CN1127771C - Energy storage device and manufacturing method thereof - Google Patents

Abstract

A dry-type preform assembly (10) includes a plurality of capacitor chips (110, 112, 114) of true bipolar construction stacked and bonded together to form a unitary, unitary structure. Each capacitor chip (114) includes two conductive electrodes (111A, 111B) separated by a predetermined distance. The capacitor chip (114) further comprises two identical dielectric pads (121, 123) disposed between the electrodes (111A, 111B), which are aligned with each other to separate and electrically insulate the electrodes. When the electrodes (111A, 111B) and the pads (121, 123) are bonded together, each capacitor chip forms at least one filled air gap (130).

Description

Energy storage device and manufacturing method thereof

technical field

This invention relates generally to energy storage devices, and more particularly to bipolar double layer capacitor type energy storage devices and methods of making the same.

Background technique

Energy Storage Devices - Practical and reliable electrical storage devices, such as capacitors or batteries, have been well researched in recent years. Batteries typically have high energy storage capabilities; however, batteries also exhibit low power density. In contrast, electrolytic capacitors have a high power density and a limited energy density. Also, carbon-based double-layer capacitors have high energy density, but carbon electrodes have low power capacity due to their high equivalent series resistance (ESR.). Accordingly, it is highly desirable to have electrical storage devices having both high energy density and high power density.

B.E.Conway has a newly published article in J.Eletrochem.SOC. (Journal of the Electrochemical Society) 138 (#6) page 1539 (June 1991) discussing the transition from "supercapacitor" to "battery" in electrochemical energy storage. ” conversion, and determined the operating characteristics of various capacitive devices.

Canadian Patent 1,196,683, November 1985, to D. Craig discusses the use and pseudocapacitance of electrical storage devices based on oxide ceramic coated electrodes. However, capacitors obtained using this invention have inconsistent electrical characteristics and are often unreliable. These devices cannot be charged to 1.0 volts per capacitor chip and have unsatisfactorily large leakage currents. Additionally, these devices have low cycle life. Furthermore, the disclosed packaging is inefficient.

US Patent 5,121,288 to M. Matroks and R. Hackbart discusses a capacitive power supply based on Craig's patent, which cannot be used in the present invention. The structure of a capacitor as a power source for a radiotelephone is described in this patent; however, the capacitor is not described.

US Patent 5,063,340 to J. KalenoWsky discusses a capacitive power supply with a charge equalization circuit. This circuit allows charging of multiple individual capacitor chips without overcharging each individual capacitor chip. The present invention does not require a charging equalization circuit to fully charge the laminated structure of multiple individual capacitor chips without overcharging the intermediate capacitor chips.

H. Lee et al. in IEEE Transactions on Magnetics (Institute of Electrical and Electronics Engineers, Magnetism) 25 (#1) p. 324 (January 1989) and G. Bullard et al. in IEEE Transactions on Magnetics 25 (#1 ) Volume 102 (January 1989) discusses the pulse electric power characteristics of high-energy oxide ceramic-based double-layer capacitors. Various operating characteristics are discussed in this reference, but the manufacturing process is not discussed. The present invention provides a more reliable device with more efficient packaging.

Double layer capacitors based on carbon electrodes have been improved in various ways on the earlier work of Rightmhe, UK Patent 3,288,641. A.Yoshida et al. discussed in IEEE Transactions on Components, Hybrids and Manufacturing Technology (Institute of Electrical and Electronics Engineers, Components, Hybrid Circuits and Manufacturing Technology Journal) CHMH-10 Volume #1, Page 100-103 (March 1987). A double-layer capacitor composed of activated carbon fiber electrodes and anhydrous electrolyte. In addition, the packaging of this double layer capacitor is shown. The volume of this device is on the order of 0.4-1 cc, and the energy storage capacity is about 1-10 J/cc.

People such as J.Suzuki discussed in NEC Research and Devolopment (Japan Electric Company Research and Development Journal) No. 82, pp. 118-123 (July 1986) the carbon double-layer capacitor adopting a porous separator material with a thickness order of 0.004. Improved self-discharge characteristics. An inherent problem with carbon-based electrodes is that the low electrical conductivity of the material allows these devices to generate low current densities. The second difficulty is that the stacked structure of multiple capacitor chips is not formed in a true bipolar electrode structure. These challenges lead to inefficient packaging and lower energy and power densities.

Other valuable references include, for example:

"Review of Solid Micro Power Sources" published by S. Sekido in Solid State Lonics (Solid State Ions) 9, Vol. 10, No. 777-782 (1983).

M.Pham-Thi et al discussed the permeation threshold and interface optimization of carbon-based solid electrolyte double-layer capacitors in Journal of Materials Science Letters (Journal of Materials Science) 5, p. 415 (1986).

Various publications discuss the fabrication of oxide-coated electrodes, and the use of these electrodes in the chlor-alkali industry for electrochemical chlorine production. See, for example: U.S. Patent 5,055,169 to V. Hook et al., issued October 8, 1991; U.S. Patent 4,052,271 to H. Beer, issued October 4, 1977; and A . US Patent 3,562,008 to Martinsons et al. However, these electrodes generally do not possess the large surface area required for efficient double layer capacitor electrodes.

It would be beneficial to have reliable long-life electrical storage devices and improved fabrication methods. It would also be desirable to have an improved energy storage device having an energy density of at least 20-90 J/cc.

Encapsulation of Energy Storage Devices - As mentioned above, high energy and high power density electrical storage devices have been extensively studied in recent years, and for these purposes efficient encapsulation of active materials with minimal expense is important of. In a capacitor or battery, the space separating the two electrodes must electrically insulate the two electrodes, however, for effective packaging this space or gap should be as small as possible. It is therefore highly desirable to have a method of forming a spacer or gap that is substantially uniform and of small size (less than 5 mils (0.0127 cm)).

In electrical storage devices with electrolytes, such as batteries or capacitors, a common method of maintaining separation between electrodes is to employ an ion-permeable, electrically insulating porous separator. This spacer is usually located between the electrodes and maintains the desired spatial separation between the two electrodes. Porous separator materials, such as paper or glass, are beneficial for this application and are used in aluminum electrolytic capacitors and electric double layer capacitors, however, for isolation dimensions below 1 or 2 mils (0.00254-0.00508 cm) , material processing is difficult, and the material strength of capacitors is usually low. Furthermore, the cross-sectional area of the pores of these porous barrier separators is typically on the order of 50-70%.

Ionically permeable porous separator plates of polymers have been used in carbon double-layer capacitors, such as Sannada et al. IEEE pp. 224-230 (1982) and Suzuki et al. NEC Research and Deaelopment No. 82 pp. 118-123 ( as discussed in July 1986). These types of separators suffer from a small hole area, resulting in increased electrical resistance.

U.S. Patent 4,764,181 Haruyama et al. issued on August 16, 1988 discloses a method for forming an electrolytic capacitor with a thin barrier layer using a photosensitive polymer resin solution. Use of the described solution use method in porous double layer capacitor electrodes can lead to undesired filling of the porous electrodes.

Other references of general relevance include US Patents 3,718,551, 4,052,271; and 5,055,169. All applications, patents, articles, references, standards, etc. cited in this application are hereby incorporated by reference in their entirety.

In view of the foregoing, it would be beneficial to have a method of forming reliable small space separations between electrodes in electrical storage devices with large pore cross-sectional areas.

Contents of the invention

The present invention relates to a novel electrical storage device having both high energy density and high power density.

The object of the present invention is to provide a new method for manufacturing such electrical storage devices.

Another object of the present invention is to provide a reliable long-life electric storage device and an improved manufacturing method thereof.

Yet another object of the present invention is to provide efficient packaging of electrical storage devices by reducing the gap between the anode and cathode, which reduces the resistance value of the ionically conductive electrolyte.

Briefly he states that the above objects and others are achieved by an energy storage device such as a capacitor comprising a plurality of capacitive chips in a bipolar configuration. These capacitive chips are stacked and glued together to make the device an integral and unitary structure.

Each capacitive chip includes two conductive electrodes separated by a predetermined distance. The capacitive chip also includes at least one dielectric spacer interposed between the electrodes for isolating and electrically insulating the electrodes.

When the electrodes and pads are glued together, at least one filling gap is formed for each capacitor chip. Each capacitive chip also includes a high surface area (porous) conductive coating formed on one (or more) surfaces of each electrode. The coating preferably includes a set of closely spaced peripheral microprotrusions and a set of remotely spaced central microprotrusions. These microprotrusions can be formed by novel screen printing or photolithography methods. These microbumps provide structural support for the capacitor chip and provide additional insulation between electrodes.

The ionically conductive medium fills capacitor chip gaps and pores in large surface area coatings.

Description of drawings

The above and other features of the present invention and methods of achieving them will become more apparent, and the invention itself will be better understood, by reference to the following specification and accompanying drawings.

1 is a perspective view of an assembly 10 of a dry energy storage device constructed in accordance with the present invention;

FIG. 1A is a perspective view of an electrolyte-filled energy storage device 10A of the present invention;

Figure 2 is a cross-sectional view of the memory device of Figure 1 taken along line 2-2 showing a removable conductive strap 1117A within the memory device.

2A is a cross-sectional view of the memory device of FIG. 1 along line 2A-2A;

Figure 3 is an exploded schematic view of the assembly of Figure 1, wherein three capacitor chips are depicted;

FIG. 4 is a block diagram of a manufacturing process of the memory device 10A;

Figure 5 is a top view of a porous coating with microprotrusions forming part of the memory device of Figures 1-4;

FIG. 6 is a schematic diagram of a capacitive equivalent circuit of device 10A.

Figure 7 is a block diagram of the screen printing process used to fabricate microprotrusions on the coating of an energy storage device of the present invention;

8 is a perspective view of an electrode holder used in the manufacturing method of FIG. 7;

Fig. 9 is the block diagram of the method for making the microprotrusion head of the present invention in the photoengraving mode;

Figure 10 is an isometric view of a pair of heated rollers laminating photoresist to electrodes prior to photolithography;

Figure 11 is an isometric view of a mask placed over the photoresist of Figure 10;

Figure 12 is an isometric view showing exposure of unprotected portions of the photoresist of Figures 10 and 11;

13 is a cross-sectional view of an electrode forming part of an energy storage device taken along line 13-13 of FIG. 3;

Figure 14 is a cross-sectional view of two bipolar electrodes with a large surface area porous coating forming a capacitor chip on a conductive substrate:

Figure 15 is a schematic diagram of a frame used to hold a thin support material in a dip coating process;

FIG. 15A is a schematic illustration of the wires used in the framework of FIG. 15 .

Detailed ways

definition

The definitions of the following terms are not exclusive:

"Tape" means a thin strip of material used in a method of making a dry module. After the initial heating, the tape is removed to form the filled portion of the pores.

"Conductive support material" refers to any conductive metal or metal alloy, conductive polymer, conductive ceramic, conductive glass, or a combination thereof. Metals and metal alloys are preferably used to fabricate the base components, and the support material should have an electrical conductivity greater than about 10 ^-4 S/cm (Siemens/centimeter).

"Second conductive material" (having a large surface area) refers to the porous electrode coating, which may be of the same or different composition on each side of the support material. Preferred metal oxides of the present invention include those selected from Oxides of any selected metals: tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, manganese, lanthanum or metals of the lanthanide series or their Alloys or combinations thereof, and may contain additives such as calcium to increase electrical conductivity.

"Electrolyte" means an ionically conductive aqueous or anhydrous solution or material which enables a dry module to be charged.

"Cab-O-Sil ^(R) " refers to a silica filler available from Cabot Corporation of Tuscola, Illinois. Available in a variety of sizes.

"Epoxy resin" is the general definition of an epoxy resin product incorporating a specific curing agent, typically an epoxy resin incorporating a polyamine curing agent or a polyepoxide curing agent mixed with a polyamine.

"MYLAR ^(R) " refers to a polyester material of polyethylene terephthalate produced by Dupont, Inc. of Wilmington Delaware. Polyester is generally available in bulk in very thin gauges.

"Metal oxide" means any conductive metal oxide.

"Mixed metal oxide" means a conductive oxide mixture consisting of two or more metal oxides.

A "photoresist" is any photocurable material, usually an epoxy or acrylate or a combination thereof.

"ConforMASK" is a negative-working photopolymer commercially available from Dynachem of Tustin, California. This polymer should be used at 50% relative humidity or less. Dry prefabricated components for energy storage devices

Referring to the drawings, and in particular Figures 1, 2 and 3, there is shown a dry prefabricated assembly 10 of an energy storage device constructed in accordance with the present invention, which energy storage device is first assembled into a dry prefabricated assembly 10 . After filling the provided capacitor chips with electrolyte, the surfaces are heated close to and fused to the outer surfaces to form device 10A, which is then charged.

The device prefabricated assembly 10 generally includes a plurality of capacitor chips, such as capacitor chips 110, 112 and 114, which are formed, prepared and stacked according to the teachings of the present invention. FIG. 1A shows an assembled schematic diagram of an electrical storage device prefabricated assembly 10A formed from 12 stacked capacitor chips, however, it should be understood that any person skilled in the art may use any Different numbers of capacitor chips.

For ease of illustration, FIG. 3 is an exploded schematic diagram of the prefabricated assembly 10, which only shows three capacitor chips 110, 112 and 114. These capacitor chips have substantially the same design and construction, so reference is made only to FIGS. 2 , 2A, 3 and 13 . The capacitor chips 114 and 112 are described in detail.

Capacitor chip 114 includes a first conductive outer electrode or end plate 111A and a second inner conductive bipolar electrode 111B. The electrodes 111A and 111B are separated at the edges by two dielectric or electrically insulating backing layers 121 and 123 .

When the first and second electrodes 111A and 111B, insulating liner layers 121 and 123 are formed. And when the conductive porous material (oxide) layers 119 and 120 are bonded together to form capacitor die 114, a central air-filled gap 130 is formed by these elements (FIG. 2A). When assembly 10 is ready for use, gap 130 is filled with electrolyte (not shown) to produce device 10A.

To this end, an exemplary recess or fill port 122 is shown in FIG. 2A for ease of illustration only and is formed between liner layers 121 and 123 to allow electrolyte to fill gap 130 . Fill port 122 is formed by sheet or strip 117A inserted between fill layers 121 and 123 prior to fusing and bonding backing layers 121 and 123 . As the liner layers 121 and 123 are heated, the strip 117A becomes surrounded by the reflowed liner layer material, which allows the topography of the fill port 122 to be formed. The two backing layers become molten polymer sheets that cover as small an area as possible of the active conductive coatings 119 and 120 .

Now examining the electrodes 111A and 111B in more detail, the method of manufacturing these electrodes will be described later. One difference between electrodes 111A and 111B is that electrode 111A optionally includes a tab 160A for connection to a power source (not shown).

Another optional difference between electrodes 111A and 111B is that electrode 111A includes a porous conductive coating 119 deposited on a support material or structure 116, while bipolar electrode 111B includes two porous coatings 120 and 131, which are deposited on either or both sides of the support material or structure 111B. Thus, electrode 111B is a true bipolar electrode. It should be understood that both sides of the electrode 111A may be coated with a porous conductive layer.

Yet another optional difference between electrodes 111A and 111B is the rigidity of support structures 111A and 111B. The electrode 111A as the outer end plate preferably has a more rigid structure so that it can give sufficient rigidity to the overall structure of the energy storage device 10A. Electrode 111B and other similar internal electrodes do not have to be as rigid as external electrode 111A, however, when device 10A is larger, an auxiliary support structure is required, so internal electrode 111B is used as an auxiliary support structure, in this case Next, it is desirable to make the internal electrode 111B rigid.

As a result, support material 116 is thicker than support material 118 . In the preferred embodiment, support material 116 has a thickness of about 10 mils (0.0254 cm) and support material 118 has a thickness of about 1 mil (0.00254 cm), although other values are possible.

The dimensions of electrodes 111A, 111B and the remaining electrodes of memory device 10A are determined according to the desired application without departing from the scope of the present invention. For example, in one application, device 10A is compact, such as for a cardiac pacemaker. Yet in another application, the overall volume of the device is 1 cubic meter or more, for example for electric vehicles. The size of the electrodes determines the overall capacitance of the memory device 10A.

In this preferred embodiment, the electrodes, ie 111A and 111B, are rectangular, however, these electrodes and corresponding prefabricated assemblies 10 may also be of various other shapes, such as circular, square, etc. An important feature of assembly 10 is the flexibility of its design, which enables it to be used in a variety of applications.

Now examining coatings 119 and 120 in more detail, the method of forming these coatings will be described later. In the preferred embodiment, coating 119 includes a plurality of microprotrusions, while coating 120 does not include such microprotrusions. It should be understood, however, that coating 120 may alternatively be of a similar design to coating 119 without departing from the scope of the present invention.

5 is a top plan view of coating 119, which includes a micro-convex array, and is deposited on the inner face or flat side of support material 116. Coating 119 is porous, conductive, and has a large surface area. thinner. The array includes two sets of microprotrusions. The first set includes a plurality of circumferential microprotrusions 125 and the second set includes a plurality of centrally located microprotrusions 127 .

In the preferred embodiment, the peripheral boss 125 and the central boss 127 are of similar design and are generally hemispherical, however, other shapes, such as rectangular, are also within the scope of the invention. Each protrusion 125 or 127 has a diameter of approximately 6 mils (0.01524 cm), and different applications of device 10 may require microprotrusions 125 and 127 to have different designs. The center-to-center spacing of the circumferential microprotrusions 125 was about 20 mils (0.0508 cm), while the center-to-center spacing of the central microprotrusions 127 was about 40 mils (0.1016 cm).

One reason for the higher density of circumferential microprotrusions 125 is to prevent edge shorting. One reason for the lower density of central microprotrusions 127 is to create isolation between electrodes 111A and 111B with minimal masking of the electrode surfaces. To this end, it is permissible for the liner layer 121 to cover at least a portion of the microprotrusions 125, but preferably not cover the microprotrusions 127.

Circumferential microprotrusions 125 are disposed adjacently along the outer edge of coating 119 . Although only four rows of microprotrusions are depicted, those skilled in the art will understand that depending on the size and application of device 10, the number of rows may be increased. Central microprotrusions 127 are similarly disposed adjacently within central portion 132 of coating 119 in an array layout. As shown in FIG. 5 , the central microprotrusion 127 is surrounded by the peripheral microprotrusion 125 .

Microprotrusions 125 and 127 are formed on coating 119 to provide additional structural support to first and second electrodes 111A and 111B. For example, if the second electrode 111B begins to sag or bow toward the first electrode 111A, the microprotrusions 127 will prevent contact between these electrodes 111A and 111B.

FIG. 5 further shows that coating 119 also includes a plurality of openings 133A- 133G into which strips 1117A are disposed to ultimately form fill port 122 . As depicted for large electrode sizes, the notches (ie, openings) only partially extend to the central portion 132 . For small electrode sizes, the notch spans the electrode surface with both ends protruding to opposite sides, thereby simultaneously forming fill ports 133C and 133D, in which case the width of the strip is less than or equal to the space between the central microprotrusions 127. Center-center spacing, but, band (the width) is greater than the center-central spacing between the garden circumference shape micro-protrusion 125, to prevent the garden circumference shape micro-protrusion from extruding this band, and prevent it from moving out, in the garden circumference shape micro-protrusion Openings are added in the nose. Additionally, the width of the bands can be similar to the circumferential microprotrusion spacing, and no adjustments are necessary in the microprotrusion pattern.

Considering now the coating 120, which performs a similar function to the coating 119 and is deposited on the side of the electrode 111B facing the inner side of the first electrode 111A. In this preferred embodiment, coating 120 does not include bumps. In another embodiment of prefabricated assembly 10, coatings 119 and 120 have a similar structure and include microprotrusion layers.

Considering now the backing layers 121 and 123, the method of making these backing layers will be described later. Backing layers 121 and 123 are generally identical and arranged to overlap (adjacent and overlap) each other. For brevity, only the backing layer 121 will be described in detail. The backing layer 121 includes a continuous peripheral portion 143 and a hollow central portion 144 .

In the preferred embodiment, the strip 117A, or a portion thereof, is located between the backing layers 121 and 123 and passes through the hollow portion 144 of the backing layers and extends beyond the peripheral portion 143 . In another embodiment, the tape does not extend across the entire width of the backing layers, but only a portion of the tape is sandwiched between the backing layers and extends beyond both edges on one side of the backing layers.

Now returning to FIG. 1 , the next adjacent capacitor chip 112 is briefly described. Capacitor chip 112 is substantially the same as capacitor chip 114 in terms of design and construction. The capacitor chip 112 includes a bipolar electrode 111B and a second bipolar electrode 111C as first electrodes. Electrodes 111B and 111C are substantially identical and spaced from each other in alignment with each other.

Porous coating 131 identical to coating 119 is deposited on the surface of support material 118 facing electrode 111C, and coating 133 similar to coating 120 is deposited on support material or structure 140, which forms part of electrode 111C .

The capacitor chip 112 also includes two pad layers 135 and 137 , which are identical to the pad layers 121 and 123 of the capacitor chip 114 . Strip 117B forms fill port 142 between liner layers 135 and 137 .

The capacitor chip 110 is substantially the same as the capacitor chip 114 and includes a first bipolar electrode 111Y, a second electrode 1112 , two liner layers 157 and 159 , a strap 117C, a tab 160 and a filling port 162 . It should be noted that FIG. 3 does not show the internal electrodes 111Y.

Turning now to FIG. 6, there is depicted a capacitive equivalent circuit 200 representative of device 10A. This circuit 200 represents capacitor chip 114 as two capacitors C ₁ and C ₂ , and capacitor chip 112 as two capacitors C ₃ and C ₄ . Capacitor chip 110 is represented as two capacitors C ₅ and C ₆ . As a result, device 10 is roughly equivalent to a set of capacitors in series.

Porous conductive coating 119 combines with an ionically conductive medium (not shown) within capacitor chip 114 to form capacitor C ₁ . The ionically conductive medium and coating 120 form capacitor C ₂ . The coating 131 and the ionically conductive medium in the capacitor chip 112 constitute a capacitor C ₃ . The ionically conductive medium in the capacitor chip 112 and the coating 133 constitute a capacitor C ₄ . Similarly, capacitor chip 110 is represented by two containers _c5 and _C6 .

An important aspect of the invention is the bipolar configuration of the energy storage device. Using a single electrode, such as electrode 111B, forms two capacitors in series, such as capacitors _C2 and _C3 , thereby forming a bipolar electrode B. This design significantly reduces the overall size of the device 10A.

While not wanting to be bound by theory, an explanation of how capacitive energy storage devices work at the molecular level would help to understand the enormous value of a charged double layer. For simplicity, to describe Fig. 14, reference is made to Fig. 3, where the same reference numerals are used (and the porous material is a mixed metal oxide).

14 is an enlarged schematic cross-sectional view of the edges of support structures 118, 148A and conductive coatings (120, 131, 133, 133B).

The central support structure 118 is depicted as metallic, but it could be any material that is conductive and provides support for the coating. Coatings with large surface areas provide structure and geometry for energy storage. As can be seen from Figure 14, layer 120 etc. has a discontinuous surface with many fissures, micropores and mesopores which form a large surface area.

Thus, porous coatings 120 and 131 are coated on support structure 118 to form bipolar electrode 111B, and coatings 133 and 133B are coated on support structure 148A to form bipolar electrode 111c. After the prefabricated assembly 10 is assembled, the draw tape is removed, forming the fill port, and the prefabricated assembly 10 is filled with electrolyte 190, and the fill port, ie 177D, is sealed to form the device 10A.

Device 10A is then charged with the following results:

Coating 120 becomes negatively charged. The conductive support structure 118 transports electrons accordingly. Therefore, the porous coating layer 131 becomes positively charged. The ionically conductive electrolyte ionizes accordingly. An electric double layer is formed at the electrode-electrolyte interface, which constitutes each individual capacitor in circuit 200 . Accordingly, the surface of coating layer 133 becomes negatively charged, while the surface of coating layer 133B becomes positively charged. Since the porous high-surface-area oxide allows the effective surface area of the electrode to become very large, the corresponding electrical storage capacity of the device is dramatically enhanced. Method of making an energy storage device

Referring to Figures 1-5, the preferred method of manufacturing the prefabricated assembly 10 of the energy storage device 10A is generally described as follows:

(A) Support material preparation

The support material can be selectively etched or cleaned by various conventional etching or cleaning processes.

In some experiments, if the metal surface was not etched, it was smooth. Smooth surfaces can sometimes lead to insufficient adhesion of porous coatings. Etching creates a suitably rough surface.

1. Wet etching: A preferred process is to contact the metal support with an aqueous strong inorganic acid, eg sulfuric acid, hydrochloric acid. Hydrofluoric acid, nitric acid, perchloric acid or combinations thereof. Etching is usually carried out at an elevated temperature of 50 to 95°C (preferably 75°C) for about 0.1 to 5 hours (preferably 0.5 hour), followed by rinsing with water. Room temperature acid etching is possible. Alkaline etching or oxalic acid etching can also be used.

2. Dry etching: Rough support surfaces can be obtained by sputtering, plasma treatment, and/or ion milling. A preferred process is ArRF (Argon Radio Frequency) sputter etching, the etching conditions are a pressure of 0.001-1 Torr, an energy of about 1 KeV and a frequency of 13.5 MHz. Usually, the power density of 0.1-10watts/ ^cm2 is used to clean and roughen the surface within 1-60 minutes, another process is to use the reaction gas to support the material under the pressure of 0.1-30torr for 1-60 minutes For plasma etching, the reactive gas is, for example, oxygen, carbon tetrafluoride, and/or sulfur hexafluoride.

3. Electrochemical etching: The rough surface can be obtained by electrochemical oxidation treatment in chloride or fluoride solution.

(B) Coating of support material

This coating (eg oxide) is porous and mainly consists of micropores (diameter < 17A). There are large cracks 0.1-1 μm wide on the surface, and their depth is comparable to the thickness of the coating. However, more than 99% of the surface area is formed by these micropores, which have an average diameter in the range of 6-12A.

After various post-treatments, the pore structure can be altered to increase the average pore size. For example, steam post-treatment creates a bimodal pore distribution. In addition to micropores, a narrow distribution of mesopores (diameter < 17-1000A) with a diameter of about 35A formed. 85-95% of the surface area of these treated electrode coatings is formed by the microporous structure.

Using other electrode construction methods, this pore size distribution can be changed, and the use of surfactants to increase crystals or other organizational structures in the coating solution can increase the average pore size to 100-200A, and only 5-10% of the surface area source in micropores. The effective large surface area of the coating is thus 1000 to 100,000 times greater than the design surface area of the electrode.

As shown in FIG. 13, the electrode 111A includes a porous conductive coating 119 formed on at least one surface of a support material 116 that is conductive and rigid enough to support the coating 119 and give the device 10 sufficient resistance. Strong structural rigidity.

One goal of the present invention is to select the optimum energy density and power density of device 10 . This goal is achieved by reducing the thickness of the support 116 and maximizing the surface area of the coating 119 . The functional density of device 10 is further optimized by maintaining low electrical resistance.

The surface area of coating 119 is determined using the BET method well known in the art. The surface increase rate representing the surface optimization of the coating 119 is determined according to the following equation:

Surface increase rate = (BET surface area / design surface area)

In the present invention, the surface enlargement ratio can be as high as 10,000 to 100,000.

Coating 119 is porous with a porosity in the range of about 5% to 95%, with a typical porosity range of about 20% to 25% for efficient energy storage.

In conventional electric double layer capacitors, the main device resistance is derived from the carbon coating. In the present invention, the device resistance is mainly derived from the electrolyte, which has a higher resistance than the porous conductive coating.

Once prefabricated assembly 10 is filled with electrolyte, it can be charged to become device 10A. For an electrolyte, the main criteria are that it is ionically conductive and has bipolar properties. The boundary or interfacial region between the electrodes and the electrolyte is known in the art as an "electric double layer" and is used to describe the arrangement of charges in this region. A more detailed description of the electric double layer theory is given in Chapter 7 of Bokrls et al., "Modern Electrochemistry", Volume 2, Sixth Printing Edition (1977).

The surface area of the coating affects the capacitance of the device 10A if, for example, the surface enlargement factor is 1000 to 20,000 and the electric double layer capacitance density is about 10 to 500 microfarads per ^centimeter of interfacial surface area (i.e., BET surface area), Surface augmented capacitance densities of about 0.1 to 10 Farads per cm ^<2> of electrode are then achievable.

Although the electric double layer theory is described here, it should be understood that other theories or models, such as the proton injection model, are alternatives.

A high surface area (porous) conductive coating material is applied to the support material.

1. Solution method: Porous coating materials can be formed from various reactive starting compounds in solution or sol-gel compositions. Various methods of application of these raw compound components are possible, without limitation, curing, hydrolysis and/or pyrolysis processes are typically used to form coatings on support materials. Pyrolysis of metal salts is typically performed under a controlled atmosphere (nitrogen, oxygen, water, and/or other inert and oxidizing gases) with the aid of a furnace or an infrared source.

(a) Dip coating: The electrode or support structure is dipped in a solution or sol-gel, the support structure is covered with a coating of raw compound, and then cured by pyrolysis or other methods. This process can be repeated to increase coating thickness. Preferably, the support material is dipped in a metal chloride/alcohol solution and then pyrolytically treated at a temperature of about 250 to 500° C. for 5-20 minutes in an oxygen atmosphere of 5-100%.

This process is repeated until the desired coat weight is obtained. The final pyrolysis treatment is carried out at 250 to 450°C for 1-10 hours, with a typical value of about 1-30mg/ ^cm2 coating deposited on the support material to obtain an electrode cross-sectional area of about 1-10F per square centimeter capacitance density. Alternatively, a sol-gel solution is prepared with oxides of nail, silicon, titanium and/or other metals and the support material is coated as described above. By adjusting the pH value, water concentration, solvent and/or content of additives such as oxalic acid, formamide and/or surfactants, the discharge frequency characteristics of the coating can be adjusted.

Higher relative humidity can be used during the pyrolysis step to achieve conversion of the raw materials to oxides at lower temperatures. A preferred method is to maintain a relative humidity above about 50% during the pyrolysis at a temperature below 400°C.

A preferred method of dip coating thin (eg, 1 mil) support structures is to use a wire frame structure 300 to hold the support material 118 in taut (FIGS. 15 and 15A).

The wire frame structure 300 includes at least two wires 301 and 301A whose length is greater than the width of the support material 118 . Each wire 301 and 301A comprises a single wire segment tightly wound at each end by approximately 360° to form two loops 302 and 303 . The two loops are wound such that their ends are about 1 cm above the plane of the line, loops 302 and 303 are placed through holes 304 and 305 respectively in the support material. Holes 304 and 305 are located at the two corners of adjacent sides of the support material.

Two other wires 301B and 301C are similarly attached to the remaining sides of the support material to provide additional support.

(b) Spray coating: The coating solution is coated on the support material by a spray coating method, and cured and selectively repeated for increasing the coating thickness. A preferred method is to spray the coating solution onto the substrate at a temperature of 0-150° C., using an ultrasonic nozzle or other nozzles for spraying, at a flow rate of about 0.1-5 ml/min, in the presence of nitrogen, oxygen and/or Other reactions are carried out in a carrier gas composed of inert gas. Coating characteristics can be controlled by the partial pressure of oxygen and other reactive gases.

(c) Roll coating: The raw material compound coating is applied by the roll coating method, then cured and selectively repeated for increasing the coating thickness. The coatings described above for dip coating can be used here.

(d) Spin coating: the raw material compound is coated by the spin coating method in the prior art, and selectively repeated.

(e) Blade coating: The raw material compound is coated by the blade coating method and selectively repeated.

2. Electrophoretic deposition: use electrophoretic deposition technology to form a porous coating or raw material compound coating on the support material, and selectively repeat.

3. Chemical Vapor Deposition: A porous coating or a raw material compound coating is formed using a known chemical vapor deposition technique.

(c) Electrode pretreatment

Various pretreatments (conditioning) or combinations thereof have been found to be beneficial in improving the electrical properties (eg, electrochemical inertness, electrical conductivity, performance characteristics, etc.) of the coating. These treatments include, for example:

1. Steam treatment: In a closed container, between 150 and 320 ° C, under autogenous pressure, the coated electrode is in contact with water-saturated steam for 1-6 hours.

2. Reactive gas treatment: Between room temperature and 300°C, under reduced pressure or low pressure, the coated electrode is in contact with the reactive gas one or more times, such as oxygen, ozone, hydrogen, peroxide gas, carbon monoxide , nitrous oxide, nitrogen dioxide, or nitric oxide, preferably, between room temperature and 100°C, under a pressure of 0.1-2000torr, allow the coated electrode to be mixed with 5-20wt% of ozone-containing flowing air Contact 0.1-3 hours.

3. Supercritical fluid treatment: The electrodes are contacted with a supercritical fluid such as carbon dioxide, organic solvents, and/or water. The preferred method is to achieve supercritical conditions by first increasing the pressure and then increasing the temperature, and treat with supercritical water or carbon dioxide for 0.1-5 hours.

4. Electrochemical treatment: The coated electrode is placed in a sulfuric acid electrolyte, and an anodic current sufficient to release oxygen is passed through, and then a cathodic current is passed through. In one embodiment, the electrodes are subjected to a current of 10 mA/cm ² in 0.5 M sulfuric acid for about 5 minutes to generate oxygen. The electrode was then switched to a cathodic current and the open circuit potential was driven back down to a hydrogen evolution potential of 0.5 V (vs. a normal hydrogen electrode).

5. Reactive liquid treatment: contact the coated electrode with an oxidizing liquid such as hydrogen peroxide, ozone, sulfoxide, potassium permanganate, perchloric acid at a temperature of about room temperature to 100°C for 0.1-6 hours Aqueous solutions of sodium, chromium (VI) isotopes and/or combinations thereof. The preferred method is to treat with 10-100 mg/l ozone aqueous solution at 20-50 ° C for about 0.5-2 hours, followed by water washing, another method is to treat the treated in chromate or dichromate solution. coated electrodes.

(D) Isolation between electrodes

To obtain electrical isolation and a properly defined spacing between the electrodes, various methods are possible. These methods include, for example:

1. Microprotrusions: The isolation layers 125 and 127 between the coatings 119 and 120 include an array of small (in terms of area and height) protrusions, namely 125 and 127, on at least one surface of the electrode, the microprotrusions The protrusions may be constructed of thermosetting materials, thermoplastic materials, elastomeric materials, ceramic materials, or other electrically insulating materials.

There are several methods for forming these micro-protrusions, but not limited to these methods:

(a) Screen printing method: Microprotrusions are provided on the electrode surface by conventional screen printing methods, as described in detail later under the heading of "Screen Printing", in which various Elastomeric materials. Light curable plastics and thermoplastics. The preferred method is to use acid resistant epoxy or VITON( ^R) solutions.

(b) Chemical Vapor Deposition: Microprotrusions can also be placed on the electrode surface by depositing silicon dioxide, titanium dioxide and/or other insulating oxides or materials through a mask.

(c) Photolithography: Microprotrusions can also be fabricated by photolithography, as described in detail below under the heading "Photolithographic Fabrication of Microprotrusions".

2. Physically thin separator: The separator between electrodes is a thin, substantially open-structure material, such as glass. A preferred material is a 0.001-0.005 inch (0.00254-0.01270 cm) thick porous glass sheet commercially available from Whatman Paper Ltd of Clifiton, NJ.

3. Injection molded separator: The separator between porous materials can also be obtained by injection molding a thin, substantially open-structure film, such as ^NAFION® , polysulfone, or various gases and sol-gels.

4. Air isolation: The separator between the electrodes is an air gap, which is then filled with anhydrous or aqueous electrolyte.

(E) Padded

Used as a liner layer at the edge of the active electrode surface, such as liner layer 121, 123, 135. Materials for 137, 157, and 159 include any organic polymer that is stable in the electrical/chemical environment and processing conditions, suitable Polymers include, for example, polyimides, imides, ^TEFZEL® , polyethylene (high and low density), polypropylene, other polyolefins, polysulfones, ^KRATON® , other fluorinated or partially fluorinated polymers objects or a combination of them. The backing layer may be formed by screen printing methods or other methods as a preformed material.

(F) Tape for filling port

The strips (117A, 117B, and 117C) used to form fill ports, such as fill ports 122 and 142, are any suitable material having certain special properties, for example, it is different from the liner material in that it has a The higher melting temperature (Tm) of the material and it will not melt, flow or stick to the liner material under the heating conditions described herein. Typically glass, metal, ceramic, and organic polymers or combinations thereof are employed.

(G) Overlap

The stacked structure is formed by placing an end plate at the beginning, then alternately arranging the liner material, strips, and electrodes until the desired number of capacitor chips is formed, and finally ending with the placement of the second end plate, and optionally a A layer of gasket material is located on the top outer side of the stacked structure.

(H) Assembly (heating and cooling)

Heating the stack at low pressure reflows the liner material and bonds and seals the perimeter of the electrode material to adjacent electrodes in the stack; thereby forming mutually insulated capacitor chips and an assembled stack assembly .

(a) The stacked structure is heated by radio frequency induction heating (RFIH) to reflow the liner material.

(b) Uniformly heat the superimposed structure by radiant heating (RH) to reflow the material of the liner layer. The preferred method is to use (0.5-10Watts/cm ² 1-100μm radiant heating for 1-20 minutes.

(c) heating the stacked structure by conduction and/or convection heating in a furnace, optionally in an inert atmosphere, to reflow the liner material.

(I) Forming the filling port

The tape is pulled from the assembled assembly to form a dry prefabricated assembly having at least one fill port per capacitor chip.

(J) post-processing

Various subsequent reactive gas treatments of the stack or assembled stack, or combinations thereof, are beneficial in improving the overall and long-term electrical properties of the electrodes and resulting devices. These treatments include hydrogen, nitrogen oxides, carbon monoxide, ammonia, and other reducing gases or combinations thereof, between room temperature and the melting temperature Tm of the liner material, before step (H) and/or after step (I). , treatment under reduced or reduced pressure.

(K) Filling of dry prefabricated components

Dry prefabricated components are filled with ionically conductive aqueous or anhydrous electrolytes.

The preferred electrolyte is about 30% sulfuric acid in water because of its high conductivity. Non-aqueous electrolytes based on polypropylene and ethylene carbonate can also be used to achieve potentials greater than 1.2 V/capacitor chip.

The preferred method of filling dry prefabricated components with liquid electrolyte is to place the prefabricated components in the operating chamber, pump the operating chamber to less than 1 torr, and inject the electrolyte; thereby allowing the electrolyte to fill the gaps of the capacitor chips through the filling port. Alternatively, prefabricated components can be placed in the electrolyte and evacuated. The gas in the interstices of the capacitor chips is thereby removed and replaced by electrolyte.

In addition, non-liquid electrolytes (eg, solid and polymers) may also be employed. In cases where the electrodes are coated with electrolyte prior to reflow, no fill port is required.

(L) Sealing of filling port

The fill port is sealed by reflowing a secondary film of the same or a different polymer over the opening to form a hermetic device. This is usually done with an induction heater, which locally heats the film covering the fill opening.

(M) aging

The capacitor chip causes the device to fully charge by starting charging the device to 0.1 V at a charge current of approximately 4 mA/ ^cm2 .

(N) test

Termination Methods: There are several methods that can be used to make the electrical connection to the top lead-off plates of the capacitor, and these methods are described below.

1. End-exit electrode tabs (160 and 160A): The end-exit electrode plates (111A and 111Z) themselves have been cut into shapes that extend beyond the perimeter of the normal backing layer. These protrusions allow the installation of wires or straps. Typically, the protruding portion is a conductive sheet from which all oxides have been removed to expose the support material; 5 mil (0.0127 cm) thick nickel tape is spot welded to this conductive sheet,

2. Silver doped epoxy resin

Remove the oxide coating on the exposed face of the end plate or coat the end plate on one side only. A clean nickel foil or copper plate is electrically connected to the exposed surface by bonding with a conductive silver-doped epoxy. The presence of an oxide coating is also optional.

3. Lugs: Threaded titanium nuts are welded to thick titanium plates before coating. The electrical connection with the titanium nut is achieved by using bolts.

4. Pressure contact: Remove the oxide on the exposed side of the end panels, or coat the end panels on one side only, prior to assembly into a stacked structure of devices. Back-sputter the exposed support material, such as titanium, to clean the surface, being careful not to overheat the substrate when sputtering. The cleaned surface was then sputtered with titanium to lay down a clean bond layer, followed by sputtering with gold. Gold serves as a low contact resistance surface to which electrical contact can be made by pressing or wire bonding.

5. External deposition of a suitable medium such as aluminum, gold, silver, etc. by CVD or other methods.

Device resistance was measured at 1KHz. Device capacitance was determined by measuring the number of coulombs required to fully charge the device at approximately 4 mA per square centimeter of electrode area. Leakage current is measured as the current required to maintain a full charge after 30 minutes of charging.

Depending on the desired application, these devices can be fabricated in a variety of configurations, and by adjusting the relationship between device voltage, capacitor chip voltage, electrode area, and/or coating thickness, device structures can be constructed to suit specific requirements.

For every 10 μm thick coating, the electrode capacitance density (C′, in F/cm ² ) is about 1 F/cm ² . Therefore, a thicker coating is used to obtain a large capacitance. The device capacitance (C) is equal to the electrode capacitance density multiplied by the electrode area (A, in cm ² ) divided by twice the number of capacitor chips (n) (Equation 1).

The leakage current (i") is directly proportional to the electrode area, while the equivalent series resistance (ESR) is inversely proportional to the electrode area (Equation 2). Typical values for the leakage conduction current (1") are less than 20 μA/cm ² .

The total number of capacitor chips (n) in the device is equal to the total device voltage (V) divided by the capacitor chip voltage (V') (Equation 3). Capacitor chip voltages as high as about 1.2V can be achieved with aqueous electrolytes.

The device height depends on the capacitor chip gap (h') and the support structure thickness (h"), determined by the number of capacitor chips and the capacitance density of the electrodes (unit: F/cm ² ), see Equation 4.

The equivalent series resistance (ESR) of the device is a function of the product of the number of capacitor chips, the capacitor chip gap (h'), the resistivity of the electrolyte (r), and a constant of about 2 divided by the area (Equation 5).

Equation 1 C=C'A/2n

Equation 2 i"αAα1/ESR

Equation 3 n=v/v'

Equation 4 h/cm=n(0.002C’+h’+h”)

Equation 5 ESR＝2nh’r/A

By studying the necessary conditions such as voltage, energy and resistance, devices are constructed to meet the needs of various applications. The following examples are not meant to be limiting:

For electric vehicle applications, 100KJ to 3MJ devices are used. A high voltage (about 100 to 1000 V) high energy (1-5 F/cm ² ) storage device with an electrode area of about 100 to 10000 cm ² is employed.

For electrothermal catalytic converter applications to reduce automotive cold cranking, 10 to 80 KJ units are used. This device is approximately 12 to 50 V and has electrodes of 1-5 F/ ^cm2 with an area of 100 to 1000 ^cm2 . It is also possible to choose to form a device by connecting several devices in parallel to meet the electrical requirements.

For shock generator applications, about 200 to 400 V devices are employed with electrodes of 1-3 F/cm ² with an area of 0.5 to 10 cm ² .

For UPS applications, various series/parallel device configurations are available.

screen printing

Studying screen printing method 250 now, with reference to Figures 7 and 8, method 250 is mainly used in the preparation of a series of micro-protrusions 125 and 127 on the surface of the coating to be used in electrical storage devices such as capacitors or batteries in general, and In particular, it is used as a gap isolation layer in the type prefabricated component energy storage device 10 .

The substrate is usually a thin metal, such as titanium, zirconium, or alloys thereof, and the substrate is usually in the form of a thin metal plate, as is commonly used in existing capacitors.

The substrate is coated on one or both sides with a porous carbon compound or porous oxide coating. This step is accomplished by methods commonly used in the art. The oxide coating serves as the charge storage area of the device.

Additionally, a stack of stacked battery electrodes (such as lead for lead acid) and electrolytic capacitor electrodes (such as alumina and tantalum) can be fabricated.

It is important that the planar surfaces of adjacent coated substrates or electrodes do not touch each other and are uniformly isolated. The desired uniform isolation was achieved with epoxy microprotrusions.

Sample support: The thin flat substrate to be coated is held (or supported) so that microprotrusion formation is precise and precise on the flat surface of the substrate. The electrode holder 275 is especially important for thin metal sheets (0.1 to 5 mils) (0.000254 to 0.0127 cm), especially around 1 mil (0.00254 cm), where a Detrimental dents which can cause significant and undesirable changes in the physical and electrical properties of the final device.

Electrode holder 275 includes a porous ceramic holder 276, which is beneficial because the pore size is small enough that dents do not appear when pumped to a moderate or high vacuum. The flat ceramic surface of the ceramic holder 276 must be in intimate contact with the surface of the electrode 111A without deforming the metal or damaging the coating. A vacuum of at least 25 inches Hg is preferred for porous ceramics. The vacuum is preferably between about 25 and 30 inches Hg, especially 26 to 29 inches Hg.

In addition, the ceramic substrate should be flush with the surface of any mechanical support to ensure uniform protrusion of the epoxy resin through the mesh holes, where flush means between the surface of the support and the coating surface for electrical storage. No significant difference, ± 6 mils (0.0127 cm) between the two surfaces per 6 inches of length.

The electrode holder 275 also includes a metal frame 277, which should also be as flat as possible to form uniformly sized bumps from one side of the electrode to the other.

Electrode holders 275 are available from a number of commercial establishments, such as Ceramicon Designs, Colorado. Additionally, sample holder 276 can be fabricated from commercially available metals, alloys, or ceramics.

Typically, a 5 inch (12.7 cm) by 7 inch (17.78 cm) coated sheet electrode is formed.

The metal bracket 277 has a plurality of positioning pins at key positions, such as three positioning pins 278, 279 and 280, which cooperate with corresponding holes 281, 282 and 283 respectively to align and position the electrode 111A. Holes 281, 282, and 283 are typically located as close as possible to the periphery of electrode 111A to save useful electrode surface, or alternatively, alignment pins are aligned with the electrode edge without using alignment holes.

A die (not shown) having a predetermined open pattern is laid and fixed in a conventional screen printing frame (not shown), and the screen is removed.

The mixed epoxy components and fluid epoxy resin are placed on the surface of the stencil and then spread to obtain a flat coating. This can be done with a pressure bar, scraper or squeegee.

In general, constant temperature and humidity are important to obtain a flat coating.

The stencil is then carefully removed, leaving fluid epoxy bumps on the surface of the oxide. The epoxy bumps are then cured using rapid heating at 100 to 150° C. or light in the atmosphere.

The electrodes with microprotrusions are then combined with other electrodes and assembled either wet or dry. If dry, the dry module 10 is filled with electrolyte before charging.

It is important that the cured epoxy resin does not react with the liquid electrolyte that is ultimately used to fabricate capacitors with multilayer electrodes.

The cured micro-protrusions play a role in maintaining uniform spacing between electrodes.

As can be seen from Figure 6, the edges of the flat surface of the electrode have protrusions 125 which are denser than those protrusions 127 of the active or central portion of the electrode. These tabs 125 enhance support at the edges to maintain uniform separation. Alternatively, sticks can also be used.

From these teachings it is clear that the following are possible:

Since the support stiffness will vary, increasing or decreasing the thickness of the substrate electrode will allow for an increase or decrease in the microprotrusion isolation space.

Other thermosetting materials, thermoelastic materials, light curing epoxies or epoxy resin derivatives commonly used in the art may be used.

Other microprotrusion pattern elements may be used, such as squares, lines, crosses, and the like. In particular, the rods at the edges add mechanical support.

Optionally, the screen can be heated if necessary to bring the flowable epoxy to a temperature where its viscosity is suitable for short-term printing.

This heating step followed by screen printing of the flowable epoxy has to be done quickly because the working time of the epoxy is significantly reduced.

The fabricated electrical storage device having microprotrusions 125 and 127 is beneficial as a battery, capacitor, or similar device.

Lithographic Fabrication of Microprotrusions

This method mainly uses photolithography technology to manufacture a series of micro-protrusions on the surface of the electrode substrate or the alloy, referring to FIGS. 10 , 11 and 12 . The substrate is usually in the form of a thin metal plate as is commonly used in prior art capacitors.

A thin film of photoresist 381 was applied to the surface of electrode 111A by vacuum deposition using a commercially available Dynachem ConforMASK film applicator and Dynachem Vacuum Applicator Model 724/30, or by letting light The resist film 381 and the electrode 111A are passed through a pair of heated rollers 384 and 385 .

Exposure is performed using a standard 1-7KW high voltage exposure light source, such as a mercury vapor lamp 389 .

ConforMask film applicators are developed using standard conditions, such as 0.5-1.0% sodium carbonate or potassium carbonate monohydrate, in a developing tank or a conveyorized aqueous developer. After developing, the electrodes with micro-protrusions can be neutralized in 10% dilute sulfuric acid solution. This removes any unwanted unreacted film leaving reacted microprotrusions stuck to the electrode surface.

The resulting material is subjected to a final curing process that includes high voltage irradiation and heat treatment using conventional high voltage curing equipment and convection air ovens for optimum physical and electrical performance characteristics.

A plurality of electrodes are assembled to make, for example, a capacitor, as described above. The microprotrusions achieve the desired uniform isolation. business application

As a primary or secondary power source, and/or as a capacitor, energy storage device 10A has a variety of applications. Its specification is 0.1V to 100000V or 0.1cm ³ to 10 ⁵ cm ³ . Typical voltage ranges include a combination of ranges used in automotive and other applications.

These applications include the following applications: Typical voltage range for automotive applications Typical dimensions (cm ³ ) Inner tubes and seat shock absorbers 1-100 1-1000 Seat heaters 1-100 1-100 Electronic heating catalysts 1-1000 1- 1,000,000 Electric Vehicle Engine 100-1000 100-1,000,000 Hybrid Electric Vehicle Engine 1-1,000 10-100,000 Internal Combustion Engine/Ultracapacitor Engine 1-100 100-100,000 Electric Commutator 1-1,000 1-100 Regenerative Brake/Shock Absorption 1-1000 5-100 light and battery ignition 1-1000 2-100 light and ignition only 1-100 1-100 medical application cardiac shock generator 10-500 0.1-100 pacemaker 1-300 0.1-300 nerve stimulator or similar devices 0.1-300 0.1-300 implantable and external devices 0.1-300 0.1-300 surgical power tools 10-700 1-10 ambulatory monitoring equipment 1-100 1-100 automated liquid chromatography 1-100 1 -20 Automated clinical laboratory analysis 1-100 1-20 Computed tomography (CT) scanner 1-1000 1-100 Dental equipment 1-200 1-10 Digital radiography equipment 1-500 1-1000 Electronic surgery Equipment 1-100 1-10 Optical Fiber 1-100 1-100 Inspection 1-10 1-10 Hearing Aid 1-10 0.1-1.0 Infusion Device 1-100 0.1-10 Magnetic Resonance Imaging (MRI) 1-1000 1-1000 Nuclear Medicine Diagnostic Equipment 1-1000 1-100 Electrical Patient Monitoring System 1-200 1-100 Respiratory Therapy Equipment 1-500 1-100 Surgical Laser 1-1000 1-1000 Electrical Surgical Support System 1-100 1-1000 Ultrasound Diagnostic Equipment 1-100 1-100 Automotive Engine System Gear Shift 1-1000 100-10000 Golf Cart 1-1000 100-10000 Farm Tools, Subway 1-1000 100-100000 Regenerative Brake 1-1000 1-100 Office/Commercial Electronic Application Computing Device 1-120 0.5-10 Network communication 1-120 1-100 Commercial audio amplifier 1-1000 1-10 Commercial flash/strobe light 1-1000 1-10 Commercial power tool 1-1000 1-100 Commercial camera 1-120 1-10 Computer 1-120 1-10 Duplicator 1-120 1-10 Dictation Recording Equipment 1-100 1-1000 Motor 1-1000 1-1000 Electronic Lock 1-120 1-10 Electronic Synthesizer/PDAs 1- 100 1-5 Emergency lighting system 1-440 1-1000 Fax equipment 1-120 1-10 Microphone 1-120 1-3 Pagination machine 1-120 1-2 Printer 1-120 1-10 Security system 1-120 1 -100 Transmissive slide lamp 1-120 1-100 Uninterruptible power supply 1-1000 1-100000 Vibration preventer 1-1000 1-100000 Wireless network 1-1000 1-1000 Consumer electronics application audio system Pocket/household type 1-120 1-10 Portable recorder/CD 1-120 1-5 Walkman/Pocket stereo 1-120 1-5CB radio device 1-120 1-10 Amateur radio transceiver device 1-120 1-100 Cam tape Loop Automatic Recorder 1-120 1-10 Home Satellite Dish Reflector 1-120 1-10 Microphone 1-120 1-3 Monitor and CRT 1-1000 1-100 Flashlight 1-1000 1-3 Receiver , Transceiver 1-1000 1-10 Telephone answering device 1-120 1-5 Network, wireless phone 1-120 1-3 Toys and game consoles 1-120 1-10 Television equipment 1-1000 1-10 Household type 1- 1000 1-10 Portable 1-1000 1-10 Video Cassette Recorders (VCRs) 1-120 1-10 Video Disc Players 1-120 1-10 Video Game Consoles 1-120 1-10 Watches/Clocks 1-120 1- 100 Consumer Appliances Air Purifiers 1-120 1-100 Pocket Sealers 1-150 1-100 Agitators 1-120 1-10 Clocks-Total 1-120 1-100 Alarms and Consoles 1-120 1-10 Coffee Mill 1-120 1-10 Coffee Processor 1-120 1-10 Convection Oven 1-1000 1-1000 Corn Popper 1-120 1-10 Curl Iron/Brush 1-120 1- 5 Deep Fryer 1-230 1-100 Electric Blanket 1-120 1-10 Flashlight 1-100 1-10 Floor Polisher 1-220 1-100 Food Processor 1-120 1-10 Hair Dryer 1- 120 1-5 heating pad 1-120 1-5 home security system 1-120 1-100 iron 1-120 1-5 cutting machine 1-120 1-3 beauty appliance 1-120 1-5 mixer 1-120 1 -5 Microwave 1-230 1-10 Power Tools 1-230 1-100 Security System 1-230 1-100 Shaving 1-120 1-3 Smoke Detector 1-120 1-5 Timer 1-120 1-3 Toaster/Oven 1-120 1-5 Toothbrush (electric) 1-120 1-3 Vaporizer 1-120 1-10 Water interrupter 1-120 1-10 Vortex (handy) 1 -120 1-100 Main household consumer appliances Compactors 1-120 1-10 Dishwashers 1-220 1-100 Dryers 1-120 1-100 Freezers 1-220 1-100 Multifunctional stoves utilizing waste heat 1 -220 1-1000 (Ranges) Refrigerator 1-120 1-100 Washing Machine 1-220 1-100 Water Heater 1-220 1-100 Outdoor Equipment Insect Killer 1-120 1-10 Outdoor Fence 1-120 1-100 Electric Mower Grass Mower 1-220 1-100 Ride-On Mower 1-1000 1-1000 Ride-On Tractor 1-1000 1-10000 Rotary Tiller 1-1000 1-10000 Snowplow/Blower 1-220 1-1000 Lawn Mowing Device 1-220 1-100 Other applications Electric deicer 1-1000 1-100 Electronic fuse 1-1000 1-10 Laser 1-1000 1-100 Phase radar 1-1000 1-1000 Remote sprinkler 1-1000 1-10000 Storage for load leveling in power plants, i.e. storage of alternately generated energy (solar, fuel cells, wind turbines 1-1000 1-10,000,000 rounds/etc.)

Military Application Defense 1-10,000 0.1-10.000.000

For a particular application, multiple devices are connected in series and/or in parallel to achieve the desired performance.

Manufacture of dry precast components

The following examples are for illustration and demonstration only, and they should not be considered as limiting the invention in any way.

example 1

Manufacture of dry precast components

(A) Coating method

The support structure was fabricated by etching a 1 mil (0.00254 cm) piece of titanium with 35% _HNO3 /1.5% HF at 60°C for 5 minutes. The end plates are 5 mil (0.0127 cm) titanium.

The oxide coating solution was 0.2M ruthenium trichloride trihydrate and 0.2M niobium pentachloride in t-butanol (reagent grade).

The etched Ti flakes were dip-coated by dipping in the solution under ambient conditions. The coated sheet was left in the solution for about 1 second and then removed.

After each coating, the oxide was dried at 70°C for 10 minutes, thermally decomposed at 350°C for 10 minutes, and then removed to cool to room temperature, all in ambient atmosphere.

Repeat the dipping step for up to 10 coats (or any desired number), rotating the Ti sheet to dip each side alternately. The thickness is about 10 microns.

The fully coated titanium sheets were subjected to a final anneal at 350°C for 3 hours in ambient atmosphere.

(B) Electrode pretreatment

Under its own pressure, the coated electrode was exposed to saturated steam at 280° C. for 3 hours in a sealed container.

(C) Interval

Microprotrusions were screen printed on one side of the electrodes as detailed below under the heading "Screen Printing". The epoxy compound was EP21AR, obtained from Masterbond of Hackensack, NJ.

The epoxy bumps were cured at 150°C for 4 hours in air. The coated electrode is then molded into the desired shape.

(D) Padded

On the side of the electrode with a micro-protrusion, a modified high-density polyethylene (HDPE, modified in terms of anti-puncture and adhesion) with a thickness of 1.5mil (0.00381cm) and a width of 30mil (0.0762cm) is set. Same with the electrodes, then pulse heat the stack. HDPE ^(R) is the PJX2242 grade available from Phillips-Joanna of Ladd, Illinois.

(E) belt

A 0.9 mil (0.00229 cm) thick, 10 mil (0.0254 cm) wide strip of Dupont ^{T2 TEFZEL®} film 90ZM slit in the machine direction was placed across the narrow dimension of the pad and electrode surfaces and aligned between the microprotrusions. allow. The band can be positioned in one of three positions, center, center left, or center right.

A second HDPE is placed on the first backing to sandwich the tape between the two backings.

Pulse heat is applied to the second liner to bond to the first liner and hold the tape in place.

(F) Overlap

Alignment fixtures on non-metallic (ceramic) start with 5mil (0.0127cm) end plate, stack electrode/micro-protrusion/pad/tape/pad assembly, make the assembly reach the desired number of capacitor chips, and finally use The 5mil (0.0127cm) smooth end plate termination assembly is superimposed, and the tape is set in a three-unit repeating cycle in a position staggered to the left, center, and right (end perspective), and the light pressure is applied through a ceramic pressure plate on the The top of the stack so that the light pressure can maintain uniform alignment and contact across the stack.

(C) reflow

The stacked assembly was heated using a radio frequency induction heater (2.5KW). The stacked assembly was centered on a 3 inch (7.62 cm) diameter coil over three revolutions and heated at 32% of the set power for 90 seconds. Allow the fused assembly to cool to room temperature.

(H) Remove the tape

Carefully pull on the exposed end of the tape to remove the tape, leaving an open fill hole.

Example 2

Another method of making dry prefabricated components

(A) Coating method

A support structure was prepared by etching a 1 mil (0.00254 cm) piece of titanium with 50% HCl at 75°C for 30 minutes. The end plates are 2 mil (0.00508 cm) titanium.

The oxide coating solution was 0.3M ruthenium trichloride trihydrate and 0.2M tantalum pentachloride in isopropanol (reagent grade).

The etched Ti flakes were dip-coated by dipping in the solution under ambient conditions. The coated sheet was dipped into the solution for about 1 second and then removed.

After each coating, the oxide was dried at 70°C for 10 minutes in ambient atmosphere and thermally decomposed at 330°C for 15 minutes in a flow of 50 vol% oxygen and 50 vol% nitrogen at 3 cubic feet per hour, Then remove and cool to room temperature in ambient atmosphere.

Repeat the dipping step for up to 30 coats (or any desired number), rotating the Ti sheet to alternately dip each side.

The fully coated titanium sheets were subjected to final annealing for 3 hours under the above conditions.

(C) Interval

VITON ^(R) microprotrusions were screen printed on one side of the electrodes as detailed below under heading "VII. Screen Printing".

The ^VITON® microprotrusions were cured at 150°C for 30 minutes in air. The coated electrode is then molded into the desired shape.

(D) Padded

A modified high-density polyethylene (HDPE, modified in terms of anti-puncture and adhesion) with a thickness of 1.0mil (0.00254cm) and a width of 20mil (0.0508cm) is set on both sides of the electrode, and its peripheral boundary is the same as that of the electrode, and then the pulse Heating Laminate, HDPE is PJX2242 grade, obtained from Phillips-Joanna of Ladd, Illinois.

(E) belt

A strip of 1 mil (0.00254 cm) diameter ^TEFLON® coated tungsten wire is provided across the narrow dimension of the pad and electrode surface and aligned between the microprotrusions, the strip can be positioned center, left of center, or center One of these three positions on the right.

(F) Overlap

Stacked electrode/microbump/pad/tape/pad assembly, assembly starts with 2mil (0.00508cm) end plate to desired number of capacitor chips and ends with 2mil (0.00508cm) flat end plate , the line belt is set in a position with three units as the repeating period according to the left, middle and right staggered positioning (end perspective).

(C) reflow

The HDPE liner was subjected to reflow of the thermoplastic at 125°C for 120 minutes in nitrogen. The assembly was cooled to room temperature under nitrogen.

(H) Ribbon removal

Pull the exposed end to remove the cord, leaving an open fill hole.

Example 3

Another manufacturing method of dry prefabricated components

(A) Coating method

A support structure was prepared by etching a 1 mil (0.00254 cm) piece of titanium with 50% HCl at 75°C for 30 minutes. The end plates are 10 mil (0.0254 cm) titanium.

The oxide coating solution was 0.2M ruthenium trichloride trihydrate and 0.2M tantalum pentachloride in isopropanol (reagent grade).

The etched Ti flakes were dip-coated by immersion in the solution under ambient conditions. The coated sheet was dipped into the solution for about 1 second and then removed.

After each coating, the oxide was dried at 70°C for 10 minutes, thermally decomposed at 300°C for 5 minutes, and then removed to cool to room temperature, all in ambient atmosphere.

Repeat the dipping step for up to 10 coats (or any desired number), rotating the Ti sheet to dip each side alternately.

The fully coated sheets were subjected to a final anneal at 300° C. for 3 hours in ambient atmosphere.

(B) Electrode pretreatment

Under its own pressure, the coated electrode was exposed to saturated steam at 260° C. for 2 hours in a sealed container.

(C) Interval

Microprotrusions were screen printed on one side of the electrode, as detailed below under the heading "VII, Screen Printing". The epoxy compound was grade EP21AR from Masterboud, Hackensack, NJ.

The epoxy bumps were cured at 150°C for 4 hours in air. The coated electrode is then molded into the desired shape.

(D) Padded

On the side of the electrode with a micro-protrusion, a modified high-density polyethylene (HDPE, modified in terms of anti-puncture and adhesion) with a thickness of 1.5mil (0.00381cm) and a width of 30mil (0.0762cm) is set. Same with the electrodes, then pulse heat the stack. HDPE ^(R) is a PJX2242 grade available from Phillips-Joanna of Ladd, Illinois.

(E) belt

A strip (TEFZEL ^(R) ) 1 mil (0.00254 cm) thick by 10 mil (0.0254 cm) wide was placed across the narrow dimension of the pad and electrode surface and aligned between the microprotrusions. The band can be positioned in one of three positions: center, left of center, or right of center.

A second layer of HDPE ^(R) liner is placed over the first liner to sandwich the tape between the two layers of liner.

Pulse heat is applied to the second liner to bond to the first liner and hold the tape in place.

(F) Overlap

Stack electrode/microbump/pad/tape/pad assemblies starting with 10 mil (0.0254cm) end plates to the desired number of capacitor chips. Start with a 10mil (0.0254cm) terminal plate, reach the desired number of capacitor chips, and terminate the stack with a 10mil (0.0254cm) flat terminal plate, with a three-unit repeating cycle according to left, middle, Right staggered positioning (end perspective).

(G) reflow

The gasket was subjected to reflow of the thermoplastic at 160°C for 45 minutes in nitrogen. The assembly was cooled to room temperature under nitrogen.

(H) Removal belt

Carefully pull the exposed end to remove the tape, leaving the fill hole open.

Example 4

Another manufacturing method of dry prefabricated components

(A) Coating method

The support structure was made by etching a 1 mil (0.00254 cm) piece of titanium with 50% HCl at 75°C for 30 minutes. The end plates are 5 mil (0.0127 cm) titanium.

The oxide coating solution was 0.2 M (ruthenium trichloride trihydrate and 0.2 M (di-isopropxide)) bis(2,4-pentanedioic acid) in ethanol (reagent grade). (Pent-anedinate)) Titanium.

The etched Ti flakes were dip-coated by dipping in the solution at ambient conditions, the coated Ti flakes were immersed in the solution for about 1 second and then removed.

After each coating, the oxide was dried at 70°C for 10 minutes, thermally decomposed in oxygen at 350°C for 5 minutes, and then removed to cool to room temperature, all in ambient atmosphere.

The dip coating step is repeated for up to 30 coats (or any desired number), rotating the Ti sheet to alternately invade each side.

The fully coated titanium sheets were subjected to final annealing at 350°C for 3 hours in an oxygen atmosphere.

(C) Interval

Microprotrusions were formed by thermal spraying through a mask on one side of the electrode. The thermal spray material was TEFLON ^(R) , available from EI Du Pont de Nemoure & Co, Wilmington, Delaware.

The ^TEFLON® microprotrusions were cured at 300°C for 0.5 hour in air, followed by molding the coated electrode into the desired shape.

(D) Padded

On the side of the electrode with a micro-protrusion, a modified high-density polyethylene (HDPE, modified in terms of anti-puncture and adhesion) with a thickness of 1.5mil (0.00381cm) and a width of 30mil (0.0762cm) is set. Same with the electrodes, then pulse heat the stack. HDPE is PJX2242 grade, obtained from Phillips-Joanna of Ladd, Illinois.

(E) belt

A strip (TEFZEL ^(R) ) 1 mil (0.00254 cm) thick by 10 mil (0,0254 cm) wide was placed across the narrow dimension of the pad and electrode surface and aligned between the microprotrusions. The band can be positioned in the center. One of three positions left of center or right of center.

A second HDPE ^(R) liner was placed over the first liner, with the tape sandwiched between the two liners.

Pulse heat is applied to the second liner to bond it to the first liner and hold the tape in place.

(F) Overlap

Stacked electrode/microbump/pad/wire tape/pad assembly starting with 5mil (0.0127cm) end plate elements to desired number of capacitor chips and ending with 5mil (0.0217cm) flat end plate Termination assembly, band set in a three-unit repeating cycle left, center and right staggered positioning (end perspective).

(G) reflow

The thermoplastic was reflowed at 190°C for 30 minutes in the pad under nitrogen, and the assembly was cooled to room temperature under nitrogen.

(H) Ribbon removal

Carefully pull on the exposed end to remove the tape, leaving an open fill hole.

Example 5

Another method of making dry prefabricated components

(A) Coating method

The support structure was made by etching a 0.8 mil (0.002032 cm) piece of zirconium with 1% HF/20% HNO ₃ at 20° C. for 1 minute. The end plate is 2 mil (0.00508 cm) zirconium.

The oxide coating solution was 0.2M ruthenium trichloride trihydrate and 0.1M tantalum pentachloride in isopropanol (reagent).

The etched Ti flakes were dip-coated by dipping in the solution under ambient conditions. The coated Ti sheets were immersed in the solution for about 1 second and then removed.

After each coating, the oxide was dried at 85°C for 10 minutes, thermally decomposed at 301°C for 7 minutes, and then removed to cool to room temperature, all in ambient atmosphere.

Repeat the dipping step for up to 10 coats (or any desired number), rotating the Ti sheet to dip each side alternately.

The fully coated Ti flakes were subjected to a final anneal at 310 °C for 2 h in ambient atmosphere.

(C) Interval

Microprotrusions were formed on one side of the electrode by thermal spraying through a mask. The thermal spray material was TEFLON ^(R) , available from EI DuPont de Nemours & co., Wilmington, Delaware.

The ^TEFLON® microprotrusions were cured in air at 310°C for 1 hour. The coated electrode is then molded into the desired shape.

(D) Padded

A 1.5 mil (0.00381 cm) thick, 30 mil (0.0762 cm) wide polypropylene liner is placed on the side of the electrode with a micro-protrusion, and its peripheral boundary is the same as that of the electrode, and then pulsed to heat the stack.

(E) belt

A 1 mil (0.00254 cm) diameter tungsten strip coated with ^TEFLON® was placed across the narrow dimension of the pad and electrode surface and aligned between the microprotrusions. The band can be positioned in one of three positions: center, left of center, or right of center.

A second polypropylene backing was placed over the first backing, with the cord tape sandwiched between the two backings.

Pulse heat is applied to the second liner to bond to the first liner and hold the tape in place.

(F) Overlap

Stacked electrode/microbump/pad/wire tape/pad assembly starting with 2mil (0,00508cm) termination plate elements to desired number of capacitor chips and progressing from 2mil (0.00508cm) flat termination Plate termination assembly, band set in a position staggered left, center and right (end perspective) with a repeating cycle of three units.

(G) reflow

The thermoplastic was reflowed at 195°C for 60 minutes against the liner under nitrogen. The assembly was cooled to room temperature under nitrogen.

(H) Ribbon removal

Pull the exposed end to apply the tape, leaving the fill hole open.

Example 6

Filling of Capacitor Chip Air Gap Intervals

The dry prefabricated module 10 is filled with electrolyte solution as follows. Any of a number of possible dry prefabricated module configurations may be employed.

(H) backfill

The tape is manually removed, the fill hole is opened, and the stacked assembly is placed in a vacuum chamber and evacuated to below 35 mTorr for 5 to 60 minutes. The air was removed by nitrogen, and the 3.8M _H2SO4 liquid electrolyte was introduced into the _vacuum chamber and filled into the vacuum space between the electrodes.

(I) Seal fill hole opening

Remove the electrolyte-filled assembly from the vacuum chamber, rinse with deionized water, remove excess electrolyte, and dry. A HDPE film ((1.5 mil (0.00381 cm) thick)) was placed over the entire fill orifice and the entire orifice was sealed by pulse heating.

(J) adjust

The device was charged until fully charged, starting at 0.1 V/capacitor chip and increasing by 0.1 V/capacitor chip, up to 1 V/capacitor chip.

(K) test

The device was tested in a conventional manner, and the leakage current of 1V/capacitor chip was less than 25 μA/cm ² , and the capacitance density per capacitor chip was greater than 0.1 F/cm ² . The height of a 10V device is 0.05 inches or less, the height of a 40V device is 0.13 inches or less, and the height of a 100V device is 0.27 inches or less.

The properties of various geometries and configurations based on sulfuric acid electrolyte are shown in Table 1

Table 1

Performance of supercapacitor devices Area/cm ² 2 2 2 2 25 25 Voltage 10 40 100 100 100 100 C/MF 26 6.7 2.6 10 150 753 ESR/milliohm 100 330 780 780 62 70 Volume/cc 0.29 0.73 1.6 1.6 11 32 Joule(J)/cc 4.5 7.4 8.1 31 69 111A Watt/cc 860 1660 2000 2000 3670 1100

Example 7

Another filling method for dry prefabricated components

The dry prefabricated assembly 10 is filled with electrolyte solution in the following steps. Any of a number of possible dry prefabricated module configurations may be employed.

(H) backfill

Remove the wire to open the fill hole. Put the stacked assembly into a vacuum chamber and evacuate to 35 millitorr for 5 to 60 minutes, remove the air by nitrogen, introduce a liquid anhydrous electrolyte containing 0.5MKPF6 in propylene carbonate (propylene carbonate) into the vacuum chamber and fill it with Vacuum space between electrodes.

(I) Seal fill hole opening

Remove the electrolyte-charged components from the vacuum chamber and remove excess electrolyte. A HDPE film (1.5 mil (0.00381) thick) was placed over the entire fill hole opening and pulsed heat sealed the entire hole.

(J) adjust

Charge the device until fully charged, starting at 0.1V/capacitor chip and increasing to 1.5V/capacitor chip.

(K) test

The device was tested conventionally, and the leakage current was about 100 μA/cm ² at 1.5 V/capacitor chip, and the capacitance density was about 4 mf/cm ² for a device with 10 capacitor chips.

Example 8

The post-processing conditions of the device

The following is a table (Table 3) of the electrical properties of devices utilizing various gas post-conditioning techniques to adjust the resting potential of electrodes, whereby multiple capacitor chip devices filled with 4.6M sulfuric acid electrolyte can be charged to at least 1V/capacitor chip, A decrease in leakage current can be observed. This treatment is performed before, during and/or after reflow of the liner material. The gas treatment temperature is lower than that used for the reflow of the liner, and the atmosphere in the reflow is changed to an inert gas such as nitrogen or argon. For processing after reflow of the gasket material, the joints are removed prior to processing, during which the vacuum is periodically evacuated and the reactive gas charged.

table 3

Device performance corresponding to various post-adjustments gas T/℃ t/min 1”/μA/cm ² V/capacitor chip H ₂ 50 20 8 1.0 CO 100 170 40 1.0 CO 90 103 12 1.0 CO 90 165 20 1.0 CO 80 120 25 1.1 NO 75 20 27 1.0 NO 95 140 twenty one 1.1 NH ₃ 85 30 26 1.0

      Forming micro-protrusions using screen printing

Example 9

Fabrication of Epoxy Microprotrusions on Porous Coatings on Thin Substrates by Screen Printing

(A) Screen Preparation - A 325 mesh stainless steel screen was laid on a standard screen printing frame. The screen is edge bonded (Dexer Epoxy 608 clear) to a smaller 1-1.5 mil (0.00254-0.00381 cm) thick brass sheet with drilled holes (diameter 6.3 mil (0.016 cm) cm)) or etched into the desired pattern. Remove the screen mesh in the area covered by the brass sheet, leaving the remaining edge of the brass sheet bonded to the mesh to fit on the frame.

(B) Sample Holder - Vacuum is drawn on a porous aluminum holder plate with an average pore diameter of 10 μm, which is used to hold a 1 mil (0.00254 cm) thick porous oxide film during the printing process. object coating.

(C) Epoxy resin - add silica filler, modify the two-component epoxy resin MasterBond EP21AR to the required viscosity (can be denatured: 300000 ~ 400000cps). Filled epoxy resins of the desired viscosity are commercially available from Master Bond, Inc. of Haokensack, New Jersey. The epoxy was prepared as directed and had an effective dwell time of about 30 minutes as a flowable fluid.

(D) Screen printing parameters

Rolling speed: 1-2 inches/second

Paint point (snap off): 20-30mil (0.0508-0.0762cm)

Constant temperature and humidity of the epoxy resin is important to ensure uniform coating. Typical conditions are about 40-70% relative humidity and a temperature of about 20-25°C.

(E) Printing epoxy resin pattern - make an epoxy resin bump array with a height of 1mil (0.00254cm) and a diameter of about 7.5mil (0.019cm), and a typical pattern on the electrode is by 40mil (0.1016cm) The array of micro-protrusions deposited at intervals between centers is formed. In addition, the screen-printed epoxy topography was cured at 150°C for a minimum of 4 hours by reducing the center-to-center spacing to 20 mil (0.508 cm) and increasing the density of microprotrusions at the periphery of the electrodes.

Example 10

      Epoxy resin micro-protrusions formed by screen printing

(A) Screen Preparation - 230 or 325 mesh screens (8 x 10 inch stainless steel) with a latex-free surface were mounted on standard printing frames and used as base blocks. An etched, drilled or punched stencil (6.0 x 8.5 molybdenum) was edge bond positioned on the back side of the screen using Dexter Epoxy 608 Clear from Dexter. ^MYLAR® was placed over the entire cross screen member and pressure was applied to smooth the epoxy into a uniform layer.

The screen was then tapped, epoxy was applied to the top surface of the screen, and a MYLAR( ^R) sheet was placed over the entire area to smooth the epoxy. The MYLRAR ^(R) sheet on top of the screen was then removed. The screen stencil assembly was then placed in an oven at 120°C to cure the epoxy in ambient atmosphere for 5 minutes. The epoxy can also be cured at ambient temperature for 30-60 minutes.

Immediately after removing the screen stencil from the oven, carefully peel off the ^MYLAR® on the back side of the screen. Then use a sharp edge to cut off the top mesh screen, care must be taken to avoid the stencil bursting out. Since the screen is removed from the stencil pattern, any thermally stable thermosetting adhesive such as epoxy can be applied to the periphery of the cut screen stencil and covered with ^MYLAR® to smooth the epoxy and secure the edges of the screen on the template. Allow the epoxy to cure for 5 minutes in the oven. The resulting component is a stencil that is stretched taut from the screen, ready for printing.

(B) Sample holder—use a porous ceramic holder (as shown in Figure 8) plate (CeramiconDesigns, Golden, Colorado, P-6-C material), a porous oxide coating with a thickness of 1 mil) and 0.00254 cm) was clamped during the printing process, and vacuum was drawn through a porous ceramic plate. The ceramic plate is cut to size (the size and shape of the substrate to be printed). The ceramic plate is then inserted into an aluminum (steel, etc.) frame 277 and epoxy or other adhesive that can be mounted to a screen printer. The ceramic plate is then carefully ground to be as flush as possible with the metal frame. Locating pins 278, 279 and 280 are added and holes 281, 282 and 283 are used to hold substrate 111A in place.

(C) Epoxy Resin - Master Bond ^EP21ART® (a two-component epoxy resin (33 wt% polyamine curing agent and 67 wt% liquid epoxy resin) with a viscosity of about 150000-600000 cps). The epoxy resin was prepared as directed. The effective residence time as a flowable fluid is about 30 minutes.

(D) Screen printing parameters

Rolling speed: 1-2 inches/second (depending on the viscosity of the epoxy resin)

Snap off: 20-30mil (0.0050-0.0076cm) (related to the tension of the screen and can be adjusted appropriately)

(E) Printed epoxy resin pattern—make an epoxy resin bump array with a height of 1-1.25 mil (0.00254-0.00316 cm) and a diameter of 7.5 mil (0.019 cm). A typical pattern on the electrode consists of an array of microprotrusions deposited at 40 mil (0.1 cm) center-to-center spacing. In addition, by reducing the center-to-center spacing to 20 mil (0.0508 cm), the density of microprotrusions around the periphery of the electrode was increased. The screen-printed epoxy resin configuration was cured at 150° C. for 4-12 hours in ambient atmosphere.

Example 11

Another screen printing parameter

(A) Spacer Protrusions—The spacer protrusions have a height ranging from 0.001 to 0.004 inches (0.00254 to 0.01016 cm) and a width of 0.006 to 0.012 inches (0.01524 to 0.03038 cm). Spacer tabs can be dots, squares, rectangles, or a combination of these shapes. The width of the bump increases with the height of the bump.

(B) Isolation pattern—two patterns are used on the electrode substrate, the active area and the bonded border area. The isolation protrusions in the active area are positioned at a center-to-center interval of 0.040×0.040 inches (0.1016×0.1016cm) and are usually circular point. The bonded border region had increased bump density with a center-to-center spacing of 0.020 x 0.020 inches (0.0508 x 0.0508 cm). Rows of rectangles alternate between columns of dots.

(C) Screen preparation—the design of the isolation configuration was done in a CAD (Computer Aided Design) system. This CAD electronic data is converted into a Gerber pattern file, which is used in screen manufacturing to generate artwork to make stencils of the desired thickness for the screen printing machine. The screen is ready for SMT (Screen Manufacturing Technology, Santa Clara, California).

(D) Electrode vacuum plate (workpiece fixture)—a porous ceramic plate (GeramlconDesigns, Goden, Colorado, P-G-C material) trimmed to be 0.050 smaller than the periphery of the electrode and fitted into the designed aluminum plate and bonded with epoxy resin, Mount the aluminum plate in the screen printing machine. The top and bottom surfaces are ground and parallel, and a plurality of pins are inserted around the centered electrode edge to form corner stops for positioning the electrode substrate.

(E) Epoxy resin - by adding silica filler, modify the two-component epoxy resin Master Bond EP21AR to the desired viscosity (thixotropic 300000 ~ 400000CPS). Filled epoxy resins of the desired viscosity are commercially available from Master Bond, Inc. of Hackeusack of New Transit. Epoxy was prepared according to the instructions, and the potable time as a flowable fluid was about 30 minutes.

(F) Screen printing parameters

Thick film screen printing machine

Rolling hardness tester 40～100 type A

Rolling speed 1～2 inches/second

Rolling pressure 10-15 lbs

Roll down brake 0.010～maximum, inches

Paint point (snap off) 0.010～0.030 inches (0.0254～0.0762cm)

Example 12

Thermal roll lithography fabrication of microprotrusions

(A) A 1.5 mil (0.0038 cm) high conformance solder mask, ^ConforMASK® 2000, was cut to the same size as the electrodes.

(B) After removing the separator 382 between the photoresist film 381 and the electrode 111A, disposing a Confor ^MASK® film on the electrode material surface 111A whereby the photoresist film 381 is applied, the stack is passed through heating at 150°F. Rollers (384 and 385) adhere the photoresist film 381 to the electrode surface 111A. The polyester cover sheet 382A on the outside of the photoresist film is then removed.

(C) A dark area mask 387 containing rows of transparent holes (openings 388 ) is placed on the photoresist 381 . A typical pattern consists of an array of holes 6 mil (0.0212 cm) in diameter with a 40 mil (0.1 cm) center-to-center spacing, with three rows of high density at the electrode boundaries (20 mil (0.0508 cm) center-to-center spacing.

(D) Film 381 was exposed through aperture 388 and mask 387 to a conventional ultraviolet light source, ie mercury vapor lamp 389, for about 20 seconds. The mask is then removed.

(E) Develop or strip the unexposed areas of the photoresist by placing in a bath containing 1% potassium carbonate for 1.5 minutes.

(F) Then wash the surface of the electrode with micro-protrusions (discrete dots) with deionized water, place it in a 10% sulfuric acid tank for 1.5 minutes, and finally rinse with deionized water.

(G) The microprotrusions 13 were first exposed to UV light and the final curing of the microprotrusions (discrete dots) was performed in a conventional air oven at 300°F for 1 hour.

The fabricated electrode 111A can be used directly or treated as described above.

Example 13

Vacuum deposition of photoresist

(A) A 2.3 mil (0.0058 cm) high performance solder mask, Confor ^MASK® 2000, was cut slightly larger than the electrodes.

(B) Using a Dynachem Vacuum Applicator Model 724 or 730, a photoresist film 381 was vacuum deposited onto the electrode 111A using standard operating conditions (160°C, 0.3 mbar) and placed on the support backplane. The polyester cover 382A is removed.

(C) A dark area mask 387 including rows of transparent holes 388 is provided on the photoresist film 831 . A typical pattern consists of an array of 6 mil (0.0015cm) diameter holes with 40 mil (0.102cm) center-to-center spacing, with three rows of high density (20 mil (0.0054cm) center-to-center spacing) hole.

(D) exposing the film to a non-parallel ultraviolet light source with a power of 3-7KW for 20-40 seconds.

(E) The unexposed areas of the photoresist were developed and stripped with 0.5% potassium carbonate in a conveyorized spray developer, rinsed with deionized water, and turbo dried.

(F) The final curing of the micro-protrusion pull staples is carried out in a two-step process. First, the micro-protrusions are exposed to ultraviolet light in a Dynachem UVCS933 device, and then placed in a forced-air oven to dry at 300-310°F. for 75 minutes.

The fabricated electrodes can be used directly, or further processed as described above.

Example 14

      Surfactants for porosity control

With stirring and slight heating, 32 grams of cetyltrimethylammonium bromide were added to 1 liter of isopropanol. After about 1 hour, 73 grams of TaCl ₅ and 47 grams of RuCl ₃ ·H ₂ O were added to the clear solution. The standard coating process was accomplished with an intermediate pyrolysis at 300°C for 5 minutes and a final pyrolysis at 300°C for 3 hours. The average pore diameter of the coating increased to about 45A. After ² hours post treatment at 260°C in 680 psig steam, the average pore size increased to 120A.

A 25 wt% aqueous solution of cetyltrimethylammonium chloride can also be used to improve the pore size of the resulting coating.

Example 15

                                   

Another construction is made by sandwiching a liner of thermoelastic material such as KRATON ^(R ) between two layers of HDPE liner. The device characteristics are the same as before.

Example 16

Inclusion of a second material to condition the electrolyte to increase its volume

The addition of porous hydrophobic material to each capacitor chip accommodates any increase in the volume of the electrolyte due to increased temperature.

This material is provided within the capacitor die, either as liner material within the border HDPE liner, or as a wafer replacement part of the spacer material.

A commonly used material is PTFE material from WL Gore & Associates, Inc., 1-3 mil thick. The water inlet pressure of the PTFE material is preferably 20-100 ^psi .

Example 17

Another Electrode Pretreatment

After the electrode has micro-protrusions, pads and pull tape (after step E), the electrode is placed in 1M sulfuric acid, and the open circuit potential is adjusted to about 0.5 V (relative to a normal hydrogen electrode) using a cathodic current generated without hydrogen, Electrodes immersed in deionized water are transferred to an inert atmosphere such as argon, where they are dried and assembled.

Although only a few embodiments of the present invention have been shown and described here, it should be understood that for those skilled in the art, various improvements and changes can be made according to improved methods to make electric storage devices such as batteries or capacitors, Improvements are made in life, charging/recharging performance, and low leakage current without departing from the spirit and scope of the present invention. All such improvements and changes are intended to come within the scope of the appended claims.

Claims (42)

1. A dry prefabricated assembly for an energy storage device, comprising: At least one first capacitor chip for storing energy comprising in combination: a. a first conductive electrode; b. a second conductive electrode, said first and second electrodes being separated by a first predetermined distance: and c. first dielectric liner means disposed between said first and second electrodes for separating and electrically insulating said first electrode from said second electrode; Thus, when the first electrode, the second electrode and the first gasket having the central opening are bonded together, the first capacitor chip is formed with an air-filled gap formed therebetween. 2. The dry prefabricated assembly according to claim 1, wherein said first capacitor chip further comprises: a. a first high surface area conductive coating formed on one surface of said first electrode, said first coating being disposed between said first electrode and said backing means; and b. a second high surface area conductive coating formed on one surface of said second porous electrode, said second coating being disposed between said second electrode and said first backing means; c. a coating comprising a plurality of bumps on the first coating, the second coating, or a combination thereof, wherein the bumps provide structural support to the first capacitor die and are formed between the first and second Additional insulation is provided between the two electrodes. 3. A dry prefabricated assembly according to claim 2, wherein said first capacitor chip further comprises a first filling hole formed by said liner means to allow electrolyte to flow into said filling hole. 4. The dry prefabricated assembly of claim 3, wherein said first capacitor die further comprises a first wire strap inserted within said first fill hole; and Wherein when the first tape is removed, the first filling hole is opened and the filling air gap becomes accessible. 5. The dry prefabricated assembly according to claim 1 or 4, further comprising at least one second capacitor chip, wherein said first capacitor chip and said second capacitor chip are stacked and connected so that the dry prefabricated assembly is constituted as an overall structure. 6. A dry prefabricated assembly according to claim 5, wherein said second conductive electrode is a bipolar electrode shared by said first and second capacitor chips: wherein said second capacitor chip further comprises a third conductive electrode disposed face-to-face with said second conductive electrode; Wherein the first and second conductive electrodes are separated by a second predetermined distance. 7. The dry prefabricated assembly according to claim 6, wherein a third coating is formed on the second flat surface of said second electrode such that said second coating is disposed between said second electrode and said between the second liner means; and Wherein the second capacitor chip includes a plurality of discrete bumps on the surface of each electrode. 8. The dry prefabricated assembly according to claim 7, wherein said second capacitor chip further comprises a large surface area and conductive coating formed on one surface of said third electrode; and Wherein the fourth coating is disposed between the third electrode and the second pad means. 9. The dry prefabricated assembly according to claim 8, wherein said second capacitor chip further comprises a second filling hole formed in said second liner means. 10. A dry prefabricated assembly according to claim 9, further comprising an external connection for connection to a power source. 11. The dry prefabricated assembly of claim 8, wherein each of said first and third coatings includes an additional layer having a set of peripheral protrusions and a central set of discrete protrusions, the protrusions The headers are arranged in an array. 12. A dry prefabricated assembly according to claim 11, wherein each boss is 6 mil (0.015 cm) in diameter; The center-to-center spacing of the peripheral protrusions is 20mil (0.0508cm); The center-to-center spacing of the central protrusion is 40 mil (0.102 cm); The peripheral and central bumps have a dielectric composition. 13. The dry prefabricated assembly of claim 6, wherein said first and second predetermined distances are equal. 14. A dry prefabricated assembly according to claim 1 or 5, wherein each of said first and second liner means comprises two dielectric liners disposed in alignment with each other; and Wherein the first strip is disposed between the pads, thereby forming the first filling hole. 15. The dry assembly of claim 6, wherein said first, second and third electrodes are identical and rectangular. 16. In the composition of claim 1, porous hydrophobic polymeric material is further contained in each filling gap, so as to alleviate the increase of static pressure of water with the increase of temperature. 17. The porous hydrophobic polymeric material of claim 44, wherein the material comprises polytetrafluoroethylene having a water ingress pressure of between 760 and 7600 Torr. 18. A capacitor prefabricated assembly, comprising at least one first capacitor chip, the capacitor comprising: a. a first conductive electrode; b. a second conductive electrode, said first and second electrodes being separated by a first predetermined distance; and c. a first dielectric peripheral liner disposed between said first and second electrodes, separating and electrically insulating said first electrode from said second electrode; Thereby, when said first electrode, said second electrode and said first spacer means are bonded together to form a first capacitor chip, a filled air gap is formed therebetween. 19. The capacitor prefabricated assembly according to claim 18, wherein the first capacitor chip further comprises: a. a first coating formed on one surface of said first electrode, said first coating being disposed between said first electrode and said backing means; and b. a second coating formed on one surface of said second electrode, said second coating having to be disposed between said second electrode and said first backing means; c. a layer having a plurality of discrete bumps; and Wherein said bumps provide structural support to the first capacitor chip and provide additional insulation between said first and second electrodes. 20. The capacitor pre-assembly according to claim 19, further comprising at least one second capacitor chip; wherein the first and second capacitor dies are stacked and bonded together to provide an integral structure for the capacitor; said second conductive electrode is a double electrode shared by said first and second capacitor chips; The second capacitor chip further includes a third conductive electrode disposed face-to-face with the second conductive electrode; and The first and second conductive electrodes are separated by a second predetermined distance. 21. Conductive coating for use in dry prefabricated assemblies of energy storage devices comprising a high surface area porous layer coated on a support. 22. A coating according to claim 21, wherein the porous layer comprises a metal oxide or mixed metal oxide and has a large effective surface area consisting essentially of micropores and mesopores. 23. A method of storing energy using a prefabricated assembly according to any one of claims 1-20, wherein said prefabricated assembly is filled with an ionically conductive electrolyte, sealed and charged. 24. A method of manufacturing a dry prefabricated assembly comprising the steps of forming at least one first capacitor chip: a. separating the first conductive electrode from the second conductive electrode by a first predetermined distance; b. disposing a first dielectric liner between said first and second electrodes to separate and electrically insulate said first and second electrodes; Thereby, when said first electrode, said second electrode and said first spacer means are bonded together to form said first capacitor chip, a filled air gap is formed therebetween. 25. A method of manufacturing a capacitor prefabricated assembly, comprising the steps of forming at least one first capacitor chip: a. separating the first conductive electrode from the second conductive electrode by a first predetermined distance; b. placing a first dielectric liner means between said first and second electrodes to separate and electrically insulate said first and second electrodes; Thereby, when said first electrode, said second electrode and said first spacer means are bonded together to form said first capacitor chip, a filled air gap is formed therebetween. 26. A method of manufacturing a capacitor prefabricated assembly, comprising the steps of forming at least one first capacitor chip: a. separating the first conductive layer means from the second conductive layer means by a first predetermined distance; b. providing first dielectric liner sealing means between said first and second conductive layer means to separate and electrically insulate said first and second conductive layer means; Thus, when the first conductive layer for storing charges, the second conductive layer means for storing charges and the first spacer means for separating the electrode surfaces are bonded together to form the first When a capacitor chip is formed, a filled air gap is formed between them. 27. The method of manufacturing dry prefabricated components according to claim 24, further comprising the steps of: a. forming a first porous conductive coating on one surface of the first electrode, the first coating being disposed between the first electrode and the backing means; b. forming a second porous conductive coating on one surface of said second electrode, said second coating being disposed between said second electrode and said first backing means; c. forming a plurality of discrete micro-protrusions under said first coating, said protrusions providing structural support for said first capacitor chip; and providing additional insulation between said first and second electrodes. 28. A method of making a dry prefabricated assembly of an electrical storage device for charge storage, which may have electrode surfaces in contact with an anhydrous or aqueous electrolyte, the method comprising: (a) preparing a substantially planar sheet of electrically conductive support material coated on each of its planar sides with the same or a different thin layer of a second electrically conductive material having a large surface area, the two planar sides of the electrically conductive support being selectable separately It is a sheet whose outer edge surface is any of the following structures: (i) having a thin layer of a second conductive material, (ii) partially without the second conductive material, or (iii) no second conductive material; (b) an ion-permeable or semi-permeable interstitial spacer that is stable in aqueous or non-aqueous electrolytes as follows: (i) on the surface of at least one side of the second thin layer of conductive material, deposit a group of electrically insulating microprotrusions with a substantially uniform height, (ii) providing a pre-cut ion-permeable or semi-permeable thin barrier on one surface of the second conductive material, or (iii) formed on at least one side of the conductive material as a thin ion-permeable or semi-permeable layer, or (iv) Make a thin air gap as an isolation layer; (c) one or more thin layers of synthetic organic polymers selected from the group consisting of thermoplastic, thermoelastic and thermosetting polymeric thing; (d) disposing on or in the liner material at least one thin strand of a different material, optionally spanning the sheet, which has a higher melting point than the polymer material of the liner and which will not melt under processing conditions , flow or permanently bond to the pad: (e) Repeated stacks of thin flat finished products in the form of sheets coated with high surface area coatings and barrier layers from step (d), optionally with terminals formed by thicker supports plate: (f) applying heat to the stack formed in step (e) and applying pressure effective to cause the synthetic liner material to flow, bond and seal the edges of the stack to form a conductive sheet coated with a second conductive material a solid stack of layers alternated with ion-permeable barrier layers, optionally such that the liner material constitutes a continuous integral polymeric encapsulation; (g) the solid stack produced in step (f) may be cooled in its entirety in an inert atmosphere; (h) removing at least one thin line strip of different material located between each layer to form at least one small opening between the layers of the conductive sheet coated with the second conductive material. 29. The method of claim 27 or 28, wherein said microprotrusions are ceramic, organic elastomer, thermoplastic, or thermosetting material or combinations thereof. 30. The method according to claim 29, wherein, after step (e) and before step (f), or after step (h), the integral member of the stack is processed in the following steps: (j) Vacuumize the dry prefabricated components to fully remove the remaining gas; (k) contacting dry prefabricated components with one or more reducing gases at near ambient pressure; (l) Heating the components and reducing gas at 20-150°C for 0.1-5 hours: (m) evacuating dry prefabricated components; (n) replacing the reducing atmosphere with an inert gas; and (o) optionally repeating steps (j), (k), (l), (m) and (n) at least once. 31. The method of claim 28, wherein after step (e) and before step (f), or after step (h), the stacked integral components are processed as follows: (j) Vacuumize the dry prefabricated components to fully remove the remaining gas; (k) contacting dry prefabricated components with one or more reducing gases at near ambient pressure; (l) heating the components and reducing gas at 20-150°C for 0.1-5 hours; (m) evacuating dry prefabricated components; (n) replacing the reducing atmosphere with an inert gas: and (o) optionally repeating steps (j), (k), (l), (m) and (n) at least once. 32. A method according to claim 30 or 31, wherein the vacuum in steps (j), (m) and (o) is about 250 millitorr or less. 33. A method according to claim 31 or 32, wherein the reducing gas is selected from hydrogen, carbon monoxide, hydrogen oxide, ammonia or combinations thereof; The inert gas is selected from helium, neon, nitrogen, helium or combinations thereof; One or more reducing gases and one or more inert gases are sequentially contacted with the components. 34. The method of claim 28, wherein: In step (b) spacer material is disposed on the top side of the device, the spacer material between the electrodes being in a sufficient excess in volume such that when heated in step (f), the excess spacer material surrounds the outer edge of the support Extrusion, thereby creating a seamlessly sealed integral surface at the edges of stacked components. 35. The method of claim 28, wherein: In step (a), the support has a second conductive material on the peripheral surface, In step (b), the microprotrusions are positioned on the surface of the second conductive material, In step (c), the liner material is thermoplastic, In step (e), the end piece is a thicker support, In step (f), excess gasket material is provided to form a continuous integrally sealed package, In step (g), the stacked assembly is cooled to room temperature, In step (h), the ribbon may be metal, ceramic, organic polymer or a combination thereof. 36. An improved method of fabricating an electrical storage device for charge storage comprising: evacuating a dry prefabricated unit manufactured according to any one of the methods of claims 28 to 35, Contact the vacuumized dry prefabricated assembly with aqueous inorganic acid or anhydrous organic electrolyte for a certain period of time, enough to backfill the gaps between the support sheets with filling holes, remove electrolyte from all external surfaces, and Close and seal the fill hole opening. 37. A dry prefabricated assembly according to claim 1 or 5, wherein said first electrode comprises a first conductive porous coating formed on a surface of said first electrode such that said first electrode a coating is between said first electrode and said backing means; and Wherein said second electrode is bipolar. 38. A dry prefabricated assembly according to claim 37, wherein said second electrode includes a first conductive porous coating formed on one surface thereof such that said first conductive porous coating is located between said second electrode and said second electrode. Between the first liner means. 39. A dry prefabricated assembly according to claim 38, wherein said first electrode further comprises spacer means formed on said first coating to keep said first electrode separated from said second electrode. 40. The dry prefabricated assembly according to claim 39, wherein said second electrode further comprises a second conductive porous coating formed on the other surface thereof. 41. The dry prefabricated assembly according to claim 39, wherein said first coating of said first electrode and said first and second coatings of said second electrode are laminated from metal oxides, mixed metal oxides compounds, metal nitrides and polymers. 42. A dry prefabricated assembly according to claim 39, wherein said spacer means comprises a plurality of protrusions; and The bumps give structural support to the first capacitor chip and provide secondary insulation between the first and second electrodes.

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