KR101503759B1 - fluoride ion electrochemical cell - Google Patents

Abstract

The present invention provides an electrochemical cell that can have excellent electrical performance, especially high specific energy, useful discharge rate capacity, and excellent cycle life. The electrochemical cells of the present invention are versatile and include primary and secondary cells for use in a range of critical applications including the use of portable electrical devices. The electrochemical cell of the present invention also exhibits improved safety and stability compared to conventional primary lithium batteries and lithium ion secondary batteries. For example, the electrochemical cell of the present invention comprises a secondary electrochemical cell using an anion charge carrier having storage capacity by an anode and a cathode comprising an anion host material, which is a metal lithium or dissolved lithium Completely eliminating the need for ions.

Description

{Fluoride ion electrochemical cell}

In recent decades there has been a breakthrough in expanding the performance of electrochemical storage and conversion devices in a variety of fields, including portable electronic devices, aircraft and spacecraft technologies, and biomedical devices.

Current state of the art electrochemical storage and conversion devices have design and performance attributes specifically designed to meet a wide range of application requirements and operating environments. For example, from a high energy density battery with a very low self-discharge rate and a high discharge reliability for an implanted medical device, a low-cost, lightweight rechargeable battery that provides a long operating time for a wide range of portable electronic devices, provides extremely high discharge rates in a short period of time Advanced electrochemical storage systems have been developed over a range of high capacity military and aerospace batteries.

Despite the advances and widespread adoption of this diverse range of advanced electrochemical storage and conversion systems, significant pressure continues to stimulate research into extending the functionality of the system to enable it to be applied to a wider range of devices. For example, the growing demand for high-power portable electronic products has been of great interest in the development of safe and light primary and secondary batteries that provide higher energy densities. In addition, the demand for miniaturization of consumer electronics and devices continues to stimulate research into new designs and materials that reduce the size, weight, and form factor of high-performance batteries. In addition, the continued development of the electric vehicle and aerospace industries has also created a demand for mechanically robust, high reliability, high energy density, and high power density batteries that can have excellent device performance in a useful range of operating environments.

Many advances in recent electrochemical storage and conversion technologies are directly attributable to the discovery and adoption of novel materials for battery components. Lithium battery technology, for example, has grown at least in part because of the discovery of new electrodes and electrolytes used in this system. New materials for lithium battery systems, from new discovery and optimization of bipolar intercalation host materials such as fluorinated carbon materials and nanostructured transition metal oxides to the development of high performance non-aqueous electrolytes Implementation of the strategy has revolutionized its design and performance capabilities. In addition, the development of negative electrode intercalation host materials has led to the discovery and commercialization of lithium ion secondary batteries with high capacity, excellent stability and useful cycle life. As a result of these advances, lithium-based battery technology has now been widely employed in critical applications, including primary and secondary electrochemical cells for portable electronic systems.

Commercial primary lithium battery systems typically use lithium metal cathodes to generate lithium ions, which move through the liquid or solid electrolyte during discharge and cause an intercalation reaction at the anode containing the intercalation host material . Dual intercalation lithium ion secondary batteries have also been developed wherein the lithium metal is a lithium ion intercalator for negative cathodes such as carbon (e.g., graphite, coke, etc.), metal oxides, metal nitrides, and metal phosphides. Lt; / RTI > host material. Simultaneous lithium ion intercalation and deintercalation reactions allow lithium ions to move between positive and negative intercalation electrodes during discharge and charging. The adoption of lithium-ion intercalation host materials for cathodes has a significant advantage in avoiding the use of metal lithium which is susceptible to safety problems due to the high reactivity and non-epitaxial deposition characteristics of lithium.

Lithium elements rarely have a unique combination of attractive properties for use as electrochemical cells. First, lithium is the lightest metal in the periodic table with an atomic weight of 6.94 AMU. Second, lithium has a very low electrochemical oxidation / reduction potential (ie -3.045 V for NHE (standard hydrogen reference electrode)). Due to the unique combination of these properties, lithium-based electrochemical cells have very high specific capacities. Material strategies for lithium battery technology and advances in electrochemical cell design include (i) high cell voltages (e.g., up to about 3.8 V), (ii) substantially constant (e.g., flat) discharge profiles, (iii) (E.g., up to 10 years), and (iv) compatibility with an operating temperature range (e.g., -20 to 60 degrees Celsius). As a result of these beneficial properties, the primary lithium-ion battery can be used as a power source in the range of portable electrical equipment and other important device applications such as electronics, information technology, communication, biotechnology, sensing, Widely used.

State-of-the-art lithium ion secondary batteries provide excellent charge-discharge characteristics and are thus widely adopted as power sources for electronic devices such as cell phones and portable computers. US Patent Nos. 6,852,446, 6,306,540, 6,489,055 and " Lithium Batteries Science and Technology " edited by Gholam-Abbas Nazri and Gianfranceo Pistoia, Kluer Academic Publishers, 2004 are directed to lithium and lithium ion battery systems, Which is incorporated herein by reference.

As mentioned above, lithium metals are extremely reactive, especially with water and many organic solvents, and this property requires the use of an intercalation host material on the cathode in secondary lithium-based electrochemical cells. Significant research in this area has resulted in a range of useful intercalation host materials such as LiC ₆ , Li _x Si, Li _x Sn, and Li _x (CoSnTi) in the system. However, the use of an intercalation host material at the cathode inevitably resulted in a cell voltage as low as the amount of free energy of insertion / dissolution of lithium in the intercalation electrode. As a result, conventional state-of-the-art dual-intercalation lithium-ion electrochemical cells are currently limited to providing an average operating voltage of about 4 volts or less. This requirement for the composition of the cathodes also leads to a considerable loss in the specific energy that can be achieved in this system. In addition, the incorporation of an intercalation host material into the cathode does not completely eliminate safety hazards. For example, the charging of this lithium ion battery system should be performed under highly controlled conditions to avoid overcharging or heating which may lead to decomposition of the anode. In addition, undesired side reactions involving lithium ions can occur in this system, leading to the formation of reactive metal lithium, which can affect critical safety issues. During charging at high or low temperatures, the lithium deposit grows across the separator causing internal shorting within the cell and generating heat, pressure, and possible fire from combustion of the organic electrolyte and reaction with oxygen air and moisture of the metallic lithium Resulting in the formation of a dendride that can be formed.

Dual-carbon cells using a lithium insertion reaction for electrochemical storage have also been developed wherein anions and cations generated by the dissolution of a suitable electrolyte salt provide a source of charge stored on the electrode. During charging the system, a cation of an electrolyte, such as lithium ion (Li ⁺⁾ are going through an insertion reaction in the negative electrode containing a carbonaceous cation host material, negative ions of the electrolyte, for example, PF ₆ ^- comprises a carbonaceous negative ion host material Lt; RTI ID = 0.0 > anion < / RTI > During the discharge, the insertion reaction proceeds inversely and releases the positive and negative ions, respectively, at the positive and negative electrodes. However, state-of-the-art dual-carbon cells can not provide an energy density as great as that provided by a lithium ion cell because of the substantial limit of the salt concentration that can be obtained in this system. Also, some of the double-carbon cells are subject to severe loss of capacity after the cycle, due to the stress imparted by the insertion and de-insertion of polyatomic anionic charge carriers such as PF ₆ ^- . In addition, dual-carbon cells have limitations on achievable discharge rates and charge rates, and many such systems use electrolytes containing lithium salts, which can increase safety issues in some operating conditions. The dual carbon cell is described in U.S. Patent No. 4,830,938; 4,865, 931; 5,518,836; And 5,532,083, and "Energy and Capacity Projections for Practical Dual-Graphite Cells", JR Dahn and JA Seel, Journal of the Electrochemical Society, 147 (3) 899-901 (2000) Unless otherwise indicated, are incorporated herein by reference.

The battery consists of an anode (cathode during discharge), a cathode (anode during discharge) and an electrolyte. The electrolyte contains an ionic species which is a charge carrier. The electrolyte in the battery can be of several different types: (1) pure cation conductors (e.g., beta-alumina conducts only Na ⁺ ); (2) pure anionic conductors (e.g., high temperature ceramics conduct only O ^- or O ^2- anions); Of LiPF ₆ to conduct the ^both-while using a KOH aqueous solution that conducts with both K ⁺ on both sides, some of the lithium battery is Li ⁺ and PF ₆ ^-, and (3) mixed ionic conductors (e.g., some Alkaline batteries OH Organic solution is used). During charging and discharging, the electrodes exchange electrolytes and ions and exchange electrons with external circuitry (load or charger).

There are two types of electrode reactions.

1. Cationic Electrode Reaction : In this reaction, the electrode captures or releases the cation Y ⁺ from the electrolyte and electrons from the external circuit:

Electrode + Y ⁺ + e ^- → Electrode (Y).

Examples of cationic electrode reactions include: (i) carbon anodes in lithium ion batteries: 6C + Li ⁺ + e ^- > LiC ₆ (charge); (Ii) Lithium cobalt oxide cathode in a lithium ion battery: 2Li _0.5 CoO ₂ + Li ⁺ + e ^- ? 2LiCoO ₂ (discharge); (Ⅲ) rechargeable alkaline battery Ni (OH) ₂ cathode in: Ni (OH) ₂ → NiOOH + H ⁺ + e ^- (charging); (Ⅳ) salt water (saline) MnO ₂ in Zn / MnO ₂ primary ^{_{battery: MnO 2 + H + + e}} → HMnO 2 ( discharge).

2. Anion-based electrode reaction : In this reaction, the electrode captures or emits anion X ^- from the electrolyte and electrons from the external circuit:

Electrode + X ^- → Electrode (X) + e ^-

Examples of anionic based electrode reactions include: (i) Cadmium anodes in nickel cadmium alkaline batteries: Cd (OH) ₂ + 2e ^- ? Cd + 2OH ^- (charge); And (ii) the magnesium alloy in the magnesium primary battery: Mg + 2OH ^- ? Mg (OH) ₂ + 2e ^- (discharge).

An existing battery is either a pure cation type or a mixed ion type chemistry. As far as the applicant's knowledge is concerned, a battery with purely negative ion type chemistry is not known at present. Pure cationic and mixed ion type batteries are provided below:

1. Pure Cation-type Batteries : Lithium-ion batteries are an example of pure cation-type chemistry. The electrode half reaction and the cell response of the lithium ion battery are as follows:

● Carbon anode:

6C + Li ⁺ + e ^- → LiC ₆ (charge)

Lithium cobalt oxide cathode:

2Li _0.5 CoO ₂ + Li ⁺ + e ^- ? 2LiCoO ₂ (discharge)

● Cell response:

2LiCoO ₂ + 6C? 2Li _0.5 CoO ₂ + LiC ₆ (charge)

2Li _0.5 CoO ₂ + LiC ₆ ? 2LiCoO ₂ + 6C (discharge)

2. Mixed ion type batteries: nickel / cadmium alkaline battery is an example of a mixed ion-type batteries. Electrode half reactions and cell reactions on nickel / cadmium alkaline batteries are provided as follows:

● Ni (OH) ₂ cathode (cation type):

Ni (OH) ₂ ^- & gt ^; NiOOH + H ⁺ + e ^- (charge)

● Cadmium anode (negative ion type):

Cd (OH) ₂ + 2e ^- ? Cd + 2OH ^- (charge)

● Cell response:

Cd (OH) ₂ + 2Ni (OH) ₂ ? Cd + 2NiOOH + 2H ₂ O (charge)

_{Cd + 2NiOOH + 2H 2 O →} Cd (OH) 2 + 2Ni (OH) 2 ( discharge)

The Zn / MnO ₂ battery is an example of a mixed ion type battery. The electrode half reaction and the cell response of the Zn / MnO ₂ battery are as follows:

● Zn anode (negative ion type):

Zn + 2OH ^- ? ZnO + H ₂ O + 2e ^- (discharge)

● MnO ₂ cathode (cation type):

MnO ₂ + H ⁺ + e → HMnO ₂ (discharge)

● Cell response:

Zn + 2MnO ₂ + H ₂ O? ZnO + 2HMnO ₂ (discharge)

As is apparent from the foregoing, there is a need in the art for a secondary electrochemical cell for a wide range of critical device applications, including the rapidly growing demand for high performance portable electronic devices. In particular, there is a need for a secondary electrochemical cell that can provide useful cell voltage, capacity and cycle life while at the same time providing excellent stability and safety. There is a need for alternative intercalation-based electrochemical cells that eliminate or reduce intrinsic safety problems in the use of lithium in primary and secondary battery systems.

Cross reference of related application

This application claims the benefit of US Provisional Patent Application 60 / 779,054, filed March 3, 2006; U.S. patent application (Attorney docket no. 4823-P, inventor Rachid Yazami) filed on January 25, 2007 and entitled "Fluoride Ion Batteries (FIB)"; U.S. Application 11 / 677,541, filed February 21, 2007; U.S. Application 11 / 675,308, filed February 15, 2007; Claims priority of U.S. Patent Application 11 / 560,570, filed November 16, 2006; Each of these applications is incorporated herein by reference to the extent not inconsistent with the disclosure herein.

The present invention provides an electrochemical cell that can provide excellent power source performance, especially high specific energy, useful discharge rate capability, and excellent cycle life. The electrochemical cells of the present invention are versatile and include primary and secondary cells for use in a wide range of important applications including the use of portable electrical devices. The electrochemical cell of the present invention also exhibits improved safety and stability compared to conventional primary lithium batteries and lithium ion secondary batteries. For example, the electrochemical cell of the present invention includes a cathode comprising an anionic host material and a secondary anionic electrochemical cell using an anion charge carrier that can be received by a cathode, Thereby completely eliminating the need for lithium ions.

The present invention provides a novel active electrode material strategy, an electrolyte composition and an electrochemical cell design that enable fundamentally a new class of primary and secondary electrochemical cells. There is provided an anion charge carrier host material and a high performance electrolyte for a positive electrode and a negative electrode capable of achieving a new electrochemical cell platform capable of achieving useful performance properties such as specific energy higher than the specific energy of conventional lithium ion batteries of the state of the art. In one embodiment, for example, the present invention provides a combination of various anion charge carrier-host materials for anodes and cathodes that enable secondary electrochemical cells capable of exhibiting cell voltages above about 3.5V. In addition, the combination of the anode and cathode materials of the present invention enables a secondary electrochemical cell having a great cycle life and excellent discharge stability in cycling. Moreover, aqueous and non-aqueous electrolyte compositions are provided that provide synergistic performance improvements that are important in improving device performance, stability, and safety at high cell voltages. For example, the present invention provides a high performance electrolyte having an anion receptor and / or cation acceptor compatible with an anion charge carrier active electrode host material that provides a secondary cell capable of stable discharge at high cell voltages.

In one aspect of the present invention, the present invention provides an anionic electrochemical cell using an anion charge carrier that can be accommodated by a positive electrode and a negative electrode comprising an anion host material. This aspect of the invention includes both primary and secondary electrochemical cells. In one embodiment, the electrochemical cell of this aspect of the invention comprises a positive electrode; cathode; And an electrolyte interposed between the anode and the cathode, wherein the electrolyte is capable of conducting the anion charge carrier. The anodes and cathodes of this embodiment include various anion host materials that reversibly exchange electrolyte and anion charge carriers during electrochemical cell charging or discharging. In the context of this specification, the term " exchange " refers to the release or acceptance of anionic charge carriers at the electrode through an oxidation or reduction reaction during electrochemical cell discharging or charging. In this context, " accepting " anionic charge carriers includes trapping anion charge carriers by the host material, insertion of anion charge carriers into the host material, intercalation of the anion charge carriers into the host material and / And the chemical reaction of the charge carrier with the host material. The acceptance includes alloying chemical reactions with the host material, surface chemical reactions and / or bulk chemical reactions with the host material.

During the discharge, the reduction half reaction occurring in the anode leads to the release of the anion charge carrier from the anode to the cathode, and the oxidation half reaction occurring at the cathode causes the acceptance of the anion charge carrier by the cathode. Thus, in these embodiments, the anion charge carriers are released from the anode while the electrochemical cell is being discharged, moved through the electrolyte, and received by the cathode. This dynamic process proceeds inversely while charging in the secondary electrochemical cell of the present invention. Thus, during charging in this embodiment, the reduction half reaction occurring at the cathode results in the release of the anion charge carrier into the electrolyte, and the half oxidation reaction occurring at the anode results in the acceptance of the anion charge carrier from the electrolyte to the anode do. Therefore, during discharging and charging of the electrochemical cell, the anion charge carrier is transported through the electrolyte and the electron is transported through the external circuit connecting the anode and the cathode, so that the release and the acceptance of the anion charge carrier occur at the same time.

The selection of the composition and phase of the electrode host material, the electrolyte and the anion charge carrier in this aspect of the invention is important for approaching the electrochemical cell configuration useful in the present invention. First, the selection of the composition of the anion host material and the anion charge carrier for the positive and negative electrodes at least partially determines the cell voltage of the electrochemical cell. Thus, in some embodiments, selecting the anion host material that provides a sufficiently low standard electrode potential at the cathode and the anion host material that provides a sufficiently high standard electrode potential at the anode to yield a cell voltage useful for a given application good. Second, the choice of the composition of the anion host material, the electrolyte and the anion charge carrier for the positive and negative electrodes establishes the kinetics at the electrode to determine the discharge rate capability of the electrochemical cell. Third, the use of electrode host materials, electrolytes, and anion charge carriers that do not cause fundamental structural changes or degradation at the anode and cathode during charging or discharging are useful for secondary electrochemical cells exhibiting excellent cycling performance.

In one embodiment of this aspect, the present invention provides fluoride ion primary and secondary electrochemical cells having fluoride ions (F < ^- >) as anionic charge carriers. An electrochemical cell using the fluoride ion charge carrier of the present invention is referred to as a fluoride ion electrochemical cell. The use of a fluoride ion charge carrier in the electrochemical cell of the present invention provides numerous benefits. First, the redox voltage stability window (from -3.03 V vs. NHE) of the low atomic weight of fluorine (18.998 AMU), high electron affinity (-328 kJ mol ^-1 ) and fluoride ion (F ^- To + 2.87V compared to NHE)) results in an electrochemical cell with high voltage, high energy density, and high specific capacitance. Second, fluoride ions can participate in reversible intercalation and / or intercalation reactions in many electrode host materials that have small atomic diameters and do not cause severe degradation or severe structural deformation of the electrode host material during cycling in the secondary electrochemical cell have. This characteristic results in a secondary fluoride ion electrochemical cell having a large cycle life (e.g., about 500 cycles or more). Third, fluoride ions are stable with respect to decomposition at the electrode surface at a useful range of voltages (-3.03 V vs. NHE versus + 2.87 V vs. NHE), thus providing improved performance stability and safety of the electrochemical cell. Fourth, a considerable number of fluoride ion host materials can be used for anodes and cathodes to provide electrochemical cells with large specific capacities and cell voltages.

As will be apparent to those skilled in the art, the present invention includes a wide variety of anionic electrochemical cell configurations with the following anionic charge carriers besides fluoride ions: BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , BiF ₆ ^- AlF ₄ ^- , GaF ₄ ^- , InF ₄ ^- , TF ₄ ^- , SiF ₅ ^- , GeF ₅ ^- , SnF ₅ ^- , PbF ₅ ^- , SF ₇ ^- , IF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- (CF ₃ SO ₂ ) ₂ N- and C ₄ F ₉ SO ₃ ^- .

Other anionic charge carriers useful in the electrochemical cell of the present invention include those having the formula: C _n F _{2n + 1} BF ₃ ^-1 where n is an integer greater than one. The use of anion charge carriers other than fluoride ions requires the incorporation of host materials that are suitable for the anodes and cathodes, which are capable of accepting anion charge carriers during discharge and charging and providing the desired cell voltage and capacity. In one embodiment, the anionic charge carrier is an anion other than OH ^- and HSO ₄ ^- , or SO ₄ ^2- .

In one embodiment, the electrolyte of the fluoride ion electrochemical cell of the present invention comprises a solvent and a fluoride salt, wherein the fluoride salt is at least partially dissolved in the electrolyte to generate fluoride ions in the electrolyte. The electrolyte in the electrochemical cell of the present invention comprises a fluoride salt having the formula: MF _n wherein M is a metal and n is an integer greater than zero. In some embodiments, for example, M is an alkali metal such as Na, K, or Rb, or M is an alkaline earth metal such as Mg, Ca, or Sr. In one embodiment, M is a non-lithium metal to provide improved safety and stability compared to conventional lithium battery and lithium ion batteries of the current state of the art. In some embodiments, the concentration of the fluoride salt in the electrolyte is selected in the range of about 0.1M to about 2.0M.

An electrolyte for an anionic electrochemical cell of the present invention, including a fluoride ion electrochemical cell, includes an aqueous electrolyte and a non-aqueous electrolyte. Electrolyte compositions useful in anionic electrochemical cells preferably have one or more of the following properties. First, the electrolyte for some applications preferably has a high ionic conductivity with respect to anionic charge carriers, such as for fluoride ions. For example, some electrolyte useful in the present invention is a solvent, solvent mixture and / or fluoride ion anion charge carriers with the anion charge carrier, such as more than 0.0001 S㎝ ^-1, 0.001 S㎝ ^-1 or more, or 0.005 or more S㎝ ^-1 Lt; RTI ID = 0.0 > conductivity. ≪ / RTI > Second, the electrolyte of some embodiments may dissolve an electrolyte salt, such as a fluoride salt, to provide a source of anionic charge carriers at a concentration useful in the electrolyte. Third, the electrolyte of the present invention is preferably stable with respect to decomposition at the electrode. For example, the electrolytes of embodiments of the present invention include stable solvents, electrolyte salts, additives, and anionic charge carriers at high electrode voltages, such as differences between positive and negative electrodes above about 4.5V. Fourth, the electrolyte of the present invention, which is preferable for some applications, shows excellent safety such as flame retardancy.

Optionally, the electrolyte of the present electrochemical cell comprises one or more additives. In one embodiment, the electrolyte comprises an anion receptor, such as a fluoride ion acceptor capable of coordinating with the fluoride ion of the fluoride salt, and / or a cation receptor, such as a cation acceptor capable of coordinating with the metal ion of a fluoride salt, for example. Useful anionic receptors of the present invention are electron donor ligands such as fluorinated borane, fluorinated boronate, fluorinated borate, phenyl boron based compounds and aza-ether boron based compounds. withdrawing ligand, but are not limited to, a fluorinated boronic anion receptor. Cationic receptors useful in the electrolytes of the electrochemical cell of the present invention include crown ethers, lariat ethers, metallacrown ethers, calixcrowns (e.g., Calix (aza) crown), tetrathia Tetrathiafulvalene crown, calixarenes, calix [4] arenediquinoes, tetrathiafulvalene, bis (calix crown) tetrathiafulvalene, and derivatives thereof. But is not limited to. In some embodiments, the electrolyte of the present invention includes other inorganic, organic, or gaseous additives. The additives in the electrolyte of the present invention can be used to improve the conductivity of the anionic charge carrier, for example, by improving the formation of a solid electrolyte interface (SEI) or by reducing the accumulation of discharge products, (ii) (Iii) improve electrode wettability, (iv) reduce electron conductivity, and (v) improve the kinetics of anionic charge carriers at the electrode. In one embodiment, the electrolyte includes but is not limited to Lewis acids or Lewis bases such as: BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , BiF ₆ ^- , AlF ₄ ^- , GaF _{4 ^{-, InF 4 -, TlF 4}} -, SiF 5 -, GeF 5 -, SnF 5 -, PbF 5 -, SF 7 -, IF 6 -, ClO 4 -, CF 3 SO 3 -, (CF 3 SO 2) ₂ N ^- , C ₄ F ₉ SO ₃ ^- and NR ₄ ⁺ (R = H or alkyl group C _n H _{2n + 1} , n = integer).

The active material for the positive and negative electrodes of the fluoride ion electrochemical cell of the present invention includes a fluoride ion host material capable of receiving fluoride ions from the electrolyte during discharge and charging of the electrochemical cell. In this regard, the acceptance of the fluoride ion includes insertion of the fluoride ion into the host material, intercalation of the fluoride ion into the host material, and / or reaction of the fluoride ion with the host material. The acceptance includes alloying reactions with host materials, surface reactions and / or bulk reactions. The use of a fluoride ion host material capable of reversibly exchanging fluoride ions with an electrolyte without severe degradation of the fluoride ion host material during cycling is preferred for the secondary fluoride ion battery of the present invention.

In one embodiment, the cathode of the fluoride ion electrochemical cell of the present invention has a low standard reduction potential, such as a fluoride compound, preferably below about -1 V for some applications, and more preferably below about -2 V for some applications ≪ / RTI > fluoride ion host material. Useful for the negative electrode a fluoride ion host material of an electrochemical cell of the present invention include, but are not limited to: LaF _x, CaF _x, AlF _x, EuF _x, LiC _6, Li _x Si, Li _x Ge, Li _{x (CoTiSn), SnF x,} InF x, VF x, CdF x, CrF x, FeF x, ZnF x, GaF x, TiF x, NbF x, MnF x, YbF x, ZrF x, SmF x, LaF x and CeF _x . The preferred fluoride host material for the cathode of an electrochemical cell is an elemental fluoride MF _x where M is an alkaline earth metal (Mg, Ca, Ba), M is a transition metal and M is a Group 13 (B, Al, Tl), or M is a rare earth element (atomic number Z is between 57 and 71). The present invention also includes a negative electrode fluoride ion host material comprising a polymer (s) capable of reversibly exchanging fluoride ions comprising anionic charge carriers. Examples of such conjugated polymers include, but are not limited to, polyacetylene, polyaniline, polypyrrole, polythiophene and polyparaphenylene. Polymeric materials useful for cathodes in the present invention are described in Manecke, G. and Strock, W., " Encyclopedia of Polymer Science and Engineering ", 2nd Edition, Kroschwitz, J., I., Editor. John Wiley, New York, 1986, vol. 5, pp. 725-755, which is incorporated herein by reference, unless inconsistent with the disclosure herein.

In one embodiment, the anode of the fluoride ion electrochemical cell of the invention is a fluoride ion having a high standard reduction potential, such as a fluoride compound, preferably at least about 1 V in some applications, and more preferably at least about 2 V in some applications Host material. In one embodiment, the fluoride ion host material of the anode is an intercalation host material capable of accepting fluoride ions capable of generating a fluoride ion intercalation compound. &Quot; Intercalation " refers to the generation of an intercalation compound through a host / guest solid state redox reaction involving an electrochemical charge transfer involving insertion of a mobile guest ion, such as a fluoride ion, . The major structural features of the host material are preserved after insertion of the guest ions through the intercalation. In some host materials, the intercalation refers to the process by which guest ions are trapped in interlayer gaps (e.g., galleries) of the host material forming the layer.

Fluoride ion host materials useful for the anode of an electrochemical cell of the present invention, _{CF x, AgF x, CuF x} , NiF x, CoF x, PbF x, CeF x, MnF x, AuF x, PtF x, RhF x, VF x , OsF _x , RuF _x, and FeF _x . In one embodiment, the fluoride ion host material of the anode is a partially fluorinated carbonaceous material having the formula CF _x , where x is the average atomic ratio of fluorine atoms to carbon atoms and is selected in the range of from about 0.3 to about 1.0. Carbonaceous materials useful in the anode of this embodiment are selected from the group consisting of graphite, coke, multiwall carbon nanotubes, multilayer carbon nanofibers, multilayer carbon nanoparticles, carbon nanofillers and carbon nanorods. The present invention also includes a positive electrode fluoride ion host material comprising a polymer (s) capable of reversibly exchanging fluoride ions comprising anionic charge carriers. Examples of such conjugated polymers for use in an anode include, but are not limited to, polyacetylene, polyaniline, polypyrrole, polythiophene and polyparaphenylene.

In one aspect, the present invention provides a fluoride ion electrochemical cell that exhibits improved device performance over current technology electrochemical cells such as lithium ion batteries. In a fluoride ion electrochemical cell, any fluoride ion host material combination for the anode and cathode is good for obtaining useful device performance. For example, the use of a cathode containing a partially fluorinated CF _x anode (where x is selected in the range of about 0.3 to 1) and LiC ₆ or LaF _x is preferred over an average operating cell of at least 4 V, It is useful for obtaining voltage. Other useful cathode host material / negative electrode host materials in combination that provide superior device performance of the present invention CuF _x / LaF _x, AgF _x / LaF _x, CoF _x / LaF _x, NiF _x / LaF _x, MnF _x / LaF _{x, CuF x / AlF x, AgF x} / AlF x, NiF x / AlF x, NiF x / ZnF x, including, AgF _x / ZnF _x and MnF _x / ZnF _x, but are not limited to (wherein making an electrode combination [Anode host material] / [anode host material].

In one embodiment, the fluoride ion electrochemical cell of the present invention has an average operating cell voltage of at least about 3.5 V, and preferably an average operating cell voltage of at least about 4.5 V in some applications. In one embodiment, the fluoride ion electrochemical cell of the present invention has a specific energy of at least about 300 Whkg- ¹ , preferably at least about 400 Whkg- ¹ . In one embodiment, the present invention provides a fluoride ion secondary electrochemical cell having a cycle life of at least about 500 cycles.

Solvents useful in the electrolytes of the present invention can dissolve, at least in part, electrolyte salts, such as fluoride salts, and also include propylene carbonate, nitromethane, toluene (tol); Ethyl methyl carbonate (EMC); Propylmethyl carbonate (PMC); Diethyl carbonate (DEC); Dimethyl carbonate (DMC); Methyl butyrate (MB, 20 < 0 >C); n-propyl acetate (PA); Ethyl acetate (EA); Methyl propionate (MP); Methyl acetate (MA); 4-methyl-1,3-dioxolane _{(4MeDOL) (C 4 H 8} O 2); 2-methyl tetrahydrofuran _{(2MeTHF) (C 5 H 10} O); 1,2 dimethoxyethane (DME); Methyl formate (MF) (C ₂ H ₄ O ₂ ); Dichloromethane (DCM); ? -butyrolactone (? -BL) (C ₄ H ₆ O ₂ ); Propylene carbonate _{(PC) (C 4 H 6} O 3); But are not limited to, one or more solvents selected from the group consisting of ethylene carbonate (EC, 40 캜) (C ₃ H ₄ O ₃ ). Electrolytes, including solvents, electrolyte salts and fully fluorinated or partially fluorinated analogs of anionic charge carriers, and their components, have the disadvantage that the fluorination of these materials provides improved stability with respect to decomposition at high electrode voltages and provides beneficial safety, It is good for some applications because it provides. In the context of the present disclosure, a fluoro analog is a molecule in which (i) an analogue in which each hydrogen atom of a solvent, salt or anion charge carrier molecule is completely fluorinated by substitution by a fluorine atom, and (ii) a hydrogen of a solvent, salt or anion charge carrier molecule Includes analogs in which at least one atom is partially fluorinated by being replaced by a fluorine atom. Preferred anionic charge carriers for the electrolyte are F ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , BiF ₆ ^- , AlF ₄ ^- , GaF ₄ ^- , InF ₄ ^- , TlF ₄ ^- , SiF ₅ ^- But not limited to, GeF ₅ ^- , SnF ₅ ^- , PbF ₅ ^- , SF ₇ ^- , IF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- and C ₄ F ₉ SO ₃ ^- , But is not limited thereto.

The following references describe electrolytic compositions useful in the practice of the present invention, including fully fluorinated and partially fluorinated solvents, salts, and anionic charge carriers, which are incorporated herein by reference in their entirety, (1) Li [C ₂ F ₅ BF ₃ ] as an Electrolyte Salt for 4 V Class Lithium-Ion Cells, Zhi-Bin Zhou, Masayuki Takeda, Takashi Fujii, Makoto Ue, Journal of Electrochemical Society, 152 (2): A351-A356, 2005; (2) Fluorinated Superacidic Systems, George A. Olah, Surya GK Prakash, Alain Goeppert, Actualite Chimique, 68-72 Suppl. 301-302, Oct-Nov 2006; (3) Electrochemical properties of Li [ C n F 2n + 1 BF 3] as Electrolyte Salts for Lithium-ion Cells, Makoto Ue, Takashi Fujii, Zhi-Bin Zhou, Masayuki Takeda, Shinichi Kinoshita, Solid State Ionics, 177: 323 -331, 2006; (4) Anodic Stability of Several Anions Examined by AB Initio Molecular Orbital and Density Functional Theories, Makoto Ue, Akinori Murakami, Shinichiro Nakamura, Journal of Electrochemical Society, 149 (12): A1572-A1577, 2002; (5) Intrinsic Anion Oxidation Potentials, Patrik Johansson, Journal of Physical Chemistry, 110_12077-12080, 2006; (6) Nonaqueous Liquid Electrolytes for Lithium-based Rechargeable Batteries, Kang Xu, Chem. Rev., 104: 4303-4417, 2004; (7) The Electrochemical Oxidation of Polyfluorophenyltrifluoroborate Anions in Acetonitrile, Leonid A. Shundrin, Vadim V. Bardin, Hermann-Josef Frohn, Z. Anorg. Allg. Chem. 630: 1253-1257, 2004.

In another aspect, the present invention provides a method of making an electrochemical cell comprising: (i) providing a positive electrode; (Ii) providing a cathode; (Iii) providing an electrolyte capable of conducting an anion charge carrier between the anode and the cathode, wherein during the charging or discharging of the electrochemical cell, the anode and the cathode are disposed between the anode and the cathode, A method of manufacturing an electrochemical cell that can be reversibly exchanged with an electrolyte is provided.

In another aspect, the present invention provides a method of manufacturing a semiconductor device comprising: (i) a cathode; cathode; And an electrolyte capable of conducting an anion charge carrier interposed between the anode and the cathode, wherein the anode and the anode are electrically connected to the anion charge carrier during charging or discharging of the electrochemical cell, Providing an electrochemical cell that reversibly exchanges with the electrolyte; And (ii) discharging the electrochemical cell. The method of this aspect of the invention may further comprise the step of charging the electrochemical cell. In some embodiments of this aspect of the invention, the anionic charge carrier is a fluoride ion (F ^- ).

In another aspect, the present invention provides a fluoride ion secondary electrochemical cell comprising: (i) a cathode comprising a first fluoride ion host material and having a first standard electrode potential; (Ii) a cathode comprising a second fluoride ion host material and having a second standard electrode potential, wherein the difference between the first standard electrode potential and the second standard electrode potential is about 3.5 V or more; And (iii) an electrolyte interposed between the anode and the cathode, the electrolyte being capable of conducting a fluoride ion charge carrier and comprising a fluoride salt and a solvent, wherein at least a portion of the fluoride salt is in a dissolved state, A fluoride ion secondary electrochemical cell in which the anode and the cathode reversibly exchange the fluoride ion charge carrier with the electrolyte during the charging or discharging of the electrochemical cell, do. In some embodiments of this aspect of the invention, the anionic charge carrier is a fluoride ion (F ^- ).

In the drawings, the same numbers refer to the same elements, and the same numbers appearing in more than one drawing refer to the same elements. In addition, the following definitions apply:

The "standard electrode potential" (E °) refers to the electrode voltage when the solute concentration is 1 M, the gas pressure is 1 atm, and the temperature is 25 degrees Celsius. The standard electrode potentials used herein are measured relative to standard hydrogen electrodes.

&Quot; Anion charge carrier " refers to a negative charge ion that is provided in the electrolyte of an electrochemical cell and moves between the positive and negative electrodes while the electrochemical cell is being discharged and charged. Anionic charge carriers useful in the electrochemical cell of the present invention include fluoride ions (F ^- ) and the following other anions BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , BiF ₆ ^- , AlF ₄ ^- , GaF _{^{4 -, InF 4 -, TlF}} 4 -, SiF 5 -, GeF 5 -, SnF 5 -, PbF 5 -, SF 7 -, IF 6 -, ClO 4 -, CF 3 SO 3 -, (CF 3 SO 2 ) ₂ N ^-, and C ₄ F ₉ SO ₃ ^- .

&Quot; Fluoride ion host material " refers to a material capable of accepting fluoride ions. In this regard, acceptance includes inserting fluoride ions into the host material, intercalating fluoride ions into the host material, and / or reacting the fluoride ions with the host material. Fluoride ion host materials useful for the anode or the cathode in an electrochemical cell of the present invention _{LaF x, CaF x, AlF x} , EuF x, LiC 6, Li x Si, Li x Ge, Li x (CoTiSn), SnF x, InF _{x, VF x, CdF x,} CrF x, FeF x, ZnF x, GaF x, TiF x, NbF x, MnF x, YbF x, ZrF x, SmF x, LaF x and _{CeF x, CF x, AgF x} , _{CuF x, NiF x, CoF x} , PbF x, CeF x, MnF x, AuF x, PtF x, RhF x, VF x, OsF x, RuF x and include, for FeF _x, but it is not limited to this. Preferably, the fluoride host material for the cathode of the electrochemical cell is an elemental fluoride MF _x where M is an alkaline earth metal (Mg, Ca, Ba), M is a transition metal and M is a Group 13 (B, Al, Ga, In , Tl), or M is a rare earth element (Z between element numbers 57 and 71)

The term " intercalation " refers to the interaction of an intercalation compound (s) with a host / guest solid state redox reaction involving an electrochemical charge transfer process in which an ion is inserted into a host material and coupled with the insertion of a mobile guest ion such as a fluoride ion . ≪ / RTI > The major structural features of the host material are preserved after insertion of the guest ions through the intercalation. In some host materials, the intercalation refers to the process by which guest ions are trapped in interlayer gaps (e.g., galleries) of the host material forming the layer. Examples of intercalation compounds include fluoride ion intercalation compounds that are intercalated into a host material, such as a fluoride host material or a carbon host material, in which the fluoride ions form a layer. Host materials useful for forming the intercalation compounds for electrodes of the present invention include, but are _{not limited to} , CF _x , FeF _x , MnF _x , NiF _x , CoF _x , LiC ₆ , Li _x Si, and Li _x Ge. It does not.

The term " electrochemical cell " refers to a device and / or device component that converts chemical energy into electrical energy or electrical energy into chemical energy. An electrochemical cell has two or more electrodes (e.g., an anode and a cathode) and an electrolyte, wherein the electrode reaction occurring on the electrode surface results in a charge transfer process. An electrochemical cell includes, but is not limited to, a primary battery, a secondary battery, and an electrolysis system. Typical cell and / or battery structures are known in the art including, for example, U.S. Patent Nos. 6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem. Soc. 147 (3) 892-898 (2000).

The term " capacity " is a characteristic of an electrochemical cell that refers to the total amount of charge that an electrochemical cell such as a battery can hold. Capacity is typically expressed in ampere-hours. The term " specific capacity " refers to the capacity output per unit weight of an electrochemical cell such as a battery. The non-dose is typically expressed in units of ampere-hour kilogram- ¹ .

The term " discharge rate " refers to the current through which an electrochemical cell is discharged. The discharge current can be expressed in units of ampere-hours. Alternatively, the discharge current may be normalized to the rated capacity of the electrochemical cell and expressed as C / (Xt), where C is the capacity of the electrochemical cell, X is the variable and t is the It is a specific unit of time, such as one hour, as shown.

&Quot; Current density " refers to current flow per unit electrode area.

In some embodiments, the anode, cathode, or both are nanostructured materials. The term " nanostructured " refers to materials and / or structures having a plurality of discrete structural regions of at least one physical dimension (e.g., height, width, length, cross-sectional dimension) of less than about one micron. In this regard, the structural region refers to a feature, component or portion of a material or structure having a distinct composition, morphology and / or phase. The nanostructured material useful as the cathode active material comprises nanostructured composite particles having a plurality of fluorinated carbon domains and a non-fluorinated carbon domain. In some embodiments, the nanostructured material of the present invention comprises a plurality of structural regions having different compositions, morphologies and / or phases intermixed on a very microscopic scale (e.g., less than at least a few tens of nanometers). The nanostructured material used as the negative electrode active material includes nanostructured composite particles having a plurality of fluorinated metal regions and non-fluorinated metal regions. The preferred nanostructured fluorinated metal host material for the cathode of an electrochemical cell comprises an alkaline earth metal (Mg, Ca, Ba), a transition metal, a Group 13 element (B, Al, Ga, In, Tl) and a rare earth element Number Z between 57 and 71). In some embodiments, the nanostructured material for the cathode of the present invention comprises a plurality of structural regions having different compositions, morphologies and / or phases intermixed on a very microscopic scale (e.g., less than at least a few tens of nanometers) . &Quot; Active material " refers to a material in an electrode that participates in an electrochemical reaction that stores and / or transfers energy in an electrochemical cell.

As used herein, the expression " subfluorinated carbonaceous material " refers to a multi-phase carbonaceous material having a non-fluorinated carbonaceous component. As used herein, the term " unfluorinated carbonaceous component " is intended to encompass all types of carbon nanotubes, including graphite, coke, multiwall carbon nanotubes, carbon nanofibers, carbon nanofillers, multilayer carbon nanoparticles, carbon nanofillers, The same non-fluorinated carbon composition and / or phases, and also includes a slightly fluorinated carbon composition and / or phases. In this regard, and slightly fluorinated (fluorinated slightly) it is, and the carbon-carbon bond refers to a composition in combination with different fluorine, weakly share the fluorine such as on a CF ₁ and CF _2. The polyphasic partially fluorinated carbonaceous material comprises at least one non-fluorinated carbonaceous phase, and at least one fluorinated phase (e.g., poly (carbon monofluoride (CF ₁ )), poly (dicarbon monofluoride, etc.) Based on the total weight of the composition. Partially fluorinated carbonaceous materials include nanostructured materials having fluorinated and non-fluorinated regions. The partially fluorinated carbonaceous material comprises a carbonaceous material exposed to a fluorine source under conditions which result in incomplete or partial fluorination of the carbonaceous starting material. The methods of making the partially fluorinated carbonaceous materials useful in the present invention and the related partially fluorinated carbonaceous materials are described in U. S. Patents < RTI ID = 0.0 > of U. < / RTI > patents filed on October 18, 2005, June 6, 2006, 11 / 253,360, 11 / 422,564 and 11 / 560,570, which are incorporated herein by reference in their entirety, unless otherwise indicated herein. A range of carbonaceous materials, including graphite, coke, and carbonaceous nanomaterials such as multi-wall carbon nanotubes, carbon nanofibers, multi-layer carbon nanoparticles, carbon nanofillers and carbon nanorods, Lt; / RTI >

As used herein, a carbon nanomaterial has at least one dimension that is between one nanometer and one micron. In one embodiment, at least one dimension of the nanomaterial is between 2 nm and 1000 nm. For carbon nanotubes, nanofibers, nanofillers or nanorods, the diameter of tubes, fibers, nano-whiskers or nanorods is within this size range. In the case of carbon nanoparticles, the diameter of the nanoparticles falls within the above-mentioned size range. Carbon nanomaterials suitable for use in the present invention include materials having a total impurity less than 10% and carbon materials doped with elements such as boron, nitrogen, silicon, tin and phosphorus.

As used herein, the term " nanotube " refers to a discrete fibril in the form of a tube, typically characterized by a diameter of about 1 nm to about 20 nm. In addition, the nanotubes typically exhibit a length that is greater than about 10 times the diameter, preferably greater than about 100 times the diameter. The term " multi-wall " used to describe a nanotube refers to a nanotube having a layered structure, wherein the nanotube is a continuous multi-layered outer region of ordered atoms and a separate inner core region or Lumen. ≪ / RTI > These layers are arranged substantially concentric to the longitudinal axis of the fibrils. In the case of carbon nanotubes, these layers are graphene layers. Carbon nanotubes are synthesized in various forms such as single-, double-, and multi-wall carbon nanotubes and are designated SWCNT, DWCNT, and MWCNT, respectively. Diameter size ranges from about 2 nm at SWCNTs and DWCNTs to about 20 nm at MWCNTs. In one embodiment, the MWNTs used in the present invention have a diameter greater than 5 nm, greater than 10 nm, 10-20 nm, or about 20 nm.

The electrode is an electrical conductor in which ions and electrons are exchanged with an electrolyte and an external circuit. &Quot; Positive electrode " and " cathode " are used contemporaneously in this description and refer to an electrode having a higher electrode potential (i.e., higher than the cathode) in an electrochemical cell. &Quot; Negative electrode " and " anode " refer to an electrode that is used synonymously in this description and has a lower electrode potential (i.e., lower than the anode) in an electrochemical cell. Reduction of the cathode refers to the acquisition of the electron (s) of the species, and reduction of the anode refers to the loss of the electron (s) of the species. The positive and negative electrodes of the present electrochemical cell may further comprise a conductive diluent such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, and metallic powder, and / or a binder such as a polymeric binder . In some embodiments, the useful binder in the anode includes a fluoropolymer such as polyvinylidene fluoride (PVDF). The positive and negative electrodes of the present invention can be provided with a variety of useful composition and shape factors known in the electrochemical and battery arts, including thin electrode designs such as thin film electrode configurations. Electrodes are prepared as disclosed herein and as known in the art, including, for example, the disclosures of U.S. Patent Nos. 4,052,539, 6,306,540, and 6,852,446. In some embodiments, the electrode is typically fabricated by depositing a slurry of electrode material, electrically conductive inert material, binder, and liquid carrier in the electrode current collector and then evaporating the carrier leaving the aggregate in electrical contact with the current collector .

&Quot; Electrode potential " refers to a voltage that is typically measured relative to a reference electrode and is due to the presence of chemical species in various oxidized (valence) states within or contacting the electrode.

&Quot; An electrolyte " means an ionic conductor that can be in a solid state, in a liquid state (most common) or less rarely in a gas (e.g., a plasma).

&Quot; Cation " refers to positively charged ions, and " anion " refers to negatively charged ions.

The present invention provides primary and secondary anionic electrochemical cells that can replace lithium ion batteries and lithium ion batteries of the current state of the art using active electrode materials comprising fluoride ion charge carriers and fluoride ion host materials . Advantages of the present electrochemical cell for a lithium-based system include obtaining a higher specific capacity, greater average operating voltage and improved safety.

An anionic electrochemical cell of the present invention comprising a fluoride ion electrochemical cell is characterized in that it comprises an anion comprising a different anion charge carrier host material and an oxidation and reduction reaction occurring simultaneously with the acceptance and release of an anion charge carrier by the anode It works on principle. In this system, the anionic charge carriers are reciprocated between the positive and negative electrodes during discharging and charging of the anionic electrochemical cell. The following electrode half reactions, cell reactions and electrolyte reactions are provided to illustrate and describe the basic principles by which the anionic electrochemical cells of the present invention operate.

1. Electrode reaction

A ^- is an anion charge carrier, PA _n is a positive anion host material, and NA _m is a negative anion host material.

In the primary battery, only the discharge reaction occurs:

At the anode, A ^- is released:

(1)

(One)

● At the cathode, A ^- is occluded:

(2)

(2)

Thus, the overall cell response is:

(3)

(3)

In a rechargeable battery, equations (1) and (2) are reversed during charging, so the overall cell response is:

(4)

(4)

2. Electrolyte Formation Reaction :

The present invention includes multiple sources of dissolved A ^- anions in electrolytes interposed between an anode and a cathode:

(I) a soluble compound such as a salt C _q A _p ; Wherein C is a monovalent, divalent, trivalent cation or polyvalent cation (C ^{n +} , 1? ^N? 6). For example, if C is a monovalent cation, the salt equilibrium is written as:

(5)

(5)

Wherein the use of cationic acceptor R and / or anion acceptor R ' can improve solubility:

(6)

(6)

(7)

(7)

(Ⅱ) ^A-soluble anionic XA _p to ^release;

(8)

(8)

Optionally, cationic acceptor R and / or anion acceptor R 'may be provided to the electrolyte to enhance the solubility of A < ^- >.

The half-reactions, cell reaction and an electrolyte, the reaction of the fluoride ion conductive electrochemical cell of the present invention containing electrolyte is provided ^- as an example of this concept, to LiC ₆ anode, CF _x cathode and F in.

Discharge reaction :

Cathode: LiC ₆ + F ^- > 6C + LiF + e ^-

(The cathode accepts F ^- during discharge)

Anode: CF _x + xe ^- > C + xF ^-

(Anode discharges F ^- during discharge)

Cell reaction: xLiC ₆ + CF _x ? (1 + 6x) C + xLiF

(F ^- is moved between anode and cathode during discharge)

Electrolyte: Optionally, both types of reactions can enhance F ^- lysis:

LiF + yLA? Li ⁺ + (LA) _y F ^- , or

LiF + zLB - > Li (LB) _z ⁺ + F ^-

(Lewis acids such as LA = PF ₅ , BF ₃ or anion receptors, Lewis bases such as LB = PF ₆ ^- , BF ₄ ^- or cationic receptors: crown ethers).

To further describe and illustrate the anionic electrochemical cell of the present invention, the following discussion compares this system to conventional lithium ion battery technology. A typical lithium ion battery (LIB) includes three basic elements: (1) a carbon-based anode (anode), (2) a lithium cation (Li ⁺ ) conductive electrolyte, and (3) a transition metal oxide anode for example, LiCoO _2). The lithium cation (Li ⁺ ) is a charge carrier in this system, and the electrochemical cell functions through simultaneous intercalation and deintercalation reactions occurring in the anode and cathode in cooperation with the charge transfer between the electrodes. During the charging and discharging of the lithium ion battery, Li ⁺ ions are reciprocated between the cathode and the anode. The reversible dual-intercalation mechanism of this battery results in the term " rocking chair " or " shuttle-cock ".

Figure 1a provides a schematic diagram illustrating a lithium ion battery during charging. During charging, lithium ions are released from the anode (i.e., referred to as the cathode in FIG. 1A), moved through the electrolyte, and received by the cathode (i.e., referred to as the anode in FIG. 1A). As shown in Figure 1A, the direction of the electron flow during charging is from anode to cathode. 1B provides a schematic diagram illustrating a lithium ion battery during discharge. During discharge, lithium ions are released from the cathode (i.e., referred to as the anode in Figure IB), moved through the electrolyte, and received by the anode (i.e., the cathode in Figure IB). As shown in Fig. 1B, the direction of the electron flow during discharging is from the cathode to the anode.

Figure 2 provides a schematic diagram illustrating the average operating potential and cell voltage of various cathode and anode materials for a conventional lithium ion battery. The average operating voltage of an electrochemical cell is generated, in part, by the difference between the chemical potential of Li ⁺ at the cathode and the anode. In the example shown in Fig. 2, the difference between the electrode potentials of Li _x C ₆ and Li _x CoO ₂ is approximately 4V. The LIB cell extension reaction of this example is as follows:

The theoretical energy density of this example LIB system can be calculated as:

In the electrochemical cell of the present invention, the charge carrier is a negatively charged anion. For example, an anion charge carrier in a fluoride ion electrochemical cell is a fluoride ion (F ^-1 ). Similar to a lithium ion battery, the fluoride ion electrochemical cell of the present invention operates on the principle of simultaneous intercalation and deintercalation reactions occurring in the anode and cathode in cooperation with the charge transfer between the electrodes. While the fluoride ion electrochemical cell is charging and discharging, the F ^- ions are reciprocated between the anode and the cathode.

Figure 3a provides a schematic diagram illustrating a fluoride ion electrochemical cell during discharge. During discharge, the fluoride anions are released from the anode (i.e., referred to as the cathode in Figure 3A), moved through the electrolyte, and received by the cathode (i.e., referred to as the anode in Figure 3A). As shown in FIG. 3A, the direction of the electron flow during discharging is from the cathode to the anode. While the fluoride ion electrochemical cell is being charged, the fluoride anion is released from the cathode and migrates through the electrolyte and is received by the anode. During charging, the direction of the electron flow is from the anode to the cathode. The discharge and acceptance of fluoride ions during discharging and charging results from the oxidation and reduction reactions occurring at the electrodes.

Similar to the discussion above relating to lithium ion batteries, the open circuit voltage of a fluoride ion electrochemical cell is due, at least in part, to the difference in chemical potentials of the fluoride ion at the cathode and anode. The positive and negative electrodes are capable of reversibly exchanging the electrolyte and F < ^- > as high-voltage and low-voltage fluorides, respectively, for example:

Positive electrode: CF _x , AgF _2-x , CuF _3-x , NiF _3-x , ...

Cathodes: LaF _3-x , CaF _2-x , AlF _3-x , EuF _3-x , ...

Figure 3b provides a schematic diagram showing the average operating potential for an exemplary embodiment corresponding to an electrolyte comprising a LaF _{3 -x} cathode, a CF _x anode, and an MF provided to the organic electrolyte, where M is K or Rb, The same metal). Suitable parameters, half reactions and cell reactions are summarized below with respect to this example:

Cathode : LaF ₃

Anode : CF _y

Electrolyte : MF (M = K, Rb, ...) in the organic electrolyte

Electrode reaction :

(9)cathode:

(9)

(10)anode:

(10)

Cell response :

(11)

(11)

As shown in Fig. 3B, the difference in electrode potentials in this example is about 4.5V. The theoretical cell voltage considering La ³⁺ / La and CF _x / F ^- redox couple and open circuit voltage OCV is expected to be about 4.5V larger than that of conventional lithium ion batteries (See calculation below). The theoretical energy density of this example fluoride ion battery (FIB) system can be calculated as:

FIB energy density :

Cell reaction (3) and at x = 1, y = 0; (LaF ₃ + 3CF _y + LaF _{3 (1-x)} + 3CF _{x + y} ),

The theoretical energy density is:

This calculation provides the ratio of the theoretical energy density for the exemplary fluoride ion electrochemical cell and the illustrative lithium ion battery described in Equation 3.7 above:

Table 1 provides a comparison of the performance attributes and compositions of the lithium ion batteries and fluoride ion electrochemical cells described above. Advantages of the present fluoride ion batteries (FIBs) include (i) enhanced safety of the fluoride ion electrochemical cell, (ii) higher operating voltage of the fluoride ion electrochemical cell, (iii) greater energy density in the fluoride ion electrochemical cell, And (iv) a lower cost of the fluoride ion electrochemical cell.

Comparison of performance properties and composition of lithium ion battery and fluoride ion electrochemical cell LIB FIB comment anode _{LiCoO 2, Li (NiCoMn) O} 2, LiFePO 4 _{CF x, AgF x, CuF x} , NiF x Solid fluoride is more stable than oxide cathode LiC ₆ , Li _x Si, Li _x Sn, Li _x (CoSnTi) LaF _x , EuF _x , LiC ₆ High capacity cathodes in FIBs Electrolyte LiPF ₆ in EC-DME-DMC MF (M = Li, K, Rb) in PC (or nitromethane) Inexpensive and more stable electrolyte in FIB Voltage (V) 3-5V 3.5-5.5V Higher operating voltage. High stability at high voltage energy 340 Wh / kh (theory) LaF ₃ / CF _x couple of 1560 (theoretical) 3.7x energy density in FIBs safety Lithium is unstable Fluoride is very stable. Do not use soluble metal Increased safety due to more robust chemistry cost High when Co is used Except Ag, most cathodes and cathodes are inexpensive FIB will be 4-5x cheaper with $ / Wh

Fluoride ion batteries (FIBs) are pure anion type batteries in which the anode and cathode reactions involve the acceptance and emission of fluoride anions F ^- . FIBs can be primary batteries and rechargeable batteries depending on the reversibility of the electrode reaction. However, both primary and rechargeable FIBs require F ^- anion conducting electrolytes. Fluoride ion batteries can be further classified into two classes.

In the first class, both the positive and negative electrodes contain fluoride anions. A fluoride ion electrochemical cell having a LaF ₃ anode and a CF _x cathode is an example of this first class. The half-electrode and cell reactions of the (LaF ₃ / CF _x ) system are as follows:

LaF ₃ anode:

LaF ₃ + 3ye ^- ? LaF _{3 (1-y)} + 3y F ^- (charge)

CF _x Cathode:

CF _x + xe ^- ? C + xF ^- (discharge)

Cell response:

xLaF ₃ + 3yC? xLaF _{3 (1-y)} + 3y CF _x (charge)

_{xLaF 3 (1-y) +} 3y CF x → xLaF 3 + 3yC

Other examples of fluoride ion electrochemical cells of this first class include (anode / cathode) _{couple: (LaF 3 / AgF x)} , (LaF 3 / NiF x), (EuF 3 / CF x), (EuF 3 / CuF _x ). &_lt; / RTI >

In the second class, only one electrode contains a fluoride anion. A fluoride ion electrochemical cell having a LiC ₆ anode and a CF _x cathode is an example of this second class. (LiC ₆ / CF _x ) system, the electrode half reaction and the cell reaction are as follows:

LiC ₆ anode:

LiC ₆ + F ^- ? 6C + LiF + e ^- (discharge)

CF _x Cathode:

CF _x + xe ^- ? C + xF ^- (discharge)

Cell response:

_{x LiC 6 + CF x → (} 6x + 1) C + xLiF ( discharge)

(6x + 1) C + x LiF? X LiC ₆ + CF _x (charge)

Other example of the second class of fluoride ion electrochemical cell is one containing the following (anode / cathode) couples, but are not limited to: (LiC ₆ / AgF _x), (LiC ₆ / NiF _x), (Li _x Si / CF _x ) and (Li _x Si / Cu F _x ).

Aspects of the invention are further illustrated and described in the following examples.

FIG. 1a provides a schematic diagram illustrating a lithium ion battery during charging, and FIG. 1b provides a schematic diagram illustrating a lithium ion battery during discharge.

Figure 2. Schematic representation of the average operating potential and cell voltage of various cathode and anode materials for conventional lithium ion batteries.

Figure 3. Figure 3a provides a schematic diagram illustrating the fluoride ion battery (FIB) of the present invention during discharge. Figure 3b provides a schematic diagram showing the average operating potential for an exemplary embodiment corresponding to an electrolyte comprising LaF _3-x cathode, CF _x anode, and MF provided in an organic electrolyte, where M is K or Rb, The same metal).

Figure 4. Figure 4 provides the crystal structure of carbon fluoride.

Figure 5. Figure 5 provides an X-ray diffraction pattern (CuK _alpha irradiation) of the various anode materials evaluated. The diffraction pattern of carbon nanofibers, KS 15 and commercial CF ₁ is shown in FIG.

Figure 6 provides the discharge profile of the CF ₁ anode for various discharge rates in the C / 20 to C range at room temperature.

Figure 7. Figure 7 provides the discharge profile of the CF _0.530 , KS15 anode for various discharge rates in the C / 20 to C range at room temperature.

Figure 8. Figure 8 provides a CF _0.647, the discharge profile of the anode KS15 for various discharge rate of C / 20 to 6C range at room temperature.

Figure 9. Figure 9 provides a discharge profile of CF _0.21 , carbon nanofiber anode for various discharge rates ranging from C / 20 to 6C at room temperature.

10 provides the discharge profile of the carbon nanofiber anode at CF _{0.59 for} various discharge rates ranging from C / 20 to 6C at room temperature.

Figure 11. Figure 11 provides a discharge profile of CF _0.76 , carbon nanofiber anode for various discharge rates ranging from C / 20 to 6C at room temperature.

Figure 12. Figure 12 provides a discharge profile of CF _0.82 , carbon nanofiber anode for various discharge rates ranging from C / 20 to 4C at room temperature.

Figure 13. Figure 13 provides the charge-discharge profile of a CF _0.82 , multi-walled nanotube anode for the 1.5V to 4.6V voltage range. Voltage is plotted on the Y axis (left), current is plotted on the Y axis (right), and time plotted on the X axis.

Figure 14. Figure 14 provides a charge-discharge profile of a CF _0.82 , multi-walled nanotube anode for the 1.5V to 4.8V voltage range. Voltage is plotted on the Y axis (left), current is plotted on the Y axis (right), and time plotted on the X axis.

Figure 15. Figure 15 provides the charge-discharge profile of the CF ₁ anode for the 1.5V to 4.8V voltage range. Voltage is plotted on the Y axis (left), current is plotted on the Y axis (right), and time plotted on the X axis.

Figure 16. Figure 16 provides a plot of voltage (V) versus hours in a Li / CF _x half cell configuration for 4.6V and 4.8V. A discharge capacity increase of 0.25% was observed at 4.8V.

Figure 17. Figure 17 provides a plot of the Li / CF _x cell arrangement halves the voltage (V) versus relative capacity rate (%) of CF with _0.647 KS15 positive electrode with respect to the voltage of 4.8V to 5.4V range. As it is shown in Figure 17, CF _0.647 KS15 positive electrode capacity higher charge cut over a range of 4.8V to 5.4V - increases with the turn-off voltage.

Figure 18. Figure 18 provides a cycle capacity curve of discharge capacity (mAh / gC) versus number of cycles for various anode materials evaluated. This data demonstrates that a 120 mAh / gC rechargeable capacity was achieved in a Li / CF _x half-cell configuration charged to 4.8 V at a 2C-rate.

Figure 19 provides a plot of the discharge cycle versus number of cycles of the multi-wall nanotube anode at CF _{0.82 for} a voltage of 14.6V, 4.8V.

Figure 20. Figure 20 provides a plot of the discharge rate performance of the LiMn ₂ O ₄ anode.

Figure 21. Figure 21a provides a plot of discharge voltage versus time, with two time points (1) and (2) where the x-ray diffraction pattern is measured. Thin graphite electrodes were used (50 microns thick 3-4 mg). FIG. 21B shows the x-ray diffraction patterns obtained at the two time points (1) and (2) shown in FIG. 21A. FIG. 21C shows the x-ray diffraction pattern obtained at the two time points (1) and (2) shown in FIG. 21A on an enlarged scale. The diffraction pattern in Figures 21b and 21c shows the step formation of intercalated fluoride ions (mixing of step 2 and step 3). It is also seen in the diffraction pattern of Figures 21b and 21c that the graphite phase completely disappears at 5.2V and reappears at 3.2V.

Figure 22 provides the electronic energy loss spectrum (EELS) of the anodic material charged to 5.2V. Only pure fluorine was observed in the sample and no other species such as B or P were present indicating that other anions in the electrolyte were not intercalated.

Example 1: Preparation of Li / CF _x  Fluoride ion secondary electrochemical cell with half cell configuration

1.a. Introduction

To illustrate the advantages of the present fluoride ion electrochemical cell, cells comprising a CF _x anode and a metallic cathode were prepared and evaluated for their electrochemical performance. The results shown here demonstrate that fluoride ion electrochemical cells exhibit useful rechargeable capacity at room temperature under reasonable charge-discharge ratios.

1.b. Experiment

Two types of fluorocarbon CF _x were synthesized and used as the anode in the lithium cell of this example; 1) coke stoichiometric (commercial) CF ₁ and 2) graphite and multiwall carbon nanotubes (MWNTs) based partially fluorinated CF _x (x <1). The fluorocarbon was obtained by hot fluorination of coke graphite or MWNT carbon powder of the formula:

C (s) + x / 2 F ₂ (g) CF _x (s) (s = solid and g = gas)

Several types of fully fluorinated and partially fluorinated carbons, referred to as CF _x in this example, have been investigated for their use as anode active materials:

(1) Commercial CF _x (where x = 1.0); This partially fluorinated carbonaceous material was obtained from Lodestar, NY, USA and corresponds to our PC10 product, a completely fluorinated coke material. This partially fluorinated carbonaceous material is referred to synonymously as "commercial", "commercial CF _x ", and "CF _x (x = 1)" throughout the drawings and this example;

(2) partially fluorinated carbon synthesized by fluorination of synthetic graphite (x = 0.530, CF _{x of} 0.647); This partially fluorinated material was synthesized by partial fluorination of synthetic graphite manufactured by Timcal, Switzerland. This partially fluorinated graphite material is referred to in the drawings and throughout this example as &quot; KS15 &quot;. The composition of this material are cleared further characterized with reference to a fluorine-to-carbon atomic ratio (i.e., the variable x in the general formula CF _x) of; And

(3) partially fluorinated carbon (x = 0.21, 0.59, 0.76, 0.82 CF _x ) synthesized by fluorination of multiwalled carbon nanotubes (MWNTs); This partially fluorinated material was synthesized by partial fluorination of MWNTs from MER, Tucson, AZ, USA. This partially fluorinated material is referred to synonymously as &quot; carbon nanofibers &quot;,&quot; MWNT &quot;,&quot; multiwall carbon nanotubes &quot; in the drawings and throughout the examples. The compositions of the materials are cleared further characterized with reference to a fluorine-to-carbon atomic ratio (i.e., the variable x in the general formula CF _x) of.

The positive electrode was formed by adding acetylene black graphite (ABG) to the selected CF _x material and PVDF as a binder, and the proportions were 75 wt%, 10 wt%, and 15 wt%, respectively. These three materials were mixed together with dibutyl phthalate DBP (20 wt%) in an acetone solution. The solution was then evaporated to finally obtain a CF _x anode (thickness 100-120 탆). The film was cut into a diameter (15.2 mm), washed with methanol and dried overnight at 80 ° C in a vacuum. The weight of this electrode was 10 to 20 mg. Structure of coin type Li / CF _x test battery; (Sanyo Celgard, diameter (19 mm), thickness (25 탆), strong, low electrical resistivity and high porosity (55%).) Li / PC-DME-LiBF ₄ / CF _x , 2016 coin cell.

1.c. Experiment result

Figure 4 provides the crystal structure of carbon fluoride. Figure 5 provides a commercial CF ₁ and x- ray diffraction pattern (CuK _α irradiation) of the various evaluation positive electrode material comprising the various parts of a fluorinated carbonaceous material. Various partially fluorinated KS15 graphite samples (i.e., CF _x ; x = 0.53 and 0.647), various partially fluorinated carbon nanofiber samples (i.e., MWNTs, CF _x ; x = 0.210, 0.590, 0.760 and 0.820); And the diffraction pattern of the CF ₁ sample used (i.e., CF _x ; x = 1) is shown in FIG.

The characteristics of various fluorinated carbon materials were also investigated electrochemically. In these experiments, cyclic chronopotentiometry (constant current) was used following the discharge and charge of the cell. The applied current was calculated as the theoretical capacity. Thus, for various fixed C / n rates (C / 10 ~ 1C), the current I could be determined:

m _{CF x} = mass of active material (g), Q _th = theoretical capacity in mAh / g

Note: Q _th is expressed in mAh / g of CF _x during the first discharge and mAh / g of C during cycling.

In this measurement, the first discharge and the subsequent cycling reaction were as follows:

First discharge :

Cycling reaction :

Figures 6-12 provide a first discharge curve of many anode carbonaceous active materials. Figure 6 provides the discharge profile of the commercial CF ₁ anode for various discharge rates in the C / 20 to C range at room temperature. Figure 7 provides the discharge profile of the CF _0.530 , KS 15 anode for various discharge rates in the C / 20 to C range at room temperature. Figure 8 provides a CF _0.647, the discharge profile of the anode KS15 for various discharge rate of C / 20 to 6C range at room temperature. Figure 9 provides a discharge profile of CF _0.21 , carbon nanofiber anode for various discharge rates ranging from C / 20 to 6C at room temperature. Figure 10 provides a discharge profile of CF _0.59 , carbon nanofiber anode for various discharge rates ranging from C / 20 to 6C at room temperature. Figure 11 provides CF _0.76 , discharge profile of the carbon nanofiber anode for various discharge rates in the range of C / 20 to 6C at room temperature. Figure 12 provides a discharge profile of CF _0.82 , carbon nanofiber anode for various discharge rates ranging from C / 20 to 4C at room temperature. The observed discharge profile matches the first discharge cell response: CF _x + Li ⁺ + xe ^- ? C + xLiF (3.2V-1.5V versus Li).

Figures 13-15 provide plots showing cycling tests of various anode carbonaceous active materials. Figure 13 provides the charge-discharge profile of a CF _0.82 , multi-walled nanotube anode for the 1.5V to 4.6V voltage range. Voltage was plotted on the Y axis (left), current was plotted on the Y axis (right), and time plotted on the X axis. Figure 14 provides a charge-discharge profile of a CF _0.82 , multi-walled nanotube anode for a voltage range of 1.5V to 4.8V. Voltage was plotted on the Y axis (left), current was plotted on the Y axis (right), and time plotted on the X axis. Figure 15 provides the charge-discharge profile of the CF ₁ anode for the 1.5V to 4.8V voltage range. Voltage was plotted on the Y axis (left), current was plotted on the Y axis (right), and time plotted on the X axis. These figures show that the tested anode material, especially CF _x ; x = 0.82, MWNT (see Figs. 13 and 14) can be cycled to show a stable cycle capacity. Figure 16 shows the results for CF _x for 4.6V and 4.8; x = 0.82, provides a plot of voltage (V) versus hours of a Li / CF _x half cell configuration with an MWNT anode. An increase in discharge capacity of 0.25%, corresponding to an increase in charge voltage from 4.6V to 4.8V, is observed. Figure 17 provides a plot of the Li / CF _x cell arrangement halves the voltage (V) versus relative capacity rate (%) of CF with _0.647 KS15 positive electrode with respect to the voltage of 4.8V to 5.4V range. As it is shown in Figure 17, CF _0.647 KS15 positive electrode capacity higher charge cut over a range of 4.8V to 5.4V - increases with the turn-off voltage. Figures 16 and 17 show a measurable increase in discharge capacity due to an increase in the charging voltage for the tested CF _x material. The observed charge-discharge profile shown in Figures 13-17 corresponds to the cycling cell response: C + yA ^{- -} CA _y + ye ^- (vs. Li to 1.5V-4.8V) (A ^- = anion = F ^- ) , Li ⁺ does not participate in the cycling reaction.

18 is a graph showing the effect of various fluoropolymers on the various evaluated anode materials including commercial CF ₁ , partially fluorinated KS15 graphite (CF _x , x = 0.53 & 0.647) and partially fluorinated MWNTs (CF _x ; x = 0.21, 0.59, 0.76 and 0.82) The discharge capacity (mAh / gC) versus the cycle capacity curve for the number of cycles. The charge voltage for this measurement was 4.6 V, except for the highest plot (dashed line) corresponding to the anode with the charge voltage of 4.8 V and the partially fluorinated MWNTs with CF _x , x = 0.82 . Similar to the charge-discharge profile shown in FIGS. 16 and 17, a significant increase in discharge capacity is observed for partially fluorinated MWNTs with CF _x , x = 0.82 at the same time as increasing the charge voltage from 4.6 V to 4.8 V.

As can be seen in Figure 18, the cell configuration with a commercial CF ₁ active cathode material does not exhibit very good cycling, most likely due to the severe degradation of the structural integrity of CF _{1 that} occurs during the first discharge. It is likely that the porosity of the cathode active material contributes to the decomposition which can be caused by the exfoliation initiated by the reaction between the fluoride ion and the lithium ion. Conversely, the partially fluorinated carbonaceous materials studied (e.g., graphite, MWNTs) exhibit very good cycling performance. This seems to be due to the reduced fluorine content and reduced porosity of this material compared to commercial CF _x , x = 1. Because of the partially fluorinated MWNTs is greater than the mechanical integrity than the agreed commercial graphite and CF ₁ plausible (mechanical integrity), it is important to note that the most excellent cycling performance.

The data in Fig. 18 show that 120 mAh in a Li / CF _x half-cell configuration with an anode having an active material containing partially fluorinated MWNTs having CF _x , x = 0.82 and charged to 4.8 V at a 2C- / gC Explain that rechargeable capacity has been achieved. For comparison purposes, FIG. 20 provides a plot of the discharge rate performance of the LiMn ₂ O ₄ anode. This measurement shows that the partially fluorinated CFx material made from multi-walled carbon nanotubes surpasses commercially available LiMn ₂ O ₄ as the anode of a lithium rechargeable battery.

Figure 19 provides a plot of the discharge cycle versus number of cycles of the multi-wall nanotube anode at CF _{0.82 for} a voltage of 14.6V, 4.8V. In these plots, the discharge capacity (y-axis; mAh / gC) is a plot for the number of cycles in any unit. Fig. 19 shows that stable discharge characteristics were observed for at least about 50 cycles for this positive electrode active material.

An X-ray diffraction pattern of the anode was obtained under various experimental conditions to confirm that the fluoride ion participated in the oxidation and reduction reactions at the anode. Figure 21A provides a plot of the time at which the discharge voltage versus the two time points (1) and (2) where the x-ray diffraction pattern is measured. An X-ray diffraction pattern was also obtained for the unused anode. Thin graphite electrodes were used (50 microns thick 3-4 mg). FIG. 21B shows the x-ray diffraction pattern obtained at the two time points (1) and (2) shown in FIG. 21A. FIG. 21C shows the x-ray diffraction pattern obtained at the two time points (1) and (2) shown in FIG. 21A on an enlarged scale.

The diffraction pattern of Figures 21b and 21c, corresponding to a charge of up to 5.2 V and a subsequent discharge of up to 3.2 V, shows the step formation of intercalated fluoride ions (mixture of step 2 and step 3). Specifically, the appearance of the (002) -2, (003) -3 and (004) -3 peaks indicate that intercalated fluoride anions are present upon charging and discharging. As shown by the comparison between the diffuse patterns corresponding to the unused anode, the anode at 5.2 V and the anode at 3.2 V, the graphite phase completely disappeared when charged to 5.2 V and subsequently discharged to 3.2 V It appears again. The C (002) graphite peaks present in the diffraction pattern corresponding to 3.2 V show that graphite is present when the fluoride ions de-intercalate. In addition, the sharp peak width of the C (002) graphite peak in the 3.2 V diffraction pattern indicates that graphite retains its structural integrity when charged and discharged. This result demonstrates that the fluoride ion intercalation and deintercalation processes are reversible and do not result in a phase change from crystalline graphite to amorphous carbon. The results cycling cell _{^{reaction: C + yA - ↔ CA y}} + ye - (1.5V - for Li to 4.8V) (A ^- = an anion = F ^-), and consistent with, Li ⁺ does not participate in the cycling reaction additional Provide evidence.

Electrode Energy Loss Spectrum (EELS) was obtained for the conditions corresponding to filling the electrochemical cell up to 5.2 V to further investigate the composition of the partially fluorinated graphite active material. EELS is useful in techniques to characterize the elemental composition of a material because it is highly sensitive to the presence of elements in the sample and can very accurately identify elements in the material. Figure 22 provides the EELS spectrum of the cathode active material charged to 5.2V. Only two peaks are shown in Fig. 22, and both of these peaks may be due to the presence of fluorine in the cathode active material. There are no peaks corresponding to other non-carbon elements such as B or P. This observation provides evidence that other anions in the electrolyte, such as PF ₆ ^- or BF ₄ ^- , were not intercalated.

1.d. conclusion

The partially fluorinated carbon material, CF _x, is an excellent example of a cathode material for a fluoride anion rechargeable battery. This shows stable cycle life, high capacity, high discharge voltage and high charge / discharge rate capacity. X-ray diffraction studies coupled with electron energy loss spectroscopy studies show that carbon carrier fluoride anions can be reversibly intercalated into the carbon matrix, whether the carbon matrix is made of graphite, coke or multi-walled carbon nanotubes . Staging occurs, leading to similarities between fluoride anion intercalation and lithium cation intercalation at the Li _x C ₆ cathode. The fluorine anion storage capacity increases by about 150% with charge cutoff voltage between 4.5V and 5.5V.

Example 2: Anion and cation receptor for fluoride ion electrochemical cell

This example provides a summary of anionic and cationic receptors useful in the present invention. Many fluoride ion acceptors capable of improving the solubility of the fluoride salt and improving the ion conductivity of the electrolyte in the electrochemical cell of the present invention are specifically exemplified.

In one embodiment, the electrolyte of the present invention comprises an anionic receptor having the chemical structure AR1:

Wherein R ₁ , R ₂ and R ₃ are independently selected from an alkyl group optionally substituted with one or more halogen, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether containing F, an aromatic group, an ether Group, a thioether group, a heterocyclic group, an aryl group, or a heteroaryl group.

In one embodiment, the electrolyte of the present invention comprises a borate anion receptor compound having the chemical structure AR2:

Wherein R ₄ , R ₅ and R ₆ are independently selected from the group consisting of an alkyl group optionally substituted with one or more halogen, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether including F, an aromatic group, , An aryl group or a heteroaryl group. In one embodiment, R ₄ , R _5, and R ₆ are the same. In one embodiment, each of R ₄ , R _5, and R ₆ is an F-containing moiety.

In one embodiment, the electrolyte of the present invention comprises a phenylboronic anion receptor compound having the chemical structure AR3:

Wherein R ₇ and R ₈ are independently selected from the group consisting of an alkyl group optionally substituted by one or more halogen, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether including F, an aromatic group, a heterocyclic group, Or a heteroaryl group. In one embodiment, R ₇ and R ₈ are the same. In one embodiment, each R ₇ and R ₈ is an F-containing moiety. In one embodiment, the, R ₇ and R ₈ are together an aromatic (including phenyl optionally substituted) forming, comprising the F substituents and F- containing moiety of substituents as shown by the formula AR4 :

Wherein X _A and X _B are one or more hydrogen or represent a non-hydrogen ring substituent independently selected from the group consisting of F, including halogen, alkyl, alkoxide, thiol, thioalkoxide, ether or thioether. In one embodiment, the at least one substituent is an F-containing moiety.

In one embodiment, the electrolyte of the present invention is a tris (hexafluoroisopropyl) borate (THFIB; MW = 511.9 AMU) anion receptor having the chemical structure AR5:

Or tris (2,2,2-trifluoroethyl) borate (TTFEB; MW = 307.9 AMU) having the chemical structure AR6 Anion Receptor:

Or tris (pentafluorophenyl) borate having the chemical structure AR7 (TPFPB; MW = 511.98 AMU) anion receptor:

Or bis (1,1,3,3,3-hexafluoroisopropyl) pentafluorophenylboronate (BHFIPFPB; MW = 480.8 AMU) anion receptors having the structure AR8.

Useful anion receptors to the electrolyte of the present invention is _{(CH 3 O) 3 B,} (CF 3 CH 2 O) 3 B, (C 3 F 7 CH 2 O) 3 B, [(CF 3) 2 CHO] 3 B, _{[(CF 3) 2 C (} C 6 H 5) O] 3 B, ((CF 3) CO) 3 B, (C 6 H 5 O) 3 B, (FC 6 H 4 O) 3 B, (F _{2 C 6 H 3 O) 3} B, (F 4 C 6 HO) 3 B, (C 6 F 5 O) 3 B, (CF 3 C 6 H 4 O) 3 B, [(CF 3) 2 C 6 H ₃ O] ₃ B, and (C ₆ F ₅ ) ₃ B, but are not limited thereto.

Useful cationic receptors of the present invention include, but are not limited to, crown ethers, lariat ether, metal crown ethers, calix crown (such as Calix (aza) Cryant), tetrataphyl valen crown, calixaren, calix [ But are not limited to, quinoa, tetrathiafulvalene, bis (calix crown) tetrathiafulvalene, and derivatives thereof.

The following references describe anionic and / or cationic receptors which are useful in the practice of the present invention, and are incorporated herein by reference unless they are contradictory to the present disclosure: (1) Evidence for Cryptand-like Behavior in Bibracchial Lariat Ether (BiBLE) Complexes Obtained from X-ray Crystallography and Solution Thermodynamic Studies, Kristin A. Arnold, Luis EcheoGoyen, Frank R. Fronczek, Richard D. Grandour, Vinicent J. Gatto, Banita D. White, George W. Gokel, J. Am. Chem. Soc., 109: 3716-3721, 1987; (2) Bis (calixcrown) tetrathiafulvalene Receptors. Maria-Jesus Blesa, Bang-Tun Zhao, Magali Allain, Franck Le Derf, Marc Salle, Chem. Eur. J. 12: 1906-1914, 2006; (3) Studies on Calix (aza) crowns, Ⅱ. Synthesis of Novel Proximal Doubly Bridged Calix [4] arenes by intramolecular ring Closure of syn 1,3- and 1,2- to ω'-Chloraolkylamides, Istavan Bitter, Alajos Grun, Gabor Toth, Barbara Balazs, Gyula Horvath, Laszlo Toke, Tegrahedron 54: 3857-3870,1998; (4) Tetrathiafulvalene Crowns: Redox Switchable Ligands, Franck Le Derf, Miloud Mazari, Nicolas Mercier, Eric Levillain, Gaelle Trippe, Amedee Riou, Pascal Richomme, Jan Becher, Javier Garin, Jesus Orduna, Nuria Gallego-Planas, Alain Gorgues, Marc Salle, Chem. Eur. J. 7.2: 447-455, 2001; (5) Electrochemical Behavior of Calix [4] arenediquinones and Their Cation Binding Properties, Taek Dong Chung, Dongsuk Choi, Sun Kil Kang, Sang Swon Lee, Suk Kyu Chang, Hasuck Kim, Journal of Electroanalytical Chemistry, 396: 431-439 , 1995; (6) Experimental Evidence for Alkali Metal Cation - π Interactions, George W. Gokel, Stephen L. De Wall, and Eric S. Meadows, Eur. J. Chem., 2967-2978, 2000; (7) π-Electron Properties of Large Condensed Polyaromatic Hydrocarbons, S. E. Stein, R. L. Brown, J. Am. Chem. Soc., 109: 3721-3729, 1987; (8) Self-Assembled Organometallic [12] Metallacrown-3 Complexes, Holger Piotrowski, Gerhard Hilt, Axel Schulz, Peter Mayer, Kurt Polborn, Kay Severin, Chem. Eur. J., 7, 15: 3197-3207, 2001; (9) First- and Second-Sphere Coordination Chemistry of Alkali Metal Crown Ether Complexes, Jonathan W. Steed, Coordination Chemistry Reviews 215: 171-221, 2001; (10) Alkali metal ion complexes of functionalized calixarenes - a competition between pendent arm and anion bond to sodium; R. Abidi, L. Baklouti, J. Harrowfield, A. Sobolev; J. Vicens, and A. White, Org. Biomol. Chem., 2003, 1, 3144-3146; (11) Transition Metal and Organometallic Anion Complexation Agents, Paul D. Beer, Elizabeth J. Hayes, Coordination Chemistry Review, 240: 167-189, 2003; (12) Versatile Self-Complexing Compounds Based on Covalently Linked Donor-Acceptor Cyclophanes, Yi Liu, Amar H. Flood, Ross M. Moskowitz, J. Fraser Stoddart, Chem. Eur. J. 11: 369-385, 2005; (13) Study of Interactions of Various Ionic Species with Solvents Toward the Design of Receptors, N. Jiten Singh, Adriana C. Olleta, Anupriya Kumar, Mina Park, Hai-Bo Yi, Indrajit Bandyopadhyay, Han Myoung Lee, P. Tarakeshwar, Kwang S. Kim, Theor. Chem. Acc. 115: 127-135, 2006; (14) A Calixarene-amide-tetrathiafulvalene Assembly for the Electrochemical Detection of Anions, Bang-Tun Zhao, Maria-Jesus Blesa, Nicolas Mercier, Franck Le Derf, Marc Salle, New J. Chem. 29: 1164-1167, 2005.

STATEMENT REGARDING INTEGRATION AND DEFORMATION BY REFERENCE

All references throughout this application, including, for example, registered or granted patents, or the like; Patent application publication; And non-patent documents or other source materials are incorporated herein by reference in their entirety, to the extent that each reference is not, at least in part, inconsistent with the disclosure herein, even if individually incorporated by reference For example, a partially contradictory reference is incorporated as a reference except for the partially contradictory portion of the reference).

The terms and expressions used herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions to exclude any equivalents of the features shown and described or portions thereof, It is to be understood that various modifications are possible within the scope of the claims. Thus, although the present invention has been specifically disclosed by preferred embodiments, exemplary implementations and optional modifications, it will be understood by those skilled in the art that changes and variations of the concepts herein disclosed may be utilized by those skilled in the art, It is to be understood that they are considered to be within the scope of the invention as defined by the following claims. It will be apparent to those skilled in the art that the specific embodiments provided herein are illustrative of useful embodiments of the present invention and that the present invention may be practiced using numerous different devices, apparatus components, method steps, As will be apparent to those skilled in the art, methods and apparatus useful in the present process can include a number of optional compositions and processing elements and steps.

When a group of substituents is disclosed herein, the individual members of the group and all subgroups, including any isomers, enantiomers, diastereomers of members of that group, are to be understood as being individually disclosed. When a Makish group or other group is used herein, all individual members of the group and all possible combinations and subcombinations of the group are individually included in the disclosure. When a compound is described herein but the specific isomer, enantiomer, or diastereomer of the compound is not specified, e.g., by chemical or chemical name, the description is intended to include the individual isomers, And enantiomers. Also, unless otherwise specified, all isotopic variations of the compounds disclosed herein are intended to be encompassed by the disclosure. For example, it is to be understood that any one or more of the hydrogens in the disclosed molecule may be replaced by deuterium or tritium. Isotopic variation of molecules is generally useful because the analysis of molecules and the standard of chemical or biological studies are related to the use of molecules or molecules. Methods for making such isotopic variations are known in the art. The specific designation of the compounds is intended to be illustrative since those skilled in the art are known to be able to designate the same compounds differently.

Many molecules disclosed herein contain one or more ionizable groups (such as a group in which hydrogen can be removed (e.g., -COOH) or a group in which hydrogen may be added (e.g., an amine), or a quaternarizable group Amine, for example). It is contemplated herein that all possible ionic forms of such molecules and salts are included separately in the disclosure. With respect to the salts of the present compounds, those skilled in the art can choose from a wide variety of available counterions suitable for the preparation of the salts of the present invention for a given application. In particular applications, the choice of a given anion or cation for the preparation of a salt may result in increased or decreased solubility of the salt.

All formulas or combinations of ingredients described or exemplified herein may be used for the practice of the invention unless otherwise stated. It will be understood that whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges as well as individual values included in a given range are intended to be included in the disclosure. Any subranges or individual values in the ranges or subranges included in the description herein may be excluded from the scope of the claims herein.

All patents and publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which the invention pertains. The references cited herein are incorporated herein by reference in their entirety and represent the state of the art for the date of issue or date of submission and are hereby intended to exclude certain prior art implementations where necessary using this information. For example, when the composition of a substance is claimed, the compound that is known prior to the applicant's invention, and in which a usable ingredient is provided, for example, a viable disclosure in the references cited herein, is intended to be included in the composition of matter claims herein, It should be understood.

As used herein, the term "comprising" is synonymous with "including", "containing", or "characterized by" and is inclusive, open, It does not exclude non-existing elements or method steps. As used herein, &quot; consisting of &quot; excludes any element, step, or ingredient not expressly stated in a claim element. As used herein, &quot; consisting essentially of &quot; does not exclude a substance or step that does not materially affect the basic new properties of the claims. In the examples of the present application, any of the terms "comprising," "consisting essentially of," and "consisting of" may be replaced by any two of the other terms. The invention illustratively described herein may suitably be practiced without any elements or elements, limitations or limitations not explicitly set forth herein.

Those skilled in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods not specifically illustrated in the practice of the invention may be used without undue experimentation Will recognize. All technically known equivalents of functionality for any materials and methods are intended to be included in the present invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding the features shown or described or some of them, It should be noted that this is possible. Thus, although the present invention has been specifically disclosed by preferred embodiments and optional, modifications and variations of the concepts disclosed herein may be resorted to by those skilled in the art, and such modifications and variations are possible in light of the above- Are considered to be within the scope of the present invention.

Claims (46)

As an electrochemical cell, anode; cathode; And An electrolyte interposed between the anode and the cathode and capable of conducting an anion charge carrier, wherein the electrolyte comprises a solvent and a fluoride salt, the fluoride salt being at least partially dissolved in the electrolyte, Wherein the fluoride salt has the formula MF _n , M is a metal other than lithium, and n is an integer greater than 0; / RTI &gt; Wherein the anode and the cathode reversibly exchange the anion charge carrier with the electrolyte while the electrochemical cell is charged or discharged, and the anion charge carrier is the fluoride ion (F &lt; ^- &gt;). delete delete delete The electrochemical cell according to claim 1, wherein M is an alkali metal or an alkaline earth metal. delete The electrochemical cell of claim 1, wherein M is Na, K, or Rb. delete delete The electrochemical cell of claim 1, wherein the electrolyte further comprises an anion receptor. The electrochemical cell of claim 1, further comprising a fluoride ion acceptor capable of coordinating with the fluoride ion from the fluoride salt. The electrochemical cell of claim 1, wherein the electrolyte further comprises a cation acceptor capable of coordinating with the metal ion from the fluoride salt. The electrochemical cell according to claim 1, wherein the electrolyte is an aqueous electrolyte. The electrochemical cell according to claim 1, wherein the electrolyte is a non-aqueous electrolyte. The electrochemical cell according to claim 1, wherein the cathode is a fluoride ion host material. The electrochemical cell according to claim 15, wherein the fluoride ion host material of the negative electrode is a fluoride compound. 16. The method of claim 15, wherein the fluoride ion host material of the negative electrode LaF _x, CaF _x, AlF _x, EuF _x, LiC _6, Li _x Si, Li _x Ge, Li _x (CoTiSn), SnF _x, InF _x, with _{VF x, CdF x, CrF x} , FeF x, ZnF x, GaF x, TiF x, NbF x, MnF x, YbF x, ZrF x, SmF x, is selected from the group consisting of LaF _x and CeF _x Electrochemical cell. The electrochemical cell according to claim 15, wherein the fluoride ion host material of the negative electrode is a polymer selected from the group consisting of polyacetylene, polyaniline, polypyrrole, polythiophene and polyparaphenylene. The electrochemical cell according to claim 15, wherein the cathode has a standard electrode potential of -1 V or less. The electrochemical cell according to claim 15, wherein the cathode has a standard electrode potential of -2 V or less. The electrochemical cell according to claim 1, wherein the anode is a fluoride ion host material. The electrochemical cell according to claim 21, wherein the fluoride ion host material of the anode is an intercalation host material capable of accepting the fluoride ion to generate a fluoride ion intercalation compound. The electrochemical cell according to claim 21, wherein the fluoride ion host material of the anode is a fluoride compound. 22. The method of claim 21, wherein the fluoride ion host material of the anode CF _x, AgF _x, CuF _x, NiF _x, CoF _x, PbF _x, CeF _x, MnF _x, AuF _x, PtF _x, RhF _x, VF _x , OsF _x , RuF _x, and FeF _x . 25. The method of claim 24, wherein the fluoride ion host material of the anode is a partially fluorinated carbonaceous material having the formula CF _x , wherein x is selected from the range of 0.3 to 1.0 as the average atomic ratio of fluorine to carbon atoms; Wherein the carbonaceous material is selected from the group consisting of graphite, coke, multiwall carbon nanotubes, multilayer carbon nanofibers, multilayer carbon nanoparticles, carbon nanofillers, and carbon nanorods. The electrochemical cell according to claim 21, wherein the anode has a standard electrode potential of 1 V or more. The electrochemical cell according to claim 21, wherein the anode has a standard electrode potential of 2V or more. The electrochemical cell according to claim 1, wherein the positive electrode and the negative electrode are different fluoride ion host materials. The method of claim 1, wherein the anode comprises a first anion charge carrier host material and the cathode further comprises a second anion charge carrier host material; Said first and said second combination of anion charge carriers host material (X / Y) is CF _x / LiC _6; CF _x / LaF _x ; _{CuF x / LaF x, AgF x} / LaF x, CoF x / LaF x, NiF x / LaF x, MnF x / LaF x, CuF x / AlF x, AgF x / AlF x, NiF x / AlF x, NiF x / ZnF _{x, x} AgF / ZnF and MnF _{x x} / _x ZnF electrochemical cell is selected from the group consisting of. The electrochemical cell of claim 1, having a standard cell potential of at least 3.5V. 2. The electrochemical cell of claim 1, wherein the fluoride ions are released from the anode while the electrochemical cell discharges and are accommodated by the cathode. The electrochemical cell of claim 1, wherein the fluoride ions are released from the negative electrode and are accommodated by the positive electrode during charging of the electrochemical cell. The electrochemical cell of claim 1, comprising a primary electrochemical cell. The electrochemical cell of claim 1, comprising a secondary electrochemical cell. 35. The electrochemical cell of claim 34, having a cycle life of at least 500 cycles. The electrochemical cell of claim 1, wherein the electrochemical cell has a specific energy of 300 Wh kg ^-1 or more. The electrochemical cell according to claim 1, wherein the anode, the electrolyte, and the cathode do not contain lithium. As a secondary electrochemical cell, A positive electrode comprising a first fluoride ion host material and having a first standard electrode potential; A negative electrode including a second fluoride ion host material and having a second standard electrode potential, the negative electrode having a difference between the first standard electrode potential and the second standard electrode potential of not less than 3.5 V; And An electrolyte interposed between the anode and the cathode and capable of conducting a fluoride ion charge carrier and comprising a fluoride salt and a solvent, wherein at least a portion of the fluoride salt is in a dissolved state, whereby the fluoride ion An electrolyte in which the fluoride salt has a formula MF _n , M is a metal other than lithium, and n is an integer greater than 0; / RTI &gt; Wherein the positive electrode and the negative electrode reversibly exchange the fluoride ion charge carrier with the electrolyte while the electrochemical cell is charged or discharged, and the fluoride ion charge carrier is the fluoride ion (F &lt; ^- &gt;). delete 39. The electrochemical cell of claim 38, wherein M is Na, K, or Rb. 39. The electrochemical cell of claim 38, wherein the electrolyte further comprises an anion receptor, a cation receptor, or both. 39. The method of claim 38, wherein the second fluoride ion host material of the negative electrode LaF _x, CaF _x, AlF _x, EuF _x, LiC _6, Li _x Si, Li _x Ge, Li _x (CoTiSn), SnF _x, InF _x, which is selected from the group consisting of VF _x, CdF _x, CrF _x, FeF _x, ZnF _x, GaF _x, TiF _x, NbF _x, MnF _x, YbF _x, ZrF _x, SmF _x, LaF _x and CeF _x Characterized by an electrochemical cell. 39. The method of claim 38, wherein the first fluoride ion host material of the anode CF _x, AgF _x, CuF _x, NiF _x, CoF _x, PbF _x, CeF _x, MnF _x, AuF _x, PtF _x, RhF _x, VF _x , OsF _x , RuF _x, and FeF _x . A method of manufacturing an electrochemical cell, Providing an anode; Providing a cathode; And An electrolyte capable of conducting an anion charge carrier between the anode and the cathode, wherein the electrolyte comprises a solvent and a fluoride salt, the fluoride salt being at least partially dissolved in the electrolyte, Providing fluoride ions, wherein the fluoride salt has the formula MF _n , M is a metal other than lithium, and n is an integer greater than 0; / RTI &gt; Wherein the anode and the cathode reversibly exchange the anion charge carrier with the electrolyte while the electrochemical cell is charged or discharged, and the anion charge carrier is the fluoride ion (F &lt; ^- &gt;). anode; cathode; And an electrolyte interposed between the anode and the cathode and capable of conducting an anion charge carrier, wherein the electrolyte comprises a solvent and a fluoride salt, the fluoride salt is at least partially dissolved in the electrolyte, Wherein the fluoride salt has the formula MF _n , M is a metal other than lithium, and n is an integer greater than 0, the electrochemical cell comprising: Providing an electrochemical cell in which the anode and the cathode reversibly exchange the anion charge carrier with the electrolyte during charging or discharging and the anion charge carrier is the fluoride ion (F ^- ); And Discharging the electrochemical cell / RTI &gt; The electrochemical cell according to claim 21, wherein the fluoride ion host material of the anode is a polymer selected from the group consisting of polyacetylene, polyaniline, polypyrrole, polythiophene and polyparaphenylene.

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