TW201419648A - Hybrid electrochemical energy storage devices - Google Patents

Abstract

Electrochemical energy devices such as batteries, flow cells and EDLCs that employ redox active electrolytes are disclosed. Redox active electrolytes for use in these devices also are disclosed that includes one or more redox active salts and optional additive salts. Electrochemical energy devices such as batteries, flow cells and EDLCs that employ the disclosed electrolytes may exchange more than one electron per redox species and may achieve much higher energy densities.

Description

Hybrid electrochemical energy storage device

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention was made with government support under Contract No. DEAR0000070 awarded by the Higher Research Projects Agency. The government has certain rights in the invention.

RELATED APPLICATIONS The present application claims priority to U.S. Provisional Patent Application No. 61/680,689, filed on Aug.

Electrochemical energy storage devices that store and supply electrical energy or current, such as batteries, capacitors, hybrid or asymmetric cells, are characterized by ion transport. In a battery, ions are stored in the entirety of the electrode particles. In an electrochemical double layer capacitor (EDLC), ions accumulate on the surface of the electrode particles but remain in the electrolyte. A pseudo capacitor is an example of ion storage in electrode particles of an EDLC. However, with respect to the battery, the ions remain near the surface of the electrode particles and do not diffuse into the entirety of the particles.

In another variation of ion transport, ions are stored in the electrolyte as a whole. In this variation, the ionic species undergo a reversible faradaic charge transfer reaction at the surface location of the electrode material, but instead of entering the electrode particles, the oxidized/reduced ionic species will diffuse back to the electrolyte. This type of ion transport is the basis for the cathode and anode in a flow battery. Since the ionic charge is stored in the entire volume of the electrode particles, the battery has a high capacity.

However, due to continuous strain changes that occur during cycling, the battery experiences a long period of capacity degradation. EDLC has a lower energy density, but has very good long-term stability because there is no strain change.

Flow batteries use redox reactions in electrolyte species to store charge, and only require contact between the electrolyte species and a conductive electrode surface to exchange electrons. The flow battery has better long-term stability than the battery. However, conventional flow battery chemistry can only operate with one electron transfer per redox species in the electrolyte. For example, a typical redox reaction in a vanadium flow battery is V ²⁺ <->V ³⁺ +e ^- , where vanadium ions exchange only one electron. The energy density of a flow battery is proportional to the amount of exchanged electrons per unit volume of the electrolyte.

Electrochemical energy devices, such as batteries, EDLC, and flow batteries, have found a wide range of applications. However, there is a need for improved electrochemical energy devices, including improved electrolytes used in such devices.

Electrochemical energy devices using redox active electrolytes, such as batteries, flow batteries, and EDLC, are disclosed. Redox active electrolytes for use in these devices are also disclosed. Electrochemical energy devices (eg, batteries, flow batteries, and EDLC) using the disclosed electrolytes can exchange more than one electron per redox species and achieve higher energy densities.

Typically, the electrochemical energy storage device uses a cathode and an anode separated by an ion exchange membrane, optionally with a porous separator membrane. The apparatus uses a redox active electrolyte solution comprising one or more redox active salts and optionally additional salts. Redox active salts provide one or more redox active anions and can undergo a reversible electron exchange reaction. Typically, at least one of the redox active anions is a polyatomic ion. The flow battery can use one or more (eg, two) redox active electrolytes.

A redox active electrolyte may also be used in a hybrid electrochemical energy storage device in which one electrode uses a redox active electrolyte and the other electrode is a battery type (Faraday) electrode or an EDLC type double layer electrode.

The disclosed electrochemical energy storage device includes a cathode, an anode, and a cation permeation separator membrane positioned between the cathode and the anode. The apparatus comprises a redox active electrolyte, wherein the electrolyte comprises one or more redox active salts, for example, Mo ₆ Cl ₁₂ , HMo ₆ Cl ₁₃ , LiMo ₆ Cl ₁₃ , Li ₂ MoO ₄ , Li ₂ Mo ₂ O ₇ , Na ₂ MoO ₄ , Na ₂ Mo ₂ O ₇ , NaMo ₆ Cl ₁₃ , NaMo ₆ Cl ₁₃ , Li ₂ WO ₄ , Li ₂ W ₂ O ₇ , and combinations thereof for use in the redox active electrolyte A redox active anion is produced. The redox active anions may be any of a polymeric anion, a polymeric side oxymetallate, and a metal cluster ion. The polymeric anion is any one of the formula [M _n r] ^y- or [M _n r] ^y- , wherein M is any of V, Nb, Ta, Cr, Mo and W cations, n is 2 to 6, r is any of O, F, Cl, wherein ^y is an anion charge in [M _n r] ^y- , in the formula (M _n Xv) ^z- , M is Mo, W, Nb, Tc , Ru, Rh, Ta, Re, Os, or Ir, X is a ligand, v is from 7 to 24, and n is from 2 to 7. The polymeric side oxymetallates may be of the formula MX ₆ octahedron or of the formula [ZO ₄ (MO ₃ ) _n ] ^y− or the formula AM ₆ O ₂₄ ^n- or AM ₁₂ O ₄₀ ^n- or A ₂ M ₁₈ O ₆₂ Any one of ^n- , wherein M is any one of Si, Ge, Ga, B, P, V, Nb, Ta, Cr, Mo or W, and X is any one of oxygen, sulfur, fluorine, and molecular formula [ZO ₄ (MO ₃ ) _n ] ^y− , Z is any of Si, P, S, Ge, As, Se, and M is any of Mo, W, Nb, V, Tc, n is 6 To 22, and y is an anion charge, in the formula AM ₆ O ₂₄ ^n- or AM ₁₂ O ₄₀ ^n- or A ₂ M ₁₈ O ₆₂ ^n- , A is B, Al, Ga, Si, Ge, Sn, P Any of As, Sb, Se, Te, and M is any of V, Nb, Ta, Mo or W, and m is an anion charge.

The metal cluster ions are of the formula M ₆ X ₈ ⁿ⁺ , or Mo ₆ X ₁₂ , wherein M is Nb, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, Re, Os, Ir, Pt, Any of Au, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, and X is S, Se, Te, F, Cl, Br, I, At Any one, and n is a charge on the ion, wherein X is a F, Cl, Br, I, At, a halide of a basic Mo (including NMo ₆ X ₁₂ ) in the formula Mo ₆ X ₁₂ , wherein X is any of F, Cl, Br, I, At, and N is any of Na, K, Rb, Cs.

In the electrochemical energy storage device, the anode may be any of lithium metal, sodium, graphitic carbon, nickel metal hydride, metallic zinc, magnesium, and lead. The cation film may be any of a tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octane sulfonic acid copolymer and a polyethylene oxide. When the electrochemical energy storage device is a capacitor, the negative electrode is an EDLC type electrode, and the cathode includes a redox active electrolyte, and the capacitor may be an electrochemical double layer capacitor including an electrode having a redox active electrolyte.

The redox active salts have one or more redox active anions, wherein the redox active ions are heteropolymeric anions comprising a transition metal core and at least one ligand. The metal core includes any one of W, Y, Zr, Nb, Tc, Ru, Rh, Ta, Re, Os ions, and the ligands may be O ^2- , S ² , F ^- , Cl ^- , Br ^- , I ^- , CH ₃ , C ₂ H ₅ , C ₃ H ₇ and C ₄ H ₉ , amines, carbonates, phenols, ethers, and combinations thereof. The heterogeneous polymeric anions can include a transition metal core and from 6 to 8 ligands.

The cation permeable membrane can be infiltrated by a cation such as NH ⁴⁺ , tetramethylammonium, NMe ⁴⁺ , tetraethylammonium, NEt ⁴⁺ , tetrabutylammonium, NBu ⁴⁺ , and combinations thereof.

The heterogeneous polymeric anions may comprise a transition metal core having six transition metal ions selected from Groups 4-7, wherein the transition metal ions are from F, Cl, Br, I, S, O, An octahedral form surrounded by 8 or more ligands selected from the group of Se and Te.

The electrochemical energy storage device can be a flow battery. The flow battery includes an anode portion, a cathode portion, and an ion selective membrane for separating the anode portion from the cathode portion, the anode portion including a conductive material for use with an anolyte solution contacting the conductive material Electronic exchange. The cathode portion includes a conductive material for electronic exchange with a catholyte solution contacting the conductive material. At least one of the anolyte and the catholyte comprises a redox active electrolyte. The anolyte and catholyte may be the same or different.

The electrochemical energy storage device can also be a hybrid battery comprising a negative electrode, a cation permeation separator membrane, and a redox active electrolyte cathode, wherein the negative electrode is suitable for being present in the redox active electrolyte A cation undergoes a redox reaction. The negative electrode may be any of lithium metal, sodium, graphitic carbon, lithium titanate, LiVO ₂ , nickel metal hydride, metal zinc, magnesium, and lead. The negative electrode may also be lithium metal, and the cathode may be carbon treated with a redox active LiMo ₆ Cl ₁₃ electrolyte solution.

Materials The redox active salts used in the redox active electrolyte can be used in electrochemical energy storage devices. The redox active electrolyte can include one or more redox active salts dissolved in an electrolyte solvent. Salts which can be used have one or more cations and one or more redox active anions ("RAA"). The RAA typically can exchange more than one electron at one electrode.

Examples of redox active salts which may be used include, but are not limited to, transitional alkali metal salts such as, but not limited to, alkali metal molybdates and alkali metal tungstates. Other redox active salts which may be used include Keggin-type anionic salts, Dawson-type anionic salts, and metallic cluster type salts. Mixtures of these salts can also be used.

Examples of alkali metal molybdates include, but are not limited to, Li ₂ MoO ₄ , Li ₂ Mo ₂ O ₇ , Na ₂ MoO ₄ , Na ₂ Mo ₂ O ₇ and mixtures thereof available from Sigma-Aldrich. Examples of alkali metal tungstates include, but are not limited to, Li ₂ WO ₄ , Li ₂ W ₂ O ₇ and mixtures thereof available from Sigma-Aldrich. Examples of Keggin-type anionic salts include, but are not limited to, molybdates (such as, but not limited to, Li ₃ SiW ₁₂ O ₄₀ ), alkali metal tungstates (such as, but not limited to, Li ₃ SiW ₁₂ O ₄₀ ), and bismuth molybdenum Salts such as, but not limited to, (Zn ₂ H)SiMo ₁₂ O ₄₀ and mixtures thereof, can be synthesized as described below. Examples of Dawson-type anionic salts include, but are not limited to, copper molybdenum salts including, but not limited to, Li ₄ S ₂ Mo ₁₈ O ₆₂ and Na ₄ S ₂ Mo ₁₈ O ₆₂ , and tungstates, including, but not Limited to Li ₆ P ₂ W ₁₈ O ₆₂ , Na ₄ P ₂ W ₁₈ O ₆₂ and mixtures thereof. Examples of metal cluster compounds include, but are not limited to, HMo ₆ Cl ₁₃ , LiMo ₆ Cl ₁₃ , NaMo ₆ Cl _{13 ,} and mixtures thereof, as well as any of the combinations described above available from American Elements Co.

Redox active salts (for example, those described above for redox active electrolytes) have good solubility, high conductivity, chemical inertness, and stability in the electrode operating voltage range of an electrochemical energy device using the electrolyte. . Redox active salts are capable of undergoing a reversible electron transfer reaction. High conductivity can be derived from salts that dissociate into positive and negative ions in solution and diffuse immediately through the solvent. Typical high conductivity is about 0.1 S/cm, while moderate conductivity is about 0.1 mS/cm.

The solubility of the redox active salts can vary widely depending on various factors such as solvent and temperature. Typically, the salts have a good solubility of from about 10" ³ M to about 5 M, for example from about 0.1 M to about 5 M, or from about 1 M to about 5 M.

A salt additive salt additive for a redox active electrolyte can be used together with a redox active salt to further increase the electrolyte conductivity and ionic strength of the redox active electrolyte. Salt additives are selected to be compatible with redox active salts and electrolyte solvent forms using redox active salts.

Examples of the additional organic electrolyte salts include, but are not limited to, alkyl ammonium, e.g., hexafluorophosphate, tetraethylammonium (TEA-PF _6); lithium fluoride salts, such as, but not limited to, LiPF _6, LiBF ₄ , LiAsF ₆ and mixtures thereof; lithium oxyhalide salts such as, but not limited to, LiClO ₄ ; organic sulfur type salts, for example, lithium bistrifluoromethanesulfonimide (TFSI); and organoboronic acid salts, For example, lithium bis(oxalate) borate (LiBOB).

Examples of additional salts for aqueous electrolytes include, but are not limited to, HCl, alkali metal halides such as, but not limited to, NaCl, KCl, KBr, KI, NaBr, NaI, LiCl, LiBr, LiI, RbCl, RbBr , RbI and combinations thereof; alkaline earth metal halides such as, but not limited to, MgCl _- , MgBr ₂ , MgI ₂ , CaCl ₂ , CaBr ₂ , CaI ₂ , alkali metal hydroxides (such as, but not limited to, NaOH, KOH , RbOH, CsOH; and sulfates such as, but not limited to, H ₂ SO ₄ and mixtures thereof).

A solvent organic solvent and a water solvent for the redox active electrolyte can be used in the redox active electrolyte. Examples of organic solvents include, but are not limited to, alkylene carbonates, aryl carbonates, alkyl carbonates such as, but not limited to, dimethyl carbonate, propylene carbonate, diethyl carbonate, acetonitrile, and the like Combine. Examples of the aqueous solvent include, but are not limited to, water, aqueous hydrochloric acid, aqueous sulfuric acid, aqueous alkali metal halides, for example, KCl solution, NaCl solution, and combinations thereof.

The redox active anion (RAA) provided by the redox active salt used in the redox active electrolyte is an anisotropic polymeric anion (HPA) comprising one or more ligands coordinated to one or more The core of multiple metal ions. The core of an HPA includes one or more transition metal ions, wherein a transition metal ion can have two or more accessible valence states.

HPA uses a transition metal ion having a multivalent state, for example, one or more transition metals in any of columns 5 and 6 of the periodic table, for example, Mo, W, Y, Zr, V, Nb, Tc, Ru, Rh, Ta, Re, Os, and combinations thereof. Suitable HPAs include the following species: (1) polymeric anions, for example, [M _n r] ^y- , wherein M is any of V, Nb, Ta, Cr, Mo and W cations, n is 2 to 6 r is an anion such as O, F, Cl; and y is a negative valence, from 1 to 4. (2) a polymeric side oxymetallate and a derivative thereof, which employs a polymeric ion structure comprising an MX ₆ octahedron, wherein M represents V, Nb, Ta, Cr, Mo, or W, and wherein M is octagonal Body coordination with a ligand X, for example, oxygen, sulfur, fluorine, and combinations thereof; (3) metal cluster ions, wherein the basic unit is M ₆ octahedron, wherein M represents 0 to 1 Any one or more of V, Nb, Ta, Cr, Mo, and W in a low oxidation state, and wherein the basic unit is coordinated with an anion or other ligand, wherein the anion is typically a halide, such as And not limited to, F, Cl, Br, I, O, S, Te, or an organic ligand such as, but not limited to, DMF.

The ligand may be a non-metal that coordinates around the core of the transition metal cluster. Examples of non-metal ligands include, but are not limited to, O ² , S ² , F ^- , Cl ^- , Br ^- , I ^- and its combination. The ligand may include an organic species such as a cycloalkyl group such as, but not limited to, a cyclized butane and a cyclized pentane; and a linear and branched alkyl group such as, but not limited to, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ and -C ₄ H ₉ . Further, the ligand may be a combination of a non-metal and an alkyl group, for example, -CH ₂ F, -CH ₂ Cl, -CH ₂ Br and -CHF ₂ . The ligand may also be an alkylamine such as, but not limited to, methylamine, ethylamine, propylamine, and combinations thereof; alkylene oxides, for example, ethylene carbonate, propylene carbonate, and combinations thereof; alkyl carbonates, For example, but not limited to, dimethyl carbonate, ethyl methyl carbonate, and mixtures thereof; phenols such as, but not limited to, phenolic acids; and alkyl ethers such as, but not limited to, diethyl ether; and combinations thereof.

HPA's can be used in several forms. In the concept of the first aspect, the HPA's may be polymeric anions, for example, in a aqueous environment by transition metals (eg, Mo, W, Nb, Tc, Ru, Rh, Ta, Re, Os, Ir, and combinations thereof) Formed by. These polymeric anionic HPA's have the formula (M _n Xv) ^z- , wherein M is one or more transition metals coordinated by y ligands (X), n is 2 to 7, and v is 7 to 24 or more, for example, 7 to 24, and z represents the charge of the anion. The ligand (X) can include any of the above discussed. Non-limiting examples of polymeric anionic HPAs include, but are not limited to, Mo ₇ O ₂₄ ^6- , W ₆ O ₁₉ ² , and combinations thereof.

In the concept of the second aspect, the HPA may be a polymeric side oxymetallate anion, wherein the transition metal ion is typically surrounded by 6 ligands to form an octahedron, which is assembled to form 2 or more Octahedral composite structure. These polymeric side oxymetallate anionic HPAs have a transition metal ion core which may include semimetal ions such as Si, Ge, Ga, B, P, and combinations thereof. The transition metal ion core may include transition metal ions of column 4, such as, but not limited to, ions of any one or more of Fe, Cr, Co, and Mn. Non-limiting examples of polymeric side oxymetallate anionic HPA include, but are not limited to, a Keggin structure type polymeric side oxymetallate of the formula [ZO ₄ (MO ₃ ) _n ] ^y wherein Z is Si, P, S Any one or more of Ge, As, Se and combinations thereof, M is any one or more of Mo, W, Nb, V, Tc and combinations thereof, and y is an anion charge. Non-limiting examples of Keggin structure type polymeric side oxymetallate anions include, but are not limited to, SiMo ₁₂ O ₄₀ ^3- , PMo ₁₂ O ₄₀ ^3- , H ₂ CoW ₁₂ O ₄₀ ^6-, and combinations thereof.

In a third aspect, the HPA can be a metal cluster anion that can undergo multiple reversible electron transports, and the metal cluster anion is an aggregate formed by octahedrons of transition metals coordinated by eight nearest neighboring ligands. An anion to provide a positively charged cluster core of the formula M ₆ X ₈ ⁿ⁺ , wherein M is a transition metal of Groups 4-7, such as, but not limited to, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, and combinations thereof, and X is a copper halide such as, but not limited to, S, Se, Te, F, Cl, Br, I, At, and combinations thereof, and n is The charge of the ion. Metal cluster anions include transition metal cores such as, but not limited to, Mo, W, Y, Zr, Nb, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, Re, Os, Ir, Pt , Au, and combinations thereof, wherein the core is coordinated with a variety of ligands and combinations thereof, which provide an anion-total negative charge. Ligands can include, but are not limited to, halides, polar (hydrophilic) aprotic solvents, linear and branched alkyl groups, and combinations thereof. Halides which may be used include, but are not limited to, Cl ^- , Br ^- , I ^- , and combinations thereof; polar (hydrophilic) aprotic solvents which may be used include, but are not limited to, tertiary guanamines, for example, N N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP); acetonitrile (CAN), dimethyl sulfoxide (DMSO), and mixtures thereof. Linear and branched alkyl groups which may be used include, but are not limited to, -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₅ H ₁₁ , and combinations thereof.

Metal cluster anions typically exhibit bonding forces in the cluster core and a lower oxidation state compared to heterogeneous polymeric anions. The metal cluster anion compound includes, but is not limited to, a Mo halide of the formula Mo ₆ X ₁₂ wherein X is a halide, for example, F, Cl, Br, I, At, and combinations thereof; and a molecular formula of NMo ₆ X ₁₂ Alkaline Mo halides wherein X is a halide, for example, F, Cl, Br, I, At, and combinations thereof, and N is an alkali metal, for example, Na, K, Rb, Cs, and combinations thereof. Various organic ligands may be substituted for the external halide to form an organometallic cluster compound of the formula Mo ₆ X _12-x R _x wherein 0≤ x ≤ 4, and R is a polar (hydrophilic) aprotic Solvents such as, but not limited to, tertiary decylamine, for example, N,N-dimethylformamide (DMF); N-methyl-2-pyrrolidone (NMP), acetonitrile (CAN), dimethyl Aachen (DMSO), and mixtures thereof. Non-limiting examples of organometallic cluster compounds include, but are not limited to, Mo ₆ Cl ₁₂ (DMF) ₂ , wherein DMF is dimethylformamide. Other examples of metal cluster compounds that can be used include, but are not limited to, MoCl ₂ , wherein the basic unit is a Mo ₆ octahedron surrounded by Cl ⁻ ions. Additional examples of metal cluster compounds that may be used include, but are not limited to, Mo halides such as, but not limited to, Mo ₆ Cl ₁₂ , Mo ₆ I ₈ ⁴⁺ , Mo ₆ Cl ₈ ⁴⁺ , Mo ₆ Br ₈ ^{4 +} , W halides (such as, but not limited to, W ₆ Br ₈ ⁴⁺ , W ₆ I ₈ ⁴⁺ , W ₆ Cl ₈ ⁴⁺ ), and basic Mo-type salts (such as, but not limited to, LiMo ₆ Cl ₁₃ ), and combinations thereof.

Polymeric side oxymetallate anions suitable for use in HPA for the polymerization of pendant oxymetals of HPA compounds and their derivatives include the construction of a octahedral of any V, Nb, Ta, Mo and W surrounded by six ligands. The ligand, wherein the ligand is mainly oxygen, but may also include sulfur, antimony or selenium. Polymeric side oxymetallate anions that may be used include, but are not limited to, homopolymeric anionic clusters, for example, M ₆ O ₁₉ ^2- , M ₇ O ₂₄ ^6- , M ₈ O ₂₆ ^4- , M ₁₂ O ₃₈ ^4- And heteropolymeric anions, for example, AM ₆ O ₂₄ ^n- (Anderson ion), AM ₁₂ O ₄₀ ^n- (Keggin ion), and A ₂ M ₁₈ O ₆₂ ^n- (Dawson ion), wherein A is a heterogeneous ion For example, but not limited to, B, Al, Ga, Si, Ge, Sn, P, As, Sb, Se, Te, and combinations thereof, and M is V, Nb, Ta, Mo or W, and combinations thereof.

The polymeric side oxymetallate anion can be formed by a first column of transition metals (eg, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and combinations thereof); a second column of transition metals (eg, Y, Zr, Tc, Ru, Pd, Ag, Cd, In, Sn, Sb, Te and combinations thereof, and a third column of transition metals (eg, La, Hf, Re, Os, Ir, Pt, Au, Hg, Tl) , Pb, Bi and combinations thereof are modified in place of any one or more of V, Nb, Ta, Mo and W. The polymeric side oxymetallate anion can also be modified by incorporating additional heterogeneous ions into the structure of the polymeric ion. Additional heterogeneous ions that can be incorporated into the coordination framework of the polymeric ion include, but are not limited to, B, Al, Ga, Si, Ge, Sn, P, As, Sb, Se, Te, and combinations thereof, typically, and The addition can be accomplished by adding an oxide of a substituent ion to the initial precursor used in the synthesis of these materials.

Acid-polymerized anion, redox active organic electrolyte molybdenum, a redox active organic electrolyte having a redox active molybdate polymeric anion having a transition metal anion (for example, MoO ₄ ^2- or Mo ₂ O ₇ ^2- ) can be prepared by The mono oxide (for example, a transition metal oxide, for example, MoO ₃ ) is dissolved in an organic, basic solvent, and the resulting solution is concentrated to saturation and cooled to precipitate a molybdate polymeric anion, oxidized. Reducing the active salt. By way of example, 100 grams of molybdic acid is dissolved in commercially available tetraethylammonium hydroxide (TEAH) at a temperature of from about 45 ° C to about 55 ° C. The resulting solution was concentrated to saturation and then cooled to allow tetraethylammonium dimolybdate to precipitate. The salts were dried in vacuum for 24 hours.

The redox active organic electrolyte of the tetraethylammonium dimolybdate can be dissolved to a concentration of about 0.1 M at about 20 ° C to about 60 ° C by using the salt in an organic salt such as acetonitrile. Prepared at approximately 1.0 M.

Preparation of a side oxymetallate salt of a heterogeneous polymeric acid (for example, molybdenum decanoic acid, phosphotungstic acid, and tungstic acid) by chemically polymerizing a side oxymetalate directly by ion exchange with an acid or from a precursor . Heteropolymeric acids, for example, molybdenum decanoic acid, phosphotungstic acid, and tungstic acid are commercially available from Sigma-Aldrich and Strem Chemicals. The preparation from the precursor requires a reaction between the cationic precursor and a transition metal anion precursor. Anionic precursors include, but are not limited to, molybdenum decanoic acid, phosphotungstic acid, and tungstic acid. Cationic precursors include, but are not limited to, transition metal carbonates such as, but not limited to, nickel carbonate, zinc carbonate, and combinations thereof. Carbonate can be used to replace other transition metal salts include, but are not limited _{to, NH 3 OH, NEt 3 OH} , NBu 3 OH, LiOH, or KOH, and combinations thereof.

Example 1 Metallization Molybdate Side Oxygen: Preparation of Nickel Phosphorus from Precursor 224 g (0.1 mol) of phosphomolybdic acid from Sigma-Aldrich, H ₃ [PMo ₁₂ O ₄₀ ]·23H ₂ O, dissolved in 400 ml In water, add 19.52 grams of nickel carbonate. The mixture was heated to 65 ° C and stirred for 0.5 hours, and the resulting green solution was cooled and filtered, then evaporated to crystallize to hydrated nickel phosphomolybdate, Ni ₃ [PMo ₁₂ O ₄₀ ] ₂ · 34H ₂ O.

Example 2 Metallization Molybdate Side Oxygen: Preparation of Zinc Phosphorus from Precursor The procedure used to produce nickel phosphomolybdic acid was used except that nickel carbonate was replaced by 20.62 grams of zinc carbonate.

Example 3 Metallized molybdate side oxygen: Preparation of sodium phosphorus from the precursor 28.42 g (0.10 mol) sodium citrate hydrate Na ₂ SiO ₃ ·9H ₂ O, 24.2 g (0.10 mol) Na ₂ MoO ₄ · 2H ₂ O, and 158.4 g (1.1 mol) of MoO ₃ were added to 400 ml of deionized water at room temperature. The solid was dissolved under reflux for 2 hours. The resulting yellow solution was filtered and evaporated to give a hydrated crystal of sodium molybdate.

Example 4 Metallized molybdenum acid side oxygen: Preparation of lithium phosphorus by ion exchange 224 g (0.1 mol) phosphomolybdic acid was dissolved in 400 ml of water at room temperature, and the solution was passed through a lithium ion exchange column to allow Li ion to replace the solution. Proton in the middle. The treated solution is filtered and evaporated to form a lithium phosphomolybdic acid crystal. The crystals were dried in a vacuum at 90 ° C for 3 days before being applied to an organic electrolyte.

Preparation of Heteropolymerized Anionic Redox Active Organic Electrolyte Redox Active Heteropolymer Anionic Salts are soluble in an organic solvent electrolyte to form a redox active organic electrolyte. The pH of the electrolyte can be adjusted using an acid or a base such as HCl (more acid), KOH (more base). The heteropolymeric anionic salt can be dissolved in an organic solvent, for example, acetonitrile, dimethylformamide, dimethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, tetrahydrofuran, dimethylhydrazine, methyl ethyl The base, dimethyl hydrazine, or a combination thereof, forms a redox active organic electrolyte, which may have higher voltage stability than the corresponding aqueous electrolyte. The heteropolymeric anionic salts can also be dissolved in a mixture of an organic electrolyte and an aqueous electrolyte.

Preparation of heterogeneous polymeric anion redox active aqueous electrolyte redox active heteropolymeric anionic aqueous electrolyte can be prepared by dissolving one or more redox active heteropolymeric anionic salts in water and adjusting the pH with an acid or a base (eg, HCl (more acid), KOH (more base) is achieved. Other bases which can be used to adjust the pH include, but are not limited to, ammonium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), and mixture.

Example 5: Preparation of an aqueous electrolyte 200 g of phosphomolybdic acid was dissolved in 100 ml of distilled water at room temperature.

Preparation of Heterogeneous Polymeric Anion Redox Active Organic Electrolyte Generally, a redox active organic electrolyte solution having a concentration of about 0.01 M to about 1 M can be formed by dissolving a redox active heteropolymeric anionic salt in an organic solvent.

Example 6: Preparation of redox active organic electrolyte 10 g of lithium phosphomolybdic acid was dissolved in 100 ml of dimethyl hydrazine at room temperature to form a 0.06 M organic redox active electrolyte.

The preparation of the cluster ionic compound cluster ionic compound can be prepared by reducing the transition metal pentahalide MX ₅ by passing the corresponding transition metal M at a high temperature. By way of example, Mo ₆ Cl ₁₂ can be formed by the chemical formation of MoCl ₅ and Mo. Prepare by metering the mixture, which is sealed under vacuum in a Vycor glass tube and heated to about 800 ° C to about 850 ° C for about 1 day to about 5 days to form Mo ₆ Cl ₁₂ .

Compound Molybdenum Cluster Chlorination Base Preparation The alkali molybdenum chloride cluster compound as HPA can be prepared by subjecting an alkali halide, a transition metal halide, and a transition metal to a vacuum reaction at a high temperature.

Example 7: Preparation of ₁₃ Cl ₆ LiMo chloride cluster compound A stoichiometric amount of LiCl, MoCl ₅ and Mo (all commercially available) was prepared and sealed in a Vycor glass tube under vacuum. The mixture was heated to 800 ° C for 20 days and then cooled to room temperature at 1 ° C/min to form LiMo ₆ Cl ₁₃ .

The redox active organic electrolyte molybdenum lithium chloride is used to prepare an alkali electrolyte of a base transition metal halide metal cluster compound such as, but not limited to, an alkali chloride molybdenum cluster compound such as, but not limited to, LiMo ₆ Cl ₁₃ It can be prepared by dissolving from about 10 grams to about 100 grams of LiMo ₆ Cl ₁₃ in about 100 milliliters to about 1000 milliliters of acetonitrile at room temperature to form an organic electrolyte of a lithium molybdenum chloride solution. As an alternative to acetonitrile, a solvent mixture such as dimethyl carbonate-ethylene carbonate (1:1 wt) can be used to replace acetonitrile.

The organic electrolyte and the organic electrolyte supporting the electrolyte molybdenum chloride to prepare lithium molybdenum chloride and the supporting electrolyte can be dissolved in lithium by using about 10 to about 20 g of a lithium salt (for example, LiPF ₆ , LiBF ₄ or a mixture thereof). It is prepared in an organic solution of molybdenum chloride (to a concentration of about 0.1 M to about 2 M, preferably about 1 M) to form a supporting electrolyte. Next, about 1 gram to about 10 grams of LiMo ₆ Cl _{12 is} added to about 100 milliliters of the supporting electrolyte to form an organic electrolyte of lithium molybdenum chloride.

Preparation of Salts and Salt-Containing Electrolytes of RAA Small polymeric anions can be used as small polymeric anions of the number of cations of 6 or less of RAA including, but not limited to, molybdate anions (eg, MoO ₄ ^2- or Mo ₂ O ₇ ^2- ), a tungstate anion (for example, WO ₄ ^2- and W ₂ O ₇ ^2- ), a vanadate anion (for example, V ₂ O ₇ ^4- and V ₄ O ₁₂ ^4- ), And citrate ions (for example, Nb ₆ O ₁₉ ^8- ).

In an alkaline aqueous solution having a pH of >7 (for example, an aqueous solution of molybdic acid-ammonium hydroxide), the main anions are typically MoO ₄ ^2- and NH ⁴⁺ . Commercially available salts that can be used as a source of MoO ₄ ^2- anions (eg, in alkaline solutions) include, but are not limited to, Li ₂ MoO ₄ , K ₂ MoO ₄ , (NH ₄ ) ₂ Mo ₂ O ₇ , ZnMoO ₄ , and combinations thereof. Sources of tungstate ions include, but are not limited to, Li ₂ WO ₄ , (NH ₄ ) ₁₀ H ₂ (W ₂ O ₇ ) ₆ salts. These salts are available from sources such as Sigma-Aldrich, Alfa Aesar et al.

a small polymeric anion of an acid salt, an aqueous electrolyte of molybdenum to prepare a small polymeric anion of molybdate, an aqueous electrolyte having a small anion (for example, MoO ₄ ^2- or Mo ₂ O ₇ ^2-) , which can be obtained by a monooxide (for example, MoO) ₃ or molybdate is prepared by dissolving in a base solution (for example, aqueous ammonium hydroxide, TMAH, TEAH, or a combination thereof) to form a solution. The solution is then concentrated to saturation, for example, by adding a greater amount of molybdate. The saturated solution is cooled to crystallize to form salts.

Ammonium Salt of Molybdate Ammonium 2 MoO ₃ is dissolved in an aqueous ammonium hydroxide solution (to a concentration of about 0.1 M to about 1.0 M) at a pH of from about 7 to about 14, at a temperature of from about 30 ° C to about 80 ° C. The solution is then concentrated to saturation and cooled. The remaining MoO ₃ was redissolved by adding a small amount of ammonium hydroxide, and then the solution was cooled to 0 ° C to obtain crystals of ammonium dimolybdate.

Example 8 Aqueous Ammonium Molybdate: Preparation of ammonium dimolybdate was dissolved in distilled water at a temperature of about 20 ° C (to a concentration of about 0.1 M to 1.0 M).

Anionic aqueous electrolyte molybdenum clusters The preparation of aqueous electrolytes of chlorinated molybdenum chloride cluster anions (eg, Mo ₆ Cl ₈ ^4- anions) can be prepared by placing from about 1.67 grams to about 16.7 grams of Mo ₆ Cl ₁₂ in the chamber. The solution is dissolved in about 100 ml to about 500 ml of an aqueous solution of about 0.1 M to about 3 M of HCl to form an acidic electrolyte comprising Mo ₆ Cl ₈ ^4- anion.

The metal counter cation (CounterCation) present in the salt in the redox active electrolyte may be present in the metal counter cation of any redox active salt and the additional salt utilized in the redox active electrolyte for use in the electrolyte solvent The solubility, as well as the ability to act to support the electrolyte and interact with the other electrode of the device, was chosen.

The metal counter cation present in the salt can be sufficiently dissolved in an aqueous solvent and an organic solvent (for example, by generating an acid of a transition metal ion cluster compound), thereby forming a supporting electrolyte, whereby the transition metal ion cluster The core and the ligand can be effectively turned into an anion, and the metal counter cation is (H ⁺ ).

The solubility of the metal counter cation in an organic solvent can be achieved by using a cation (for example, Li ⁺ , Na ⁺ , and combinations thereof). Improved solubility can be achieved by the use of an organic external ligand (eg, DMF). Examples of metal counter cations in organic solvents include, but are not limited to, Li ⁺ , lithium intercalation materials such as graphitic carbon, and elemental lithium.

The choice of metal counter cations can be based on interaction with an electrode. In an aqueous solvent, an anode (e.g., but not limited to, a nickel metal hydride alloys, e.g., LaNi _5, Pb metal, and combinations thereof) may be a protic host. In aqueous solvents, the cathode includes, but is not limited to, Ni(OH) ₂ , MnO ₂ , and combinations thereof. When the anode is an electrochemical double layer capacitor (EDLC) electrode, for example, a activated carbon compression body, metal countercations that can be used include, but are not limited to, NH ⁴⁺ , alkyl substituted ammonium, for example, tetramethylammonium. (NMe ⁴⁺ ), tetraethylammonium (NEt ⁴⁺ ), tetrabutylammonium (NBu ⁴⁺ ), and combinations thereof, wherein Me is methyl, Et is ethyl, and Bu is butyl.

A flow battery of an electrochemical device using two redox active electrolyte electrodes including a reaction vessel, an anode, a cathode, and a cation permeable membrane is shown in Fig. 2. Each of the anodes and cathodes contains densely packed conductive particles for electronic exchange with ions in an electrolyte (e.g., a redox active electrolyte). Conductive particles can include, but are not limited to, carbon felt, activated carbon, acetylene black, graphite, nickel foam, and mixtures thereof. The anode and cathode are separated by a cation permeable membrane such as, but not limited to, a Li ⁺ cation permeable membrane of a PVDF-PEO polymer mixture (eg, tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-) 7-octane sulfonic acid copolymer).

During operation of a flow battery, a catholyte solution having a redox active cation will pass through the cathode chamber whereby the cation is oxidized to a higher oxidation state. A catholyte solution having a redox active anion will pass through the anode compartment whereby the anion is reduced to a lower oxidation state, and in order to maintain electrical neutrality, cations from the cathode compartment migrate through the separator membrane into the anode compartment. This will continue until all ions are completely converted to their charge state. The cathode electrolyte and the anolyte can be supplied to the battery at a temperature of about 5 ° C to about 55 ° C. Upon discharge, the (fully charged) catholyte and anode electrolyte flow in opposite directions through the cathode and anode compartments, and the reaction is allowed to proceed in reverse to produce an output voltage across the current collector.

Cathodic electrolyte solutions that can be used include, but are not limited to, LiMo ₆ Cl ₁₃ , lithium phosphomolybdic acid, and mixtures thereof. Anode electrolyte solutions that can be used include, but are not limited to, LiMo ₆ Cl ₁₃ , lithium phosphomolybdic acid, and mixtures thereof. The cathode electrolyte and the anode electrolyte may be the same or different.

The catholyte solution and the anolyte solution are supplied to the flow battery at a rate sufficient to produce the desired electrical output. The rates of supply of the cathode electrolyte and the anolyte may be the same or different. The supply temperature of the solution may range from about 5 °C to about 55 °C. The supply temperatures of the cathode electrolyte and the anode electrolyte may be the same or different.

Flow Battery 1 - Organic Redox Active Electrolyte FIG. 2 shows an overflow cell 1 including a reaction vessel 5, wherein each of the anode chamber 20 and the cathode chamber 15 contains a packaged conductive material 20 (eg, a conductive carbon material, For example, carbon felt), which is separated by a Li ⁺ cation permeable membrane 25 (eg, PVDF-PEO of Figure 2). During operation, an organic redox active electrolyte of one of the metal cluster compounds (eg, LiMo ₆ Cl ₁₃ ) in an organic solvent (eg, acetonitrile) flows through each of the cathode chamber and the anode chamber to reach a An external anolyte tank (not shown) and an external cathode electrolyte tank (not shown). The Mo ₆ Cl ₈ ^4- ion in the electrolyte is reduced at the anode and oxidized at the cathode to create a chemical potential difference between the anode and the cathode. In order to maintain electrical neutrality, Li ⁺ ions cross from one electrode chamber to the other through the cation membrane. During discharge, the reaction direction is reversed and an output voltage is generated across the current collector 30 located on the side of the flow cell where current can be drawn.

The flow battery 2 - aqueous redox active electrolyte flow battery 2 is the same as the flow battery 1, except that the cathode electrolyte solution used on the anode side contains 1 M CrCl ₃ in 2 M HCl acid, and the cathode electrolyte solution on the cathode side For 0.1 M Mo ₆ Cl ₁₂ in 2M HCl. The membrane is Nafion which is permeable to H ⁺ .

Mixed EDLC (a redox active electrolyte electrode and an EDLC electrode) Figure 3 shows a hybrid EDLC-redox active capacitor 40 using an anode in the form of an EDLC type electrode and a redox active cathode. The hybrid capacitor includes a double layer negative electrode 45 (eg, YP 50 activated carbon), a separator film 55 (eg, Nafion), and a redox active positive electrode 60, such as a YP 50 activated carbon electrode, which includes a A redox active liquid electrolyte solution (for example, 1.0 M Mo ₆ Cl ₁₂ aqueous solution enclosed in a container (for example, a stainless steel coin type battery)). A current collector 50, such as stainless steel, is attached to the surface of the double layer negative electrode and the redox active electrode. In operation, reactive ions accumulate in the double layer negative electrode.

The cluster compound is preferred as the RAA in the redox active positive electrode because of its ability to achieve a high oxidation state, for example, the +12 Mo ₆ core can achieve +13 and +14 oxidation.

Mixed EDLC anode, organic solvent redox active electrolyte cathode capacitor - A mixed EDLC anode can be prepared from a mixture of 85% wt activated carbon, 5% wt acetylene black, and 10% wt polytetrafluoroethylene (Teflon). The mixture was compressed at 3000 PSI to produce a film carbon anode having a thickness of 100 μm. The disc of the film carbon anode is placed in a coin type battery. A 20 micron thick, porous polyethylene separator membrane (e.g., Hipore from Asahi Kasei) is placed on the film anode, and an electrode structure (e.g., the thin film carbon anode material) as the redox active electrolyte cathode is placed The upper portion of the separator membrane to create a three-layer assembly. The collection was immersed in 1 M tetrabutylammonium molybdenum chloride (TBA ₂ -Mo ₆ Cl ₁₄ ) in an acetonitrile:ethylene carbonate electrolyte solution for one hour to allow the electrolyte to be injected into the collection. ^THEO

Hybrid battery (redox active electrolyte electrode and battery electrode) Fig. 4 shows a hybrid battery-redox active electrolyte cathode using a negative electrode, a cation permeation separator membrane, and a redox active electrolyte cathode. The battery type negative electrode 70 undergoes a redox reaction with the cationic component of the electrolyte. Battery-type negative electrodes that can be used in hybrid batteries include, but are not limited to, lithium metal, which is a reversible electrode for lithium ions, sodium, which is a reversible electrode for Na ions, graphite carbon, lithium titanate, LiVO ₂ , all of which are It is capable of inserting lithium ions, nickel metal hydride, metal zinc, magnesium, and lead, each of which can be used as a negative electrode in an aqueous solution system. The battery type graphite carbon electrode is available from MTI, while all other metals are commercially available (Sigma, Alfa). Nickel metal hydrides are available from suppliers such as Molport. A current collector, such as stainless steel, is attached to the surface of the negative electrode and the redox active electrolyte cathode. A cation permeation separator membrane 75 is between the redox active electrolyte cathode 80 and the negative electrode 70. Cationic separator membranes that may be used include, but are not limited to, Nafion, wherein the cation is H+. As far as the Li+ cation is concerned, a polyethylene oxide (PEO)-based polymer electrolyte can be used as a cation separator membrane. A porous separator membrane (e.g., a polypropylene or polyethylene based separator from Celgard and Asahi Kaseim) may alternatively or in combination with a cation separator membrane be used to limit the diffusion of RAA while Allows for a high degree of diffusion of the cations and also provides an additional volume for the electrolyte solution.

Next, a non-limiting example of a hybrid battery will be described. The hybrid battery uses lithium metal as a negative electrode, and uses a redox-active LiMo ₆ Cl ₁₃ electrolyte solution (1M LiMo ₆ Cl ₁₃ in a ratio of 70:30 (mole) of dimethyl carbonate and ethyl carbonate). A high surface area carbon electrode in the mixture solvent) acts as a redox active electrolyte cathode, and a 0.04 mm thick Nafion permeable membrane separates the negative electrode from the cathode. A stainless steel current collector 90 is attached to the anode and cathode.

A hybrid battery anode, a redox active organic solvent electrolyte battery anode can be prepared by compressing lithium metal onto a copper foil to form a Li layer having a thickness of up to about 100 μm. A Li permeable membrane is placed on top of the lithium layer. The Li permeable membrane may be a polyethylene oxide (PEO), a PEO polymer containing a dissolved Li salt (for example, LiClO ₄ , LiPF ₆ , or a mixture thereof), and a plasticizer (for example, propylene carbonate). Ester). A typical PEO film can be made by dissolving about 5 grams of PEO in about 25 milliliters of acetonitrile, pouring the solution onto a non-stick surface, and allowing it to dry.

When PEO is used in a Li permeable film, the film may have a thickness of up to about 50 μm. A porous polymer separator (e.g., a polyethylene film such as Hipore from Asahi Kaseim) is placed on the Li permeable membrane. The separator membrane can have a thickness of from about 10 μm to about 50 μm. A carbon cathode consisting of 85% activated carbon, 5% acetylene black, and 10% polytetrafluoroethylene binder from Sigma-Aldrich was placed on the porous polymer separator to form a hybrid battery anode. The carbon cathode disk may have a thickness of from about 20 μm to about 200 μm, for example, about 100 μm. Carbon cathodes typically have a porosity of from about 20% to about 50% (e.g., from about 25% to about 40%). Both the porous polymer separator and the cathode are immersed in a redox active organic electrolyte which will typically include Li cations. Non-limiting examples of the redox active organic electrolyte include lithium hexafluorophosphate and dehydrated lithium phosphomolybdic acid dissolved in 1 M ethylene carbonate: dimethyl carbonate.

A hybrid battery anode, a redox active aqueous electrolyte cathode-anode can be prepared from a Pb metal film having a thickness of from about 100 μm to about 500 μm. The disc of the Pb film was placed on a porous membrane immersed in sulfuric acid and placed in a coin-type battery can to form an anode. The membrane may be a microporous three layer membrane (PP/PE/PP), for example, C480 from Celgard. Typically, the films have a porosity of from about 40% to about 60%. A cation permeable membrane, e.g., Nafion ^TM is placed on top of the anode. A carbon cathode (e.g., from Sigma Aldrich) is placed over the cation permeable membrane to form a mixed electrode, redox active electrolyte electrode assembly. Typically, the carbon cathode has 85% activated carbon, 5% acetylene black, and 10% polytetrafluoroethylene adhesive from Sigma-Aldrich, which is composed of a thickness of about 100 μm and is immersed in a molybdenum containing dissolved to 1 M before use. Acid H ₄ [SiMo ₁₂ O ₄₀ ] in 1 M HCl electrolyte.

Discharge/Charge of the Mixed, Redox Active Electrolyte Electrode The RAA (eg, in the form of a polymeric side oxymetallate) is in its highest oxidation state prior to discharging the mixed, redox active electrolyte electrode. During discharge, the RAA is attracted to the electrode particles as shown in Figure 1. Upon reaching the electrode particles, the RAA is reduced by obtaining one or more electrons. The reduced RAA diffuses away from the electrode particles to be replaced by a new RAA. This will continue until the electrode reaches a fully discharged state, at which point the available RAA is in a lower oxidation state. In order to maintain electrical neutrality in the redox active electrolyte, a cation (or anion) is transferred between the cathode electrode and the anode electrode, for example, through a separator membrane, or a specific ion permeable membrane.

The redox active electrode can be assembled in a discharged state, and after the collection, the mixed redox active electrolyte electrode can be discharged by an electric current, whereby electrons can be taken from the positive electrode and supplied to the negative electrode, where In the concept, a cluster compound having a high oxidation state can undergo an oxidation reaction in a redox active positive electrode and an electron donating carbon particle in a negative electrode.

Flow Battery Operation During discharge of a flow battery, a voltage is applied across the current collector of the reaction vessel to produce a positive potential on the cathode. The cathode electrolyte is supplied through the cathode electrode chamber of the battery, whereby the RAA in the redox active electrolyte is oxidized to a higher oxidation state. During the flow of the catholyte, the anolyte is supplied through the anode electrode chamber whereby the cations are reduced to a lower oxidation state. In order to maintain charge neutrality in the catholyte and anolyte solutions, cations from the cathode electrode compartment pass through the separator membrane to the anode electrode compartment. This can continue until the ions are switched to their charged state. During discharge of the flow battery, the charged anode and cathode electrolyte solutions are fed back to the reaction vessel and the reaction is allowed to reverse to produce an output voltage. The output voltage is generated across the current collector such that energy can be removed from the battery.

Mixed EDLC Operation In a mixed EDLC device, charge transfer at the positive redox active EDLC electrode is compensated by equal amount of charge transfer at the negative EDLC electrode. A cationic species from the dissolved salts in the redox active electrolyte migrates toward the negative EDLC electrode and accumulates on the particles of the negative electrode, as exemplified in FIG. This way of storing charge in the EDLC electrode achieves very fast kinetics and can have high energy capacity and high power.

Hybrid Battery Operation When the negative electrode is a battery electrode, the cation is reduced and stored in (or on) the negative electrode of the cell, as exemplified in FIG. Such a manner of storing electric charge in a hybrid battery using a redox active electrolyte can provide a high capacity per unit volume.

1. . . Overflow battery

5. . . Reaction vessel

15. . . Cathode chamber

20. . . Anode chamber, package conductive material

25. . . Li ⁺ cation permeable membrane

30. . . Current collector

40. . . Mixed EDLC-redox active capacitor

45. . . Double layer negative electrode

50. . . Current collector

55. . . Separator membrane

60. . . Redox active positive electrode

70. . . Battery type negative electrode

75. . . Cationic permeation separator membrane

80. . . Redox active electrolyte cathode

90. . . Stainless steel current collector

Figure 1 is a schematic diagram of redox active anions (RAA) and electron transport between electrode particles at an electrode; Figure 2 shows a schematic of a flow battery; Figure 3 shows a schematic of a hybrid electrochemical energy device Wherein, the negative electrode is an electrochemical double layer capacitor (EDLC) electrode; and FIG. 4 shows a schematic diagram of a hybrid electrochemical energy storage device, wherein the negative electrode is a battery type (Faraday) electrode.

1. . . Overflow battery

5. . . Reaction vessel

15. . . Cathode chamber

20. . . Anode chamber, package conductive material

25. . . Li ⁺ cation permeable membrane

30. . . Current collector

Claims (19)

An electrochemical energy storage device comprising a cathode, an anode, and a cation permeation separator membrane between the cathode and the anode, wherein the apparatus comprises a redox active electrolyte, wherein the electrolyte comprises a selected from the group consisting of Mo ₆ Cl ₁₂ ,HMo ₆ Cl ₁₃ ,LiMo ₆ Cl ₁₃ ,Li ₂ MoO ₄ ,Li ₂ Mo ₂ O ₇ ,Na ₂ MoO ₄ ,Na ₂ Mo ₂ O ₇ ,NaMo ₆ Cl ₁₃ ,NaMo ₆ Cl ₁₃ ,Li ₂ WO ₄ , Li ₂ W ₂ O ₇ , and one or more redox active salts of the group of combinations thereof for use in generating redox active anions in the redox active electrolyte. The apparatus of claim 1, wherein the redox active anions comprise any of a polymeric anion, a polymeric side oxymetallate, and a metal cluster ion. The device of claim 2, wherein the polymeric anion comprises any one of the formula [M _n r] ^y- or the formula (M _n Xv) ^z- , wherein M is V, Nb, Ta, Any one of Cr, Mo and W cations, n is 2 to 6, and r is any one of O, F, and Cl, wherein ^y is an anion charge in [M _n r] ^y- , the molecular formula (M _n Xv) ^z- , M is Mo, W, Nb, Tc, Ru, Rh, Ta, Re, Os, or Ir, X is a ligand, v is 7 to 24, and n is 2 to 7. The device of claim 2, wherein the polymeric side oxymetallate comprises a molecular formula MX ₆ octahedron or a molecular formula [ZO ₄ (MO ₃ ) _n ] ^y− , or a molecular formula AM ₆ O ₂₄ ^n- Or any of AM ₁₂ O ₄₀ ^n- , wherein M is any one of Si, Ge, Ga, B, P, V, Nb, Ta, Cr, Mo, or W, and X is oxygen, sulfur, fluorine Any one of the formulas [ZO ₄ (MO ₃ ) _n ] ^y− , X is any one of Si, P, S, Ge, As, Se, and M is Mo, W, Nb, V, Tc Any of them, n is 6 to 22, and y is an anion charge, and the formula is AM ₆ O ₂₄ ^n- or AM ₁₂ O ₄₀ ^n- or A ₂ M ₁₈ O ₆₂ ^n- , A is B, Al, Ga Any of Si, Ge, Sn, P, As, Sb, Se, Te, and M is any of V, Nb, Ta, Mo or W, and m is an anion charge. The device of claim 2, wherein the metal cluster ions comprise the molecular formula M ₆ X ₈ ⁿ⁺ , wherein M is Nb, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, Re, Os, Ir, Pt, Au, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, and X is S, Se, Te, F, Cl Any of Br, I, At, and n is a charge on the ion, or a molecular formula of Mo ₆ X ₁₂ , wherein X is any of F, Cl, Br, I, At, a halide of basic Mo NMo ₆ X _{12 is} included wherein X is any of F, Cl, Br, I, At, and N is any of Na, K, Rb, Cs. The apparatus of claim 1, wherein the anode is any one of lithium metal, sodium, graphitic carbon, nickel metal hydride, metallic zinc, magnesium, and lead. The device of claim 1, wherein the cation membrane is a tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octane sulfonic acid copolymer and polyethylene oxidation. Any of the things. The device of claim 1, wherein the device is a capacitor, the negative electrode is an EDLC type electrode, and the cathode comprises the redox active electrolyte. The device of claim 1, wherein the device is a flow battery. The device of claim 1, wherein the salts have one or more redox active anions, wherein the redox active ions are heteropolymeric anions comprising a transition metal core And at least one ligand, wherein the metal core comprises any one of W, Y, Zr, Nb, Tc, Ru, Rh, Ta, Re, Os ions, and the ligand is O ^2- , S ^2- , F ^- , Cl ^- , Br ^- , I ^- , CH ₃ , C ₂ H ₅ , C ₃ H ₇ and C ₄ H ₉ , amines, carbonates, phenols, ethers, and combinations thereof Any of them. The device of claim 10, wherein the heterogeneous polymeric anion comprises a transition metal core and 6 to 8 ligands. The device of claim 1, wherein the cation permeable membrane is permeable to a cation selected from the group consisting of NH ⁴⁺ , tetramethylammonium, NMe ⁴⁺ , tetraethylammonium, NEt ⁴⁺ , tetrabutylammonium, NBu ⁴⁺ , and combinations thereof. The apparatus of claim 12, wherein the heterogeneous polymeric anion comprises a transition metal core having six transition metal ions selected from Groups 4-7, wherein the transition metal ions are An octahedral form surrounded by 8 or more ligands selected from the group consisting of F, Cl, Br, I, S, O, Se, and Te. The apparatus of claim 9, wherein the flow battery comprises: an anode portion, a cathode portion, and an ion selective membrane for separating the anode portion from the cathode portion, the anode portion Conductive material for electronic exchange with an anolyte solution contacting the conductive material, the cathode portion having a conductive material for electronic exchange with a catholyte solution contacting the conductive material, wherein the anolyte and cathode At least one of the electrolytes includes a redox active electrolyte. The device of claim 14, wherein the anolyte and the catholyte are the same or different. The device of claim 8, wherein the capacitor comprises an electrochemical double-layer pad container comprising an electrode having the redox active electrolyte. The device of claim 1, wherein the device is a hybrid battery having a negative electrode, a cation permeation separator membrane, and a redox active electrolyte cathode, wherein the negative electrode is suitable for A cation present in the redox active electrolyte undergoes a redox reaction. The apparatus of claim 17, wherein the negative electrode is any one of lithium metal, sodium, graphitic carbon, lithium titanate, LiVO ₂ , nickel metal hydride, metal zinc, magnesium, and lead. The device of claim 17, wherein the negative electrode comprises lithium metal and the cathode is carbon treated with a redox active LiMo ₆ Cl ₁₃ electrolyte solution.