JP5615497B2 - Fluoride ion electrochemical cell - Google Patents

Description

Detailed Description of the Invention

[Cross-reference of related applications]
[001] This application refers to US Provisional Application No. 60779054 filed on Mar. 3, 2006, and "Fluoride Ion Batteries (FIB)" whose inventor filed on Jan. 25, 2007 is Rachid Yazami. US Provisional Patent Application, Attorney Docket No. 4823-P, US Patent Application No. 16775541 filed on February 21, 2007, US Patent Application No. 1 filed on February 15, 2007 No. 1675308, US Patent Application No. 1560570, filed Nov. 16, 2006, and claims the benefit of priority. Each of these applications is hereby incorporated by reference in its entirety to the extent that it is not inconsistent with the disclosure herein.

[Background of the invention]
[002] In the electrochemical storage and conversion devices that extend the performance of these systems in various fields, including portable electronic devices, aircraft and spacecraft technology, and biomedical equipment over the past 20-30 years, A breakthrough has been made. Current state-of-the-art electrochemical storage and conversion devices have design and performance attributes that are specifically designed to provide compatibility with a variety of application requirements and operating environments. For example, from low energy self-discharge rates for implantable medical devices and high energy density batteries with high discharge reliability, to low cost, lightweight rechargeable batteries that provide long run times for a wide range of portable battery devices, extremely fast Advanced electrochemical storage systems have been developed, ranging from high capacity batteries for military and aerospace applications that can provide high discharge rates.

  [003] Despite the development and wide adoption of this variety of advanced electrochemical storage and conversion systems, great pressure continues to stimulate research to expand the functionality of these systems, thereby further A wide range of device applications are possible. The great growth in demand for high-power portable electronic products has generated a great deal of interest, for example, in the development of safe and lightweight primary and secondary batteries that provide higher energy density. In addition, the demand for miniaturization in the field of consumer electronics and instrumentation continues to stimulate research on new designs and material strategies to reduce the size, mass and form factor of high performance batteries. In addition, due to constant development in the field of electric vehicles and aerospace engineering, it is a mechanically robust, reliable, high energy density and high power density battery capable of excellent device performance in a useful range of operating environments. There is also a need for

  [004] Many recent advances in electrochemical storage and conversion technology are directly attributable to the discovery and integration of new materials for battery components. Lithium battery technology continues to evolve rapidly, for example, as new electrodes and electrolyte materials are discovered, at least in part, for these systems. New material strategies for lithium battery systems, from pioneering discovery and optimization of cathode intercalation host materials such as fluorinated carbon materials and nanostructured transition metal oxides to the development of high performance non-aqueous electrolytes Implementation has revolutionized the design and performance of these systems. In addition, the development of intercalation host materials for negative electrodes has led to the discovery and commercial implementation of lithium ion-based secondary batteries that exhibit high capacity, excellent stability and useful cycle life. As a result of these advances, lithium-based battery technology is now widely adopted in a variety of important applications, including primary and secondary electrochemical cells for portable electronic systems.

  [005] In commercial primary lithium battery systems, lithium metal is typically used to produce lithium ions that are transported via a liquid or solid phase electrolyte during discharge and undergo an intercalation reaction at the positive electrode containing the intercalation host material. A negative electrode is used. Double intercalation lithium ion secondary batteries in which lithium metal is replaced by lithium ion intercalation host materials for negative electrodes such as carbon (eg, graphite, coke, etc.), metal oxides, metal nitrides, metal phosphides, etc. Has been developed. When lithium ion insertion and de-insertion reactions occur simultaneously, lithium ions can move between the intercalation positive electrode and the intercalation negative electrode during discharge and charging. Incorporating lithium-ion intercalation host materials for negative electrodes is an important advantage that avoids the use of metallic lithium, which is prone to safety problems during recharging due to the high reactivity and non-epitaxial deposition properties of lithium There is.

  [006] Elemental lithium has a unique combination of properties that make it attractive for use in electrochemical cells. First, lithium is the lightest metal in the periodic table with an atomic mass of 6.94 AMU. Second, lithium has a very low electrochemical oxidation / reduction potential (i.e., -3.045 V vs. NHE (standard hydrogen reference electrode). This unique combination of properties allows a lithium-based electrochemical cell. The material strategy for lithium battery technology and advances in electrochemical cell design allow (i) high battery voltages (eg, up to about 3.8V), (ii) nearly Useful including constant (eg flat) discharge profile, (iii) long shelf life (eg up to 10 years) and (iv) compatibility with various operating temperatures (eg -20 to 60 degrees Celsius) Electrochemical cells have been realized that can provide the best device performance, and as a result of these beneficial properties, primary lithium batteries can be used in a variety of portable electronic devices and Child equipment, information technology, communications, biomedical engineering, sensing, are widely used as power sources in military and other important device applications including lighting.

  [007] State-of-the-art lithium ion secondary batteries provide excellent charge-discharge characteristics and are therefore also widely adopted as power sources in portable electronic devices such as cell phones and portable computers. U.S. Pat. Nos. 6,852,446, 6,306,540, 6,489055, and Gholam-Abas Nazri and Gianfranco Pistoia, “Lithium Batteries Science and Technology”, Kluer Acium Lithium Ion 200 Lithium Ion. And are incorporated herein by reference in their entirety.

[008] As described above, lithium metal is particularly highly reactive with water and many organic solvents, and due to this property, intercalation host materials for negative electrodes in lithium-based secondary electrochemical cells. It is necessary to use The considerable research in this _{field, LiC 6, Li x Si,} Li x Sn, etc. Li x (CoSnTi), various useful intercalation host materials for these for the system is obtained. However, by using an intercalation host material for the negative electrode, the battery voltage inevitably decreases by an amount corresponding to the free energy of lithium insertion / dissolution into the intercalation electrode. As a result, conventional state-of-the-art dual intercalation lithium ion electrochemical cells currently only provide an average operating voltage of about 4 volts or less. This requirement for the composition of the negative electrode also significantly loses the specific energy available in these systems. Furthermore, the safety risk is not completely eliminated by incorporating an intercalation host material for the negative electrode. These lithium ion battery systems must be charged under fairly controlled conditions, for example, to avoid overcharging or heating that can cause the positive electrode to decompose. Furthermore, undesirable side reactions involving lithium ions can occur in these systems, resulting in the formation of reactive metallic lithium that affects significant safety concerns. During charging at high speeds or low temperatures, the deposition of lithium forms dendrites that can grow across the separator and cause an internal short circuit in the battery, burning the organic electrolyte and oxygen and moisture in the metal lithium air This reaction generates heat, pressure and, in some cases, a fire.

[009] Double carbon batteries utilizing a lithium insertion reaction have also been developed for electrochemical storage. In these batteries, anions and cations generated by the decomposition of suitable electrolyte salts provide a source of charge that is stored in the electrode. During charging of these systems, electrolyte cations such as lithium ions (Li ⁺ ) undergo an insertion reaction in the negative electrode including the carbonaceous cation host material, and electrolyte anions such as PF ₆ ⁻ are positive electrodes including the carbonaceous anion host material. Into the insertion reaction. At the time of discharge, the insertion reaction is reversed, and as a result, cations and anions are released from the positive electrode and the negative electrode, respectively. However, state-of-the-art dual carbon batteries cannot provide as much energy density as the energy density provided by lithium ion batteries because the concentration of salt obtained in these systems is substantially limited. In addition, part of a double carbon batteries, PF ₆ ^- the pressure applied by the insertion and removal insertion polyatomic anion charge carrier, such as, susceptible to significant loss of capacity after the cycle. In addition, dual carbon batteries are limited with respect to achievable discharge rates and charge rates, and in many of these systems, electrolytes containing lithium salts are utilized, but lithium salts can be used under some operating conditions. May cause safety issues. Double carbon batteries are described in U.S. Pat. Nos. 4,830,938, 4,865,931, 5,518,836 and 5,320,833, and “Energy and Capacity Projections for Practical Dual-Graphic Cells”, J. Pat. R. Dahn and J.M. A. Seeel, Journal of the Electrochemical Society, 147 (3) 899-901 (2000). These references are incorporated herein by reference to the extent they do not conflict with the present disclosure.

A battery is composed of a positive electrode (cathode during discharge), a negative electrode (anode during discharge), and an electrolyte. The electrolyte includes ionic species that are charge carriers. The electrolyte in the battery can be of several different types: (1) pure cation conductor (eg beta alumina conducts only with Na ⁺ ), (2) pure anion conductor (eg O ⁻ or O ²⁻ (3) mixed ionic conductors (eg, some alkaline batteries use an aqueous KOH solution that conducts either OH ⁻ or K ⁺ , while some lithium ion batteries use Li An organic solution of LiPF _{6 that} conducts either ⁺ or PF ₆ ⁻ may be used. During charging and discharging, the electrodes exchange electrolytes and ions, and exchange electrons with external circuits (loads or chargers).

[011] There are two types of electrode reactions.
1. Cation-based electrode reactions : In these reactions, the electrode captures or releases cations Y ⁺ from the electrolyte and electrons from the external circuit.
Electrode + Y ⁺ + e ⁻ → Electrode (Y)
Examples of electrode reactions based on cations include (i) carbon anode in lithium ion batteries: 6C + Li ⁺ + e ⁻ → LiC ₆ (charge), (ii) lithium cobalt oxide cathode in lithium ion batteries: 2Li _0.5 CoO ₂ + Li ⁺ + e ⁻ → 2LiCoO ₂ (discharge), (iii) Ni (OH) ₂ cathode in rechargeable alkaline battery: Ni (OH) ₂ → NiOOH + H ⁺ + e ⁻ (charge), (iv) _MnO in saline Zn / MnO ₂ primary battery ^{_{2: MnO 2 + H + +}} e - → HMnO 2 ( discharge) are included.
2. Anion-based electrode reactions : In these reactions, the electrode captures or releases anions X ⁻ from the electrolyte and electrons from the external circuit.
Electrode + X ⁻ → Electrode (X) + e ⁻
Examples of anion-based electrode reactions include (i) a cadmium anode in a nickel-cadmium alkaline battery: Cd (OH) ₂ + 2e ⁻ → Cd + 2OH ⁻ (charge) and (ii) a magnesium alloy in a magnesium primary battery Anode: Mg + 2OH ⁻ → Mg (OH) ₂ + 2e ⁻ (discharge) is included.

[012] Existing batteries have pure cation or mixed ion chemistry. To the best of Applicants' knowledge, there are currently no known batteries with pure anionic chemistry. Examples of pure cationic and mixed ion batteries are shown below.
1. Pure cation type battery : Lithium ion batteries are an example of pure cation type chemistry. The electrode half reaction and the battery reaction for the lithium ion battery are as follows.
・ Carbon anode:
6C + Li ⁺ + e ⁻ → LiC ₆ (charging)
・ Lithium cobalt oxide cathode:
2Li _0.5 CoO ₂ + Li ⁺ + e ⁻ → 2LiCoO ₂ (discharge)
・ Battery reaction:
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 battery : A nickel / cadmium alkaline battery is an example of a mixed ion battery. The electrode half reactions and battery reactions for nickel / cadmium alkaline batteries are as follows.
Ni (OH) ₂ cathode (cation type):
Ni (OH) ₂ → NiOOH + H ⁺ + e ⁻ (charge)
・ Cadmium anode (anion type):
Cd (OH) ₂ + 2e ⁻ → Cd + 2OH ⁻ (charge)
・ Battery reaction:
Cd (OH) ₂ + 2Ni (OH) ₂ → Cd + 2NiOOH + 2H ₂ O (charging)
Cd + 2NiOOH + 2H ₂ O → Cd (OH) ₂ + 2Ni (OH) ₂ (discharge)
A Zn / MnO ₂ battery is an example of a mixed ion battery. The electrode half-reaction and battery reaction for the Zn / MnO ₂ battery are as follows.
-Zn anode (anionic type):
Zn + 2OH ⁻ → ZnO + H ₂ O + 2e ⁻ (discharge)
・ MnO ₂ cathode (cation type)
MnO ₂ + H ⁺ + e ⁻ → HMnO ₂ (discharge)
・ Battery reaction:
_{Zn + 2MnO 2 + H 2 O} → ZnO + 2HMnO 2 ( discharge)

  [013] As is apparent from the above, there is a need in the art for secondary electrochemical cells for a variety of important device applications, including the rapidly growing demand for high performance portable electronics. Specifically, there is a need for a secondary electrochemical cell that exhibits excellent stability and safety while at the same time providing useful battery voltage, specific capacity and cycle life. There is a need for alternative insertion / intercalation based electrochemical cells that eliminate or reduce the safety issues inherent in the use of lithium in primary and secondary battery systems.

[Summary of Invention]
The present invention provides an electrochemical cell capable of excellent power supply performance, particularly high specific energy, useful discharge rate capability and excellent cycle life. The electrochemical cell of the present invention is versatile and includes primary and secondary batteries useful for a variety of important applications, including use in portable electronic devices. The electrochemical cell of the present invention also exhibits improved safety and stability over conventional state-of-the-art primary lithium batteries and lithium ion secondary batteries. For example, the electrochemical cells of the present invention include secondary anionic electrochemical cells that use anionic charge carriers that can be accommodated by positive and negative electrodes containing an anionic host material, and these anionic charge carriers allow these systems The need for metallic lithium or dissolved lithium ions in is completely eliminated.

  [015] The present invention provides novel active electrode material strategies, electrolyte compositions and electrochemical cell designs that enable fundamentally new primary and secondary electrochemical cells. Anionic charge carrier host materials for positive and negative electrodes and high performance electrolytes are provided. Anionic charge carrier host materials enable new electrochemical cell platforms that can achieve useful performance attributes such as specific energy higher than that of conventional state-of-the-art lithium ion batteries. In one embodiment, for example, the present invention provides a combination of different anionic charge carrier host materials for the positive and negative electrodes that allow a secondary electrochemical cell that can exhibit a battery voltage of about 3.5V or greater. In addition, the combination of the positive electrode material and the negative electrode material of the present invention enables a secondary electrochemical cell having a long cycle life and excellent discharge stability during cycling. Furthermore, aqueous and non-aqueous electrolyte compositions are provided that provide synergistic performance enhancements that are important to improve device performance, stability and safety at high battery voltages. For example, the present invention provides high performance electrolytes having anion and / or cation receptors compatible with anion charge carrier active electrode host materials that provide secondary batteries capable of stable discharge rates at high battery voltages To do.

  [016] In one aspect, the present invention provides an anionic electrochemical cell that utilizes anionic charge carriers that can be accommodated by a positive electrode and a negative electrode comprising an anionic 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, a negative electrode, and an electrolyte provided between the positive electrode and the negative electrode, and the electrolyte can conduct anionic charge carriers. The positive and negative electrodes of this embodiment comprise different anionic host materials that reversibly exchange electrolytes and anionic charge carriers during charging or discharging of the electrochemical cell. In the context of this description, the term “exchange” refers to releasing or containing anionic charge carriers at the electrode by oxidation and reduction reactions during charging or discharging of the electrochemical cell. In this context, “accommodation” of anionic charge carriers includes trapping of anionic charge carriers by the host material, insertion of anionic charge carriers into the host material, intercalation of anionic charge carriers into the host material, and / or anionic charge. Includes chemical reaction with carrier host material. Housing includes alloying chemistry, surface chemistry with the host material, and / or bulk chemistry with the host material.

  [017] During discharge, an anion charge carrier is released from the positive electrode to the electrolyte by a reduction half reaction occurring at the positive electrode, and an anion charge carrier is accommodated by the negative electrode by an oxidation half reaction occurring at the negative electrode. Thus, in these embodiments, during discharge of the electrochemical cell, anionic charge carriers are released from the positive electrode, move through the electrolyte, and are accommodated by the negative electrode. This kinetic process is reversed during charging in the secondary electrochemical cell of the present invention. Therefore, during charging in these embodiments, the anion charge carriers are released to the electrolyte by the reduction half reaction that occurs at the negative electrode, and the anion charge carriers are accommodated from the electrolyte to the positive electrode by the oxidation half reaction that occurs at the positive electrode. Thus, anion charge carriers are transported through the electrolyte, and electrons are transported through an external circuit connected to the positive and negative electrodes, so that release and containment of anionic charge carriers occur simultaneously during discharge and charging of the electrochemical cell.

  [018] The selection of the composition and phase of the electrode host material, electrolyte and anionic charge carrier in this aspect of the invention is important in the present invention to access useful electrochemical cell configurations. First, the battery voltage of the electrochemical cell is determined, at least in part, by selecting the composition of the anion host material for the positive and negative electrodes and the anion charge carrier. Therefore, selecting an anion host material that provides a sufficiently low standard electrode potential at the negative electrode, and an anion host material that provides a sufficiently high standard electrode potential at the positive electrode, such that the battery voltage is useful for a given application Selecting is useful in some embodiments. Second, by selecting the composition of the anion host material for the positive and negative electrodes, the electrolyte, and the anion charge carrier, the kinetics at the electrode is established, thus determining the discharge rate capability of the electrochemical cell. Third, the use of electrode host materials, electrolytes, and anion charge carriers that do not undergo basic structural changes or degradation at the positive and negative electrodes during charge and discharge is beneficial for second electrochemical cells that exhibit superior cycling performance. It is.

[019] In one embodiment of this aspect, the present invention provides fluoride ion primary and secondary electrochemical cells having fluoride ions (F ^-1 ) as anionic charge carriers. The electrochemical cell utilizing fluoride ion charge carriers of the present invention is referred to as a fluoride ion electrochemical cell. The use of fluoride ion charge carriers in the electrochemical cell of the present invention provides many advantages. First, low atomic mass (18.998 AMU), high electron affinity of fluorine (-328 kJmol ⁻¹ ) and about 6 V (−3.03 V vs. NHE to +2.87 V vs. NHE) of fluoride ion (F ⁻ ). A redox voltage stability window results in an electrochemical cell with high voltage, high energy density and high specific capacity. Second, fluoride ions have a small atomic radius, and therefore reversible in many electrode host materials without causing significant degradation or significant structural deformation of the electrode host material during cycling in a secondary electrochemical cell. Can be involved in general insertion and / or intercalation reactions. This property results in a secondary fluoride ion electrochemical cell with a long cycle life (eg, about 500 cycles or more). Third, fluoride ions are stable against degradation at the electrode surface at useful voltage ranges (−3.03 V vs. NHE to +2.87 V vs. NHE), thereby improving the performance stability and safety of the electrochemical cell. Increases nature. Fourth, a significant number of fluoride ion host materials can be used for the positive and negative electrodes, resulting in electrochemical cells with high specific capacity and battery voltage.

[020] On the other hand, as will be apparent to those skilled in the art, the present invention includes a wide range of anionic electrochemical cell configurations having anionic charge carriers other than fluoride ions, including but not limited to the following.

Other anionic charge carriers useful in the electrochemical cells of the present invention include anionic charge carriers having the formula C _n F _{2n + 1} BF ₃ ⁻¹ _{where n} is an integer greater than ₁ . Use of anionic charge carriers other than fluoride ions is suitable hosts for positive and negative electrodes that can accommodate anionic charge carriers during discharge and charge and can provide the desired battery voltage and specific capacity It is necessary to incorporate materials. In one embodiment, the anionic charge carrier is an anion other than OH ⁻ and HSO ₄ ^— , or SO ₄ ²⁻ .

[021] In one embodiment, the electrolyte of the fluoride ion electrochemical cell of the present invention includes a solvent and a fluoride salt, and the fluoride salt is at least partially such that fluoride ions are generated in the electrolyte. Present in the electrolyte in a dissolved state. The electrolyte in the electrochemical cell of the present invention comprises a fluoride salt having the formula MF _n where M is a metal and n is an integer greater than 0. In some embodiments, for example, M is an alkali metal such as Na, K, Rb, or M is an alkaline earth metal such as Mg, Ca, Sr. In various embodiments, M is a metal other than lithium so that safety and stability are enhanced relative to conventional state-of-the-art lithium batteries and lithium ion batteries. In some embodiments, the concentration of the fluoride salt in the electrolyte is selected from the range of about 0.1M to about 2.0M.

[022] The electrolyte for the anionic electrochemical cell of the present invention including the fluoride ion electrochemical cell includes an aqueous electrolyte and a non-aqueous electrolyte. Useful electrolyte compositions for anionic electrochemical cells preferably have one or more of the following properties. First, electrolytes for some applications preferably have high ionic conductivity with respect to anionic charge carriers, for example for fluoride ions. For example, the electrolyte of part useful in the present invention, solvent, solvent mixture, and / or 0.0001Scm ^-1 or more, 0.001Scm ^-1 or higher, or 0.005Scm ^-1 or more, fluoride ion anion charge carriers Including additives that provide conductivity for anionic charge carriers. Second, an electrolyte salt, such as a fluoride salt, can be dissolved so that the electrolyte for some embodiments provides an anion charge carrier source at a useful concentration in the electrolyte. Third, the electrolyte of the present invention is preferably stable against decomposition at the electrode. For example, the electrolyte of one embodiment of the present invention comprises a solvent, an electrolyte salt, an additive, an anionic charge carrier that is stable at a high electrode voltage, such as the difference between a positive electrode voltage and a negative electrode voltage of about 4.5 V or higher. including. Fourth, the electrolyte of the present invention preferable for some applications exhibits excellent safety characteristics such as flame retardancy.

[023] In some cases, the electrolyte of the electrochemical cell of the present invention includes one or more additives. In one embodiment, the electrolyte contains an anion receptor, such as a fluoride ion anion receptor capable of coordinating fluoride ions of a fluoride salt, and / or a cation acceptor, eg, a metal ion of a fluoride salt. Includes cation receptors that can be coordinated. Useful anion receptors in the present invention include electron-withdrawing coordinates such as fluorinated boranes, fluorinated boronates, fluorinated borates, compounds based on phenylboron, compounds based on aza-etherboron, and the like. Examples include, but are not limited to, fluorinated boron fluoride based anion receptors. Useful cation receptors for the electrolyte of the electrochemical cell of the present invention include crown ethers, lariat ethers, metallacrown ethers, calixcrowns (eg, calix crowns). , Tetrathiafulvalene crowns, calixarenes, calix [4] arenequinones, tetrathiafulvalenes, bis (calixcrown) tetrathiafulvalenes, and derivatives thereof, but are not limited to these. In some embodiments, the electrolyte of the present invention includes other inorganic, organic, or gaseous additives. Additives in the electrolytes of the present invention can, for example, promote the formation of a solid electrolyte interface (SEI) or reduce the build-up of discharge products (i) conductivity of anionic charge carriers. Useful for enhancing (ii) reducing flammability, (iii) increasing electrode wettability, (iv) reducing electronic conductivity, and (v) enhancing the kinetics of anion charge carriers at the electrode is there. In one embodiment, the electrolyte includes, but is not limited to, Lewis acids or Lewis bases as described below.

(R = H or alkyl group C _n H _{2n + 1} , n = integer)

  [024] The active material for positive electrode and negative electrode of the fluoride ion electrochemical cell of the present invention includes a fluoride ion host material that can accommodate fluoride ions from the electrolyte during discharge and charge of the electrochemical cell. In this context, the inclusion of fluoride ions includes insertion of fluoride ions into the host material, intercalation of fluoride ions into the host material, and / or reaction of fluoride ions with the host material. Housing includes alloying reactions, surface reactions and / or bulk reactions with host materials. The secondary fluoride ion battery of the present invention uses a fluoride ion host material that can reversibly exchange electrolyte and fluoride ions without significant deterioration of the fluoride ion host material during cycling. preferable.

[025] In one embodiment, the negative electrode of the fluoride ion electrochemical cell of the present invention has a low standard reduction potential, preferably about -1 V or less for some applications, more preferably about- Fluoride ion host materials such as fluoride compounds that are 2 V or less are included. Useful fluoride ion host materials for negative electrodes of electrochemical cells 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, including but LaF _x and CeF _x However, it is not limited to these. Preferred fluoride host materials for the negative electrode of an electrochemical cell are those in which M is an alkaline earth metal (Mg, Ca, Ba), M is a transition metal, and M is a Group 1 (B, Al, Elemental fluoride MF _x belonging to Ga, In, Tl) or M is a rare earth element (atomic number Z between 57 and 71). The present invention also includes negative electrode fluoride ion host materials comprising one or more polymers capable of reversibly exchanging fluoride ions containing anionic ion charge carriers. Examples of such conjugated polymers are, but are not limited to, polyacetylene, polyaniline, polypyrrole, polythiophene and polyparaphenylene. Polymeric materials useful for the negative electrode in the present invention can be found in Manecke, G., incorporated herein by reference to the extent not inconsistent with the disclosure herein. and Strock, W.M. ^{, In "Encyclopedia of Polymer Science and} Engineering, 2 nd Edition, Kroschwitz, J., I., Editor.John Wiley, New York, 1986, vol.5, are further described in pp.725-755, it has been described .

  [026] In one embodiment, the positive electrode of the fluoride ion electrochemical cell of the present invention has a high standard reduction potential, preferably about 1 V or higher for some applications, more preferably about 2 V or higher for some applications. A fluoride ion host material such as a fluoride compound. In one embodiment, the positive electrode fluoride ion host material is an intercalation host material that can accommodate fluoride ions to form fluoride ion intercalation compounds. “Intercalation” refers to the formation of intercalation compounds by inserting ions into a host material by a host / guest solid-phase redox reaction that includes an electrochemical charge transfer process involving the insertion of mobile guest ions such as fluoride ions. Refers to the process to do. The main structural features of the host material are preserved after insertion of guest ions by intercalation. In some host materials, intercalation refers to a process in which guest ions are attracted to the interlayer gap (eg, gallery) of the layered host material.

  [027] Useful fluoride ion host materials for the positive electrode of the electrochemical cell of the present invention include CFx, AgFx, CuFx, NiFx, CoFx, PbFx, CeFx, MnFx, AuFx, PtFx, RhFx, VFx, OsFx, RuFx And FeFx, but are not limited to these. In one embodiment, the positive electrode fluoride ion material is a partially fluorinated carbonaceous material having the formula CFx, where x is the average atomic ratio of fluorine atoms to carbon atoms, from about 0.3 to about 1. A range of 0 is selected. Useful carbonaceous materials for the positive electrode of this embodiment are selected from the group consisting of graphite, coke, multi-wall carbon nanotubes, multi-walled carbon nanofibers, multi-walled carbon nanoparticles, carbon nanowhiskers, and carbon nanorods. The present invention also includes a cathode fluoride ion host material comprising one or more polymers capable of reversibly exchanging fluoride ions containing anionic ion charge carriers. Examples of such conjugated polymers useful for the positive electrode include, but are not limited to, polyacetylene, polyaniline, polypyrrole, polythiophene and polyparaphenylene.

[028] In one aspect, the present invention provides fluoride ion electrochemical cells that exhibit enhanced device performance relative to state-of-the-art electrochemical cells such as lithium ion batteries. The combination of some fluoride ion host materials for the positive and negative electrodes in fluoride ion electrochemical cells is particularly beneficial for accessing useful device performance. For example, using a partially fluorinated CF _x positive electrode where _x is selected over a range of about 0.3-1 and a negative electrode comprising LiC ₆ or LaF _x is about 4 V or higher, in some embodiments Is useful for accessing average operating battery voltages above about 4.5V. Other useful positive electrode / negative electrode host material combinations of the present invention that provide superior device performance include CuFx / LaFx, AgFx / LaFx, CoFx / LaFx, NiFx / LaFx, MnFx / LaFx, CuFx / AlFx, AgFx / AlFx, NiFx / AlFx, NiFx / ZnFx, AgFx / ZnFx and MnFx / ZnFx (the convention corresponding to [positive electrode host material] / [negative electrode host material] is used to indicate electrode combinations).

[029] In one embodiment, the fluoride ion electrochemical cell of the present invention has an average operating battery voltage of about 3.5V or higher, preferably an average operating battery voltage of about 4.5V or higher for some applications. . In one embodiment, the fluoride ion electrochemical cell of the present invention is from about 300Whkg ^-1 or more, preferably about 400Whkg ^-1 or more specific energy. In one embodiment, the present invention provides a fluoride ion secondary electrochemical cell having a cycle life of about 500 cycles or more.

[030] Useful solvents for the electrolytes of the present invention can at least partially dissolve electrolyte salts such as fluoride salts, which include propylene carbonate, nitromethane, toluene (tol), ethyl methyl Carbonate (EMC), propyl methyl carbonate (PMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl butyrate (MB, 20 ° C.), n-propyl acetate (PA), ethyl acetate (EA), methyl pro Pionate (MP), methyl acetate (MA), 4-methyl-1,3-dioxolane (4MeDOL) (C ₄ H ₈ O ₂ ), 2-methyltetrahydrofuran (2MeTHF) (C ₅ H ₁₀ O), 1, 2 dimethoxyethane (DME), methyl formate (MF) _{(C 2 4} O _2), dichloromethane (DCM), .gamma.-butyrolactone _{(γ-BL) (C 4} H 6 O 2), propylene carbonate _{(PC) (C 4 H 6} O 3), ethylene carbonate (EC, 40 ℃) ( One or a plurality of solvents selected from the group consisting of (C ₃ H ₄ O ₃ ) are included, but not limited thereto. Electrolytes and their components, including fully or partially fluorinated analogs of solvents, electrolyte salts and anionic charge carriers, are useful for some applications. This is because the fluorination of these materials increases the stability to decomposition at high electrode voltages and provides beneficial safety properties such as flame retardancy. In the context of this description, the fluorine analog includes (i) a fully fluorinated analog in which each hydrogen atom of the solvent, salt or anionic charge carrier molecule is replaced with a fluorine atom, and (ii) a solvent, And partially fluorinated analogs in which at least one hydrogen atom of the salt or anionic charge carrier molecule is replaced by a fluorine atom. Preferred anionic charge carriers in the electrolyte include, but are not limited to, the following anionic charge carriers.

[031] The following references describe electrolyte compositions useful in embodiments of the present invention, including fully fluorinated and partially fluorinated solvents, salts and anionic charge carriers. Yes. These documents are incorporated herein by reference in their entirety to the extent that they are not inconsistent with the present disclosure. _{(1) Li [C 2 F} 5 BF 3] as an Electrolyte Salt for 4V Class Lithium-Ion Cells, Zhi-Bin Zhou, Masayuki takeda, Takashi Fujii, Makoto Ue, Journal of Electrochemical Society, 152 (2): A351- (356) Fluorinated Superacid Systems, George A. A356, 2005; Olah, Surya G .; K. Prakash, Alain Goeppert, Actulite Chimique, 68-72 Suppl. 301-302, Oct-Nov 2006; (3) Electrochemical properties of Li [C _n F _{2n + 1} BF _3, as Electroly Salts for Lithium-ion Cells, Makito Ue, Hakoto Ue, Takatoh. Solid State Ionics, 177: 323-331, 2006; (4) Anodical Severity of Severe Extensive by AB Initial Molecular Orbital and Density mi, 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 Polyfluorinated trifluorate Anions in Acetonitrile, Leonid A., et al. Shundrin, Vadim V.D. Bardin, Hermann-Josef Fron, Z. Anorg. Allg. Chem. 630: 1253-1257, 2004

  [032] In another aspect, the present invention provides a method for making an electrochemical cell. The method includes: (i) providing a positive electrode; (ii) providing a negative electrode; and (iii) providing an electrolyte capable of conducting anion charge carriers between the positive electrode and the negative electrode. Thus, the positive and negative electrodes can reversibly exchange electrolytes and anionic charge carriers during charging or discharging of the electrochemical cell.

[033] In another aspect, the present invention provides a method for generating a current. The method includes (i) providing an electrochemical cell; and (ii) discharging the electrochemical cell, the electrochemical cell being provided between the positive electrode, the negative electrode, and the positive electrode and the negative electrode. And an electrolyte capable of conducting anionic charge carriers, wherein the positive and negative electrodes can reversibly exchange the electrolyte and anionic charge carriers during charging or discharging of the electrochemical cell. The method of this aspect of the invention can further comprise charging the electrochemical cell. In some embodiments of this aspect of the invention, the anionic charge carrier is a fluoride ion (F ⁻ ).

[034] In one aspect, the present invention provides a fluoride ion secondary electrochemical cell. The fluoride ion secondary electrochemical cell includes (i) a first fluoride ion host material, a positive electrode having a first standard electrode potential, and (ii) a second fluoride ion host material, A negative electrode 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; (iii) the positive electrode and the negative electrode An electrolyte comprising a fluoride salt and a solvent, wherein at least part of the fluoride salt is present in a dissolved state, whereby the electrolyte An electrolyte that generates fluoride ion charge carriers in an electrolyte, and the positive electrode and the negative electrode reversibly exchange the electrolyte and fluoride ion charge carriers during charging or discharging of the electrochemical cell. Door can be. In some embodiments of this aspect of the invention, the anionic charge carrier is a fluoride ion (F ⁻ ).

[Detailed Description of the Invention]
[057] Referring to the drawings, like numerals indicate like elements and the same number appearing in more than one drawing refers to the same element. In addition, the following definitions apply below.

“Standard electrode potential” (E ^o ) refers to the electrode potential when the solute concentration is 1 M, the gas pressure is 1 atm, and the temperature is 25 degrees Celsius. The standard electrode potential used in this specification Is measured against a standard hydrogen electrode.

[059] "Anionic charge carriers" refer to negatively charged ions provided in the electrolyte of an electrochemical cell that move between the positive and negative electrodes during discharge and charging of the electrochemical cell. Anionic charge carriers useful in the electrochemical cells of the present invention include, but are not limited to, fluoride ions (F ⁻ ) and the following other anions.

[060] "Fluoride ion host material" refers to a material that can accommodate fluoride ions. In this context, housing includes insertion of fluoride ions into the host material, intercalation of fluoride ions into the host material, and / or reaction of fluoride ions with the host material. Useful fluoride ion host material of the positive electrode or the negative electrode for the electrochemical cells 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, CFx , AgFx, CuFx, NiFx, CoFx, PbFx, CeFx, MnFx, AuFx, PtFx, RhFx, VFx, OsFx, RuFx and FeFx. A preferred fluoride host material for the negative electrode of an electrochemical cell is elemental fluoride MF _x , where M is an alkaline earth metal (Mg, Ca, Ba), M is a transition metal, M is the first It belongs to Group 3 (B, Al, Ga, In, Tl) or M is a rare earth element (atomic number Z between 57 and 71).

[061] "Intercalation" refers to the insertion of ions into a host material by a host / guest solid-phase redox reaction, including an electrochemical charge transfer process involving the insertion of mobile guest ions such as fluoride ions. Refers to the process of forming intercalation compounds. The main structural features of the host material are preserved after insertion of guest ions by intercalation. In some host materials, intercalation refers to a process in which guest ions are attracted to the interlayer gap (eg, gallery) of the layered host material. Examples of intercalation compounds include fluoride ion intercalation compounds in which fluoride ions are inserted into a host material such as a layered fluoride host material or a carbon host material. Useful host material to form an interlayer compound for an electrode of the present _{invention, CF x, FeFx, MnFx,} NiFx, CoFx, LiC6, including but LixSi and LixGe, but are not limited to.

  [062] The term "electrochemical cell" refers to devices and / or device components that convert chemical energy into electrical energy or electrical energy into chemical energy. An electrochemical cell has two or more electrodes (eg, a positive electrode and a negative electrode) and an electrolyte, and an electrode reaction that occurs at the electrode surface results in a charge transfer process. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries and electrolysis systems. Common batteries and / or battery structures are known in the art. For example, US Pat. Nos. 6,489,055, 4,052,539, 6,306,540, Seel and Dahn J., et al. Electrochem. Soc. 147 (3) 892-898 (2000).

[063] 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 usually expressed in units of ampere-hours. The term “specific capacity” refers to the output capacity per unit weight of an electrochemical cell such as a battery. Specific capacity is usually expressed in units of ampere-hour kg- ¹ .

  [064] The term "discharge rate" refers to the current that discharges an electrochemical cell. The discharge current can be expressed in units of ampere-hours. Alternatively, the discharge current can be normalized to the rated capacity of the electrochemical cell, where C is the capacity of the electrochemical cell, X is a variable, and t is 1 hour as used herein. It can be expressed by C / (Xt) which is an equal specified unit time.

  [065] "Current density" refers to the current that flows per unit electrode area. In some embodiments, the positive electrode, the negative electrode, or both are nanostructured materials. The term “nanostructure” refers to a material and / or structure having a plurality of discontinuous structural domains having at least one physical dimension (eg, height, width, length, cross-sectional dimension) less than about 1 micron. . In this context, a structural domain refers to a feature, component or part of a material or structure that has a characteristic composition, form and / or phase. Nanostructured materials useful as positive electrode active materials include nanostructured composite particles having multiple fluorinated carbon domains and non-fluorinated carbon domains. In some embodiments, the nanostructured materials of the present invention comprise a plurality of structural domains in which different compositions, forms and / or phases are mixed on a very fine scale (eg, less than at least tens of nanometers). including. Nanostructured materials useful as negative electrode active materials include nanostructured composite particles having a plurality of fluorinated metal domains and non-fluorinated metal domains. Preferred nanostructured fluorinated metal host materials for the negative electrode of electrochemical cells include alkaline earth metals (Mg, Ca, Ba), transition metals, Group 1 elements (B, Al, Ga, In, Tl) Including, but not limited to, the rare earth metals (atomic number Z between 57 and 71). In some embodiments, the nanostructured material for the negative electrode of the present invention comprises a plurality of different compositions, forms, and / or phases mixed on a very fine scale (eg, less than at least tens of nanometers). Including structural domains.

  [066] "Active material" refers to a material in an electrode that participates in an electrochemical reaction that stores and / or distributes energy in an electrochemical cell.

[067] As used herein, the expression "partially fluorinated carbonaceous material" refers to a multiphase carbonaceous material having a non-fluorinated carbonaceous component. As used herein, “non-fluorinated carbonaceous component” includes non-fluorine such as graphite, coke, multi-wall carbon nanotube, carbon nanofiber, carbon nanowhisker, multi-layer carbon nanoparticle, carbon nanowhisker and carbon nanorod. Carbonized compositions and / or phases are included, and slightly fluorinated carbon compositions and / or phases are also included. Slightly fluorinated in this context refers to carbon that is weakly bound to fluorine, as opposed to compositions in which carbon is covalently bonded to fluorine as seen in the CF ₁ and C ₂ F phases. The multi-phase partially fluorinated carbonaceous material includes one or more non-fluorinated carbonaceous phases and one or more fluorinated phases (eg, poly (carbon monofluoride (CF ₁ ), poly (one fluorocarbon)). A partially fluorinated carbonaceous material includes nanostructured materials having fluorinated and non-fluorinated domains.Partially fluorinated carbonaceous material Includes carbonaceous materials that have been exposed to a fluorine source under conditions that result in incomplete or partial fluorination of the carbonaceous starting material, partially fluorinated carbonaceous materials useful in the present invention, and partial fluorine Related methods for making carbonaceous materials are described in U.S. Patent Application No. 1253360, filed on Oct. 18, 2005, Jun. 6, 2006 and Nov. 16, 2006, respectively. No. 422564 and No. 1560570, which are incorporated herein by reference in their entirety to the extent they do not conflict with the present description. Various carbonaceous materials, including graphite, coke, and carbonaceous nanomaterials such as multi-wall carbon nanotubes, carbon nanofibers, multi-layer carbon nanoparticles, carbon nanowhiskers, and carbon nanorods, are useful for the fluorinated active material. is there.

  [068] The carbon nanomaterials used herein have at least one dimension between 1 nanometer and 1 micron. In one embodiment, at least one dimension of the nanomaterial is between 2 nm and 1000 nm. For carbon nanotubes, nanofibers, nanowhiskers or nanorods, the diameter of the tube, fiber, nanowhisker or nanorod is within this size range. For carbon nanoparticles, the diameter of the nanoparticles is within this size range. Carbon nanomaterials useful for use with the present invention include materials with a total impurity level of less than 10% and carbon materials doped with elements such as boron, nitrogen, silicon, tin, phosphorus.

  [069] As used herein, the term "nanotube" refers to a tube-shaped discontinuous fibril typically characterized by a diameter of about 1 nm to about 20 nm. In addition, nanotubes typically exhibit a length greater than about 10 times the diameter, preferably greater than about 100 times the diameter. The term “multi-wall”, used to describe nanotubes, refers to nanotubes having a layered structure, and thus nanotubes are composed of an outer region of a plurality of consecutive layers of ordered atoms and a separate inner core. Region or lumen. These layers are arranged substantially concentrically about the longitudinal axis of the fibrils. In carbon nanotubes, these layers are graphene layers. Carbon nanotubes are synthesized in different forms as single-walled, double-walled and multi-walled carbon nanotubes, denoted as SWCNT, DWCNT and MWCNT, respectively. The diameter dimension ranges from about 2 nm for SWCNT and DWCNT to about 20 nm for NWCNT. In one embodiment, the MWNT used in the present invention has a diameter greater than 5 nm, greater than 10 nm, 10-20 nm, or about 20 nm.

  [070] Electrode refers to an electrical conductor that exchanges ions and electrons with the electrolyte and outer circuit. “Positive electrode” and “cathode” are used interchangeably in this description and refer to an electrode having a higher electrode potential (ie, higher than a negative electrode) in an electrochemical cell. “Negative electrode” and “anode” are used interchangeably in this description and refer to an electrode having a lower electrode potential (ie, lower than a positive electrode) in an electrochemical cell. Cathodic reduction refers to the acquisition of one or more electrons of a chemical species, and anodic oxidation refers to the emission of one or more electrons of a chemical species. The positive electrode and negative electrode of the electrochemical cell may further include a conductive diluent such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, metal powder, and / or a polymer binder. Can further comprise a binder. Useful binders for the positive electrode in some embodiments include fluoropolymers such as polyvinylidene fluoride (PVDF). The positive and negative electrodes of the present invention can be provided in various useful configurations and form factors known in the electrochemical and battery science arts, including thin electrode designs such as thin film electrode configurations. As disclosed herein, and as known in the art, including, for example, the disclosures in U.S. Pat. Nos. 4,052,539, 6,306,540, 6,852,446, An electrode is produced. In some embodiments, a viscosity typically deposits a slurry of electrode material, conductive inert material, binder and liquid carrier onto the electrode current collector and then evaporates the carrier to make electrical contact with the current collector. The electrode is made by leaving a coherent mass.

  [071] "Electrode potential" refers to the voltage that is usually measured relative to a reference electrode because chemical species in different oxidation (valence) states exist in or in contact with the electrode.

  [073] "Cation" refers to a positively charged ion, and "anion" refers to a negatively charged ion.

  [074] The present invention provides primary and secondary anionic electrochemical cells utilizing fluoride ion charge carriers and an electrode active material comprising a fluoride ion host material, thereby providing a conventional state-of-the-art lithium battery and An alternative to lithium ion batteries is provided. Advantages of the electrochemical cell of the present invention over lithium based systems include access to higher specific capacity, greater average operating voltage and improved safety.

[075] The anionic electrochemical cells of the present invention, including fluoride ion electrochemical cells, are designed for simultaneous oxidation and reduction reactions involving the inclusion and release of anionic charge carriers by positive and negative electrodes containing different anionic charge carrier host materials. Operates based on the principle. In these systems, anionic charge carriers go back and forth between the positive and negative electrodes during discharge and charging of the anionic electrochemical cell. The following electrode half reactions, battery reactions and electrolyte reactions are provided to describe and explain the basic principles on which the anionic electrochemical cell of the present invention operates.
1. Electrode reaction A ^- is an anion charge carrier, the PA _n positive electrode anion host material, the NA _m is the negative electrode anion host material.
In the primary battery, only the discharge reaction occurs.
In-positive, A ^- is released.

· In the negative electrode, A ^- is closed.

Therefore, the overall battery reaction is as follows.

In rechargeable batteries, equations (1) and (2) are reversed during charging, so the overall battery reaction is as follows.

2. Electrolyte Formation Reaction In the present invention, several dissolved A ^- anion sources are included in the electrolyte between the positive electrode and the negative electrode.
(I) soluble compounds such as salts _C q _{A p;} wherein, C is a monovalent, divalent, trivalent cation or a multivalent cation ^{(C n +, 1 ≦ n} ≦ 6) is. For example, when C is a monovalent cation, the salt dissolution equilibrium is described as follows:

Here, when the cation receptor R and / or the anion receptor R ′ is used, the solubility can be increased.

(Ii) A ^- Soluble releasing anion XA _p ^-;

Optionally, cation receptor R and / or anion receptor R ′ can be provided in the electrolyte to increase the solubility of A ⁻ .

[076] As examples of these concepts, the half reaction, battery reaction and solution reaction during discharge of the fluoride ion electrochemical cell of the present invention including LiC ₆ negative electrode, CFx positive electrode and F-conductive electrolyte are provided below. To do.
Discharge reaction :
Negative electrode: LiC ₆ + F ⁻ → 6C + LiF + e ⁻ (the negative electrode accommodates F ⁻ during discharge)
Positive electrode: CFx + xe ⁻ → C + xF− (the positive electrode releases F ⁻ during discharge)
Battery reaction: xLiC ₆ + CFx → (1 + 6x) C + xLiF (F ⁻ moves between the positive electrode and the negative electrode during discharge)
Electrolyte: Optionally, F by two reactions ^- can increase dissolution of.
LiF + yLA → Li ⁺ + (LA) _y F ⁻ , or LiF + zLB → Li (LB) _z ⁺ + F ⁻
(LA = PF ₅ , BF ₃ , Lewis acid such as anion receptor, LB = PF ₆ ⁻ , BF ₄ ⁻ , cation receptor, ie Lewis base such as crown ether).

[077] To further illustrate and describe the anionic electrochemical cell of the present invention, the following discussion compares the system of the present invention with conventional lithium ion battery technology. A typical lithium ion battery (LIB) has three basic components: (1) a carbon-based negative electrode (anode), (2) a lithium cation (Li +) conductive electrolyte, and (3) a transition metal oxide positive electrode ( Cathode) (eg, LiCoO ₂ ). The lithium cation (Li +) is a charge carrier in these systems, and these electrochemical cells operate by simultaneous insertion and de-insertion reactions at the positive and negative electrodes in response to electron transfer between the electrodes. . When the lithium ion battery is charged and discharged, Li + ions reciprocate between the negative electrode and the positive electrode. The reversible dual intercalation mechanism of these batteries results in the term “rocking chair” or “shuttle cock” battery.

  [078] FIG. 1A provides a schematic diagram illustrating a lithium ion battery during charging. Upon charging, lithium ions are released from the positive electrode (ie, represented as the cathode in FIG. 1A), travel through the electrolyte, and are accommodated by the negative electrode (ie, represented as the anode in FIG. 1A). As shown in FIG. 1A, the direction of the flow of electrons during charging is from the positive electrode to the negative electrode. FIG. 1B provides a schematic diagram illustrating a lithium ion battery during discharge. Upon discharge, lithium ions are released from the negative electrode (ie, represented as the anode in FIG. 1B), travel through the electrolyte, and are accommodated by the positive electrode (ie, represented as the cathode in FIG. 1B). As shown in FIG. 1B, the direction of electron flow during charging is from the negative electrode to the positive electrode.

[079] FIG. 2 provides a schematic diagram showing the average working potential of different negative and positive electrode materials and the battery voltage for a conventional lithium ion battery. The average operating voltage of an electrochemical cell arises in part from the difference in chemical potential of Li ⁺ ions at the negative and positive electrodes. In the example shown in FIG. 2, the difference in electrode potential between Li _x C ₆ and Li _x CoO ₂ is about 4V. The LIB battery expansion reaction for this example is as follows.

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

[080] In the electrochemical cell of the present invention, the charge carrier is a negatively charged anion. For example, in a fluoride ion electrochemical cell, the anion charge carrier is fluoride ion (F ⁻¹ ). Similar to lithium ion batteries, the fluoride ion electrochemical cell of the present invention operates by fluoride ion insertion and desorption reactions that occur simultaneously at the positive and negative electrodes in response to electron transfer between the electrodes. During charging and discharging of the fluoride ion electrochemical cell, F ⁻ ions reciprocate between the negative electrode and the positive electrode.

  [081] FIG. 3A provides a schematic diagram illustrating a fluoride ion electrochemical cell during discharge. Upon discharge, fluoride anions are released from the positive electrode (ie, represented as the cathode in FIG. 3A), travel through the electrolyte, and are accommodated by the negative electrode (ie, represented as the anode in FIG. 3A). . As shown in FIG. 3A, the direction of electron flow during discharge is from the negative electrode to the positive electrode. Upon charging of the fluoride ion electrochemical cell, fluoride anions are released from the negative electrode, move through the electrolyte, and are accommodated by the positive electrode. The direction of the flow of electrons during charging is from the positive electrode to the negative electrode. Release and containment of fluoride ions during discharge and charge is caused by oxidation and reduction reactions occurring at the electrodes.

[082] Similar to the above description regarding the lithium ion battery, the open circuit voltage in the fluoride ion electrochemical cell is generated, at least in part, due to the difference in chemical potential of fluoride ions between the negative electrode and the positive electrode. The positive electrode and the negative electrode are a high voltage fluoride and a low voltage fluoride, respectively, and can exchange the electrolyte and F ₋ reversibly. For example, the positive electrode and the negative electrode are as follows.
The positive _{electrode: CF x, AgF 2-x} , CuF 3-x, NiF 3-x, ···
Negative electrode: LaF3 _-x , CaF2 _-x , AlF3 _-x , EuF3 _-x , ...

[083] FIG. 3B shows an embodiment example corresponding to a LaF _3-x negative electrode, a CF _x positive electrode, and an electrolyte containing MF, where M is a metal such as K or Rb, provided in the organic electrolyte solution. 1 provides a schematic diagram showing the mean working potential for For this example, the relevant parameters, half reactions, and battery reactions are summarized below.
Negative electrode : LaF ₃
Positive electrode : CF _y
Electrolyte : MF in organic electrolyte (M = K, Rb,...)
Electrode reaction :
Negative electrode:

Positive electrode:

Battery reaction :

[084] As shown in FIG. 3B, the difference in electrode potential for this example is about 4.5V. The theoretical battery voltage takes into account the La ³⁺ / La and CF _x / F ⁻ redox pairs, and the open circuit voltage OCV at the end of charging is expected to be about 4.5V. This open circuit voltage OCV is greater than the open circuit voltage of a conventional lithium ion battery (see calculation above). The theoretical energy density for this example fluoride ion battery (FIB) system can be calculated as follows.
FIB energy density:
When x = 1 and y = 0 by battery reaction (3);

The theoretical energy density is

This calculation shows that the theoretical energy density ratio for the above-described fluoride ion electrochemical cell example and lithium ion battery example is equal to 3: 7.

[085] Table 1 shows a comparison of the performance attributes and compositions of the lithium ion batteries and fluoride ion electrochemical cells described above. Advantages of the fluoride ion battery (FIB) of the present invention include (i) improved safety of the fluoride ion electrochemical cell, (ii) higher operating voltage of the fluoride ion electrochemical cell, (iii) fluoride Higher energy density in ion electrochemical cells, and (iv) lower cost of fluoride ion electrochemical cells.

[086] fluoride ion battery (FIBs), the anode and cathode reactions fluoride anions F ^- is a pure anionic cell with the housing and release. FIBs may be primary batteries or rechargeable batteries depending on the reversibility of the electrode reaction. However, both primary FIBs and rechargeable FIBs require an F ^- anion conducting electrolyte. Fluoride ion batteries can be further classified into two classes.

[087] In the first class, both the positive electrode and the negative electrode contain fluoride anions. A fluoride ion electrochemical cell with a LaF ₃ anode and a CF _x cathode is an example of this first class. The electrode half reaction and battery reaction for this (LaF ₃ / CF _x ) system are as follows.
LaF ₃ anode:
LaF ₃ + 3ye ⁻ → LaF _{3 (1−y)} + 3yF ⁻ (charge)
CF _x cathode:
CF _x + xe ⁻ → C + xF ⁻ (discharge)
Battery reaction:
xLaF ₃ + 3yC → xLaF _{3 (1-y)} + 3yCF _x (charge)
xLaF _{3 (1-y)} + 3yCF _x → xLaF ₃ + 3yC
Other examples of this first class of fluoride ion electrochemical cells include (anode / cathode) pairs: (LaF ₃ / AgF _x ), (LaF ₃ / NiF _x ), (EuF ₃ / CF _x ), (EuF ₃ / CuF _x ) is included, but is not limited thereto.

[088] In the second class, only one electrode contains fluoride anions. A fluoride ion electrochemical cell with a LiC ₆ anode and a CF _x cathode is an example of this second class. The electrode half reaction and battery reaction for this (LiC ₆ / CF _x ) system are as follows.
LiC ₆ anode:
LiC ₆ + F ⁻ → 6C + LiF + e ⁻ (discharge)
CF _x cathode:
CF _x + xe ⁻ → C + xF ⁻ (discharge)
Battery reaction:
xLiC ₆ + CF _x → (6x + 1) C + xLiF (discharge)
(6x + 1) C + xLiF → xLiC ₆ + CF _x (charging)
Other examples of this first class of fluoride ion electrochemical cell include (anode / cathode) pairs: (LiC ₆ / AgF _x ), (LiC ₆ / NiF _x ), (Li _x Si / CF _x ) And (Li _x Si / CuF _x ).

[089] Aspects of the invention are further described and illustrated in the following examples.
Example 1: Fluoride ion secondary electrochemical cell with Li / CFx half cell configuration a. Introduction

[090] In order to demonstrate the advantages of the fluoride ion electrochemical cell of the present invention, a battery comprising a CF _x positive electrode and a metallic lithium negative electrode was constructed and evaluated for electrochemical performance. The results presented here demonstrate that fluoride ion electrochemical cells exhibit useful chargeable capacity under reasonable charge-discharge rates at room temperature.
1. b. Experiment

[091] Two types of fluorocarbon CF _x ; 1) stoichiometric (commercially available) CF ₁ based on coke, and 2) partially fluorinated CF _x based on graphite and multi-wall carbon nanotubes (MWNT) (x < 1) was synthesized and used as the positive electrode of the lithium battery in this example. Fluorocarbon is obtained by high temperature fluorination of coke graphite or MWNT carbon powder according to the following reaction.
C (s) + x / 2F ₂ (g) → CF _x (s) (s = solid and g = gas)
Called CF _x, several fully fluorinated carbon and partially fluorinated carbon, was investigated in this example for use as a positive electrode active material.
(1) Commercial CFx (where x = 1.0): This partially fluorinated carbonaceous material was obtained from Lodestar, New York, USA. This material corresponds to the PC10 product of those partially fluorinated carbonaceous materials that are fully fluorinated coke materials. This partially fluorinated carbonaceous material is referred to interchangeably in the drawings and throughout the examples as “commercially available”, “commercially available CFx” and “CFx (x = 1)”.
(2) Partially fluorinated carbon synthesized by fluorination of synthetic graphite (CFx where x = 0.530, 0.674): This partially fluorinated material is a synthesis manufactured by Timcal, Switzerland Synthesized by partial fluorination of graphite. These partially fluorinated graphite materials are referred to as “KS15” in the drawings and throughout the examples. The composition of these materials is further characterized by reference to the atomic ratio of fluorine to carbon (ie variable x in the formula CFx).
(3) Partially fluorinated carbon (CFx where x = 0.21, 0.59, 0.76, 0.82) synthesized by fluorination of multiwall carbon nanotubes (MWNT): this partial fluorination The material was synthesized by partial fluorination of MWNTS obtained from MER, Tucson, Arizona, USA. This partially fluorinated material is referred to as “carbon nanofiber”, “MWNT” and “multiwall carbon nanotube” in the drawings and throughout the examples. The composition of these partially fluorinated carbonaceous materials is further characterized by reference to the atomic ratio of fluorine to carbon (ie, variable x in the formula CFx).

[092] The positive electrode was constructed by adding acetylene black graphite (ABG) and PVDF as a binder to the selected CF _x material, the percentages being 75 wt%, 10 wt% and 15 wt%, respectively. These three materials were combined in an acetone solution with dibutyl phthalate DBP (20 wt%). Next, this solution was evaporated, and finally a thin film of a CF _x positive electrode was obtained (thickness: 100 to 120 μm). The membrane was cut to diameter (15.2 mm), washed in methanol and dried at 80 ° C. in vacuo overnight. The electrode weight is 10-20 mg. Coin-shaped Li / CF _x test battery structure: Li / PC-DME-LiBF ₄ / CF _x (reference example) 2016 coin batteries (separator: Sanyo Celgard, diameter (19 mm), thickness (25 μm), Strong, low electrical resistivity, high porosity (55%))
1. c. Experimental result

[093] FIG. 4 provides the crystal structure of fluorocarbon. FIG. 5 provides X-ray diffraction patterns (CuK _α- rays) for various positive electrode materials to be evaluated, including commercially available CF ₁ and various partially fluorinated carbonaceous materials. Various partially fluorinated carbon nanofiber samples (ie CFx with MWNTs, x = 0.210, 0.590, 0.760 and 0.820), various partially fluorinated KS15 graphite samples (ie x = 0) The diffraction patterns for CFx) of .53 and 0.647) and the commercially available CF ₁ sample (ie, CFx with x = 1) are shown in FIG.

[094] Various fluorinated carbon active materials were also characterized by electrochemical methods. In these experiments, circulating chronopotentiometry (constant current) is used to track battery discharge and charge. The applied current is calculated from the theoretical capacity. Therefore, the current I can be determined for different fixed C / n ratios (C / 10 to 1C).

m _CFx = mass of active material (g), Q _th = theoretical capacity (mAh / g)
Note: Q _th is expressed in mAh / g of CF _x during the first discharge and in mAh / g of C during the cycle.

[095] In these measurements, the first discharge and the subsequent cycle reaction were as follows.
First discharge :
CF _x + Li ⁺ + xe ⁻ → C + xLiF (3.2 V to 1.5 V vs. Li)
Cycle reaction :

(1.5 V to maximum 4.8 V vs. Li) (A ⁻ = anion = F ⁻ )

[096] FIGS. 6-12 provide initial discharge curves for a plurality of positive electrode carbonaceous active materials. FIG. 6 provides the discharge profile for a commercial CF ₁ positive electrode at room temperature for various discharge rates ranging from C / 20 to C. FIG. 7 provides the discharge profile for the CF _{0.530 KS15} positive electrode at room temperature for various discharge rates ranging from C / 20 to C. FIG. 8 provides the discharge profile for the CF _{0.647 KS15} positive electrode at room temperature for various discharge rates ranging from C / 20 to 6C. FIG. 9 provides the discharge profile for the CF _0.21 carbon nanofiber cathode at room temperature for various discharge rates ranging from C / 20 to 6C. FIG. 10 provides the discharge profile for the CF _0.59 carbon nanofiber cathode at room temperature for various discharge rates ranging from C / 20 to 6C. FIG. 11 provides discharge profiles for CF _0.76 carbon nanofiber cathodes at room temperature for various discharge rates ranging from C / 20 to 6C. FIG. 12 provides discharge profiles for CF _0.82 carbon nanofiber cathodes at room temperature for various discharge rates ranging from C / 20 to 4C. These observed discharge profiles are consistent with the following first discharge cell reaction.
CF _x + Li ⁺ + xe ⁻ → C + xLiF (3.2 V-1.5 V vs. Li)

[097] FIGS. 13-15 provide plots showing cycle tests for several positive electrode carbonaceous active materials. FIG. 13 provides the charge-discharge profile for the CF _0.82 multi-wall nanotube positive electrode in the voltage range 1.5V to 4.6V. The voltage is plotted on the Y axis (left side), the current is plotted on the Y axis (right side), and the time is plotted on the X axis. FIG. 14 provides the charge-discharge profile for the CF _0.82 multi-wall nanotube positive electrode in the voltage range 1.5V to 4.8V. The voltage is plotted on the Y axis (left side), the current is plotted on the Y axis (right side), and the time is plotted on the X axis. 15, the charging of the CF ₁ positive in the voltage range 1.5V～4.8V - to provide a discharge profile. The voltage is plotted on the Y axis (left side), the current is plotted on the Y axis (right side), and the time is plotted on the X axis. These figures show that the positive electrode materials tested, in particular CF _x , x = 0.82, MWNT (see FIGS. 13 and 14) are capable of circulating a stable cycle capacity. FIG. 16 provides a plot of voltage (V) versus time (hours) for a Li / CF _x half-cell configuration with CF _x , x = 0.82, MWNT positive electrode at 4.6V and 4.8V. A 0.25% increase in discharge capacity is observed corresponding to an increase in charge voltage from 4.6V to 4.8V. FIG. 17 provides a plot of voltage (V) versus relative capacity (%) for a Li / CF _x half-cell configuration with a CF _{0.647 KS15} positive electrode at voltages ranging from _{4.8V to 5.4V} . As shown in FIG. 17, the capacity of the CF _{0.647 KS15} positive electrode increased as the charge cutoff voltage increased over the range of 4.8V to 5.4V. FIGS. 16 and 17 show a measurable increase in discharge capacity resulting from an increase in charge voltage for the tested CFx materials. The observed charge-discharge profiles shown in FIGS.

Consistent with the cycle cell reaction of (1.5 V up to 4.8 V vs. Li) (A ⁻ = anion = F ⁻ ), demonstrating that Li ⁺ is not involved in the cycle reaction.

FIG. 18 shows commercially available CF ₁ , partially fluorinated KS15 graphite (CFx, x = 0.53 & 0.647) and partially fluorinated MWNT (CFx, x = 0.21, 0.59, 0.76 and 2 provides a cycle capacity curve of discharge capacity (mAh / g-C) versus number of cycles for various positive electrode materials evaluated, including 0.82). The charging voltage for these measurements excludes the top plot (dotted line) corresponding to a charging voltage of 4.8 V and the positive electrode containing the partially fluorinated MWNT where the active material is CFx, x = 0.82. 4.6V. Similar to the charge-discharge profiles shown in FIGS. 16 and 17, increasing the charge voltage from 4.6V to 4.8V results in a significant increase in discharge capacity for partially fluorinated MWNTs with CFx, x = 0.82. Observed.

[099] As shown in FIG. 18, the battery configuration having a commercially available CF ₁ positive electrode active material is most likely to cause significant degradation of CF ₁ structural integrity during the initial discharge. Does not show a very good cycle. The porosity of this positive electrode active material is likely to have contributed to the deterioration of the positive electrode active material that may be caused by delamination that begins with the reaction between fluoride ions and lithium ions. In contrast, the investigated partially fluorinated carbonaceous materials (eg, graphite, MWNT) exhibit very good cycling performance. This is likely due to the lower amount of fluorine and lower porosity of these materials compared to commercially available CF _x , x = 1. It is important to note that partially fluorinated MWNTs provide the best cycle performance because their mechanical integrity is likely to be superior to graphite and commercially available CF ₁ is there.

[0100] The data shown in FIG. 18 shows that a rechargeable capacity of 120 mAh / g-C is obtained in a Li / CF _x half-cell structure having an active material containing partially fluorinated MWNT where the positive electrode is CFx, x = 0.82. It has been demonstrated and has been charged at a 2C rate up to 4.8V. For comparison, FIG. 20 provides a plot of discharge rate capability for the LiMn ₂ O ₄ positive electrode. These measurements show that the partially fluorinated CF _x material made with multiwall carbon nanotubes has better performance than commercially available LiMn ₂ O ₄ as the positive electrode in lithium rechargeable batteries.

[0101] FIG. 19 provides a plot of discharge cycle versus cycle number for a CF _0.82 multi-wall nanotube positive electrode at a voltage equal to 4.6V to 4.8V. In these plots, the discharge capacity (y-axis, mAh / g-C) is a plot against the number of cycles in arbitrary units. FIG. 19 shows that stable discharge characteristics are observed for this positive electrode active material for at least about 50 cycles.

  [0102] In order to confirm that fluoride ions were involved in oxidation and reduction reactions at the electrode, X-ray diffraction patterns of the positive electrode were obtained under different experimental conditions. FIG. 21A provides a plot of discharge voltage versus time showing two time points (1) and (2) from which an X-ray diffraction pattern was taken. An X-ray diffraction pattern was also obtained for an unused positive electrode. A thin graphite electrode was used (3-4 mg at a thickness of 50 microns). FIG. 21B shows X-ray diffraction patterns acquired at the two time points (1) and (2) shown in FIG. 21A. FIG. 21C shows the X-ray diffraction patterns acquired at two time points (1) and (2) shown in FIG.

[0103] The diffraction patterns of FIGS. 21B and 21C corresponding to a charge up to 5.2V and a subsequent discharge up to 3.2V show the step formation of interlayer fluoride ions (mixture of steps 2 and 3). . In particular, the appearance of (002) -2, (003) -3 and (004) -3 peaks indicates the presence of interlayer fluoride anions during charge and discharge. As shown by the comparison of the diffraction patterns corresponding to the unused positive electrode, the 5.2V positive electrode and the 3.2V positive electrode, the graphite phase disappears completely when charged to 5.2V, up to 3.2V. Reappears when discharged. The graphite peak of C (002) present in the diffraction pattern corresponding to 3.2V indicates the presence of graphite during the de-intercalation of fluoride ions. Furthermore, the sharp peak width of the C (002) graphite peak in the 3.2 V diffraction pattern indicates that the graphite maintains its structural integrity during charge and discharge. This result demonstrates that the fluoride ion intercalation and deintercalation process is reversible and there is no phase change from crystalline graphite to amorphous carbon phase. These results are consistent with the following cycle battery reaction:

(1.5 V to maximum 4.8 V vs. Li) (A ⁻ = anion = F ⁻ ),
Provides further evidence that Li ⁺ is not involved in the cycle reaction.

[0104] In order to further characterize the composition of the partially fluorinated graphite active material for the positive electrode, an electron energy loss spectrum (EELS) was obtained for conditions corresponding to charging of the electrochemical cell up to 5.2V. EELS is a useful technique for characterizing the elemental composition of materials because it is very sensitive to the presence of elements in a sample and can identify elements in a material very accurately. FIG. 22 provides the EELS spectrum of the positive electrode active material charged to 5.2V. Although only two peaks are shown in FIG. 22, both of these peaks can be assigned to the presence of fluorine in the positive electrode active material. There are no peaks corresponding to other non-carbon elements such as B and P. This observation provides evidence that other anions in the electrolyte such as PF ₆ ⁻ and BF ₄ ⁻ were not inserted.
1. d. Conclusion

[0105] The partially fluorinated carbon material, CF _x, is an excellent example of a positive electrode material for fluoride anion rechargeable batteries. They exhibit stable cycle life, high capacity, high discharge voltage and high rate capability. X-ray diffraction with electron energy loss spectroscopy indicates that charge carrier fluoride anions are reversibly inserted into the carbon matrix and whether the latter is composed of graphite, coke or multi-wall carbon nanotubes. Staging occurs that draws similarity of fluoride anion intercalation to lithium cation intercalation to Li _x C ₆ negative electrode. The fluoride anion storage capacity increases by about 150% between 4.5V and 5.5V with charge cut-off voltage.
Example 2: Anion and cation receptors for fluoride ion electrochemical cells

  [0106] This example provides an overview of anion and cation receptors useful in the present invention. Specific examples of a plurality of fluoride ion receptors that can increase the solubility of the fluoride salt and that can increase the ionic conductivity of the electrolyte in the electrochemical cell of the present invention are shown below.

[0107] In one embodiment, the electrolyte of the present invention includes an anion receptor having the following chemical structure AR1.

Wherein R ₁ , R ₂ and R ₃ are independently an alkyl group optionally substituted with one or more halogens including F, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether , An aromatic group, an ether group, a thioether group, a heterocyclic group, an aryl group or a heteroaryl group.

[0108] In one embodiment, the electrolyte of the present invention comprises a borate-based anion acceptor compound having the following chemical structure AR2.

Wherein R ₄ , R ₅ and R ₆ are alkyl groups, aromatics optionally substituted with one or more halogens including F, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether Selected from the group consisting of a group, a heterocyclic group, an aryl group or a heteroaryl group. In one embodiment, R ₄ , R ₅ and R ₆ are the same. In one embodiment, R ₄ , R ₅ and R ₆ are each a moiety having F.

[0109] In one embodiment, the electrolyte of the present invention comprises an anion acceptor compound based on phenylboron having the following chemical structure AR3.

Wherein R ₇ and R ₈ are alkyl, aromatic, optionally substituted with one or more halogens including F, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether, It is selected from the group consisting of a heterocyclic group, an aryl group or a heteroaryl group. In one embodiment, R ₇ and R ₈ are the same. In one embodiment, R ₇ and R ₈ are each a moiety having F. In one embodiment, R ₇ and R ₈ are optionally substituted together, including a substituent that is F and a substituent that is itself a moiety having F, as shown by Formula AR4 below. Selected from aromatics including phenyl.

Wherein X _A and X _B are one or more hydrogens independently selected from the group consisting of halogens including F, alkyl, alkoxide, thiol, thioalkoxide, ether or thioether, or a non-hydrogen ring Indicates a substituent. In one embodiment, at least one of these substituents is a moiety having F.

[0110] In one embodiment, the electrolyte of the present invention comprises a tris (hexafluoroisopropyl) borate (THIB; MW = 511.9AMU) anion receptor having the following chemical structure AR5:

Or a tris (2,2,2-trifluoroethyl) borate (TTFEB; MW = 307.9 AMU) anion receptor having the following chemical structure AR6:

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

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

[0111] Useful anionic receptors in the electrolyte of the present _{invention, (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, [ Anion receptors having a formula selected from the group consisting of (CF ₃ ) ₂ C ₆ H ₃ O] ₃ B and (C ₆ F ₅ ) ₃ B are included, but are not limited to these.

  [0112] Useful cation acceptors in the present invention include crown ethers, lariat ethers, metallacrown ethers, calixcrowns (eg, calixcrowns), tetrathiafulvalene. Examples include, but are not limited to, crowns, calixarenes, calix [4] arenequinones, tetrathiafulvalenes, bis (calixcrown) tetrathiafulvalenes, and derivatives thereof.

  [0113] The following documents describe anions and / or cation receptors useful in embodiments of the present invention, which are incorporated herein by reference to the extent they do not conflict with the present disclosure. Is done. (1) Evidence for Cryptand-like Behavior in Bibliographic Lariat Ether (BiBLE) Complexes Obtained from X-ray Crystallography and Solvent Tim. Amold, Luis ecgogoyen, Frank R. et al. Fronczek, Richard D. Grandour, Vicent J. et al. Gatto, Banita D.C. White, George W. Gokel, J. et al. Am. Chem. Soc. 109: 3716-3721, 1987; (2) Bis (calixcrown) tetrathiafulvalene Receptors. Maria-Jesus Blesa, Bang-Tun Zhao, Magali Allain, Frank Le Delf, Marc Salle, Chem. Eur. J. et al. 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) Tetrathiafulvallene Crowns: Redox Switchable Ligands, Frank Le Delf, Mirau Mazari, Nicolas Mercier, Eri c Levillain, Gaelle Trippe, Amadee Rio, Pascal Richeme, Jan Becher, Javier Garin, Jesus Orduna, Nuria Gallego-Planas, Alain Gorges, Alc. Eur. J. et al. 7, 2: 447-455, 2001; (5) Electrochemical Behavior of Calix, [4] arenediquinones and Their Cun, SungKunSung, SungKongSung, Journal of Electroanalytical Chemistry, 396: 431-439, 1995; (6) Experimental Evidence for Alkaline Metal Cation-π Interactions, George W. Gokel, Stephen L. De Wall, Eric S. et al. Meadows, Eur. J. et al. Chem, 2967-2978, 2000; (7) π-Electron Properties of Large Condensed Polymeric Hydrocarbons, S .; E. Stein, R.M. L. Brown, J. et al. Am. Chem. Soc. 109: 3721-3729, 1987; (8) Self-Assembled Organometallic [12] Metallacerown-3 Complexes, Holger Piotroski, Gerhard Hilte, Axel Schulz, Peter MayrPetr. Eur. J. et al. , 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; Abidi, L.M. Baklouti, J. et al. Harrowfield, A.M. Sobolev; Vicens, and A.M. White, Org. Biomol. Chem, 2003, 1, 3144-3146; (11) Transition Metal and Organometallic Anion Complexation Agents, Paul D. et al. Beer, Elizabeth J. et al. Hayes, Coordination Chemistry Review, 240: 167-189, 2003; (12) Versatile Self-Compounding Compounds Based on Covalently Linked Donor-Acceptor Cyclophany. Flood, Ross M. et al. Moskowitz, J.M. Fraser Standard, Chem. Eur. J. et al. 11: 369-385, 2005; (13) Study of Interactions of Various Ionic Specs with Solvents, The design of Receptors, N .; Jiten singh, Adriana C.M. Olleta, Anupuriya Kumar, Mina Park, Hai-Bo Yi, Indrajt Bandyopadhyay, Han Myung Lee, P. et al. Tarakeshwar, Kwang S .; Kim, Theor. Chem. Acc. 115: 127-135, 2006; (14) A Calixarene-amide-tetrathiafulvalene Assembly for the Electronic Detection of Anions, Bang-Tun Zhao, Maria-Jesk. Chem. 29: 1164-1167, 2005.

[Statement of Incorporation by Reference and Variations]
[0114] All documents throughout this application are, for example, patents or equivalents issued or registered, patent application publications, and patent documents including non-patent documents or other source documents, each document being at least part of the disclosure of this application. Are incorporated herein by reference in their entirety as if individually incorporated by reference to the extent that they are not inconsistent (eg, partially conflicting documents are hereby incorporated by reference) Incorporated by reference except for partially contradictory parts).

  [0115] The terms and expressions employed herein are used for descriptive terms, not limitations, and the features or parts thereof shown or described when using such terms and expressions. It is recognized that various modifications are possible within the scope of the present invention as set forth in the claims. Thus, while the present invention has been specifically described by preferred embodiments, exemplary embodiments, and optional features, those skilled in the art will appreciate improvements and variations of the concepts disclosed herein. It should be understood that such improvements and variations are considered within the scope of the present invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and include many variations of the devices, device components, and method steps described in this description. It will be apparent to those skilled in the art that the present invention can be used to implement the present invention. As will be apparent to those skilled in the art, the methods and devices useful in the methods of the present invention can include many optional compositions and processing elements and steps.

  [0116] Where substituent groups are disclosed herein, all individual elements of that group and all subgroups are distinct, including any isomers, enantiomers and diastereomers of the elements of the group. It is understood that it is disclosed. Where Markush groups or other classifications are used herein, all individual elements of that group, as well as all possible combinations and sub-combinations of that group, are individually included in this disclosure. And Where a compound is described herein as not specifying a particular isomer, enantiomer, or diastereomer of the compound, for example, by formula or by chemical name, the description is Each isomer and enantiomer of the compound is intended to be included individually or in any combination. In addition, unless otherwise specified, all isotopic variations of the compounds disclosed herein are intended to be encompassed by the present disclosure. For example, it will be understood that any one or more hydrogens in the disclosed molecule can be replaced with deuterium or tritium. Isotopic variants of a molecule are usually useful as a basis in assays for that molecule and in chemical and biological studies related to that molecule or its use. Methods for producing such isotopic variants are known in the art. The specific names of the compounds are intended to be exemplary. This is because one skilled in the art can give different names to the same compound.

  [0117] Many of the molecules disclosed herein contain one or more ionic groups [from which protons are removed (eg, -COON) or protons are added (eg, amines). Or a group that can be quaternized (eg, amines). All possible ionic forms of such molecules and their salts are individually included in the disclosure herein. As regards the salts of the compounds herein, one of ordinary skill in the art can select from a variety of available counterions suitable for the preparation of the salts of the invention for a given application. In specific applications, the choice of a given anion or cation for the preparation of a salt can increase or decrease the solubility of the salt.

  [0118] Any formulation or combination of ingredients described or exemplified herein can be used to practice the invention unless otherwise indicated.

  [0119] Where a range is given herein, eg, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges are included within the given range All individual values are intended to be included in this disclosure. It will be understood that any subranges or individual values within a range or subrange that are included in the description herein can be excluded from the appended claims.

  [0120] All patents and publications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains. The references cited herein are hereby incorporated by reference in their entirety to show state of the art as of their publication date or filing date, and this information is in the prior art. It may be employed herein as necessary to exclude specific embodiments. For example, if the composition is described in the claims, it may be prior to the applicant's invention, including compounds for which a feasible disclosure is provided in the references cited herein. It is to be understood that compounds known and available in the art are not intended to be included in the claimed composition of the appended claims.

  [0121] As used herein, "comprising" is synonymous with "inclusioning", "containing" or "characterized by" and is inclusive or non-limiting and is described in additional terms. Do not exclude missing elements or method steps. As used herein, “consisting of” excludes any element, step or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic novel features of the claim. In each example herein, one of the terms “comprising”, “consisting essentially of” and “consisting of” is replaced by the other two terms. Can be replaced with one of them. The invention as described herein by way of example suitably practiced without any one or more of the elements not specifically disclosed herein, ie, without one or more limitations be able to.

  [0122] In practicing the present invention, the starting materials, biological materials, reagents, synthesis methods, purification methods, analysis methods, assay methods, biological methods other than those specifically exemplified may be excessively experimented. One skilled in the art will appreciate that it can be employed without. All functional equivalents known in the art of any such materials and methods are intended to be included in the present invention. The terms and expressions employed are used as descriptive terms and not as limitations, and the use of such terms and expressions is not intended to exclude features shown or described or equivalents thereof. Rather, it will be appreciated that various modifications are possible within the scope of the invention as set forth in the appended claims. Thus, while the present invention has been specifically described by preferred embodiments and optional features, it will be appreciated by those skilled in the art that modifications and variations of the concepts disclosed herein can be used by those skilled in the art. It should be understood that modifications and variations are considered to be within the scope of the invention as defined by the appended claims.

FIG. 1A is a schematic diagram showing a lithium ion battery during charging, and FIG. 1B is a schematic diagram showing a lithium ion battery during discharging. [036] Fig. 3 is a schematic diagram showing the average working potential of different negative electrodes and positive electrode materials, and the battery voltage of a conventional lithium ion battery. [037] FIG. 3A is a schematic view showing a fluoride ion battery (FIB) of the present invention during discharge. FIG. 3B illustrates the average effect for an example embodiment corresponding to a LaF _3-x negative electrode, a CF _x positive electrode, and an electrolyte comprising MF where M is a metal such as K or Rb, provided in the organic electrolyte. It is the schematic which shows an electric potential. [038] Fig. 3 provides a crystal structure of fluorocarbon. [039] is a diagram that provides a variety of positive electrode material according to X-ray diffraction pattern (Cu K _alpha line) to assess, carbon nanofibers, showing a diffraction pattern for KS15 and commercially available CF _1. [040] FIG. 7 is a diagram showing discharge profiles for a CF ₁ positive electrode at room temperature for various discharge rates ranging from C / 20 to C. [041] A diagram showing the discharge profile for a CF _{0.530 KS15} positive electrode at room temperature for various discharge rates ranging from C / 20 to C. [042] Figure 5 shows the discharge profile for the CF _{0.647 KS15} positive electrode at room temperature for various discharge rates ranging from C / 20 to 6C. [043] Figure 5 shows the discharge profile for a CF _0.21 carbon nanofiber cathode at room temperature for various discharge rates ranging from C / 20 to 6C. [044] Figure 5 shows the discharge profile for a CF _0.59 carbon nanofiber cathode at room temperature for various discharge rates ranging from C / 20 to 6C. [045] FIG. 7 is a diagram showing discharge profiles for a CF _0.76 carbon nanofiber positive electrode at room temperature for various discharge rates ranging from C / 20 to 6C. [046] FIG. 7 is a diagram showing discharge profiles for a CF _0.82 carbon nanofiber positive electrode at room temperature for various discharge rates ranging from C / 20 to 4C. [047] Fig. 24 is a diagram showing a charge-discharge profile for a CF _0.82 multi-wall nanotube positive electrode in a voltage range of 1.5 V to 4.6 V, where the voltage is plotted on the Y axis (left side) and the current is plotted on the Y axis ( Right) and time is plotted on the X-axis. [048] Fig. 5 is a diagram showing a charge-discharge profile for a CF _0.82 multi-wall nanotube positive electrode in a voltage range of 1.5V to 4.8V, where the voltage is plotted on the Y axis (left side) and the current is plotted on the Y axis ( Right) and time is plotted on the X-axis. [049] Fig. 19 is a diagram showing a charge-discharge profile for a CF ₁ positive electrode in the voltage range of 1.5 V to 4.8 V, with the voltage plotted on the Y axis (left side) and the current plotted on the Y axis (right side). , Time is plotted on the X-axis. [050] Fig. 15 shows a plot of voltage (V) versus time (hours) for Li / CF _x half-cell configurations at 4.6V and 4.8V, with a 0.25% increase in discharge capacity at 4.8V. Observed. [051] Figure 10 shows a plot of voltage (V) versus relative capacity (%) for a Li / CF _x half-cell configuration with a CF _{0.647 KS15} positive electrode at voltages ranging from _{4.8V to 5.4V} . As shown, the capacity of the CF _{0.647 KS15} positive electrode increased with increasing charge cut-off voltage over the range of 4.8V to 5.4V. [052] Figure 6 shows a cycle capacity curve of discharge capacity (mAh / g-C) versus number of cycles for the various positive electrode materials evaluated, and this data is 120 mAh / g-C for Li / CF _x half-cell structures. Rechargeable capacity is realized and has been demonstrated to be charged to 4.8V at 2C rate. [053] Fig. 5 shows a plot of discharge cycle versus cycle number for a CF _0.82 multi-wall nanotube positive electrode at a voltage equal to 14.6V to 4.8V. [054] This is a plot of discharge rate capability for LiMn ₂ O ₄ positive electrode. [055] FIG. 21A is a plot of discharge voltage versus time showing two time points (1) and (2) from which an X-ray diffraction pattern was taken, using a thin graphite electrode (at a thickness of 50 microns). 3-4 mg). FIG. 21B is a diagram showing X-ray diffraction patterns acquired at two time points (1) and (2) shown in FIG. 21A. FIG. 21C is a diagram showing the X-ray diffraction patterns acquired at two time points (1) and (2) shown in FIG. The diffraction patterns of FIGS. 21B and 21C show the step formation of intercalation fluoride ions (mixture of steps 2 and 3), and the diffraction patterns of FIGS. 21B and 21C show the complete disappearance of the graphite phase at 5.2V. It is also shown that it reappeared at 3.2V. [056] This is a graph showing an electron energy loss spectrum (EELS) of a positive electrode material charged to 5.2 V. Only pure fluorine is detected in the sample, and other species such as B and P are not present. It shows that the other anions in it were not inserted.

Claims (46)

A positive electrode comprising a first fluoride ion host material ;
A negative electrode comprising a second fluoride ion host material ;
An anionic electrochemical cell comprising an electrolyte provided between the positive electrode and the negative electrode and capable of conducting anion charge carriers,
The electrolyte includes a solvent and a fluoride salt, and the fluoride salt is present in the electrolyte in a partially dissolved state, whereby fluoride ions are generated in the electrolyte, and the fluoride salt has the formula MF _n , where M is a metal other than lithium and n is an integer greater than 0;
The positive and negative electrodes reversibly exchange the electrolyte and the anionic charge carriers during charging or discharging of the electrochemical cell;
The anionic charge carrier fluoride ion (F ^-) der is,
The solvent of the electrolyte is propylene carbonate, nitromethane, toluene, ethyl methyl carbonate, propyl methyl carbonate, diethyl carbonate, dimethyl carbonate, methyl butyrate, n-propyl acetate, ethyl acetate, methyl propionate, methyl acetate, 4- An electrochemical cell which is at least one selected from the group consisting of methyl-1,3-dioxolane, 2-methyltetrahydrofuran, 1,2 dimethoxyethane, methyl formate, dichloromethane, γ-butyrolactone and ethylene carbonate .   The electrochemical cell according to claim 1, wherein M is an alkali metal or alkaline earth metal other than lithium.   The electrochemical cell according to claim 1, wherein M is Na, K or Rb.   The electrochemical cell of claim 1, wherein the electrolyte further comprises an anion receptor.   The electrochemical cell according to claim 1, wherein the electrolyte further comprises a fluoride ion anion receptor capable of coordinating the fluoride ions from the fluoride salt.   The electrochemical cell according to claim 1, wherein the electrolyte further comprises a cation acceptor capable of coordinating metal ions 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 second fluoride ion host material of the negative electrode is a fluoride compound. The second fluoride ion host material of the negative electrode is 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, is selected from the group consisting of LaF _x and CeF _x, claim 2. The electrochemical cell according to 1. The electrochemical cell according to claim 1 , wherein the second 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 1 , wherein the standard electrode potential of the negative electrode is −1 V or less. The electrochemical cell according to claim 1 , wherein a standard electrode potential of the negative electrode is −2 V or less. The electricity of claim 1 , wherein the first fluoride ion host material of the positive electrode is an intercalation host material capable of accommodating the fluoride ions such that a fluoride ion intercalation compound is produced. Chemical cell. The electrochemical cell according to claim 1 , wherein the first fluoride ion host material of the positive electrode is a fluoride compound. The first fluoride ion host material of the positive electrode is selected from the group consisting of CFx, AgFx, CuFx, NiFx, CoFx, PbFx, CeFx, MnFx, AuFx, PtFx, RhFx, VFx, OsFx, RuFx and FeFx a composition, electrochemical cell according to claim 1. The partial fluoride wherein the first fluoride ion host material of the positive electrode has the formula CF _x , wherein _x is the average atomic ratio of fluorine atoms to carbon atoms, and is selected from the range of 0.3 to 1.0 a carbonaceous material, the carbonaceous material is graphite, coke, multiwall carbon nanotubes, multi-walled carbon nanofiber, multi-walled carbon nanoparticles are selected from the group consisting of carbon nanowhiskers and carbon nanorods, according to claim 16 Electrochemical cell. The electrochemical cell according to claim 1 , wherein a standard electrode potential of the positive electrode is 1 V or more. The electrochemical cell according to claim 1 , wherein a standard electrode potential of the positive electrode is 2 V or more. The electrochemical cell according to claim 1, wherein the first fluoride ion host material of the positive electrode and the second fluoride ion host material of the negative electrode are different. The first fluoride ion host material of the positive electrode is a first anion charge carrier host material , and the second fluoride ion host material of the negative electrode is a second anion charge carrier host material , the first and The second anion charge carrier host material combination (X / Y) is CFx / LiC ₆ , CFx / LaF _x , CuFx / LaFx, AgFx / LaFx, CoFx / LaFx, NiFx / LaFx, MnFx / LaFx, CuFx / AlFx The electrochemical cell of claim 1, selected from the group consisting of: AgFx / AlFx, NiFx / AlFx, NiFx / ZnFx, AgFx / ZnFx, and MnFx / ZnFx.   The electrochemical cell according to claim 1, having a standard battery voltage of 3.5 V or more.   2. The electrochemical cell according to claim 1, wherein during the discharge of the electrochemical cell, the fluoride ions are released from the positive electrode and are accommodated by the negative electrode.   2. The electrochemical cell according to claim 1, wherein during the charging of the electrochemical cell, the fluoride ions are released from the negative electrode and are accommodated by the positive electrode.   The electrochemical cell of claim 1 comprising a primary electrochemical cell.   The electrochemical cell of claim 1 comprising a secondary electrochemical cell. 27. The electrochemical cell according to claim 26 , having a cycle life of 500 cycles or more. The electrochemical cell according to claim 1, which has a specific energy of 300 Wh · kg ⁻¹ or more.   The electrochemical cell according to claim 1, wherein the positive electrode, the electrolyte, and the negative electrode do not contain lithium. A positive electrode comprising a first fluoride ion host material and having a first standard electrode potential;
A negative electrode 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 3.5 V or more When,
An electrolyte provided between the positive electrode and the negative electrode, capable of conducting fluoride ion charge carriers, comprising a fluoride salt and a solvent, and present in a state in which at least a part of the fluoride salt is dissolved and whereby said fluoride ion charge carriers in the electrolyte is an anionic secondary electrochemical cell comprising an electrolyte which occurs, the fluoride salt has the formula MF _n, wherein, M is A metal other than lithium, n is an integer greater than 0,
The positive electrode and the negative electrode reversibly exchange the electrolyte and the fluoride ion charge carriers during charging or discharging of the electrochemical cell;
The fluoride ion charge carriers fluoride ion (F ^-) der is,
The solvent of the electrolyte is propylene carbonate, nitromethane, toluene, ethyl methyl carbonate, propyl methyl carbonate, diethyl carbonate, dimethyl carbonate, methyl butyrate, n-propyl acetate, ethyl acetate, methyl propionate, methyl acetate, 4- A secondary electrochemical cell which is at least one selected from the group consisting of methyl-1,3-dioxolane, 2-methyltetrahydrofuran, 1,2 dimethoxyethane, methyl formate, dichloromethane, γ-butyrolactone and ethylene carbonate . The electrochemical cell according to claim 30 , wherein M is Na, K or Rb. 32. The electrochemical cell according to claim 30 , wherein the electrolyte further comprises an anion receptor, a cation receptor or both. The second fluoride ion host material of the negative electrode is 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, is selected from the group consisting of LaF _x and CeF _x, claim 30. The electrochemical cell according to 30 . The first fluoride ion host material of the positive electrode is selected from the group consisting of CFx, AgFx, CuFx, NiFx, CoFx, PbFx, CeFx, MnFx, AuFx, PtFx, RhFx, VFx, OsFx, RuFx and FeFx The electrochemical cell according to claim 30 , which is a composition. A method for making an anionic electrochemical cell comprising:
Providing a positive electrode comprising a first fluoride ion host material ;
Providing a negative electrode comprising a second fluoride ion host material ;
A step of providing an electrolyte capable of conducting anion charge carriers between the positive electrode and the negative electrode, wherein the electrolyte includes a solvent and a fluoride salt, and the fluoride salt is at least partially dissolved; Present in the electrolyte, thereby generating fluoride ions in the electrolyte, wherein the fluoride salt has the formula MFn, _where M is other than lithium A metal, n is an integer greater than 0,
The positive electrode and the negative electrode, wherein said electrolyte during charging or discharging of anionic electrochemical cells to anion reversibly exchanging charge carriers, the anion charge carriers fluoride ion (F ^-) der is,
The solvent of the electrolyte is propylene carbonate, nitromethane, toluene, ethyl methyl carbonate, propyl methyl carbonate, diethyl carbonate, dimethyl carbonate, methyl butyrate, n-propyl acetate, ethyl acetate, methyl propionate, methyl acetate, 4- A method which is at least one selected from the group consisting of methyl-1,3-dioxolane, 2-methyltetrahydrofuran, 1,2 dimethoxyethane, methyl formate, dichloromethane, γ-butyrolactone and ethylene carbonate . A method of generating a current,
Providing an anionic electrochemical cell;
Discharging the anionic electrochemical cell, the electrochemical cell comprising:
A positive electrode comprising a first fluoride ion host material ;
A negative electrode comprising a second fluoride ion host material ;
An electrolyte provided between the positive electrode and the negative electrode and capable of conducting anion charge carriers, wherein the electrolyte includes a solvent and a fluoride salt, and the fluoride salt is at least partially dissolved. Present in the electrolyte, thereby generating fluoride ions in the electrolyte, wherein the fluoride salt has the formula MF _n , where M is a metal other than lithium, n Is an integer greater than 0,
The positive electrode and the negative electrode, wherein said electrolyte during charging or discharging of anionic electrochemical cells to anion reversibly exchanging charge carriers, the anion charge carriers fluoride ion (F ^-) der is,
The solvent of the electrolyte is propylene carbonate, nitromethane, toluene, ethyl methyl carbonate, propyl methyl carbonate, diethyl carbonate, dimethyl carbonate, methyl butyrate, n-propyl acetate, ethyl acetate, methyl propionate, methyl acetate, 4- A method which is at least one selected from the group consisting of methyl-1,3-dioxolane, 2-methyltetrahydrofuran, 1,2 dimethoxyethane, methyl formate, dichloromethane, γ-butyrolactone and ethylene carbonate . The electrochemical cell according to claim 1 , wherein the first fluoride ion host material of the positive electrode is a polymer selected from the group consisting of polyacetylene, polyaniline, polypyrrole, polythiophene, and polyparaphenylene.   The electrochemical cell according to claim 1, wherein the concentration of the fluoride salt in the electrolyte is selected from the range of 0.1M to 2.0M.   The electrochemical cell according to claim 1, wherein M is an alkali metal other than lithium.   The electrochemical cell according to claim 1, wherein M is an alkaline earth metal.   The electrochemical cell according to claim 1, wherein M is Mg, Ca, or Sr. The electrochemical cell of claim 1, wherein the electrolyte provides a conductivity for the anionic charge carrier of 0.001 Scm ⁻¹ or greater. The electrochemical cell of claim 1, wherein the electrolyte provides a conductivity for the anionic charge carrier of 0.005 Scm ⁻¹ or greater. The first fluoride ion host material and the second fluoride ion host material are the first fluoride ion host material, the second fluoride ion host material, or the first fluoride ion host. material and the by the intercalation or insertion of fluoride ions to the second fluoride ion host material, reversibly exchanging the anion charge carriers with the electrolyte, electrochemical cell according to claim 1. The first fluoride ion host material and the second fluoride ion host material are the first fluoride ion host material, the second fluoride ion host material, or the first fluoride ion host. material and said and by chemical reaction with the fluoride ion second fluoride ion host material, reversibly exchanging the anion charge carriers with the electrolyte, electrochemical cell according to claim 1.   The electrochemical cell according to claim 1, wherein the solvent of the electrolyte is a partially or fully fluorinated solvent.