatures. The isolator 5 is also dried at elevated temperature in a vacuum environment. Once the electrodes 3 and separators 5 are dried under vacuum, they are encapsulated in a housing 7 without final sealing or capping in an atmosphere of less than 50 parts per million (ppm) water. For example, the uncovered supercapacitor 10 may be dried under vacuum throughout the temperature range of about 100 degrees Celsius to about 300 degrees Celsius. Once this final drying is complete, the electrolyte 6 can be added and the case 7 sealed in a relatively dry atmosphere (eg, an atmosphere with less than about 50 ppm moisture). Of course, other methods of assembly may be used, and the foregoing merely provides some exemplary aspects of the assembly of ultracapacitor 10 .

III. Methods of the Invention

Certain methods of the present invention for reducing impurities or making devices of the present invention are described herein below. Such purification methods are additionally applicable to any of the advanced electrolyte systems of the present invention.

A. Methods to reduce impurities

i.AES contamination

In certain embodiments, the advanced electrolyte systems (AES) of the present invention are purified to remove contaminants and provide the desired enhanced performance characteristics described herein. Accordingly, the present disclosure provides a method of purifying AES, the method comprising: mixing water into an advanced electrolyte system to provide a first mixture; separating the first mixture; collecting the advanced electrolyte system from the first mixture; The collected liquid is added with solvent to provide a second mixture; carbon is mixed into the second mixture to provide a third mixture; and the advanced electrolyte system is separated from the third mixture to obtain a purified advanced electrolyte system. In general, the method requires electrolyte selection, addition of deionized water, and activated carbon under controlled conditions. Subsequent removal of deionized water and activated carbon resulted in a substantially purified electrolyte. Purified electrolytes are especially suitable for use in supercapacitors.

This method can be used to ensure high purity of the Advanced Electrolyte System (AES) of the present invention. It should be noted that although the method is expressed in terms of specific parameters (eg, amount, formulation, time, etc.), this expression is merely an example and illustration of a method for purifying electrolytes, and is not limiting.

For example, the method may further comprise one or more of the following steps or features: heating the first mixture; wherein separating comprises allowing the first mixture to stand undisturbed until the water and AES are substantially separated; wherein adding a solvent Including adding at least one of ether, isopentenyne (pentone), cyclopentone (cyclopentone), hexane, cyclohexane, benzene, toluene, 1-4-dioxane and chloroform; wherein the mixed carbon comprises mixed carbon powder; wherein mixing the carbon comprises substantially continuously stirring the third mixture; wherein separating the AES comprises at least one of leaching the carbon from the third mixture and evaporating the solvent from the third mixture.

In the first step of the method for purifying the electrolyte, the electrolyte 6 (in some embodiments, an ionic liquid) is mixed with deionized water and then raised to a moderate temperature for a period of time. In the proof-of-concept, fifty (50) milliliters (ml) of ionic liquid was mixed with eight hundred fifty (850) milliliters (ml) of deionized water. The mixture was raised to a constant temperature of sixty (60) degrees Celsius for about twelve (12) hours with constant stirring (about one hundred twenty (120) parts per minute (rpm)).

In the second step, the mixture of ionic liquid and deionized water is allowed to separate. In this example, the mixture was transferred via a funnel and then allowed to sit for approximately four (4) hours.

In the third step, the ionic liquid is collected. In this example, the aqueous phase of the mixture is at the bottom and the ionic liquid phase is at the top. Transfer the ionic liquid phase to another beaker.

In the fourth step, the solvent is mixed with the ionic liquid. In this example, a volume of about twenty-five (25) milliliters (ml) of ethyl acetate was mixed with the ionic liquid. The mixture was then brought to moderate temperature and stirred for some time.

Although ethyl acetate is used as the solvent, the solvent may be at least one of the following: diethyl ether, pentone, cyclopentone, hexane, cyclohexane, benzene, toluene, 1-4-Dioxane, chloroform, or any combination thereof, and other materials exhibiting appropriate performance characteristics. Some desirable performance characteristics include those of non-polar solvents and high volatility.

In the fifth step, carbon powder is added to the mixture of ionic liquid and solvent. In this example, about twenty (20) weight percent (wt%) carbon (about 0.45 micron diameter) was added to the mixture.

In the sixth step, the ionic liquid is mixed again. In this example, the mixture with carbon powder was then subjected to constant stirring (120 rpm) overnight at about seventy (70) degrees Celsius.

In the seventh step, the carbon and ethyl acetate were separated in the ionic liquid. In this example, a Buchner funnel with a glass microfiber filter was used to separate the carbon. Multiple filtrations (3 times) were performed. The collected ionic liquid was then passed through a 0.2 micron syringe filter to remove substantially all carbon particles. In this example, the solvent is then separated from the ionic liquid by employing rotary evaporation. Specifically, a sample of the ionic liquid was stirred while increasing the temperature from seventy (70) degrees Celsius to eighty (80) degrees Celsius, and finally one hundred (100) degrees Celsius. At each of the various temperatures, evaporation is performed for approximately fifteen (15) minutes.

The method used to purify the electrolyte has proven to be very effective. For the sample ionic liquid, the water content was measured by titration using a titrator (Model: AQC22) supplied by Mettler-Toledo Inc. of Columbus, Ohio. Halogen content was measured with an ISE instrument (Model: AQC22) supplied by Hanna Instruments of Woonsocket, Rhode Island. Standard solutions for the ISE instrument were obtained from Hanna and included HI 4007-03 (1000 ppm chlorine standard), HI 4010-03 (1000 ppm fluorine standard), HI 4000-00 (ISA for halogen electrodes) and HI4010-00 ( TISAB solution for fluorine electrodes only). The ISE meter was calibrated with standard solutions using 0.1, 10, 100 and 1000 parts per million (ppm) standards mixed with deionized water prior to taking measurements. ISA buffer was added to the standard at a ratio of 1:50 to measure Cl- ions. The results are shown in Table 3.

table 3

Contains 1-butyl-1-methylpyrrolidine Purification data for electrolytes with tetracyanoborate

impurities Before (ppm) After (ppm) Deionized water (ppm) Cl^- 5,300.90 769 9.23E-1 F- 75.61 10.61 1.10E-1 H₂O 1080 20 --

A four-step process is used to measure halide ions. First, ^Cl- and F- ions are measured ⁱⁿ deionized water. Next, a 0.01 M ionic liquid solution was prepared with deionized water. Then, ^Cl- ions ^and F- ions are measured in the solution. An estimate of the halogen content is then determined by subtracting the amount of ions in the water from the amount of ions in the solution.

Purification criteria regarding the composition of electrolyte contaminants were also checked by analysis of leakage currents. FIG. 9 depicts the leakage current of the unpurified electrolyte in supercapacitor 10 . FIG. 10 depicts the leakage current of purified electrolyte in a similarly constructed supercapacitor 10 . As can be seen, the initial leakage current is significantly reduced, and the leakage current in the latter part of the measurement interval is moderately reduced. More information is provided based on the structure of each embodiment in Table 4.

Table 4

Test the construction of supercapacitors

parameter Figure 9 Figure 10 Cell size: Open Sub C Open Sub C Sleeve: Coated with P870 Coated with P870 Electrode material: Double-sided activated carbon (150/40) Double-sided activated carbon (150/40) Isolator: glass fiber glass fiber Electrode size: IE: 233×34mm OE: 256×34mm IE: 233×34mm OE: 256×34mm Splicing: 0.005" Aluminum (3 Tabs) 0.005" Aluminum (3 Tabs) temperature: 150℃ 150℃ Electrolyte: Unpurified AES Purified AES

Other benefits are also realized, including improved stability of the resistance and capacitance of the ultracapacitor 10 .

Leakage current can be determined in a number of ways. Qualitatively, once the device has reached equilibrium, leakage current can be considered to be the current introduced into the device. In practice, it is always or almost always necessary to estimate the actual leakage current as an equilibrium state which is generally only asymptotically approachable. Thus, leakage current in a given measurement can be estimated by measuring the current drawn into the ultracapacitor 10 while the ultracapacitor 10 is maintained at a substantially fixed voltage and exposed to a substantially fixed ambient temperature for a relatively long period of time. In some cases, a relatively long period of time may be determined by estimating the current time function as an exponential function and then passing through several (eg, about 3 to 5) characteristic time constants. Often for many ultracapacitor technologies, such durations are from about 50 hours to about 100 hours. Alternatively, if such long periods of time are not feasible for any reason, it may be possible to simply re-calculate the leakage current by estimating the current-time function as an exponential function, or any approximation function deemed appropriate. It is worth noting that the leakage current will generally depend on the ambient temperature. Therefore, in order to characterize the performance of a device at a certain temperature or within a certain temperature range, it is often important to expose the device to the intended ambient temperature when measuring the leakage current.

Note that one way to reduce the volumetric leakage current at a particular temperature is to reduce the operating voltage at that temperature. Another way to reduce the volumetric leakage current at a specific temperature is to increase the void volume of the supercapacitor. Yet another way to reduce leakage current is to reduce the load on the energy storage medium 1 on the electrode 3 .

Having disclosed various aspects of embodiments for purifying electrolytes and ionic liquids, it should be appreciated that various embodiments may be implemented. Additionally, various techniques may be implemented. For example, steps, order of steps, etc. may be adjusted.

ii. Water/Moisture Content and Removal

The case 7 of the sealed ultracapacitor 10 can be opened and the storage unit 12 sampled to detect impurities. The Karl Fischer method was used to measure the water content from the electrodes, separator and electrolyte of the cell 12 . Three measurements were taken and averaged.

In general, a method for characterizing contaminants in an ultracapacitor involves opening the case 7 to obtain its contents, sampling the contents and analyzing the sample. Techniques disclosed elsewhere herein can be used to support the characterization.

It should be noted that to ensure accurate measurement of impurities in supercapacitors and their components, including electrodes, electrolytes, and separators, assembly and disassembly can be performed in a suitable environment (eg, an inert environment in a glove box).

By reducing the moisture content in the supercapacitor 10 (eg, to below 500 parts per million (ppm) to below 1000 ppm by mass and volume relative to the electrolyte and impurities), the supercapacitor 10 may be more durable over the entire temperature range. Operates efficiently with less than 10 amps/liter of leakage current (I/L) over this temperature and voltage range.

In one embodiment, leakage current (I/L) at a particular temperature is measured by holding the voltage of the ultracapacitor 10 constant at the rated voltage (ie, the maximum rated operating voltage) for seventy-two (72) hours. During this time, the temperature remains relatively constant at a certain temperature. The leakage current of the supercapacitor 10 is measured at the end of the measurement interval.

In some embodiments, the maximum voltage rating of the ultracapacitor 10 is about 4V at room temperature. One way to ensure the performance of the ultracapacitor 10 at elevated temperatures (eg, in excess of 210 degrees Celsius) is to derate (ie, reduce) the voltage rating of the ultracapacitor 10 . For example, the voltage rating can be adjusted as low as about 0.5V so that extended durations of operation can be obtained at higher temperatures.

B. Manufacturing method of supercapacitor

In another embodiment, the present invention provides a method for fabricating a supercapacitor, the method comprising the steps of: disposing an energy storage unit comprising an energy storage medium within a housing; and using an Advanced Electrolyte System (AES) The case is filled so that the supercapacitor is fabricated to operate in a temperature range of about -40 degrees Celsius to about 210 degrees Celsius.

For example, in one specific embodiment, the AES includes a Novel Electrolyte Entity (NEE), wherein the NEE is suitable for use in high temperature supercapacitors. In certain embodiments, the ultracapacitor is configured to operate at a temperature within a temperature range of about 80 degrees Celsius to about 210 degrees Celsius (eg, in a temperature range of about 80 degrees Celsius to about 150 degrees Celsius).

In a particular embodiment, the AES includes a highly purified electrolyte, eg, wherein the highly purified electrolyte is suitable for use in high temperature capacitors. In certain embodiments, the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 210 degrees Celsius, eg, in a temperature range of about 80 degrees Celsius to about 150 degrees Celsius.

In a particular embodiment, the AES includes an enhanced electrolyte combination, eg, wherein the enhanced electrolyte combination is suitable for use in both high temperature and low temperature supercapacitors. In certain embodiments, the ultracapacitor is configured to operate at a temperature in a temperature range of about -40 degrees Celsius to about 150 degrees Celsius, eg, in a temperature range of about -30 degrees Celsius to about 125 degrees Celsius.

In one embodiment, the fabricated ultracapacitor is the ultracapacitor described herein above in Section II. Accordingly, and as described above, the advantages over existing electrolytes of known energy storage devices are selected from one or more of the following improvements: reduced overall resistance, increased long-term stability of resistance, increased overall capacitance, capacitance Improved long-term stability, increased energy density, improved voltage stability, reduced vapor pressure, wider temperature range performance of a single capacitor, improved temperature durability of a single capacitor, improved ease of manufacture, and improved cost-effectiveness.

In certain embodiments, the disposing step further comprises pretreating the components of the supercapacitor to reduce moisture therein, the components of the supercapacitor comprising: at least one of an electrode, a separator, a lead, an assembled energy storage unit, and a housing . In certain embodiments, the pretreatment includes heating the selected components substantially under vacuum at a temperature ranging from about 100 degrees Celsius to about 150 degrees Celsius. The pretreatment may include heating the selected components substantially under vacuum at a temperature ranging from about 150 degrees Celsius to about 300 degrees Celsius.

In certain embodiments, the setting is performed in a substantially inert environment.

In certain embodiments, the constructing step includes selecting an interior surface material for the casing that exhibits low chemical reactivity with the electrolyte, which may also include including the interior surface material in a substantial portion of the interior of the casing. The inner surface material can be selected from aluminum, polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE) and ceramic materials at least one of them is used as the internal surface material.

In certain embodiments, the constructing step includes forming the housing from multiple layers of material, eg, wherein forming the housing from multiple layers of material includes disposing a weldable material on the exterior of the housing.

In certain embodiments, the constructing step includes fabricating at least one of a cover and a body for the housing. The manufacturing step may include disposing a seal including an insulator and an electrode insulated from the housing in the housing. Additionally, providing the seal may include providing a glass-to-metal seal, eg, welding the glass-to-metal seal to an outer surface of the housing. In particular embodiments, disposing the seal includes disposing a hemispherical seal.

In certain embodiments, the constructing step includes disposing a fill port in the housing for filling.

In certain embodiments, the fabrication method may further include fabricating an energy storage unit, eg, by connecting an energy storage medium and a current collector to obtain an electrode; eg, connecting at least one lead to the electrode. In certain embodiments, connecting at least one lead to the electrode includes disposing at least one reference mark on the electrode. In certain embodiments, connecting the at least one lead to the electrode includes positioning each lead at a respective reference mark. In certain embodiments, connecting the at least one lead includes scavenging the energy storage medium from the current collector. In certain embodiments, connecting the at least one lead includes ultrasonically welding the lead to the current collector.

The electrodes can also be obtained by connecting a plurality of electrode elements made by connecting the energy storage medium and the current collector. A plurality of electrode elements may be connected by ultrasonically welding connecting elements to the current collector of one electrode element and the current collector of the other electrode element.

In certain embodiments, fabricating the energy storage cell includes disposing a separator between at least two electrodes. And can also include aligning each of the electrodes with the separator.

In certain embodiments, fabricating the energy storage unit includes encapsulating at least two electrodes with a separator disposed therebetween, eg, wherein the encapsulation includes rolling the storage unit into a rolled storage unit.

In certain embodiments, manufacturing the energy storage unit includes disposing a wrap over the storage unit.

In certain embodiments, disposing the energy storage cell includes bringing together a plurality of leads to provide a terminal, eg, wherein bringing the plurality of leads together includes aligning the leads together into a set of aligned leads to form a terminal. In certain embodiments, the method further includes disposing a wrapper around the set of aligned leads; folding the set of aligned leads, or coupling the set of aligned leads to contacts of the housing. Additionally, coupling may include soldering a set of aligned leads to the contacts, or soldering a set of aligned leads to one of a jumper and a bridge for coupling to the contacts of the housing.

In certain embodiments, the manufacturing method may further include electrically coupling at least one of the jumper wire and the bridge to the contacts of the housing. In particular embodiments, it may also include substantially disposing insulating material on the contacts on the interior of the housing.

In certain embodiments, the manufacturing method may further include hermetically sealing the energy storage unit within the housing, for example, wherein the hermetically sealing includes pulse welding, laser welding, resistance welding, and TIG welding together components of the housing at least one of them.

In certain embodiments, the manufacturing method may further include mating at least one cover with the body to provide a housing, eg, wherein the cover includes one of a female cover, a male cover, and a flat cover. In particular embodiments, the method may further include removing at least a portion of the multilayer material within the housing to provide a match.

In certain embodiments, the method of manufacture may further comprise purifying the AES.

In certain embodiments, the method of manufacture may further include disposing a fill port within the housing for filling, eg, wherein filling includes disposing an AES via fill port in the housing. In particular embodiments, the method further includes sealing the fill port after completing the filling, eg, fitting a compatible material into the fill port. In another step, such material may then be welded to the housing.

In certain embodiments, the filling step includes evacuating the housing at the filling port, eg, wherein the vacuum is less than about 150 mTorr, eg, wherein the vacuum is less than about 40 mTorr.

In certain embodiments, the packing step is performed in a substantially inert environment.

i. Manufacturing Technology

Furthermore, it should be recognized that certain robust assembly techniques may be required to provide efficient energy storage. Therefore, some techniques for assembly are now discussed.

Once the ultracapacitor 10 is fabricated, it can be used in high temperature applications with little or no leakage current and little resistance rise. The ultracapacitors 10 described herein can operate efficiently at temperatures from about -40 degrees Celsius to about 210 degrees Celsius with leakage currents below 10 ampere per liter (A/L) volume of the device over the entire operating voltage and temperature range normalized to the device volume. In certain embodiments, the capacitors may operate at temperatures ranging from -40 degrees Celsius to 210 degrees Celsius.

As an overview, a method of assembling a cylindrically shaped supercapacitor 10 is provided. Starting with electrodes 3, each electrode 3 is fabricated once the energy storage medium 1 is connected to the current collector 2. Multiple leads are then coupled to each electrode 3 at appropriate locations. The plurality of electrodes 3 are then oriented and assembled therebetween with an appropriate number of spacers 5 to form the storage cell 12 . The storage unit 12 can then be rolled into a cylinder and secured with wraps. In general, corresponding ones of the leads are then bundled to form each terminal 8 .

Before incorporating the electrolyte 6 (ie, the advanced electrolyte system of the present invention) into the ultracapacitor 10 (eg, before or after assembling the storage cell 12 ), the various components of the ultracapacitor 10 may be dried to remove moisture. This can be done on the unassembled parts (ie the empty casing 7 and each electrode 3 and each separator 5) and then on the assembled parts (eg the storage unit 12).

Drying can be carried out, for example, in a vacuum environment at elevated temperature. Once dried, the storage unit 12 can then be enclosed in the housing 7 without final sealing or capping. In some embodiments, the encapsulation is performed in an atmosphere having less than 50 parts per million (ppm) water. The uncovered supercapacitor 10 can then be dried again. For example, the ultracapacitor 10 may be dried under vacuum at a temperature ranging from about 100 degrees Celsius to about 300 degrees Celsius. Once this final drying has been completed, the housing 7 can then be sealed in an atmosphere having, for example, less than 50 ppm moisture.

In some embodiments, once the drying process (which may also be referred to as a "baking" process) is complete, the environment surrounding the part may be filled with an inert gas. Exemplary gases include argon, nitrogen, helium, and other gases (and combinations thereof) that exhibit similar properties.

Generally, fill ports (perforations in the surface of the housing 7) are included in the housing 7 or can be added later. Once the ultracapacitor 10 has been filled with the electrolyte 6 (ie, the advanced electrolyte system of the present invention), the fill port can be closed. Closing the fill port can be accomplished, for example, by welding a material (eg, a metal compatible with the housing 7) into or over the fill port. In some embodiments, the fill port can be temporarily closed prior to filling, so that the ultracapacitor 10 can be moved to another environment for subsequent reopening, filling, and closing. However, as discussed herein, it is believed that the supercapacitor 10 is dried and filled in the same environment.

A number of methods can be used to fill the housing 7 with the desired amount of advanced electrolyte system. In general, control of the filling process can provide increased capacitance, reduced equivalent series resistance (ESR), limited waste of electrolyte, and the like. The vacuum filling method is provided as one non-limiting example of a technique for filling the housing 7 and wetting the storage cell 12 with electrolyte 6 .

However, it should first be noted that measurements can be made to ensure that any materials that may contaminate components of the ultracapacitor 10 are clean, compatible and dry. As a general rule, "good hygiene" can be considered to be practiced to ensure that the assembly process and components do not introduce contaminants into the ultracapacitor 10 .

Under the "vacuum method", the container is arranged on the housing 7 around the filling port. A quantity of electrolyte 6 (ie, the advanced electrolyte system of the present invention) is then placed in the container in an environment substantially free of oxygen and water (ie, moisture). A vacuum is then drawn in this environment, drawing out any air from the casing and thereby drawing the electrolyte 6 into the casing 7 at the same time. The surrounding environment can then be refilled with an inert gas (eg, argon, nitrogen, etc., or some combination of inert gases) if desired. The ultracapacitor 10 can be checked to see if the desired amount of electrolyte 6 has been drawn in. This process can be repeated as needed until the desired amount of electrolyte 6 is in the supercapacitor 10 .

In some embodiments, after filling the electrolyte 6 (ie, the advanced electrolyte system of the present invention), the material may be fitted to the fill port to seal the supercapacitor 10 . For example, the material may be a metal compatible with the casing 7 and the electrolyte 6 . In one embodiment, the material is force fit into the fill port in which "cold welding" of the plug is primarily performed. In specific embodiments, as discussed further herein, the press fit may be supplemented by other welding techniques.

In general, assembly of the housing often involves disposing the storage unit 12 within the body 20 and filling the body 20 with an advanced electrolyte system. Another drying process can be performed. Exemplary drying includes heating the body 20 with the storage unit 12 and the advanced electrolyte system therein, typically under reduced pressure (eg, vacuum). Once sufficient (optional) drying has taken place, the final assembly step can be performed. In a final step, the internal electrical connections are made, the cover 24 is installed, and the body 20 is hermetically sealed with the cover 24 , eg by welding the cover 24 to the body 20 .

In some embodiments, at least one of housing 7 and cover 24 is fabricated to include a material that includes multiple layers. For example, the first material layer may comprise aluminum and the second material layer is stainless steel. In this example, stainless steel is clad to aluminum to provide a material that exhibits the desired combination of metallurgical properties. That is, in the embodiments provided herein, the aluminum is exposed to the interior of the energy storage unit (ie, the housing), while the stainless steel is exposed to the exterior. In this way, the advantageous electrical properties of aluminum are enjoyed while relying on the structural properties (and metallurgical properties, ie weldability) of stainless steel for construction. The multilayer material may include additional layers as deemed appropriate. Advantageously, this provides a relatively simple welding process for welding stainless steel to stainless steel.

When the material used to construct the body 20 includes aluminum, any type of aluminum or aluminum alloy deemed suitable by the designer or manufacturer (all of which are broadly referred to herein as "aluminum") is suitable. Various alloys, laminates, etc. may be provided (eg, clad) over the aluminum (the aluminum exposed inside the body 20). The body and/or housing 7 may be supplemented with additional materials such as structural materials or electrically insulating materials such as some polymer based materials. The material provided over the aluminium can likewise be chosen as the designer or manufacturer sees fit.

The use of aluminum is not necessary or required. In short, a choice of materials can be provided to use any material deemed appropriate by the designer, manufacturer, user, or the like. Various factors can be considered, such as reduction of electrochemical interaction with electrolyte 6, structural properties, cost, etc.

Embodiments of the supercapacitor 10 exhibiting a smaller volume can be fabricated in a prismatic form factor such that the electrodes 3 of the supercapacitor 10 face each other, at least one electrode 3 is in contact with the interior of the glass-to-metal seal, and the other electrode is in contact with the housing or glass- Internal contact of metal seals.

The volume of a particular ultracapacitor 10 can be enlarged by combining several storage units (eg, several jelly rolls welded together) in one housing 7 so that they are electrically parallel or connected in series.

In many embodiments, it is useful to use multiple ultracapacitors 10 together to provide power. To provide reliable operation, individual ultracapacitors 10 may be tested prior to use. To perform various types of testing, each ultracapacitor 10 may be tested as a single unit, in series or in parallel with multiple ultracapacitors 10 attached. The use of dissimilar metals joined by various techniques, such as by welding, can reduce the ESR of the join and increase the strength of the join. Aspects of the connection between ultracapacitors 10 are now described.

In some embodiments, the ultracapacitor 10 includes two contacts. These two contacts are the glass-to-metal seal pins (ie, the feedthrough 19 ) and the entire remainder of the housing 7 . When connecting multiple ultracapacitors 10 in series, it is often desirable to couple the interconnect between the bottoms of the casing 7 (in the case of the cylindrical casing 7 ) so that the distance to the inner leads is minimized, and therefore the resistance. In these embodiments, the opposite ends of the interconnect are often coupled to the pins of the glass-to-metal seal.

For interconnects, a common type of welding involves the use of parallel tip resistance welders. Soldering can be made by aligning the ends of the interconnects over the pins and soldering the interconnects directly to the pins. Using multiple solder joints will improve the strength and connection between the interconnect and the pin. In general, when soldering to the pins, the ends of the interconnects are shaped to match the pins well to ensure that there is substantially no excess material overlying the pins that could cause a short circuit.

An opposing tip resistance welder can be used to weld the interconnect to the pins, while an ultrasonic welder can be used to weld the interconnect to the bottom of the housing 7 . Brazing techniques can be used when the included metals are compatible.

In terms of materials used in interconnects, a common type of material for interconnects is nickel. Nickel can be used because it welds well to stainless steel and has a strong interface. Other metals and alloys can be used in place of nickel, for example, to reduce resistance in interconnects.

In general, the material chosen for the interconnect is chosen for its compatibility with the material in the pins and with the material in the housing 7 . Exemplary materials include copper, nickel, tantalum, aluminum, and nickel copper cladding. Other metals that can be used include silver, gold, brass, platinum and tin.

In some embodiments, such as where the pins (ie, feedthroughs 19 ) are made of tantalum, the interconnects may be connected using an intermediate metal, such as by employing short bridges. An exemplary bridge connection includes tantalum strips, which have been improved by welding aluminum/copper/nickel strips to the bridge using an opposing tip resistance welder. Then, use a parallel resistance welder to solder the tantalum bars to the tantalum pins.

The bridge can also be used on the contacts of the housing 7 . For example, a piece of nickel can be resistance welded to the bottom of the housing 7 . The copper bars can then be ultrasonically welded to the nickel bridges. This technique helps reduce the resistance of cell interconnects. Using a different metal for each connection can reduce the ESR of the interconnect between series cells.

Having thus described various aspects of a robust ultracapacitor 10 useful in high temperature environments (ie, up to about 210 degrees Celsius), some additional aspects are now provided and/or defined.

A wide variety of materials can be used to construct supercapacitors 10 . The integrity of the supercapacitor 10 is necessary if oxygen and moisture are to be vented and the electrolyte 6 is to be prevented from escaping. To achieve this, seam welds and any other sealing points should meet air tightness standards over the expected temperature range for operation. Furthermore, the selected materials should be compatible with other materials such as ionic liquids and solvents that can be used to formulate advanced electrolyte systems.

In some embodiments, the feedthrough 19 is formed of a metal, such as at least one of the following materials: KOVAR ^™ (a trademark of the Carpenter Technology Corporation of Reading, Pennsylvania, where KOVAR is a vacuum-fused, iron-nickel - Cobalt, low expansion alloy whose chemical composition is controlled within narrow boundaries to ensure precise and uniform thermal expansion properties), Alloy 52 (a nickel-iron alloy suitable for sealing glass and ceramics to metal), tantalum, molybdenum, niobium, tungsten, stainless steel 446 (ferritic, non-heat treatable stainless steel that provides good resistance to high temperature corrosion and oxidation) and titanium.

The body can be made of 300 series stainless steel (eg, 304, 304L, 316, and 316 alloys) using the aforementioned glass-to-metal seal. The body may also be made of metals such as at least one of various nickel alloys, such as Inconel (a family of austenitic nickel-chromium-based superalloys, which are well suited for experiencing stress) Oxidation and corrosion resistant materials for extreme environments of heat and heat) and Hastelloy (highly corrosion resistant metal alloys consisting of nickel and varying percentages of molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminium, carbon and tungsten).

The insulating material between the feedthrough 19 in the glass-to-metal seal and the surrounding body is typically glass, the composition of which is owned by each manufacturer of the seal and depends on whether the seal is under pressure or matched. Other insulating materials can be used in glass-to-metal seals. For example, a variety of polymers can be used in seals. Thus, the term "glass-to-metal" seal is merely a description of the type of seal and is not intended to imply that the seal must include glass.

The housing 7 of the ultracapacitor 10 may be made of, for example, types 304, 304L, 316 and 316L stainless steel. They can also be constructed from some aluminum alloys such as, but not limited to, 1100, 3003, 5052, 4043, and 6061. A variety of multilayer materials can be used, and can include, for example, aluminum clad to stainless steel. Other non-limiting compatible metals that can be used include platinum, gold, rhodium, ruthenium, and silver.

Particular embodiments of glass-to-metal seals that have been used in supercapacitors 10 include two different types of glass-to-metal seals. The first is from US SCHOTT in Elmsford, NY, USA. This embodiment uses stainless steel pins, glass insulators, and stainless steel bodies. The second glass-to-metal seal was from HERMETIC SEAL TECHNOLOGY of Cincinnatti, OH. This second embodiment employs tantalum leads, glass insulators, and stainless steel bodies. Numerous embodiments of different sizes may be provided.

Additional embodiments of glass-to-metal seals include embodiments using an aluminum seal and an aluminum body. Yet another embodiment of the glass-to-metal seal includes aluminum seals using epoxy or other insulating materials such as ceramic or silicon.

Many aspects of the glass-to-metal seal can be configured as desired. For example, the dimensions of the housing and pins, and the materials of the pins and housing can vary as desired. The pin can also be a tube or solid pin, as well as having multiple pins in one cover. While the most common types of materials used for pins are stainless steel alloys, copper core stainless steel, molybdenum, platinum-iridium, various nickel-iron alloys, tantalum, and other metals, some unconventional materials such as aluminum can be used. Housings are typically formed from stainless steel, titanium, and/or various other materials.

Various fastening techniques may be used in the combination of ultracapacitors 10 . For example, in the case of welding, a variety of welding techniques can be used. The following is an exemplary list of weld types and the various purposes for which each type of weld can be used.

Ultrasonic welding can be used to: solder aluminum tabs to current collectors; solder tabs to bottom cladding; solder jumper tabs to cladding bridges connected to glass-to-metal seal pins; Welded together etc. Pulse or resistance welding can be used to: solder leads to the bottom of the vessel or to pins; solder leads to current collectors; solder jumpers to clad bridges; solder clad bridges to terminal 8; solder leads to bottom cover, etc. Laser welding can be used to: weld stainless steel covers to stainless steel vessels; weld stainless steel bridges to stainless steel glass-to-metal seal pins; and weld stoppers to fill ports, etc. TIG welding can be used to: seal aluminum covers to aluminum containers; and weld aluminum seals into locations, etc. Cold welding (pressing metals together with very high force) can be used to seal fill ports etc. by force-fitting an aluminum ball/pin into the fill port.

ii. Certain advantageous embodiments of manufacture

Certain advantageous embodiments are provided herein below, which are not intended to be limiting.

In a specific embodiment, and referring to Figure 29, the components of an exemplary electrode 3 are shown. In this embodiment, electrode 3 will be used as negative electrode 3 (however, this designation is arbitrary and for reference only).

As can be noted from the description, at least in this embodiment, the isolator 5 is generally longer in length and wider in width than the energy storage medium 1 (and current collector 2). By using the larger separator 5, protection against short circuit of the negative electrode 3 and the positive electrode 3 is provided. The use of additional material in isolator 5 also provides better electrical protection for leads and terminals 8 .

Referring now to FIG. 30 , a side view of one embodiment of storage unit 12 is provided. In this embodiment, the layered stacked energy storage medium 1 includes a first separator 5 and a second separator 5 such that the electrodes 3 are electrically isolated when the storage unit 12 is assembled into a rolled storage unit 23 . It should be noted that the terms "positive" and "negative" are merely arbitrary with respect to the assembly of electrode 3 and ultracapacitor 10 and refer to functionality when configured in ultracapacitor 10 and storing charge therein. This convention, as generally applicable in the art, does not imply that charge is stored prior to assembly, or anything other than providing physical identification of the different electrodes.

Before winding the storage cell 12, the negative electrode 3 and the positive electrode 3 are aligned relative to each other. The alignment of the electrodes 3 provides better performance for the supercapacitor 10 because the path length for ion transport is generally the smallest with the highest degree of alignment. Furthermore, by providing a high degree of alignment, an oversized isolator 5 is not included, and thus the efficiency of the supercapacitor 10 is not compromised.

Referring now to FIG. 31 , one embodiment of the storage unit 12 is shown in which the electrodes 3 are rolled into a rolled storage unit 23 . One of the separators 5 is present as the outermost layer of the storage unit 12 and separates the energy storage medium 1 from the interior of the housing 7 .

"Polarity matching" may be employed to match the polarity of the outermost electrodes in the rolled storage cell 23 with the polarity of the body 20 . For example, in some embodiments, the negative electrode 3 is on the outermost side of the tightly packed package that provides the rolled storage cell 23 . In these embodiments, another degree of assurance against short circuits is provided. That is, when the negative electrode 3 is coupled to the body 20 , the negative electrode 3 is arranged in the rolled storage unit 23 as the outermost electrode. Thus, if the isolator 5 fails (eg, caused by mechanical wear caused by vibration of the supercapacitor 10 during use), the supercapacitor 10 will not be damaged between the outermost electrodes in the rolled storage cell 23 and the body 20 short-circuit and fail.

For each embodiment of the rolled storage unit 23 , reference numeral 72 may be in at least the isolator 5 . Reference numeral 72 will be used to provide for the positioning of the leads on each electrode 3 . In some embodiments, the location of the leads is provided by calculation. For example, by taking into account the inner diameter of the jelly roll and the total thickness of the separator 5 and electrode 3 combined, the placement position of each lead can be evaluated. However, practice has shown that using the reference sign 72 is more efficient and effective. The reference mark 72 may comprise, for example, a slit in the edge of the isolator 5 .

In general, reference numeral 72 is used for each new specification of storage unit 12 . That is, because new specifications for storage cell 12 may require a different thickness of at least one of the layers (in existing embodiments), the use of existing reference numerals may be at least somewhat inaccurate.

In general, reference numeral 72 is embodied as a single radial line from its center through the roll to its periphery. Thus, when the leads are mounted along reference mark 72, each lead will be aligned with the remaining leads (as shown in Figure 10). However, when the storage unit 12 is not rolled (an embodiment in which the storage unit 12 is a roll or will become a roll), the reference numeral 72 may be considered a plurality of marks (as shown in Figure 32). As a convention, regardless of the implementation or appearance of the markings of the storage unit 12, the identification of the locations for bonding leads is considered to involve the determination of a "reference mark 72" or a "set of reference marks 72."

Referring now to FIG. 32, once reference numerals 72 are established (eg, by marking the rolled-up storage unit 12), mounting sites (ie, depicted by reference numerals 72) are provided for mounting each lead. Once each mounting site is determined, for any given construction specification of storage unit 12, the relative position of each mounting site may be repeated for additional instances of the particular construction of storage unit 12.

In general, each lead is coupled to a respective current collector 2 in the storage unit 12 . In some embodiments, both the current collector 2 and the leads are made of aluminum. Generally, the leads are coupled to the current collector 2 across the width W, however the leads may be coupled to only a portion of the width W. Coupling can be achieved, for example, by ultrasonically welding the leads to the current collector 2 . To achieve the coupling, at least some of the energy storage medium 1 may be removed (where appropriate) so that each lead is properly connected to the current collector 2 . Other preparations and adjustments can be made to provide coupling as deemed appropriate.

In certain embodiments, opposing reference numerals 73 may be included. That is, provided in the same manner as reference numerals 72, a set of opposing reference numerals 73 can be made to allow for installation of leads of opposite polarity. That is, the reference mark 72 may be used for attaching the lead to the first electrode 3 , eg, the negative electrode 3 , while the opposite reference mark 73 may be used for attaching the lead to the positive electrode 3 . In embodiments in which the rolled storage unit 23 is cylindrical, opposing reference marks 73 are provided on opposite sides of the energy storage medium 1 and are longitudinally offset from reference marks 72 (as depicted).

Note that in FIG. 32 , both the reference numeral 72 and the opposite reference numeral 73 are shown as being provided on the single electrode 3 . That is, FIG. 29 depicts an embodiment only for illustrating the spatial (ie, linear) relationship of reference numeral 72 to opposing reference numeral 73 . This does not imply that the positive electrode 3 shares the energy storage medium 1 with the negative electrode 3 . However, it should be noted that in the case where the reference mark 72 and the opposite reference mark 73 are arranged by rolling up the storage unit 12 and then the isolator 5 is marked, the reference mark 72 and the opposite reference mark 73 may indeed be provided on a single isolator 5 . In practice, however, only one set of reference numerals 72 and opposite reference numerals 73 can be used to mount leads for a given electrode 3 . That is, it should be appreciated that the embodiment depicted in Figure 32 is to be supplemented with another layer of the energy storage medium 1 with another electrode 3 (which would have the opposite polarity).

As shown in Figure 33, the aforementioned assembly techniques result in a memory cell 12 comprising at least one set of aligned leads. The first set of aligned leads 91 is particularly useful when coupling the rolled storage cell 23 to one of the negative contact 55 and the positive contact 56 , while the opposite set of aligned leads 92 provide for coupling the energy storage medium 1 Connected to opposite contacts (55, 56).

The rolled storage unit 23 may be surrounded by a wrap 93 . Wrapper 93 can be implemented in a number of embodiments. For example, wrap 93 may be provided as KAPTON ^™ tape (which is a polyimide film developed by DuPont of Wilmington, Delaware) or PTFE tape. In this embodiment, the KAPTON ^™ tape is wrapped around and adhered to the rolled storage unit 23 . The wrap 93 may be provided as an adhesive free, such as a snug fit wrap 93 that is slid onto the rolled storage unit 23 . The wrap 93 may be more represented as a bag, such as a bag generally rolled into a rolled storage unit 23 (eg, the envelope 73 discussed above). In some of these embodiments, the wrapper 93 may include a material for use as a shrink-wrap, thereby providing efficient physical (in some embodiments, chemical) encapsulation of the rolled storage unit 23 . Generally, the wrap 93 is formed from a material that does not interfere with the electrochemical function of the ultracapacitor 10 . For example, the wrap 93 may also provide partial coverage as desired to facilitate insertion of the rolled storage unit 23 .

In some embodiments, the negative and positive leads are located on opposite sides of the rolled storage unit 23 (in the case of a jelly roll type of rolled storage unit 23, the negative and positive leads may be diametrically opposed) . In general, arranging the negative and positive leads on opposite sides of the rolled storage cell 23 is done to facilitate construction of the rolled storage cell 23 and to provide improved electrical isolation.

In some embodiments, once the aligned leads 91 , 92 are assembled, each of the plurality of aligned leads 91 , 92 is tied together (in situ) so that shrink wrap (not shown) can be placed in multiple around each of the aligned leads 91 , 92 . Generally, shrink wrap is formed from PTFE, but any compatible material can be used.

In some embodiments, once the shrink wrap is placed around the aligned leads 91, the aligned leads 91 are folded into the shape assumed when the ultracapacitor 10 is assembled. That is, referring to FIG. 34, it can be seen that the aligned leads are assumed to be "Z" shaped. After imparting a "Z-fold" to the aligned leads 91 , 92 and applying the shrink wrap, the shrink wrap may be heated or otherwise activated to shrink the shrink wrap into position around the aligned leads 91 , 92 . Thus, in some embodiments, the aligned leads 91, 92 may be strengthened and protected by the wrap. The use of Z-folds is particularly useful when coupling the energy storage medium 1 to the feedthrough 19 provided in the cover 24 .

Additionally, other embodiments for coupling each set of aligned leads 91 , 92 (ie, each terminal 8 ) to each contact 55 , 56 may be implemented. For example, in one embodiment, an intermediate lead is coupled to one of the feedthrough 19 and the housing 7 such that coupling with leads 91 , 92 in alignment with each set is facilitated.

Furthermore, the materials used can be selected based on properties such as reactivity, dielectric value, melting point, adhesion to other materials, weldability, coefficient of friction, cost, and other such factors. Combinations of materials (eg, layered, mixed or otherwise combined) can be used to provide the desired properties.

iii. Specific Ultracapacitor Embodiments

Some physical aspects of the exemplary ultracapacitor 10 of the present invention are shown below. It should be noted that in the following table, the term "tab" generally refers to a "lead" as discussed above; the terms "bridge" and "jumper" also refer to aspects of a lead (eg, a bridge may be coupled to a feedthrough pieces, or "pins," while jumper wires can be used to connect bridges to tabs or leads). The use of multiple connections may facilitate the assembly process, and certain assembly techniques are utilized. For example, the bridges may be laser welded or resistance welded to the pins and coupled to the jumpers by ultrasonic welding.

table 5

Table 6

Table 7

Table 8

35-38 are graphs depicting the performance of these exemplary ultracapacitors 10 . 35 and 36 depict the performance of ultracapacitor 10 at 1.75 volts and 125 degrees Celsius. 37 and 38 depict the performance of ultracapacitor 10 at 1.5 volts and 150 degrees Celsius.

In general, the ultracapacitor 10 can be used under a variety of environmental conditions and requirements. For example, the terminal voltage may be about 100mV to 10V. The ambient temperature may be about -40 degrees Celsius to +210 degrees Celsius. Typical high temperature ambient temperatures are +60°C to +210°C.

39-43 are additional graphs depicting the performance of the exemplary ultracapacitor 10 . In these embodiments, the ultracapacitor 10 is a closed cell (ie, a case). Cycle the supercapacitor 10 times, charge and discharge to 100 mA, charge to 0.5 volts, measure resistance, discharge to 10 mV, let stand for 10 seconds, and cycle again.

Tables 11 and 12 provide comparative performance data for embodiments of ultracapacitor 10 . Performance data was collected under multiple operating conditions as indicated.

Table 9

Compare performance data

Table 10

Compare performance data

Accordingly, the data presented in Tables 9 and 10 demonstrate that the teachings herein enable the performance of ultracapacitors under extreme conditions. Thus, the fabricated supercapacitors can, for example, exhibit leakage currents of less than about 1 mA/ml of cell volume, and less than about 100% ESR rise over 500 hours (which remain at voltages below about 2V and below at a temperature of about 150 degrees Celsius). Because trade-offs can be made between the various requirements of the supercapacitor (eg, voltage and temperature), the supercapacitor's rated performance (eg, capacitance, rate of increase in ESR, etc.) can be managed and can be adjusted to suit specific needs. Note that with reference to the foregoing, a general conventional definition of "rated performance" is given that takes into account the values of parameters describing operating conditions.

Figures 35 to 43 depict 1-butyl-1-methylpyrrolidine containing 1-butyl-1-methylpyrrolidine Performance of an exemplary supercapacitor of AES with tetracyanoborate at temperatures ranging from 125 degrees Celsius to 210 degrees Celsius.

Figures 44A and 44B depict 1-butyl-1-methylpiperidine containing 1-butyl-1-methylpiperidine Performance data of exemplary supercapacitors for AES of bis(trifluoromethylsulfonyl)imide.

Figures 45A and 45B depict tetradecyl containing trihexyl Performance data of exemplary supercapacitors for AES of bis(trifluoromethylsulfonyl)imide.

46A and 46B depict performance data for exemplary ultracapacitors with AES comprising butyltrimethylammonium bis(trifluoromethylsulfonyl)imide.

Figures 47A and 47B depict 1-butyl-1-methylpyrrolidine containing 1-butyl-1-methylpyrrolidine Exemplary supercapacitor performance data at 125 degrees Celsius for AES with tetracyanoborate.

FIGS. 48A and 48B and FIG. 49 depict a graph containing propylene carbonate and 1-butyl-1-methylpyrrolidine Performance data for an exemplary supercapacitor of AES with a mixture of tetracyanoborate and about 37.5% propylene carbonate by volume; capacitor at 125 degrees Celsius (FIGS. 48A and 48B) and at -40 operate in degrees Celsius (Figure 49). Another exemplary supercapacitor tested included 1-butyl-3-methylimidazole containing AES with tetrafluoroborate.

Another exemplary supercapacitor tested included 1-butyl-3-methylimidazole containing AES of bis(trifluoromethylsulfonyl)imide.

Another exemplary supercapacitor tested included 1-ethyl-3-methylimidazole containing AES with tetrafluoroborate.

Another exemplary supercapacitor tested included 1-ethyl-3-methylimidazole containing AES of tetracyanoborate.

Another exemplary supercapacitor tested included 1-hexyl-3-methylimidazole containing AES of tetracyanoborate.

Another exemplary supercapacitor tested included 1-butyl-1-methylpyrrolidine AES of bis(trifluoromethylsulfonyl)imide.

Another exemplary supercapacitor tested included 1-butyl-1-methylpyrrolidine AES of tris(pentafluoroethyl)trifluorophosphate.

Another exemplary supercapacitor tested included 1-butyl-1-methylpyrrolidine AES of tetracyanoborate.

Another exemplary supercapacitor tested included 1-butyl-3-methylimidazole containing AES of triflate.

Another exemplary supercapacitor tested included 1-ethyl-3-methylimidazole containing AES of tetracyanoborate.

Another exemplary supercapacitor tested included 1-ethyl-3-methylimidazole containing and 1-butyl-1-methylpyrrolidine and AES of tetracyanoborate.

Another exemplary supercapacitor tested included 1-butyl-1-methylpyrrolidine and AES with tetracyanoborate and ethyl isopropyl sulfone.

It should be noted that the measurements of capacitance and ESR (as shown in Table 9 and elsewhere herein) follow generally known methods. Consider first the technique used to measure capacitance.

Capacitance can be measured in a number of ways. One method involves monitoring the voltage shown at the capacitor terminals while drawing (during "discharging") a known current from the ultracapacitor or supplying (during "charging") a known current to the ultracapacitor. More specifically, one can take advantage of the fact that an ideal capacitor follows the equation:

I=C*dV/dt,

where I is the charging current, C is the capacitance, and dV/dt is the time derivative of the ideal capacitor voltage V. An ideal capacitor is one whose internal resistance is zero and whose capacitance is independent of voltage, etc. When the charging current I is constant, the voltage V is linear with time, so dV/dt can be calculated as the slope of the line or as ΔV/ΔT. However, this method is generally an approximation provided by the capacitor's effective series resistance and the voltage difference (ESR reduction), which should be taken into account when calculating or measuring capacitance. The effective series resistance (ESR) can generally be a lumped element that approximates dissipation or other effects in a capacitor. Capacitor behavior is often derived from a circuit model of an ideal capacitor in series with a resistor whose resistance value is equal to the ESR. In general, this gives a good approximation to actual capacitor behavior.

In one method of measuring capacitance, where the internal resistance is substantially voltage-independent and charging or discharging is substantially constant, the effect of ESR reduction can be largely ignored. In this case, the ESR reduction can be approximated as a constant and naturally subtracted from the calculation of the voltage change during the constant current charge or discharge. The voltage change then basically reflects the change in the charge stored on the capacitor. Therefore, the change in voltage can be calculated as an indication of capacitance.

For example, during a constant current discharge, the constant current I is known. Measuring the voltage change during discharge, ΔV, over the measured time interval ΔT, by dividing the current value I by the ΔV/ΔT ratio, an approximation of the capacitance is obtained. When I is in amperes, ΔV is in volts, and ΔT is in seconds, the capacitance result will be in farads.

As for the evaluation of ESR, the effective series resistance (ESR) of a supercapacitor can also be measured in various ways. One approach involves monitoring the voltage shown at the capacitor terminals while drawing (during "discharging") a known current from the ultracapacitor or supplying (during "charging") a known current to the ultracapacitor. More specifically, the fact that ESR follows the following equation can be exploited:

V=I*R,

where I represents the current effectively through the ESR, R represents the resistance value of the ESR, and V represents the voltage difference (ESR reduction) provided by the ESR. The ESR can generally be a lumped element that approximates dissipation or other effects in a supercapacitor. Supercapacitor behavior is often derived from a circuit model of an ideal capacitor in series with a resistor whose resistance value is equal to the ESR. In general, this gives a good approximation to actual capacitor behavior.

In one method of measuring ESR, discharge current can be drawn from capacitors that are in static state (capacitors that have not been charged or discharged with high currents). During time intervals in which the voltage change exhibited by the capacitor due to the change in the stored charge on the capacitor is less than the measured voltage change, the measured voltage change substantially reflects the capacitor's ESR. Under these conditions, the instantaneous voltage change exhibited by the capacitor can be calculated as an indication of ESR.

For example, once the discharge current has been drawn from the capacitor, an instantaneous voltage change ΔV may be exhibited during the measurement interval ΔT. As long as the capacitance C of the capacitor, discharged by a known current I, results in a voltage change during the measurement interval ΔT that is less than the measured voltage change ΔV, the ΔV during the time interval ΔT can be divided by the discharge current I to obtain an approximation of the ESR . When I is in amperes and ΔV is in volts, the ESR result will be in ohms.

Both ESR and capacitance may depend on ambient temperature. Accordingly, relevant measurements may require the user to subject the ultracapacitor 10 to a specific intended ambient temperature during the measurement.

The performance requirements for leakage current are generally defined by the prevailing environmental conditions in a particular application. For example, for a capacitor with a volume of 20mL, the practical limit for leakage current can be reduced to less than 100mA.

The nominal value of the normalization parameter may be obtained by multiplying or dividing the normalization parameter (eg, volume leakage current) by the normalization characteristic (eg, volume). For example, the nominal leakage current of a supercapacitor with a volume leakage current of 10 mA/cm3 and a volume of 50 cm3 is the product of the volume leakage current and the volume, 500 mA. Meanwhile, the nominal ESR of a supercapacitor with a volumetric ESR of 20 milliohm-cubic centimeters and a volume of 50 cubic centimeters is the quotient of the volumetric ESR and the volume of 0.4 milliohms.

iv. Examination of filling effect of supercapacitors including AES

Furthermore, to show how the filling method affects the ultracapacitor 10, two similar embodiments of the ultracapacitor 10 were constructed. One is filled under non-vacuum and the other is filled under vacuum. The electrical properties of the two embodiments are provided in Table 11. By repeating such measurements, it was noted that filling the supercapacitor 10 by applying a vacuum achieved improved performance. It has been determined that, in general, it is desirable to reduce the pressure within the housing 7 to below about 150 mTorr, and more particularly to below about 40 mTorr.

Table 11

Comparing performance of padding methods

Parameters (at 0.1V) under non-vacuum under vacuum deviation ESR@45°Φ 3.569 ohms 2.568 ohms (-28%) Capacitance@12mHz 155.87mF 182.3mF (+14.49%) Phase @12mHz 79.19 degrees 83 degrees (+4.59%)

To evaluate the efficacy of the vacuum filling technique, two different pouch cells were tested. The bagged unit comprises two electrodes 3, each based on a carbonaceous material. Each electrode 3 is arranged opposite and facing each other. Separator 5 is placed between said electrodes 3 to prevent short circuits and all are immersed in electrolyte 6 . Four measurement points are provided using two external tabs. The separator 5 used was a polyethylene separator 5 and the total volume of the unit was about 0.468 ml.

C. Methods of using supercapacitors

The present invention is also intended to include any and all uses of the energy storage devices (eg, ultracapacitors) described herein. This includes the direct use of supercapacitors, or the use of supercapacitors in other devices for any application. Such uses are intended to include the manufacture, sale, or provision of ultracapacitors to users.

For example, in one embodiment, the present invention provides a method of using a high temperature rechargeable energy storage device (HTRESD) (eg, a supercapacitor), the method comprising the steps of: obtaining an advanced electrolyte system (AES) comprising a HTRESD; cycling the HTRESD by alternately charging and discharging the HTRESD at least twice while maintaining the voltage across the HTRESD such that the HTRESD exhibits an initial peak power density of 0.01W/liter up to 150kW/liter, such that the HTRESD operates at about -40 degrees Celsius to about Operates at ambient temperatures in the temperature range of 210 degrees Celsius. In certain embodiments, the temperature ranges between about -40 degrees Celsius to about 150 degrees Celsius; between about -40 degrees Celsius to about 125 degrees Celsius; between about 80 degrees Celsius to about 210 degrees Celsius; between about 80 degrees Celsius to about Between 175 degrees Celsius; between about 80 degrees Celsius and about 150 degrees Celsius; or between -40 degrees Celsius and about 80 degrees Celsius. In certain embodiments, the HTRESD exhibits an initial peak power density of from about 0.01 W/liter to about 10 kW/liter, eg, between about 0.01 W/liter to about 5 kW/liter, eg, at about 0.01 W/liter to about 2kW/liter.

In another embodiment, the present invention provides a method of using an ultracapacitor, the method comprising: obtaining an ultracapacitor according to any one of claims 1 to 85, wherein the ultracapacitor exhibits retention at A volumetric leakage current (mA/cm3) of less than about 10 mA/cm3 at a substantially constant temperature in the range between about 100 degrees Celsius and about 150 degrees Celsius; and by alternately charging and discharging the supercapacitor at least twice Cycling the supercapacitor while maintaining the voltage across the supercapacitor such that the supercapacitor exhibits an ESR of less than about 300% after 20 hours of use when held at a substantially constant temperature in the range of about -40 degrees Celsius to about 210 degrees Celsius rise. In certain embodiments, the temperature ranges between about -40 degrees Celsius and about 150 degrees Celsius; between about -40 degrees Celsius and about 125 degrees Celsius; between about 80 degrees Celsius and about 210 degrees Celsius; between about 80 degrees Celsius and about 175 degrees Celsius ; between about 80 degrees Celsius and about 150 degrees Celsius; or between about -40 degrees Celsius and about 80 degrees Celsius.

In another embodiment, the present invention provides a method of providing a high temperature rechargeable energy storage device to a user, the method comprising: selecting a high temperature rechargeable energy storage device (HTRESD) comprising an advanced electrolyte system (AES) ), the high temperature rechargeable energy storage device exhibits an initial peak power density of 0.01 W/liter to 100 kW/liter and at least 1 hour, when exposed to ambient temperatures ranging from about -40 degrees Celsius to about 210 degrees Celsius, Durability, such as at least 10 hours, such as at least 50 hours, such as at least 100 hours, such as at least 200 hours, such as at least 300 hours, such as at least 400 hours, such as at least 500 hours, such as at least 1000 hours; and delivering the storage device such that the The user provides HTRESD.

In another embodiment, the present invention provides a method of providing a high temperature rechargeable energy storage device to a user, the method comprising: obtaining a temperature of about -40 degrees Celsius according to any one of claims 1 to 85 an ultracapacitor exhibiting a volumetric leakage current (mA/cm3) of less than about 10 mA/cm3 when maintained at a substantially constant temperature in the range between about 210 degrees Celsius; and delivering the storage device such that the user is provided with HTRESD.

incorporated by reference

All patents, published patent applications, and other references cited herein are expressly incorporated herein by reference in their entirety.

equivalent

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the appended claims. Furthermore, any numerical or alphabetical ranges provided herein are intended to include the upper and lower limits of those ranges. Additionally, in at least one embodiment, any listing or grouping is intended to represent a shorthand or convenient way of representing the listed separate embodiments; thus, each portion of the list should be considered a separate embodiment.

It should be appreciated that the teachings herein are exemplary only and not limiting of the invention. Furthermore, those skilled in the art will recognize that additional components, configurations, arrangements, etc. may be implemented while remaining within the scope of the present invention. For example, the formulation of layers, electrodes, leads, terminals, contacts, feedthroughs, caps, etc. may vary from the embodiments disclosed herein. In general, the components of an ultracapacitor and the design and/or application of an ultracapacitor utilizing electrodes are limited only by the needs of the system designer, manufacturer, operator, and/or user, and requirements that arise in any particular situation.

In addition, various other components may be included and employed for providing aspects of the teachings herein. For example, additional materials, combinations of materials, and/or redundancy of materials may be used to provide additional embodiments within the scope of the teachings herein.

While the invention has been described with reference to exemplary embodiments, it should be understood that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications will be understood to adapt to a particular instrument, situation or material in accordance with the teachings of the present invention without departing from the essential scope of the invention. Therefore, it is intended that this invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention but rather be interpreted by the claims appended hereto.

The present invention provides at least the following solutions:

Scheme 1. A supercapacitor, comprising:

An advanced electrolyte system (AES) and energy storage unit within a hermetically sealed housing, the unit electrically coupled to positive and negative contacts, wherein the ultracapacitor is configured to operate at a temperature of about -40 degrees Celsius to about 210 degrees Celsius operate at temperatures within the temperature range.

Scheme 2. The supercapacitor of scheme 1, wherein the AES comprises a Novel Electrolyte Entity (NEE).

Option 3. The supercapacitor of option 1 or 2, wherein the NEE is suitable for use in a high temperature supercapacitor.

Aspect 4. The ultracapacitor of any one of aspects 1 to 3, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 210 degrees Celsius.

Embodiment 5. The ultracapacitor of embodiment 4, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 150 degrees Celsius.

Scheme 6. The supercapacitor of scheme 1, wherein the AES comprises a highly purified electrolyte.

Scheme 7. The supercapacitor of scheme 1 or 6, wherein the highly purified electrolyte is suitable for use in a high temperature supercapacitor.

Aspect 8. The ultracapacitor of any one of aspects 1, 6, or 7, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 210 degrees Celsius.

Aspect 9. The ultracapacitor of aspect 8, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 150 degrees Celsius.

Embodiment 10. The ultracapacitor of embodiment 1, wherein the AES comprises an enhanced electrolyte combination.

Scheme 11. The supercapacitor of scheme 1 or 10, wherein the enhanced electrolyte combination is suitable for use in both high temperature and low temperature supercapacitors.

Aspect 12. The ultracapacitor of any one of aspects 1, 10, or 11, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about -40 degrees Celsius to about 150 degrees Celsius.

Embodiment 13. The ultracapacitor of embodiment 12, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about -30 degrees Celsius to about 125 degrees Celsius.

Scheme 14. The supercapacitor of any one of schemes 1 to 13, wherein the advantages over existing electrolytes of known energy storage devices are selected from one or more of the following improvements: reduced total resistance, Improved long-term stability of resistors, increased total capacitance, improved long-term stability of capacitors, increased energy density, improved voltage stability, reduced vapor pressure, wider temperature range performance of individual capacitors, improved temperature durability of individual capacitors, manufacturing Ease of access and improved cost-effectiveness.

Embodiment 15. The supercapacitor of any one of Embodiments 1 to 14, wherein the energy storage unit includes a positive electrode and a negative electrode.

Embodiment 16. The supercapacitor of any one of Embodiments 1 to 15, wherein at least one of the electrodes comprises a carbon-containing energy storage medium.

Embodiment 17. The supercapacitor of embodiment 16, wherein the carbon-containing energy storage medium comprises carbon nanotubes.

Scheme 18. The supercapacitor of scheme 16, wherein the carbon-containing energy storage medium comprises at least one of activated carbon, carbon fiber, rayon, graphene, aerogel, carbon cloth, and various forms of carbon nanotubes. one.

Item 19. The ultracapacitor of any of Items 1 to 18, wherein each electrode comprises a current collector.

Scheme 20. The supercapacitor of Scheme 2 or 10, wherein the AES is further purified to reduce impurity content.

Embodiment 21. The supercapacitor of any one of Embodiments 1 to 20, wherein the content of halide ions in the electrolyte is less than about 1000 parts per million.

Embodiment 22. The ultracapacitor of Embodiment 21, wherein the electrolyte has a halide ion content of less than about 500 parts per million.

Embodiment 23. The supercapacitor of Embodiment 21, wherein the electrolyte has a content of halide ions of less than about 100 parts per million.

Embodiment 24. The ultracapacitor of Embodiment 21, wherein the electrolyte has a halide ion content of less than about 50 parts per million.

Scheme 25. The supercapacitor of any one of schemes 21 to 24, wherein the halide ion in the electrolyte is selected from one of the halide ions selected from chloride ion, bromide ion, fluoride ion, and iodide ion species or more.

Embodiment 26. The supercapacitor of any one of Embodiments 1 to 25, wherein the total concentration of metal species in the electrolyte is less than about 1000 parts per million.

Scheme 27. The supercapacitor according to scheme 26, wherein the metal species is selected from one or more selected from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb and Zn Various metals.

Scheme 28. The supercapacitor according to scheme 26, wherein the metal species is selected from one of the metals selected from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb and Zn or more alloys.

Scheme 29. The supercapacitor according to scheme 26, wherein the metal species is selected from one of the metals selected from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb and Zn or more oxides.

Embodiment 30. The ultracapacitor of any one of Embodiments 20 to 29, wherein the total concentration of impurities in the electrolyte is less than about 1000 parts per million.

Scheme 31. The supercapacitor according to any one of schemes 20 to 30, wherein the impurities are selected from the group consisting of bromoethane, chloroethane, 1-bromobutane, 1-chlorobutane, 1-methylimidazole, One or more of ethyl acetate and dichloromethane.

Embodiment 32. The ultracapacitor of any one of Embodiments 20 to 31, wherein the total water content in the electrolyte is less than about 500 parts per million.

Embodiment 33. The ultracapacitor of Embodiment 32, wherein the total water content in the electrolyte is less than about 100 parts per million.

Embodiment 34. The ultracapacitor of Embodiment 32, wherein the total water content in the electrolyte is less than about 50 parts per million.

Embodiment 35. The ultracapacitor of Embodiment 32, wherein the total water content in the electrolyte is less than about 20 parts per million.

Embodiment 36. The ultracapacitor of any one of Embodiments 1 to 35, wherein the housing includes a barrier disposed over a substantial portion of its interior surface.

Embodiment 37. The ultracapacitor of embodiment 36, wherein the barrier comprises polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene copolymer (FEP), ethylene-tetrafluoroethylene At least one of ethylene copolymers (ETFE).

Embodiment 38. The ultracapacitor of embodiment 36, wherein the barrier comprises a ceramic material.

Embodiment 39. The ultracapacitor of embodiment 36, wherein the barrier comprises a material that exhibits corrosion resistance, desirable dielectric properties, and low electrochemical reactivity.

Embodiment 40. The ultracapacitor of embodiment 36, wherein the barrier comprises a plurality of layers of material.

Aspect 41. The ultracapacitor of any one of aspects 1 to 40, wherein the housing comprises multiple layers of material.

Embodiment 42. The supercapacitor of embodiment 41, wherein the multilayer material comprises a first material overlying a second material.

Embodiment 43. The ultracapacitor of embodiment 41, wherein the multilayer material comprises at least one of steel, tantalum, and aluminum.

Aspect 44. The ultracapacitor of any one of aspects 1 to 43, wherein the housing comprises at least one hemispherical seal.

Embodiment 45. The ultracapacitor of any one of Embodiments 1 to 44, wherein the case comprises at least one glass-to-metal seal.

Embodiment 46. The ultracapacitor of embodiment 45, wherein a pin of the glass-to-metal seal provides one of the contacts.

Embodiment 47. The ultracapacitor of embodiment 45, wherein the glass-to-metal seal comprises a feedthrough composed of a material selected from the group consisting of iron-nickel-cobalt alloys, nickel-iron alloys, tantalum, molybdenum, niobium, Tungsten and some forms of stainless steel and titanium.

Embodiment 48. The ultracapacitor of embodiment 45, wherein the glass-to-metal seal comprises a body composed of at least one material selected from the group consisting of nickel, molybdenum, chromium, cobalt, iron, copper, manganese, titanium , zirconium, aluminum, carbon and tungsten, and their alloys.

Embodiment 49. The ultracapacitor of any one of Embodiments 1 to 48, wherein the energy storage unit includes a separator to provide electrical isolation between the positive electrode and the negative electrode.

Scheme 50. The ultracapacitor of scheme 49, wherein the isolator comprises a material selected from the group consisting of polyamide, polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), alumina ( _{Al2O3 )} , glass Fibers, fiberglass reinforced plastics, or any combination of materials.

Embodiment 51. The ultracapacitor of embodiment 49 or 50, wherein the isolator is substantially free of moisture.

Embodiment 52. The ultracapacitor of embodiment 49, wherein the isolator is substantially hydrophobic.

Embodiment 53. The ultracapacitor of any one of Embodiments 1 to 52, the hermetic seal exhibiting a leak rate of no greater than about 5.0×10 ⁻⁶ atm-cubic centimeters per second.

Embodiment 54. The ultracapacitor of any one of Embodiments 1 to 52, the hermetic seal exhibiting a leak rate of no greater than about 5.0×10 ⁻⁷ atm-cc/sec.

Embodiment 55. The ultracapacitor of any one of Embodiments 1 to 52, the hermetic seal exhibiting a leak rate of no greater than about 5.0×10 ⁻⁸ atm-cubic centimeters per second.

Embodiment 56. The ultracapacitor of any one of Embodiments 1 to 52, the hermetic seal exhibiting a leak rate of no greater than about 5.0×10 ⁻⁹ atm-cc/sec.

Embodiment 57. The ultracapacitor of any one of Embodiments 1 to 52, the hermetic seal exhibiting a leak rate of no greater than about 5.0×10 ⁻¹⁰ atm-cc/sec.

Embodiment 58. The ultracapacitor of any one of aspects 1 to 57, wherein at least one contact is configured to mate with another contact of another ultracapacitor.

Embodiment 59. The ultracapacitor of any one of Embodiments 1 to 59, wherein the storage unit includes a wrapper disposed over an exterior thereof.

Embodiment 60. The ultracapacitor of embodiment 59, wherein the wrapper comprises one of PTFE and polyimide.

Embodiment 61. The ultracapacitor of any one of Embodiments 1 to 60, wherein the volumetric leakage current is less than about 1000 milliamps/liter in the temperature range.

Embodiment 62. The ultracapacitor of any one of Embodiments 1 to 61, wherein the volumetric leakage current is less than about 1000 milliamps/liter over the specified voltage range.

Embodiment 63. The ultracapacitor of any one of Embodiments 1 to 62, wherein the moisture level within the case is less than about 1000 parts per million (ppm).

Embodiment 64. The ultracapacitor of embodiment 63, wherein the moisture level within the housing is less than about 500 parts per million (ppm).

Embodiment 65. The ultracapacitor of embodiment 63, wherein the moisture level within the housing is less than about 350 parts per million (ppm).

Embodiment 66. The supercapacitor of any one of Embodiments 1 to 65, comprising a moisture content of less than about 1000 ppm in electrodes of the supercapacitor.

Embodiment 67. The ultracapacitor of embodiment 66, comprising a moisture content of less than about 500 ppm in electrodes of the ultracapacitor.

Embodiment 68. The ultracapacitor of embodiment 66, wherein the moisture level in the electrodes of the ultracapacitor is less than about 350 parts per million (ppm).

Embodiment 69. The ultracapacitor of any one of Embodiments 1 to 68, comprising a moisture content of less than about 1000 ppm in the separator of the ultracapacitor.

Embodiment 70. The ultracapacitor of embodiment 69, comprising a moisture content of less than about 500 ppm in the isolator of the ultracapacitor.

Embodiment 71. The ultracapacitor of Embodiment 69, wherein the moisture level in the isolator of the ultracapacitor is less than about 160 parts per million (ppm).

Embodiment 72. The ultracapacitor of any one of Embodiments 1 to 71, wherein the chloride ion content is less than about 300 ppm for one of the components selected from the group consisting of electrodes, electrolytes, and separators.

Embodiment 73. The ultracapacitor of any one of Embodiments 1 to 72, wherein the ultracapacitor has a volumetric leakage current (mA/cm3) of less than about 10 mA/cm3 when maintained at a substantially constant temperature.

Embodiment 74. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric leakage current of less than about 1 mA/cm 3 when maintained at a substantially constant temperature.

Embodiment 75. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric leakage current greater than about 0.0001 mA/cm 3 when maintained at a substantially constant temperature.

Embodiment 76. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric capacitance of between about 6 F/cm 3 and about 1 mF/cm 3 .

Embodiment 77. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric capacitance of between about 10 F/cm 3 and about 5 F/cm 3 .

Embodiment 78. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric capacitance of between about 50 F/cm 3 and about 8 F/cm 3 .

Embodiment 79. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric ESR of between about 20 milliohm·cubic centimeters and 200 milliohm·cubic centimeters.

Embodiment 80. The ultracapacitor of embodiment 73, wherein the ultracapacitor has a volumetric ESR of between about 150 milliohm-cubic centimeters and 2 ohm-cubic centimeters.

Scheme 81. The ultracapacitor of Scheme 73, further exhibiting a volumetric ESR of the ultracapacitor of between about 1.5 ohm·cc and 200 ohm·cc.

Scheme 82. The ultracapacitor of Scheme 73, further exhibiting a volumetric ESR of the ultracapacitor of between about 150 ohm-cubic centimeters and 2000 ohm-cubic centimeters.

Embodiment 83. The ultracapacitor of Embodiment 73, wherein the ultracapacitor exhibits less than about a 60% reduction in capacitance when held at a constant voltage for at least 20 hours.

Embodiment 84. The ultracapacitor of Embodiment 73, wherein the ultracapacitor exhibits an increase in ESR of less than about 300% when held at a constant voltage for at least 20 hours.

Embodiment 85. The method of embodiment 73, wherein the ultracapacitor exhibits a reduction in capacitance of less than about 60% when held at a constant voltage.

Scheme 86. A method for making a supercapacitor, comprising the steps of:

disposing an energy storage unit containing an energy storage medium within the housing; and

The case is filled with an Advanced Electrolyte System (AES) such that the supercapacitor is fabricated to operate in a temperature range of about -40 degrees Celsius to about 210 degrees Celsius.

Scheme 87. The method of Scheme 86, wherein the AES comprises a Novel Electrolyte Entity (NEE).

Embodiment 88. The method of embodiment 86 or 87, wherein the NEE is suitable for use in a high temperature supercapacitor.

Embodiment 89. The method of any one of Embodiments 86 to 88, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 210 degrees Celsius.

Embodiment 90. The method of embodiment 89, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 150 degrees Celsius.

Scheme 91. The method of Scheme 86, wherein the AES comprises a highly purified electrolyte.

Scheme 92. The method of Scheme 86 or 91, wherein the highly purified electrolyte is suitable for use in high temperature supercapacitors.

Embodiment 93. The method of any of Embodiments 86, 91, or 92, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 210 degrees Celsius.

Embodiment 94. The method of embodiment 93, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about 80 degrees Celsius to about 150 degrees Celsius.

Embodiment 95. The method of embodiment 86, wherein the AES comprises an enhanced electrolyte combination.

Embodiment 96. The method of embodiment 86 or 95, wherein the enhanced electrolyte combination is suitable for use in both high temperature supercapacitors and low temperature supercapacitors.

Embodiment 97. The method of any one of Embodiments 86, 95, or 96, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about -40 degrees Celsius to about 150 degrees Celsius.

Embodiment 98. The method of embodiment 97, wherein the ultracapacitor is configured to operate at a temperature in a temperature range of about -30 degrees Celsius to about 125 degrees Celsius.

Embodiment 99. The method of any one of Embodiments 86 to 98, wherein the advantages of existing electrolytes over known energy storage devices are selected from one or more of the following improvements: reduction in overall resistance, reduction in resistance Increased long-term stability of the capacitors, increased total capacitance, improved long-term stability of capacitors, increased energy density, improved voltage stability, reduced vapor pressure, wider temperature range performance of individual capacitors, improved temperature durability of individual capacitors, ease of manufacture increased efficiency and improved cost-effectiveness.

Embodiment 100. The method of embodiment 72, wherein the fabricated ultracapacitor is the ultracapacitor of any one of embodiments 1-85.

Clause 101. The method of any one of clauses 86 to 100, wherein the disposing further comprises pre-treating components of the ultracapacitor to reduce moisture therein, the components of the ultracapacitor comprising: electrodes, separators, At least one of a lead, an assembled energy storage unit, and the housing.

Embodiment 102. The method of embodiment 101, wherein the pre-treating comprises heating the selected component substantially under vacuum at a temperature ranging from about 100 degrees Celsius to about 150 degrees Celsius.

Embodiment 103. The method of embodiment 101, wherein the pre-treatment comprises heating the selected component substantially under vacuum at a temperature ranging from about 150 degrees Celsius to about 300 degrees Celsius.

Embodiment 104. The method of any one of Embodiments 86 to 103, wherein the setting is performed in a substantially inert environment.

Embodiment 105. The method of any one of Embodiments 86 to 104, wherein the constructing includes selecting an interior surface material for the shell that exhibits low chemical reactivity with respect to the electrolyte.

Embodiment 106. The method of embodiment 105, further comprising introducing the interior surface material in a substantial portion of the interior of the housing.

Scheme 107. The method of scheme 105 or 106, wherein the constructing comprises selecting aluminum, polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene copolymer (FEP), ethylene - At least one of a tetrafluoroethylene copolymer (ETFE) and a ceramic material as the inner surface material.

Clause 108. The method of any one of clauses 86 to 104, wherein the constructing comprises forming the housing from multiple layers of material.

Clause 109. The method of Clause 108, wherein the forming the housing from multiple layers of material comprises disposing a weldable material on an exterior of the housing.

Clause 110. The method of any one of clauses 86 to 109, wherein the constructing comprises fabricating at least one of a cover and a body for the housing.

Clause 111. The method of any one of clauses 86 to 110, wherein the constructing comprises disposing a filling port in the housing to effect the filling.

Embodiment 112. The method of embodiment 110, wherein the fabricating comprises disposing a seal including an insulator and an electrode insulated from the housing in the housing.

Embodiment 113. The method of embodiment 112, wherein disposing the seal comprises disposing a glass-to-metal seal.

Embodiment 114. The method of embodiment 112, wherein disposing the seal comprises disposing a hemispherical seal.

Embodiment 115. The method of embodiment 113, wherein providing the glass-to-metal seal comprises welding the glass-to-metal seal to an outer surface of the housing.

Embodiment 116. The method of any one of Embodiments 86 to 115, further comprising fabricating the energy storage unit.

Embodiment 117. The method of embodiment 116, wherein fabricating the energy storage unit comprises obtaining electrodes by connecting an energy storage medium and a current collector.

Embodiment 118. The method of embodiment 117, wherein obtaining the electrode comprises connecting a plurality of electrode elements fabricated by connecting an energy storage medium and a current collector.

Embodiment 119. The method of embodiment 118, wherein connecting the plurality of electrode elements comprises ultrasonically welding a connecting element to a current collector of one electrode element and to a current collector of another electrode element.

Embodiment 120. The method of embodiment 116, wherein fabricating the energy storage cell comprises connecting at least one lead to an electrode.

Embodiment 121. The method of embodiment 120, wherein connecting at least one lead to the electrode comprises disposing at least one reference mark on the electrode.

Embodiment 122. The method of embodiment 120, wherein connecting at least one lead to the electrode comprises arranging each lead at a corresponding reference mark.

Embodiment 123. The method of embodiment 120, wherein connecting at least one lead comprises scavenging the energy storage medium from the current collector.

Embodiment 124. The method of embodiment 120, wherein connecting at least one lead comprises ultrasonically welding the lead to the current collector.

Embodiment 125. The method of embodiment 116, wherein fabricating the energy storage cell comprises disposing a separator between at least two electrodes.

Embodiment 126. The method of embodiment 125, further comprising aligning each of the electrodes with the separator.

Embodiment 127. The method of embodiment 116, wherein fabricating the energy storage cell comprises wrapping at least two electrodes with a separator disposed therebetween.

Embodiment 128. The method of embodiment 127, wherein the wrapping comprises rolling the storage unit into a rolled storage unit.

Embodiment 129. The method of embodiment 116, wherein fabricating the energy storage unit comprises disposing a wrapper on the storage unit.

Clause 130. The method of any one of clauses 86 to 129, wherein disposing the energy storage unit comprises bringing together a plurality of leads to provide terminals.

Embodiment 131. The method of embodiment 130, wherein the bringing together the plurality of leads comprises aligning the leads together into a set of aligned leads to form a terminal.

Embodiment 132. The method of embodiment 131, further comprising disposing a wrapper around the set of aligned leads.

Embodiment 133. The method of embodiment 131, further comprising folding the set of aligned leads.

Embodiment 134. The method of embodiment 131, further comprising coupling the set of aligned leads to contacts of the housing.

Clause 135. The method of clause 134, wherein the coupling comprises soldering the set of aligned leads to the contacts.

Clause 136. The method of clause 134, wherein the coupling comprises soldering the set of aligned leads to one of a jumper and a bridge for coupling to contacts of the housing.

Clause 137. The method of any one of clauses 86 to 115, further comprising electrically coupling at least one of a jumper wire and a bridge to a contact of the housing.

Embodiment 138. The method of embodiment 137, further comprising disposing an insulating material substantially over the contacts on the interior of the housing.

Clause 139. The method of any one of clauses 86 to 138, further comprising hermetically sealing the energy storage unit within the housing.

Clause 140. The method of any one of clauses 86 to 139, further comprising mating at least one cover with the body to provide the housing.

Embodiment 141. The method of embodiment 140, wherein the cover comprises one of a concave cover, a convex cover, and a flat cover.

Embodiment 142. The method of embodiment 140, further comprising removing at least a portion of the multiple layers of material within the housing to provide the matching.

Embodiment 143. The method of embodiment 140, wherein hermetically sealing comprises welding the components of the housing together by at least one of pulse welding, laser welding, resistance welding, and TIG welding.

Scheme 144. The method of any one of Schemes 86 to 143, further comprising purifying the AES.

Clause 145. The method of any one of clauses 86 to 144, further comprising disposing a filling port within the housing to provide the filling.

Embodiment 146. The method of embodiment 145, further comprising sealing the fill port after completing the filling.

Embodiment 147. The method of embodiment 146, wherein the sealing comprises installing a compatible material into the fill port.

Embodiment 148. The method of embodiment 147, further comprising welding the material mounted to the fill port to the housing.

Clause 149. The method of clause 145, wherein the filling comprises disposing the AES over a filling port in the housing.

Embodiment 150. The method of embodiment 149, the filling comprising evacuating the filling port in the housing.

Scheme 151. The method of Scheme 150, wherein the vacuum is less than about 150 mTorr.

Scheme 152. The method of Scheme 150, wherein the vacuum is less than about 40 mTorr.

Embodiment 153. The method of embodiment 145, wherein the filling is performed in a substantially inert environment.

Scheme 154. A method of using a high temperature rechargeable energy storage device (HTRESD), the method comprising:

Obtain HTRESD including Advanced Electrolyte System (AES); and

The HTRESD was cycled by alternately charging and discharging the HTRESD at least twice for a duration of 20 hours while maintaining the voltage across the HTRESD such that the HTRESD exhibited an initial rise of 0.01 W/liter to 150 kW/liter Peak power density such that the HTRESD is used for at least 20 hours when operating at ambient temperature in a temperature range of about -40 degrees Celsius to about 210 degrees Celsius.

Embodiment 155. The method of embodiment 154, wherein the HTRESD is a supercapacitor.

Scheme 156. The method of scheme 154 or 155, wherein the temperature ranges from about -40 degrees Celsius to about 150 degrees Celsius.

Scheme 157. The method of scheme 154 or 155, wherein the temperature ranges from about -40 degrees Celsius to about 125 degrees Celsius.

Embodiment 158. The method of embodiment 154 or 155, wherein the temperature ranges from about 80 degrees Celsius to about 210 degrees Celsius.

Embodiment 159. The method of embodiment 154 or 155, wherein the temperature ranges from about 80 degrees Celsius to about 175 degrees Celsius.

Embodiment 160. The method of embodiment 154 or 155, wherein the temperature ranges from about 80 degrees Celsius to about 150 degrees Celsius.

Embodiment 161. The method of embodiment 154 or 155, wherein the temperature ranges from about -40 degrees Celsius to about 80 degrees Celsius.

Embodiment 162. The method of embodiment 154, wherein the HTRESD exhibits an initial peak power density of about 0.01 W/liter to about 10 kW/liter.

Scheme 163. The method of any one of schemes 154 to 162, wherein the HTRESD exhibits an initial peak power density of about 0.01 W/liter to about 5 kW/liter.

Embodiment 164. The method of embodiment 163, wherein the HTRESD exhibits an initial peak power density of about 0.01 W/liter to about 2 kW/liter.

Scheme 165. A method of using an ultracapacitor, the method comprising:

Obtaining the ultracapacitor of any one of schemes 1 to 85, wherein the ultracapacitor exhibits less than about 10 mA/ Cubic centimeter volume leakage current (mA/cubic centimeter); and

The ultracapacitors were cycled by alternately charging and discharging the ultracapacitors at least twice over a 20 hour duration while maintaining the voltage across the ultracapacitors for 20 hours such that the ultracapacitors were maintained at about - A substantially constant temperature in the range between 40 degrees Celsius to about 210 degrees Celsius exhibited an ESR increase of less than about 300% after 20 hours of use.

Embodiment 166. The method of embodiment 165, wherein the temperature range is between about -40 degrees Celsius and about 150 degrees Celsius.

Embodiment 167. The method of embodiment 165, wherein the temperature range is between about -40 degrees Celsius and about 125 degrees Celsius.

Embodiment 168. The method of embodiment 165, wherein the temperature range is between about 80 degrees Celsius and about 210 degrees Celsius.

Embodiment 169. The method of embodiment 165, wherein the temperature range is between about 80 degrees Celsius and about 175 degrees Celsius.

Embodiment 170. The method of embodiment 165, wherein the temperature range is between about 80 degrees Celsius and about 150 degrees Celsius.

Embodiment 171. The method of embodiment 165, wherein the temperature range is between about -40 degrees Celsius and about 80 degrees Celsius.

Scheme 172. A method of providing a high temperature rechargeable energy storage device to a user, the method comprising:

A high temperature rechargeable energy storage device (HTRESD) including an advanced electrolyte system (AES) selected for exposure to an environment in a temperature range of about -40 degrees Celsius to about 210 degrees Celsius exhibit an initial peak power density of between 0.01 W/L and 100 kW/L and an endurance period of at least 20 hours at temperature; and

The storage device is delivered such that the HTRESD is provided to the user.

Scheme 173. A method of providing a high temperature rechargeable energy storage device to a user, the method comprising:

Obtaining the ultracapacitor of any one of schemes 1 to 85, the ultracapacitor exhibiting less than about 10 mA/cubic when maintained at a substantially constant temperature in a range between about -40 degrees Celsius and about 210 degrees Celsius centimeter volume leakage current (mA/cm 3 ); and delivering the storage device such that the HTRESD is provided to the user.

Claims (10)

1. a kind of supercapacitor, comprising:

The intracorporal advanced electrolyte system (AES) of gas-tight seal shell and energy storage unit, the unit are electrically coupled to anode Contact and cathode contact part, wherein Cheng Yue -40 degrees Celsius to about 210 degrees Celsius of the ultracapacitor configurations of temperature model It is operated at a temperature of in enclosing.

2. supercapacitor according to claim 1, wherein the AES includes novel electrolytes entity (NEE).

3. supercapacitor according to claim 1 or 2, wherein the NEE is suitable for making in high temperature ultracapacitor With.

4. supercapacitor according to any one of claim 1 to 3, wherein the ultracapacitor configurations Cheng Yue 80 It degree Celsius is operated at a temperature of within the temperature range of about 210 degrees Celsius.

5. supercapacitor according to claim 4, wherein 80 degrees Celsius of the ultracapacitor configurations Cheng Yue is to about It is operated at a temperature of within the temperature range of 150 degrees Celsius.

6. supercapacitor according to claim 1, wherein the AES includes highly purified electrolyte.

7. supercapacitor according to claim 1 or 6, wherein the highly purified electrolyte is suitable for surpassing in high temperature It is used in grade capacitor.

8. according to claim 1, supercapacitor described in any one of 6 or 7, wherein the ultracapacitor configurations Cheng Yue It is operated at a temperature of within the temperature range of 80 degrees Celsius to about 210 degrees Celsius.

9. supercapacitor according to claim 8, wherein 80 degrees Celsius of the ultracapacitor configurations Cheng Yue is to about It is operated at a temperature of within the temperature range of 150 degrees Celsius.

10. supercapacitor according to claim 1, wherein the AES includes the electrolyte combination of enhancing.