CN107004912B - Electrolyte and metal hydride battery - Google Patents

Electrolyte and metal hydride battery Download PDF

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CN107004912B
CN107004912B CN201580061501.3A CN201580061501A CN107004912B CN 107004912 B CN107004912 B CN 107004912B CN 201580061501 A CN201580061501 A CN 201580061501A CN 107004912 B CN107004912 B CN 107004912B
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methylimidazole
ethyl
butyl
bis
electrolyte composition
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CN107004912A (en
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K·扬
J·内伊
D·翁
W·李
L·王
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BASF Corp
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Priority claimed from US14/540,521 external-priority patent/US20160141725A1/en
Priority claimed from US14/540,461 external-priority patent/US20160141724A1/en
Priority claimed from US14/540,445 external-priority patent/US20160141727A1/en
Priority claimed from US14/540,537 external-priority patent/US10243240B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A metal hydride battery comprising an electrolyte composition comprising a proton acid, a protic ammonium compound, a protic oxygen
Figure DDA0001292960310000011
Compound, aprotic ammonium compound, aprotic oxygen
Figure DDA0001292960310000012
Compound, aprotic

Description

Electrolyte and metal hydride battery
The present invention relates to Metal Hydride (MH) batteries comprising certain electrolyte compositions.
There has been great progress in optimizing the electrochemical performance and cycle life of metal hydride batteries by optimizing the electrodes. The electrolyte of a metal hydride cell is currently a 30 wt% aqueous solution of KOH. Aqueous KOH electrolytes are corrosive to some electrode materials. Aqueous electrolytes are also limited by the evolution potential of hydrogen and oxygen from water. The present invention is directed to improved electrolytes.
Summary of The Invention
A metal hydride battery (cell) is disclosed comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein
The electrolyte composition comprises one or more selected from protonic acid, protonic ammonium compound, protonic oxygen
Figure BDA0001292960300000011
Compound, aprotic ammonium compound, aprotic oxygen
Figure BDA0001292960300000012
Compound, aprotic
Figure BDA0001292960300000013
A compound and an ionic compound of an alkali metal or alkaline earth metal salt.
Also disclosed is a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein, and an electrolyte composition, wherein
The electrolyte composition comprises one or more ionic compounds selected from alkali or alkaline earth metal hydroxides and alkoxides and an organic solvent.
Also disclosed is a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein, and an electrolyte composition, wherein
The electrolyte composition comprises one or more ionic compounds selected from alkali metal hydroxides, water and one or more further components selected from organic solvents, further ionic compounds and additives.
Also disclosed is a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein, and an electrolyte composition, wherein
The electrolyte composition comprises one or more ionic compounds selected from carboxylate compounds and carboxylic acids.
Also disclosed is a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein, and an electrolyte composition, wherein
The cell exhibits a nominal open circuit voltage of about 1.5 to about 5.0V.
The invention also relates to a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein, and an electrolyte composition, wherein said electrolyte composition has a pH of less than or equal to about 7.
The invention also relates to a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein the half-cell charge/discharge electrochemical reaction at the positive electrode upon application of a potential across the battery is:
Figure BDA0001292960300000021
detailed disclosure
The electrolyte compositions can be used in metal hydride batteries (metal hydride batteries). A metal hydride battery comprises at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein, and an electrolyte composition in contact with the electrodes.
The active material of the negative electrode (anode material) comprises AB capable of storing hydrogenxType alloy wherein x is from about 0.5 to about 5. A is a hydride-forming element and B is a weak or non-hydride-forming element. The alloy is capable of reversibly absorbing and desorbing hydrogen.
ABxType alloys are for example of the following type (simple examples): AB (HfNi, TiFe, TiNi), AB2(Mn2Zr，TiFe2)，A2B(Hf2Fe，Mg2Ni)，AB3(NdCo3，GdFe3)，A2B7(Pr2，Ni7，Ce2Co7) And AB5(LaNi5，CeNi5)。
For example, the anode active material contains Zr, Mn, V, Fe, and Ni; zr, Mn, V, Co and Ni; ti, V and Ni; la and Ni; ti, Zr, Ni, Cr and one or more elements selected from the group consisting of Al, Si, V, Mn, Fe, Co, Cu, Nb, Ag and Pd; zr, Mo and Ni; or a lanthanide metal and at least one metal selected from Ni and Co.
The anode material may comprise a disordered multicomponent material comprising one or more host elements selected from V, Zr, Nb, La, Si, Ca, Sc, Mg, Ti and Y and one or more modifier elements selected from Cu, Mn, C, Fe, Ni, Al, Co, Mo, W, Ti, Li and Re. The host element is typically a hydride precursor. For example, the host element is one or more of Ti, Mg and V, and the modifier includes one or more of Ni, Cu, Fe and Al. Such disordered materials are disclosed in U.S. patent No. 4,623,597.
The anode material may comprise a multi-component, multi-phase alloy comprising V, Ti, Zr and Ni or V, Ti, Zr, Ni and Cr and one or more modifying elements selected from Al, Mn, Mo, Cu, W, Fe and Co. Such multiphase materials are taught in U.S. patent No.5,096,667.
The anode material may comprise a disordered material comprising (matrix alloy)aCobMncFedSneWherein the base alloy comprises 0.1 to60 atomic percent (at%) Ti, 0.1 to 40 at% Zr, 0 to 60 at% V, 0.1 to 57 at% Ni, and 0 to 56 at% Cr; b is 0 to 7.5 atomic%, c is 13 to 17 atomic%, d is 0 to 3.5 atomic%, and e is 0 to 1.5 atomic%, wherein a, b, c, d, and e equal 100 atomic%. Such alloys are disclosed in U.S. Pat. No.5,536,591.
The anode active material is, for example, LaNi5Type alloy, modified LaNi5Type alloys, TiNi type alloys or modified TiNi type alloys. For example, the anode active material contains one or more elements selected from Ti, V and Zr, and one or more elements selected from Ni, Cr, Co, Mn, Mo, Nb, Fe, Al, Mg, Cu, Sn, Ag, Zn and Pd; or the anode active material contains one or more elements selected from Sc, Y, La, Ce, Pr, Nd, Sm, and Mm, and one or more elements selected from Ni, Cr, Co, Mn, Fe, Cu, Sn, Al, Si, B, Mo, V, Nb, Ta, Zn, Zr, Ti, Hf, and W. Such alloys may also include one or more glass forming elements selected from Al, B, C, Si, P, S, Bi, In and Sb. Such materials are advantageously disordered multicomponent materials having a hydrogen storage density greater than 1.2E23/cc or greater than 1.5E 23/cc. Such a material is disclosed in U.S. patent No.5,840,440.
The anode material may comprise a modified Ti-V-Zr-Ni-Mn-Cr alloy comprising (matrix alloy)aCobFecAldSneWherein the base alloy comprises 0.1 to 60 atomic% Ti, 0.1 to 40 atomic% Zr, 0 to 60 atomic% V, 0.1 to 57 atomic% Ni, 5 to 22 atomic% Mn, and 0 to 56 atomic% Cr, b is 0.1 to 10 atomic%, c is 0 to 3.5 atomic%, d is 0.1 to 10 atomic%, and e is 0.1 to 3 atomic%. Suitable materials are taught in U.S. patent No.6,270,719.
Suitable anode materials may include AB2Type alloys, e.g. modified TiMn2An alloy comprising 2 to 5 at% Zr, 26 to 33 at% Ti, 7 to 13 at% V, 8 to 20 at% Cr, 36 to 42 at% Mn and one or more of 1 to 6 at% Ni, 2 to 6 at% Fe and 0.1 to 2 at% Al. The alloy may also beContaining up to 1 atomic% of Mm. For example Zr3.63Ti29.8V8.82Cr9.85Mn39.5Ni2.0Fe5.0Al1.0Mm0.4；Zr3.6Ti29.0V8.9Cr10.1Mn40.1Ni2. 0Fe5.1Al1.2；Zr3.6Ti28.3V8.8Cr10.0Mn40.7Ni1.9Fe5.1Al1.6And Zr1Ti33V12.54Cr15Mn36Fe2.25Al0.21. Such an alloy is disclosed in U.S. patent No.6,536,487.
Suitable anode materials may include alloys wherein A5B19La of the formula La having a type structure of 40 atomic% or moreaR1-a- bMgbNic-d-eWherein a is more than or equal to 0 and less than or equal to 0.5 atomic percent, b is more than or equal to 0.1 and less than or equal to 0.2 atomic percent, c is more than or equal to 3.7 and less than or equal to 3.9 atomic percent, d is more than or equal to 0.1 and less than or equal to 0.3, and d is more than or equal to 0 and less than or equal to 0.2. These alloys are taught in U.S. patent No.7,829,220.
The anode material may include hydrogen absorbing alloy particles containing at least Ni and a rare earth. The particles may have a surface layer and an interior, wherein the surface layer has a greater nickel content than the interior, and nickel particles having a size of 10nm to 50nm are present in the surface layer. The material may include an alloy Ln1-xMgxNia-b-cAlbZcWherein Ln is one or more rare earth elements, Z is one or more of Zr, V, Bn, Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si, P and B, x is more than or equal to 0.05 and less than or equal to 0.3 atomic percent, a is more than or equal to 2.8 and less than or equal to 3.9 atomic percent, B is more than or equal to 0.05 and less than or equal to 0.25 atomic percent, and c is more than or equal to 0.01 and less than or equal to 0.25 atomic percent. Such materials are taught, for example, in U.S. patent No.8,053,114.
The anode material may include a material having a composition containing at least A2B7Type structure and A5B19A multiphase crystalline structure of type structure and a surface layer having a nickel content greater than bulk. The alloy may be of the formula Ln1-xMgxNiy-a-bAlaMbWherein Ln is one or more rare earths including Y,m is one or more of Co, Mn and Zn, wherein x is more than or equal to 0.1 and less than or equal to 0.2 atom percent, y is more than or equal to 3.5 and less than or equal to 3.9 atom percent, a is more than or equal to 0.1 and less than or equal to 0.3 atom percent, and b is more than or equal to 0 and less than or equal to 0.2. Such a material is disclosed in U.S. patent No.8,124,281.
The anode material may include the formula Ln1-xMgx(Ni1-yTy)zWherein Ln is one or more of lanthanides, Ca, Sr, Sc, Y, Ti, Zr and Hf, T is one or more elements selected from the group consisting of V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Al, Ga, Zn, Sn, In, Cu, Si, P and B, wherein 0<x is less than or equal to 1 atom percent, y is less than or equal to 0 and less than or equal to 0.5 atom percent, and z is less than or equal to 4.5 atom percent and more than or equal to 2.5. Suitable alloys are taught in U.S. patent No.8,257,862.
The anode material may include La, Nd, Mg, Ni and Al; la, Nd, Mg, Ni, Al and Co; la, Pr, Nd, Mg, Ni and Al or La, Ce, Pr, Nd, Ni, Al, Co and Mn as taught in U.S. Pat. No.8,409,753. The alloy was prepared by mixing the elements, heating to melt and cooling under argon in a high frequency induction furnace to form a ingot.
The anode material may comprise AB2A multiphase alloy of a type major phase and a second phase. The material is modified with a modifier element. For example, the alloy includes Ti, Zr, B, Ni and a modifier. The modifier may be a light rare earth such as Y. The alloy may be of the formula TiAZrB- XYXVCNiDMEWherein A, B, C and D are each greater than 0 and less than or equal to 50 at%, X is greater than 0 and less than or equal to 4 at%, M is one or more metals selected from Co, Cr, Sn, Al and Mn, and E is 0 to 30 at%. These materials are taught in U.S. publication No. 2013/0277607.
The anode material may comprise modified A2B7A hydrogen storage alloy. For example AxByAn alloy, wherein a comprises at least one rare earth element and further comprises Mg; b comprises at least Ni, and the atomic ratio of X to Y is 1:2 to 1:5, such as 1:3 to 1: 4. The alloy may be modified with one or more elements selected from B, Co, Cu, Fe, Cr and Mn. The atomic ratio of Ni to modifier can be 50:1 to 200: 1. The rare earth includes La, Ce, Nd, Pr and Mm. The atomic ratio of rare earth to Mg may be 5:1 to 6: 1. The B element may also include Al, wherein the atomic ratio of Ni to Al may be 30:1 to 40: 1. The surface of the alloy may include a region of catalytic metal supported in a porous oxide support matrix. The catalytic metal region may be Ni or a Ni alloy.
The anode material can be an ABx high capacity hydrogen storage alloy, wherein x is from about 0.5 to about 5, and the discharge capacity is greater than or equal to 400mAh/G, greater than or equal to 425mAh/G, greater than or equal to 450mAh/G or greater than or equal to 475 mAh/G.
The anode material is, for example, a magnesium (Mg) -containing high-capacity MH alloy, such as AB, AB comprising Mg and Ni2Or A2A type B alloy. For example, the current anode material is MgNi, MgNi2Or Mg2And (3) Ni. Such Mg and Ni-containing alloys may be modified by one or more elements selected from rare earth elements and transition metals. For example, anode materials comprising Mg and Ni may be modified by one or more elements selected from Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Ce, Pr, Nd, Mm, Pd, Pt, Nb, Sc and Ca.
For example, suitable anode materials include Mg and Ni and optionally one or more elements selected from Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Ce, Pr, Nd, Mm, Pd, Pt, Nb, Sc and Ca.
Mm is "mischmetal". mischmetal is a mixture of rare earth elements. For example, Mm is a mixture comprising La, Nd and Pr, e.g. comprising Ce, La, Nd and Pr.
Magnesium-containing MH alloys are particularly susceptible to corrosion in 30 weight percent (wt%) KOH electrolytes.
For example, suitable MH alloys include MgNi, Mg0.8Ti0.2Ni，Mg0.7Ti0.3Ni，Mg0.9Ti0.1Ni，Mg0.8Zr0.2Ni，Mg0.7Ti0.225La0.075Ni，Mg0.8Al0.2Ni，Mg0.9Ti0.1Ni，Mg0.9Ti0.1NiAl0.05，Mg0.08Pd0.2Ni，Mg0.09Ti0.1NiAl0.05，Mg0.09Ti0.1NiAl0.05Pd0.1，Mg50Ni45Pd5，Mg0.85Ti0.15Ni1.0，Mg0.95Ti0.15Ni0.9，Mg2Ni，Mg2.0Ni0.6Co0.4，Mg2Ni0.6Mn0.4，Mg2Ni0.7Cu0.3，Mg0.8La0.2Ni，Mg2.0Co0.1Ni，Mg2.1Cr0.1Ni，Mg2.0Nb0.1Ni，Mg2.0Ti0.1Ni，Mg2.0V0.1Ni，Mg1.3Al0.7Ni，Mg1.5Ti0.5Ni，Mg1.5Ti0.3Zr0.1Al0.1Ni，Mg1.75Al0.25Ni and (MgAl)2Ni，Mg1.70Al0.3Ni。
For example, the anode material of the present invention is an alloy of Mg and Ni in an atomic ratio of about 1:2 to about 2:1, which may be modified by one or more elements selected from Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Ce, Pr, Nd, Mm, Pd, Pt, Nb, Sc, and Ca. The one or more modifying elements may be present at about 0.1 to about 30 atomic percent or about 0.25 to about 15 atomic percent or about 0.5 atomic percent, about 1 atomic percent, about 2 atomic percent, about 3 atomic percent, about 4 atomic percent or about 5 atomic percent to about 15 atomic percent based on the total alloy. The atomic ratio of Mg and Ni is, for example, about 1: 1.
Suitable anode materials may comprise Mg and Ni in an atomic ratio of about 1:2 to about 2:1, and further comprise Co and/or Mn. Suitable anode materials are for example Mg52Ni39Co6Mn3And Mg52Ni39Co3Mn6。
Suitable high capacity anode materials are disclosed, for example, in U.S. patent nos. 5,616,432 and 5,506,069.
The alloy may be formed by melt spinning rapid solidification and/or mechanical alloying. Other methods include RF sputtering, laser ablation.
The active material of the positive electrode (cathode material) participates in charge-discharge reactions. The active material is, for example, a nickel hydroxide active material, i.e., nickel hydroxide or modified nickel hydroxide.
The cathode material can include a heterogeneous disordered nickel hydroxide material having at least one modifier. The at least one modifier is, for example, a metal oxide alloy, a metal hydride and/or a metal hydride alloy. For example, the modifier is selected from Al, Ba, Ca, F, K, Li, Mg, Na, Sr, Bi, Co, Cr, Cu, Fe, In, LaH3，Mn，Ru，Sb，Sn，TiH2TiO and Zn. These materials are taught in U.S. patent No.5,348,822.
Suitable cathode materials may include a disordered heterogeneous nickel hydroxide matrix including at least one modifier, for example, 3 modifiers selected from F, Li, Na, K, Mg, Ba, Ln, Se, Nd, Pr, Y, Co, Zn, Al, Cr, Mn, Fe, Cu, Zn, Sc, Sn, Sb, Te, Bi, Ru and Pb. Suitable cathode materials are taught, for example, in U.S. patent No.5,637,423.
The cathode material may include nickel hydroxide modified with one or more group II elements and Co in a solid solution state. These materials are taught in U.S. patent No.5,366,831.
The cathode active material may include nickel hydroxide and one or more components selected from cobalt, cobalt hydroxide and cobalt oxide and carbon powder. The cathode material may also comprise compounds of Ca, Sr, Ba, Cu, Ag or Y, e.g. Ca (OH)2，CaO，CaF2，CaS，CaSO4，CaSi2O5，CaC2O4，CaWO4，SrCO3，Sr(OH)2，BaO，Cu2O，Ag2O，Y2(CO3)3Or Y2O3. Suitable cathode materials are taught, for example, in U.S. patent No.5,451,475.
The cathode active material may include a metal oxide and an oxide of one or more of Co, Ca, Ag, Mn, Zn, V, Sb, Cd, Y, Sr, Ba and Ca, Sr, Ba, Sb, Y or Zn. The metal oxide is, for example, nickel oxide and/or manganese oxide. Such active materials are taught in U.S. patent No.5,455,125.
The cathode material may comprise nickel hydroxide and a further component selected from Y, In, Sb, Ba and Be and Co and/or Ca. Such a material is disclosed in U.S. patent No.5,466,543.
The cathode material may be prepared by reacting nickel sulfate and ammonium hydroxide to form a nickel ammonium complex; the complex is then reacted with sodium hydroxide to form nickel hydroxide. The method can provide nickel hydroxide comprising one or more of Co, Zn, and Cd. These materials are taught in U.S. patent No.5,498,403.
The cathode active material may include nickel hydroxide and cobalt oxyhydroxide as taught in U.S. patent No.5,489,314.
The cathode material may include nickel hydroxide, cobalt monoxide and elemental zinc as taught in U.S. patent No.5,506,070.
The cathode material may include nickel hydroxide, nickel powder, a second powder, and at least one of cobalt, cobalt hydroxide, and cobalt oxide. The second powder contains one or more of Ca, Sr, Ba, Cu, Ag, and Y. These materials are taught in U.S. patent No.5,571,636.
The cathode active material may include particles of nickel hydroxide or manganese hydroxide having a conductive material at least partially embedded therein. The conductive material may be, for example, nickel alloy, copper alloy; a metal oxide, nitride, carbide, silicide or boride; or carbon (graphite). These materials are disclosed in U.S. Pat. No.6,177,213.
The cathode material may comprise nickel hydroxide particles comprising at least three modifiers selected from Al, Bi, Ca, Co, Cr, Cu, Fe, In, La, rare earth elements, Mg, Mn, Ru, Sb, Sn, Ti, Ba, Si, Sr and Zn. For example, the nickel hydroxide particles can comprise at least four modifiers, such as Ca, Co, Mg, and Zn. Such a material is disclosed in U.S. patent No.6,228,535.
Active cathode materials include, for example, nickel hydroxide and carbon materials such as graphite. The active material may also comprise a polymeric binder. The polymeric binder is, for example, a thermoplastic organic polymer, for example selected from the group consisting of polyvinyl alcohol (PVA), polyethylene oxide, polypropylene oxide, polybutylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyethylene, polypropylene, polyisobutylene, polyvinyl chloride, polyvinylidene fluoride, Polytetrafluoroethylene (PTFE), Fluorinated Ethylene Propylene (FEP), Perfluoroalkoxy (PFA), polyvinyl acetate, polyvinyl isobutyl ether, polyacrylonitrile, polymethacrylonitrile, polymethyl methacrylate, polymethacrylate, polyethyl methacrylate, allyl acetate, polystyrene, polybutadiene, polyisoprene, polyoxymethylene, polyoxyethylene, polycyclosulfide, polydimethylsiloxane, polyesters such as polyethylene terephthalate, polycarbonates and polyamides. Blends and copolymers as described above are also suitable. The polymeric binder may also be an elastomer or rubber, such as a styrene-butadiene copolymer, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-styrene-butadiene block copolymer, a styrene-ethylene-butadiene-styrene block copolymer or a styrene-acrylonitrile-butadiene-methyl acrylate copolymer. Suitable active materials are taught, for example, in U.S. patent No.6,617,072.
The cathode active material may include nickel hydroxide and nickel oxyhydroxide as taught in U.S. patent No.7,396,379.
Typically, the cathode active material particles are formed in a sintered or slurried (pasted) electrode. The slurried electrode may be made by mixing the material with various additives and/or binders and applying the slurry to a conductive support. Preferably, one or more cobalt additives are added to the slurried electrode. The cobalt additive may include Co and/or CoO to enhance conductivity, improve utilization, and reduce resistance of the positive electrode.
Typically, the cathode active material is nickel hydroxide or modified nickel hydroxide. The modified nickel hydroxide may comprise one or more modifiers, such as Co, Cd,ag, V, Sb, Ca, Mg, Al, Bi, Cr, Cu, Fe, In, a rare earth element, Mn, Ru, Sn, Ti, Ba, Si, Sr or Zn. Suitable modified nickel hydroxides are (Ni, Co, Zn) (OH)2For example in the form of a spherical powder. In the modified nickel hydroxide, the nickel is generally present at a level of 80 atomic% or more, for example 90 atomic% or more, based on the metal.
For example, MH batteries comprise at least one negative electrode comprising AB capable of reversibly storing hydrogenxA type alloy and comprises at least one positive electrode comprising a nickel hydroxide or modified nickel hydroxide active material.
A separator may be present that separates the negative electrode from the positive electrode. The separator is a nonwoven web of, for example, natural or synthetic fibers. The natural fiber comprises cotton. Synthetic fibers include polyamides, polyesters, polypropylene (PP), Polyethylene (PE), PP/PE copolymers, Polytetrafluoroethylene (PTFE), polyvinyl chloride, and glass.
The ionic compound may be selected from Bronsted acids (protonic acids) and protic ammonium compounds or oxygen
Figure BDA0001292960300000093
Protic compounds of the compounds. The bronsted acid, for example, has a pKa of less than or equal to about 5.
The ionic compound may be selected from ammonium compounds, oxygen
Figure BDA0001292960300000091
A compound which is a mixture of a compound having a structure,
Figure BDA0001292960300000092
an aprotic compound of a compound and an alkali metal or alkaline earth metal compound.
The ionic compound comprises a cation and an anion.
The alkali metal or alkaline earth metal cation comprises Li+，Na+，K+，Rb+，Cs+，Be++，Mg++，Ca++，Sr++And Ba++。
Ammonium ion is of formula+NR1R2R3R4Wherein R is1，R2，R3And R4Selected from hydrogen and hydrocarbyl, or R1-R4Two of which together are alkylene or R1-R4Three of which together are alkylene. When R is1-R4When one or more of them is hydrogen, the ammonium ion is protic. When all four R are1-R4When it is a hydrocarbyl or hydrocarbylene group, the ammonium ion is aprotic.
The ammonium ion also includes the formula R1R2N-+NR3R4R5Is/are as follows
Figure BDA0001292960300000101
A cation of which R1，R2，R3，R4And R5Selected from hydrogen and hydrocarbyl or R1And R2Together and/or R3-R5Two of which together are alkylene.
Ammonium ions also include those of the formula HO-N+R1R2R3Hydroxylammonium cation of (2), wherein R1，R2And R3Selected from hydrogen and hydrocarbyl, or R1-R3Two of which together are alkylene.
Oxygen gas
Figure BDA0001292960300000102
Ion is of the formula+OR1R2R3A positively charged group of (a), wherein R1，R2And R3Selected from hydrogen and hydrocarbyl, or R1-R3Two of which together are alkylene. When R is1-R3When one or more of them is hydrogen, oxygen
Figure BDA0001292960300000103
Is protic. When all three R are1-R3When it is a hydrocarbon group or alkylene group, the oxygen
Figure BDA0001292960300000104
Is aprotic.
Figure BDA0001292960300000105
Ion is of the formula+PR1R2R3R4A positively charged group of (2), wherein R1，R2，R3And R4Is a hydrocarbon radical, or R1-R4Two of which are alkylene groups.
Hydrocarbyl is any hydrocarbyl group that utilizes a carbon atom in combination with a cationic nitrogen, oxygen, or phosphorus. Alkylene is a ring-forming form of hydrocarbyl.
The hydrocarbon radicals are, for example, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl radicals which may be substituted by radicals selected from halogen, hydroxy, C1-C4Alkoxy, thio, C1-C4Alkylthio, amino, C1-C4Alkylamino radical, di-C1-C4Alkylamino, nitro, cyano, -COOH and-COO-substituted by one or more groups. The hydrocarbon radical may also be selected from the group consisting of-O-, -S-, -NH-and-N (C)1-C4Alkyl) -, one or more groups are interrupted. The hydrocarbyl group may be substituted with and interrupted by one or more of the groups described. For example, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl may be substituted by 1 to 3 radicals selected from the group consisting of chlorine, hydroxyl, methoxy, ethoxy, propoxy, butoxy, thio, methylthio, methylamino, ethylamino, propylamino, butylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, -COOH, -COO-, cyano and nitro, and/or may be substituted by 1 to 3 radicals selected from the group consisting of-O-, -S-, -NH-and-N (C)1-C4Alkyl) -1-3 groups are interrupted.
Hydrocarbyl groups also include polyethylene glycol and polypropylene glycol, such as R' (OC)2H4)n-or R' (OC)3H6)n-, where R' is hydrogen or alkyl, n is an integer from 1 to 50, for example from 1 to 40, from 1 to 30 or from 1 to 20, for example from 1 to 10.
When R is1-R5When two or three of them together are hydrocarbylene, this means that they form a heterocyclic ring with the N, O or P atom. Example of the ringSuch as a 5-or 6-membered ring. The heterocyclic ring may contain additional heteroatoms and may be saturated or unsaturated. Alkylene is, for example- (CH)2)4-，-(CH2)5-，-(CH3)N-CH＝C(CH3)-CH＝，＝CH-CH＝CH-CH＝CH-，＝C(CH3)-C＝CH-CH＝CH-，＝C-C(CH3)＝CH-CH＝CH-，＝C-CH＝C(CH3)-CH＝CH-，-CH＝CH-CH＝CH-，-CH2＝CH-CH2-CH2-，-CH＝CH-N＝CH-，-CH2CH2NHCH2CH2-，-CH2-CH2-N＝CH-，-CH2-CH2-O-CH2-CH2-or ═ CH- (CH)2)3-. Further heteroatoms are, for example, N, O or S.
An example of an ammonium ion ring is piperidine
Figure BDA0001292960300000111
Pyrrolines
Figure BDA0001292960300000112
2, 4-dimethylpyrazole
Figure BDA0001292960300000113
Pyrrolines
Figure BDA0001292960300000114
(Pyrrolinium), pyrrolidine
Figure BDA0001292960300000115
Pyridine compound
Figure BDA0001292960300000116
Morpholine
Figure BDA0001292960300000117
And picoline
Figure BDA0001292960300000118
Pyridine compound
Figure BDA0001292960300000119
Is wherein R is1-R4Three of which together form an example of a ring. The hydrocarbylene ring may also be cyclic to form, for example, quinolines
Figure BDA00012929603000001110
Or isoquinoline
Figure BDA00012929603000001111
Alkyl has, for example, from 1 to 25 carbon atoms, is branched or unbranched and comprises methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1, 3-trimethylhexyl, 1,1,3,3, -tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5, 5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl.
Alkenyl is an unsaturated form of an alkyl group, such as allyl.
Cycloalkyl includes cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl.
Cycloalkenyl is the unsaturated form of cycloalkyl.
Aryl includes phenyl, o-, m-or p-methylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2 methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2, 6-diethylphenyl.
Aralkyl groups include benzyl, α -methylbenzyl, α, α -dimethylbenzyl and 2-phenylethyl.
Examples of protic ammonium ions include NH4 +(ammonium), methylammonium, ethylammonium, diMethylammonium, diethylammonium, trimethylammonium (NMe)3H+) Triethylammonium, tributylammonium, diethylmethylammonium, hydroxyethylammonium, methoxymethylammonium, dibutylammonium, methylbutylammonium, anilinium, pyridine
Figure BDA0001292960300000121
2-methylpyridine
Figure BDA0001292960300000122
Imidazole
Figure BDA0001292960300000123
1-methylimidazole
Figure BDA0001292960300000124
1, 2-dimethylimidazole
Figure BDA0001292960300000125
Imidazoline
Figure BDA0001292960300000126
1-ethylimidazole
Figure BDA0001292960300000127
1- (4-sulfobutyl) -3-methylimidazole
Figure BDA0001292960300000128
1-allylimidazole
Figure BDA0001292960300000129
Quinolines
Figure BDA00012929603000001210
Isoquinoline derivatives
Figure BDA00012929603000001211
Pyrrolines
Figure BDA00012929603000001212
Pyrrolines
Figure BDA00012929603000001213
(pyrrolinium) and pyrrolidine
Figure BDA00012929603000001214
Examples of the aprotic ammonium ion include tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, n-butylammonium-triethylammonium, benzyl-trimethylammonium, tri-n-butylmethylammonium, benzyl-triethylammonium, 1-methylpyridine
Figure BDA00012929603000001215
1-butyl-3, 5-dimethylpyridine
Figure BDA00012929603000001216
1,2, 4-trimethylpyrazoles
Figure BDA00012929603000001217
Trimethylhydroxyethylammonium (choline), tris (hydroxyethyl) methylammonium, dimethyl-di (polyoxyethylene) ammonium, 1,2, 3-trimethylimidazole
Figure BDA00012929603000001218
1-butyl-3-methylimidazole
Figure BDA00012929603000001219
1-ethyl-2, 3-dimethylimidazole
Figure BDA00012929603000001220
1-allyl-3-methylimidazole
Figure BDA00012929603000001221
1-hydroxyethyl-3-methylimidazole
Figure BDA00012929603000001222
1, 3-dimethylimidazole
Figure BDA00012929603000001223
1-ethyl-1-methylpiperidine
Figure BDA00012929603000001224
4-Ethyl-4-methylMorpholine
Figure BDA00012929603000001225
1- (cyanomethyl) -3-methylimidazole
Figure BDA00012929603000001226
1- (3-cyanopropyl) pyridine
Figure BDA00012929603000001227
1, 3-bis (cyanomethyl) imidazoles
Figure BDA00012929603000001228
And 1-ethyl-3-methylimidazole
Figure BDA00012929603000001229
Azole compounds
Figure BDA00012929603000001230
Is pyrrolinium, pyrroline is pyrroline ammonium, pyrrolidine
Figure BDA00012929603000001231
Is an ammonium salt of pyrrolidine. The pyrroline may be 1-, 2-or 3-pyrroline, and thus includes the ammonium cation of the 1-, 2-or 3-pyrroline.
Figure BDA00012929603000001232
Examples of ions are
Figure BDA00012929603000001233
(H2NNH3 +)。
An example of a hydroxylammonium ion is hydroxylammonium (HO-NH)3 +)。
Proton oxygen
Figure BDA00012929603000001234
Examples of ions include H3O+(hydronium), H+O(Et)2，H2EtO+，H2MeO+，H+O(Me)2Protonated THF and protonated 2-methyl-THF.
Aprotic oxygen
Figure BDA00012929603000001235
Examples of the ions include+O(Me)3，+O(Et)3And methylated or ethylated THF or 2-methyl-THF.
Me is methyl, Et is ethyl, nBu is n-butyl, tBu (or t-butyl) is tert-butyl and THF is tetrahydrofuran. Butyl means n-butyl, if not specified.
Figure BDA00012929603000001240
Examples of ions include methyltriphenylene
Figure BDA00012929603000001236
Tetraphenyl radical
Figure BDA00012929603000001237
Tetra butyl
Figure BDA00012929603000001238
Tributyl methyl group
Figure BDA00012929603000001239
Triethyl methyl group
Figure BDA00012929603000001241
Trihexyltetradecyl
Figure BDA00012929603000001242
Triphenylpropyl radical
Figure BDA00012929603000001243
And tetra (hydroxymethyl)
Figure BDA00012929603000001244
Examples of suitable anions are hydroxides, nitrates, perchlorates, bifluorides, alkoxides, halides, phosphates, phosphinates, phosphonates, borates, carboxylates, sulfites, sulfates, sulfonates, carbonates, imides, aluminates, cyanates, methides, arsenates, silicates and antimonates.
Anionic, cationic and ionic compounds may be, for example, those disclosed in U.S. patent No.6,254,797 and U.S. publication No. 2011/0045359.
The bifluoride being HF2 -。
The alkoxide being RO-Where R is a hydrocarbyl group, such as methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, tert-butoxide or phenoxide. Alkoxides also include where R is perfluoroalkyl.
The halide is chloride, bromide, iodide or fluoride.
The phosphate includes dihydrogen phosphate, hydrogen phosphate, alkyl phosphate, dialkyl phosphate, PF6 -(hexafluorophosphates), HPO3F-(hydrogenfluorophosphates), trioxalates phosphates (TOP), tetrafluorooxalates phosphates (TFOP) and fluoro (perfluoroalkyl) phosphates such as F2P(C2F5)4，F3P(C2F5)3 -(tris (pentafluoroethyl) trifluorophosphate or FAP), F4P(C2F5)2 -，F2P(C3F7)4 -，F3P(C3F7)3 -，F4P(C3F7)2 -，F2P(C4F9)4 -，F3P(C4F9)3 -And F4P(C4F9)2 -。
The phosphinate is, for example, an alkyl phosphinate, a dialkyl phosphinate, an aryl phosphinate or a diaryl phosphinate. Such as bis (2,4, 4-trimethylphenyl) phosphinate.
Phosphonates are, for example, alkyl phosphonates, for example methyl phosphonate or hydrogen phosphonate (phosphonate).
The borate includes orthoborate, tetrahydroxyborate, tetraborate, tetraphenylborate, [ B (3,5- (CF)3)2C6H3)4]-(BARF)，B(C2O4)2 -(bis (oxalato) borate) (BOB), difluoro (oxalato) borate (dFOB), bis (trifluoroacetyl) oxalato borate (D (Ac) OB), B (C)6F5)4 -，BF4 -(tetrafluoroborate).
The carboxylate anion has the formula RCOO-Wherein R is hydrogen or a hydrocarbyl group including formate, acetate, propionate, n-butyrate, isobutyrate, n-valerate, isovalerate, octanoate, decanoate, benzoate, salicylate, thiosalicylate, 2-, 3-or 4-nitrobenzoate; citrate, oxalate, tartrate, glycolate, gluconate, malate, mandelate, carboxylate of nitrilotriacetic acid, carboxylate of N- (2-hydroxyethyl) -ethylenediaminetriacetic acid, carboxylate of ethylenediaminetetraacetic acid, carboxylate of diethylenetriaminepentaacetic acid and haloalkyl carboxylates such as monofluoroacetate, difluoroacetate, trifluoroacetate, monochloroacetate, dichloroacetate and trichloroacetate.
Sulfites include sulfites and bisulfites.
Sulfates include bisulfates, sulfates, thiosulfates and alkyl sulfates such as methyl sulfate and ethyl sulfate.
Sulfonates include alkyl, aryl sulfonates and perfluoroalkyl sulfonates, such as triflate (triflate), p-toluenesulfonate (tosylate) or methanesulfonate (mesylate).
Carbonate anions are, for example, carbonates, hydrogen carbonates or alkyl carbonates such as methyl carbonate, ethyl carbonate or butyl carbonate.
Imide anions include dicyandiamide, N (SO)2F)2 -((Bifluorosulfonyl) imide), bis (perfluoroalkylsulfonyl) imide such as [ N (SO)2CF3)2]-(bistrifluorosulfonylimide), bis (pentafluoroethylsulfonyl) imide and N (CF)3SO2)CF2)3SO2)-And (perfluoroalkylsulfonyl) (perfluoroalkylcarboxy) imide.
The aluminate includes Al (OC (CF)3)3)4 -Bis (trifluoroacetyl) oxaloaluminate (d (ac) OAl), tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate and tetrabromoaluminate.
The cyanate includes thiocyanate and cyanate.
Methides include tris (perfluoroalkylsulfonyl) methide, such as tris (trifluoromethylsulfonyl) methide, C (CF)3SO2)3 -。
Arsenate includes arsenate, arsenate hydrogen salt, arsenate dihydrogen salt and AsF6 -。
The silicate comprises SiF6 -2。
The antimonate comprises SbF6 -And Sb (OH)6 -。
For example, the protic ionic compound is H3PO4，NH4SO3CF3，NH4BF4，NH4OH，NH4Cl，NH4Br，NH4I，NH4F，NH4H2PO4，(NH4)2HPO4Ammonium methylphosphonate, pyridine tosylate
Figure BDA0001292960300000142
Chlorinated pyridines
Figure BDA0001292960300000143
Anilinium chloride, hydroxylammonium chloride, (NH)4)2SO4Sulfuric acid, sulfuric acid
Figure BDA0001292960300000141
(N2H6SO4)，(NH4)HSO4，NaHSO4，NH4BF4，H2SO4，KH2PO4，K2HPO4，NaH2PO4，Na2HPO4，HBF4，H(OEt2)BF4，HPF6，HAsF6，HClO4，HSO3CF3，H[N(SO2CF3) Or H [ N (SO)2CF2CF3)2]。
The protic ionic compound may also be oxygen which is a highly noncoordinating ion
Figure BDA0001292960300000144
Ions, e.g. Bruker Hart's acid (BARF acid), [ H (OEt)2)2][B[3,5-(CF3)2C6H3]4]. Other examples include [ H (OEt)2)2][B(C6F5)4](oxygen)
Figure BDA0001292960300000145
Acid) and [ H (OEt)2)2][Al(OC(CF3)3)4]. In these cases, the cation is protonated diethyl ether (diethyl ether oxide)
Figure BDA0001292960300000146
). Alternatively, the cation may be another protonated ether, such as protonated Tetrahydrofuran (THF).
The protic ionic compound may be a protic ionic liquid, such as ethylammonium nitrate, diethylmethylammonium trifluoromethanesulfonate (DEMA TfO), triethylammonium methanesulfonate, 2-methylpyridine
Figure BDA0001292960300000151
Triflate, ammonium fluoride, methylammonium nitrate, hydroxyethylammonium nitrate, ethylammonium nitrate, dimethylammonium nitrate, 1-methylimidazole
Figure BDA0001292960300000152
Nitrate salt, 1-ethylImidazole
Figure BDA0001292960300000153
Nitrate, tert-butylammonium tetrafluoroborate, hydroxyethylammonium tetrafluoroborate, methylbutylammonium tetrafluoroborate, triethylammonium tetrafluoroborate, imidazole
Figure BDA0001292960300000154
Tetrafluoroborate, 1-methylimidazole
Figure BDA0001292960300000155
Tetrafluoroborate, 1, 2-dimethylimidazole
Figure BDA0001292960300000156
Tetrafluoroborate, tert-butylammonium triflate, 2-fluoropyridine
Figure BDA0001292960300000157
Triflate, hydroxyethylammonium triflate, 1, 2-dimethylimidazole
Figure BDA0001292960300000158
Triflate, imidazole
Figure BDA0001292960300000159
Triflate, 1-methylimidazole
Figure BDA00012929603000001510
Bisulfate, 1-methylimidazole
Figure BDA00012929603000001511
Chloride, 1-methylimidazole
Figure BDA00012929603000001512
Trifluoromethanesulfonate, hydronium trifluoromethanesulfonate, methylammonium methanesulfonate, ethylammonium methanesulfonate, butylammonium methanesulfonate, methoxyethylammonium methanesulfonate, dimethylammonium methanesulfonate, dibutylammonium methanesulfonate, triethylammonium methanesulfonate, dimethylethylammonium methanesulfonate,hydrogen sulfate hydrate, ammonium hydrogen sulfate, methylammonium hydrogen sulfate, ethylammonium hydrogen sulfate, propylammonium hydrogen sulfate, n-butylammonium hydrogen sulfate, tert-butylammonium hydrogen sulfate, dimethylammonium hydrogen sulfate, diethylammonium hydrogen sulfate, di-n-butylammonium hydrogen sulfate, methylbutylammonium hydrogen sulfate, ethylbutylammonium hydrogen sulfate, trimethylammonium hydrogen sulfate, triethylammonium hydrogen sulfate, tributylammonium hydrogen sulfate, dimethylethylammonium hydrogen sulfate, dibutylammonium hydrogen fluorophosphate, triethylammonium hydrogen fluorophosphate, tributylammonium hydrogen fluorophosphate, dihydrogenphosphate hydrate, methylammonium dihydrogen phosphate, ethylammonium dihydrogen phosphate, propylammonium dihydrogen phosphate, n-butylammonium dihydrogen phosphate, methoxyethylammonium dihydrogen phosphate, dimethylammonium dihydrogen phosphate, dibutylammonium dihydrogen phosphate, methylbutylammonium dihydrogen phosphate, ammonium bifluoride, ammonium methyl fluoride, ammonium ethyl fluoride or ammonium dimethyl fluoride.
Carboxylic acids are protic acids/protic compounds. The carboxylic acid has the formula RCOOH, wherein R is hydrogen or hydrocarbyl. The carboxylic acid comprises a carboxylate anion.
For example, the carboxylic acid is selected from formic acid, acetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, butyric acid, 3-methylbutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, benzoic acid, salicylic acid, 2-, 3-or 4-nitrobenzoic acid; citric acid, oxalic acid, tartaric acid, glycolic acid, gluconic acid, malic acid, mandelic acid, nitrilotriacetic acid, N- (2-hydroxyethyl) -ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid and diethyleneaminepentaacetic acid.
Certain carboxylic acids fall within the definition of ionic liquids according to the present invention, such as acetic acid.
For example, the aprotic ionic compound is NMe4 +SO3CF3 -，NMe4OH，NEt4 +BF4 -，NMe4 +Cl-，NEt4 +Br-，NnBu4 +I-，NnBu4 +F-，NEt4+H2PO4 -，(NMe4)2HPO4Methyl triphenyl radical
Figure BDA0001292960300000161
Iodide, tetrakis (hydroxymethyl)
Figure BDA0001292960300000162
Chloride, tetraphenyl
Figure BDA0001292960300000163
Bromide, 1-methylpyridine
Figure BDA0001292960300000164
Chloride, benzalkonium chloride, Me3OBF4，Et3OBF4，NEt4PF6，NMe4AsF6，NMe4ClO4，NEt4SO3CF3，NMe4[N(SO2CF3)2]Or NEt4[N(SO2CF2CF3)]。
The aprotic ionic compound may also include a highly noncoordinating anion, e.g. BARF, e.g. sodium BARF, Na+B[3,5-(CF3)2C6H3]4]-. Other examples include K+B(C6F5)4 -And K+Al(OC(CF3)3)4 -。
The aprotic ionic compound can be an aprotic ionic liquid, for example tri-n-butyl methylammonium methylsulfate, 1-ethyl-2, 3-dimethylimidazole
Figure BDA0001292960300000165
Ethyl sulfate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000166
Thiocyanate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000167
Tetrachloroaluminate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000168
Methyl sulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000169
Methanesulfonic acid salt, 1-butyl-3-methylimidazole
Figure BDA00012929603000001610
Bicarbonate, 1-butyl-3-methylimidazole
Figure BDA00012929603000001611
Bisulfate salt, 1-butyl-3-methylimidazole
Figure BDA00012929603000001612
Chloride, 1,2, 3-trimethylimidazole
Figure BDA00012929603000001613
Methyl sulfate, tris- (hydroxyethyl) methylammonium methylsulfate, 1,2, 4-trimethylpyrazole
Figure BDA00012929603000001614
Methyl sulfate, 1, 3-dimethylimidazole
Figure BDA00012929603000001615
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001616
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001617
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001618
Tetrachloroaluminate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001619
Thiocyanate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001620
Methanesulfonic acid salt, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001621
Bisulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001622
Ethyl sulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001623
Nitrate salt, 1-butylpyridine
Figure BDA00012929603000001624
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001625
Dicyandiamide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001626
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001627
Hexafluorophosphate, 1-butyl-3, 5-dimethylpyridine
Figure BDA00012929603000001628
Bromide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001629
Bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001630
Bis (pentafluoroethylsulfonyl) imide, 1-ethyl-2, 3-dimethylimidazole
Figure BDA00012929603000001631
Methyl carbonate, carboxymethyl tributyl
Figure BDA00012929603000001632
Bis (trifluoromethylsulfonyl) imide, N-carboxyethyl-methylpyrrolidine
Figure BDA00012929603000001633
Bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-trimethylammonium bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-methylpyridine
Figure BDA00012929603000001634
Bis (trifluoromethylsulfonyl) imide, hexyltrimethylammonium bis (trifluoromethylsulfonyl) imide, tetrabutylphosphonium imide
Figure BDA00012929603000001635
Methanesulfonic acid salt, triethylmethylammonium methylcarbonate, 1-ethyl-1-methylpiperidine
Figure BDA00012929603000001636
Methyl carbonate, 4-ethyl-4-methylmorpholine
Figure BDA00012929603000001637
Methylcarbonate, 1-butyl-1-methylpyrrolidine
Figure BDA0001292960300000171
Methyl carbonate, triethylmethylammonium dibutylphosphate, tributylmethyl
Figure BDA0001292960300000172
Dibutyl phosphate, triethyl methyl
Figure BDA0001292960300000173
Dibutyl phosphate, tetrabutyl
Figure BDA0001292960300000174
Tetrafluoroborate, tetrabutyl
Figure BDA0001292960300000175
P-toluenesulfonate, tributylmethyl
Figure BDA0001292960300000176
Methyl carbonate, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000177
Bicarbonate, tributylmethylammonium methylcarbonate, tributylmethylammonium dibutylphosphate, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000178
Dibutyl phosphate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000179
Dibutyl phosphate, 1- (cyanomethyl) -3-methylimidazole
Figure BDA00012929603000001710
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA00012929603000001711
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA00012929603000001712
Bis (trifluoromethylsulfonyl) imide, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA00012929603000001713
Dicyandiamide, 1- (3-cyanopropyl) pyridine
Figure BDA00012929603000001714
Chloride, 1- (3-cyanopropyl) pyridine
Figure BDA00012929603000001715
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000001716
Chloride, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000001717
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (cyanopropyl) imidazole
Figure BDA00012929603000001718
Chloride, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000001719
Bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazole
Figure BDA00012929603000001720
Hexafluorophosphate, 1-butyl-3-methylimidazole
Figure BDA00012929603000001721
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001722
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001723
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000001724
Bromide, 1-butyl-3-methylimidazole
Figure BDA00012929603000001725
Bromide, 1-hexyl-3-methylimidazole
Figure BDA00012929603000001726
Chloride, tributylmethyl
Figure BDA00012929603000001727
The salt of a methyl sulfate is a salt of a methyl sulfate,triethyl methyl group
Figure BDA00012929603000001728
Dibutyl phosphate trihexyltetradecyl
Figure BDA00012929603000001729
Bis (trifluoromethylsulfonyl) imide, trihexyltetradecyl
Figure BDA00012929603000001730
Bis (2,4, 4-trimethylphenyl) phosphinic acid salt trihexyltetradecyl
Figure BDA00012929603000001731
Bromide, trihexyltetradecyl
Figure BDA00012929603000001732
Chloride, trihexyltetradecyl
Figure BDA00012929603000001733
Decanoate, trihexyltetradecyl
Figure BDA00012929603000001734
Dicyandiamide, 3- (triphenylphosphonium)
Figure BDA00012929603000001735
Yl) propane-1-sulfonate or 3- (triphenylphosphonium)
Figure BDA00012929603000001736
Yl) propane-1-sulfonic acid tosylate.
Examples of carboxylate compounds are tetramethyl ammonium benzoate, tetraethyl ammonium oxalate, tetrabutyl ammonium tartrate, sodium tartrate, potassium formate, tetramethyl ammonium acetate, 1-methylpyridine
Figure BDA00012929603000001737
Chloride, tri-tert-trimethylammonium citrate, tetramethylammonium 2-, 3-or 4-nitrobenzoate, ammonium benzoate, ammonium salicylate, ammonium oxalate, ammonium tartrate, methylRadical triphenyl radical
Figure BDA00012929603000001738
Acetate salt, tetrakis (hydroxymethyl)
Figure BDA00012929603000001739
Benzoate, tetrakis (hydroxymethyl)
Figure BDA00012929603000001740
Formate, mono-or di-potassium tartrate, mono-, di-or tri-ammonium citrate, ammonium 2-nitrobenzoate, ammonium 3-nitrobenzoate, ammonium 4-nitrobenzoate, potassium trifluoroacetate and potassium chloroacetate.
In polycarboxylic acids, ammonium and/or alkali metal and/or alkaline earth metal ions may replace one or any number of acidic hydrogens to form the carboxylate compounds of the present invention. Examples include ammonium mono-, di-and tri-basic citrates and sodium mono-, di-and tri-basic citrates.
According to the invention, the ionic liquid is an ionic compound which exhibits a melting point of 150 ℃ or less.
Otherwise, the ionic compound is a "salt" with a melting point >150 ℃.
Salts include halide salts, for example alkali or alkaline earth metal halide salts such as NaCl, KCl or KBr, and other ionic compounds having a melting point above 150 ℃. Alkali and alkaline earth metal salts include, for example, anions selected from the group consisting of nitrates, perchlorates, bifluorides, halides, phosphates, phosphinates, phosphonates, borates, carboxylates, sulfites, sulfates, sulfonates, carbonates, imides, aluminates, cyanates, methides, arsenates, silicates, and antimonates.
The ionic compounds of the present invention may comprise both cations and anions in the same molecule. Accordingly, zwitterionic compounds (inner salts) such as betaines are also included. Comprising ammonium or
Figure BDA0001292960300000181
Ions and zwitterions of sulfonate or sulfate ions. Including hydroxysultaine, 4- (triphenylphosphine)
Figure BDA0001292960300000182
Yl) butane-1-sulfonate, N- (triethylaminosulfonyl) carbamic acid methyl ester (Burgess reagent) and sulfuric acid
Figure BDA0001292960300000183
Zwitterions, as taught in U.S. patent No. 3,471,544. Including sulfamic acid.
Advantageously, at least two different ionic compounds are used in the electrolyte composition. For example, the two different ionic compounds may be a protic ionic compound and an aprotic ionic compound, or may be an ionic liquid and a salt.
For example, the electrolyte composition of the present invention may comprise at least two different ionic liquids. The electrolyte composition may comprise one or more ionic liquids and one or more salts, for example protic or aprotic ammonium salts or alkali metal salts such as alkali metal halides.
The electrolyte composition may comprise a mixture of a carboxylate compound and a carboxylic acid. The electrolyte composition may comprise a mixture of a carboxylate-containing ionic liquid and a carboxylic acid. The electrolyte composition may comprise two different carboxylic acids.
The electrolyte composition may comprise a protic acid, a protic ammonium compound or a protic oxygen
Figure BDA0001292960300000184
Compounds and ionic liquids.
When at least two different ionic compounds are present, the weight to weight ratio of the two different ionic compounds is about 99.9:0.1 to about 0.1:99.9, about 99.5:0.5 to about 0.5:99.5, about 99:1 to about 1:99, about 95:5 to about 5:95, about 90:10 to about 10:90, about 80:20 to about 20:80, about 70:30 to about 30:70, or about 60:40 to about 40: 60.
In two different ionic compounds, the cation or anion may be the same.
The electrolyte composition may contain substantially no unintentional water, such as 1000ppm or less, 100ppm or less, or 10ppm or less water, based on the total weight of the electrolyte composition.
The electrolyte composition may advantageously comprise a solvent. Alternatively, the electrolyte composition may be solvent-free. For example, when one or more ionic liquids are used in the electrolyte composition, no solvent is required. By "solvent-free" is meant that no organic solvent is present and that there is substantially no unintentional water present.
In the case of a solvent present in the electrolyte composition, the weight to weight ratio of the total amount of ionic compound to the solvent may be about 99.9:0.1 to about 0.1:99.9, about 99.5:0.5 to about 0.5:99.5, about 99:1 to about 1:99, about 95:5 to about 5:95, about 90:10 to about 10:90, about 80:20 to about 20:80, about 70:30 to about 30:70, or about 60:40 to about 40: 60.
The electrolyte compositions of the present invention are not limited by the hydrogen and oxygen evolution potentials of water. Thus, the subject of the invention is also a metal hydride battery with a nominal open circuit voltage of >1.2V (volts). The MH cells of the present invention can provide a nominal open circuit voltage of up to about 5.0V. For example, MH cells of the invention may have a nominal open circuit voltage of about 1.2 to about 5.0V, about 1.3 to about 5.0V, about 1.4 to about 5.0V, or about 1.5 to about 5.0V. For example, MH cells of the invention may have a nominal open circuit voltage of about 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or about 5.0V.
The solvent is water and an organic solvent.
The solvent may consist essentially of water, or may consist essentially of an organic solvent. The solvent may comprise water to organic solvent in varying proportions.
When the solvent consists essentially of an organic solvent, water can be present in very low levels, for example, 1000ppm or less, 100ppm or less, or 10ppm or less water based on the total weight of the electrolyte composition. When the solvent consists essentially of water, the organic solvent can only be present in the same low amount.
For example, the solvent may be a water/organic solvent mixture, wherein the weight to weight ratio of water to organic solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
The electrolyte composition may contain an organic solvent and no water. The electrolyte composition may comprise water and no organic solvent.
Suitable organic solvents are selected from, for example, organic carbonates, ethers, glymes, orthoesters, polyalkylene glycols, esters, lactones, glycols, formates, sulfones, sulfoxides, amides, alcohols, amines, ketones, nitro solvents, nitrile solvents, and combinations thereof.
The organic carbonates are cyclic or acyclic and include Ethylene Carbonate (EC), Propylene Carbonate (PC), trimethylene carbonate, 1, 2-Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, vinylene carbonate, difluoroethylene carbonate and monofluoroethylene carbonate.
Ethers and glymes include Dimethoxymethane (DMM), diethoxymethane, 1, 2-dimethoxyethane (DME or glyme), diglyme, triglyme, tetraglyme, glyme (DEE), ethylene glycol dibutyl ether, diethylene glycol diethyl ether, Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1, 3-diglyme
Figure BDA0001292960300000201
Alkane, 1, 3-Dioxolane (DIOX), 4-methyl-1, 3-dioxolane (4-MeDIOX), 2-methyl-1, 3-dioxolane (2-MeDIOX), 1, 4-dioxolane
Figure BDA0001292960300000202
Alkanes, dimethyl ether, ethyl methyl ether, diethyl ether, di-n-butyl ether, di-t-butyl ether, di-isopropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether and t-amyl methyl ether.
The orthoesters include trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2] octane and 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2] octane.
The polyalkylene glycol is C1-C4Homo-or co-oligomers or homo-or copolymers of alkylene glycols. For example polyethylene glycol (PEG) or monomethyl, dimethyl or diethyl (capped) polyethylene glycol. The polyalkylene glycols have a weight average molecular weight (Mw) of, for example, about 200 to about 1200g/mol, about 200 to about 1000g/mol, about 200 to about 900g/mol, about 200 to about 700g/mol, or about 200 to about 500 g/mol. Oligomers comprising 4 monomers and more, such as tetraethylene glycol, fluorinated tetraethylene glycol and tetrapropylene glycol. For example PEG200, PEG300, PEG400, PEG500, PEG600, PEG700, PEG800, PEG900 or PEG 1000.
Esters and lactones include gamma-butyrolactone (GBL), gamma-valerolactone, delta-valerolactone, Ethyl Acetate (EA), 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate (butyl carbitol acetate, DBA), Ethylene Glycol Diacetate (EGDA), 3-ethoxyethyl propionate (EEP), Methyl Butyrate (MB), n-pentyl acetate (NAAC), propylene glycol methyl ether acetate (PMA), Ethyl Butyrate (EB), diethyl malonate, dimethyl malonate, and dibasic ester mixtures (DBE).
Dibasic ester mixtures include, for example, the methyl esters of adipic, glutaric and succinic acids.
The diols include ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol (ethylene glycol butyl ether, EB), 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol (diethylene glycol butyl ether, DB), propylene glycol butyl ether (PB), propylene glycol methyl ether (PM), triethylene glycol (TEG), dipropylene glycol methyl ether (DPM), diethylene glycol methyl ether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diethylene glycol methyl ether, fluorinated triethylene glycol methyl ether, and fluorinated diethylene glycol butyl ether.
The formates include methyl formate, ethyl formate, isobutyl formate and tert-butyl formate.
Sulfones and sulfoxides include methylsulfonylmethane (MSM or dimethylsulfone), ethylmethylsulfone, sulfolane and Dimethylsulfoxide (DMSO).
Amides include Dimethylformamide (DMF), N-methylpyrrolidone (NMP), 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone (DMI), Hexamethylphosphoramide (HMPA) and N, N '-dimethyl-N, N' -trimethyleneurea (1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone (DMPU)).
Alcohols include, for example, Benzyl Alcohol (BA), ethanol, trifluoroethanol (2,2, -trifluoroethanol), methanol, isopropanol, tert-butanol and n-butanol.
Ketones include, for example, Methyl Ethyl Ketone (MEK) and methyl-isoamyl ketone (MIAK).
The amines include, for example, triethylamine, tributylamine, diethylenetriamine, ethylenediamine, morpholine, piperidine and pyridine.
The nitro solvent includes nitrobenzene, nitromethane and nitroethane.
Nitrile solvents include acetonitrile, propionitrile, butyronitrile and adiponitrile.
Advantageously, a mixture of solvents is used, for example a mixture of organic carbonates or a mixture of one or more organic carbonates and one or more ethers or glymes.
Suitable other organic solvents may be used, such as toluene, hexane, heptane and the like.
Additives may be incorporated into the electrolyte compositions of the present invention.
The additives are selected, for example, from corrosion inhibitors, Solid Electrolyte Interface (SEI) improvers, proton evolution improvers, self-discharge inhibitors, gas repellents, viscosity regulators, cathodic protectants, salt stabilizers, conductivity improvers and solvating agents.
Corrosion inhibitors are, for example, fluorinated oils, sodium stannate, sodium citrate or polyacrylic acid.
The solid electrolyte interface modifier is, for example, a fluoride source for fluorinating the surface of a metal hydride. The fluoride source is, for example, HF or KF. SEI improvers also include oxides or hydroxides of rare earths such as Y, which inhibit the formation of thick oxides on the negative electrode. SEI improvers also include porphines, which are used to reduce oxidation of the alloy surface. Such as Ni or Fe porphine. SEI improvers may also include vinylene carbonate, ethylene carbonate, methylene ethylene carbonate, and fluoroethylene carbonate.
Self-discharge inhibitors include surfactants such as polyglycols, polyglycol alkyl ethers, polyglycol alkyl phosphate esters and polyethoxy ethers. Including polyethylene glycol (PEG), polypropylene glycol, polysorbate 20, polysorbate 40, and polysorbate 80. Advantageously, a mixture of PEG600 and polysorbate 20 or a mixture of PEG600 and ZnO is used together.
The anti-gas additive comprises phosphate ester surfactant, propane sultone and fluoro-propane sultone.
Viscosity modifiers include, for example, DMSO.
For example, additives are used in amounts of about 0.1 wt% to about 15 wt%, based on the weight of the electrolyte composition.
If the electrolyte composition comprises KOH and water, one or more further components, for example one or more further components selected from organic solvents, further ionic compounds and additives, are also present.
For example, the electrolyte composition may comprise KOH and one or more other ionic compounds, for example one or more selected from NaOH, LiOH, mg (oh)2And Ca (OH)2Other ionic compounds of (a).
The weight to weight ratio of KOH to other ionic compounds is about 99.9:0.1 to about 0.1:99.9, about 99.5:0.5 to about 0.5:99.5, about 99:1 to about 1:99, about 95:5 to about 5:95, about 90:10 to about 10:90, about 80:20 to about 20:80, about 70:30 to about 30:70, or about 60:40 to about 40: 60.
The electrolyte composition comprising KOH advantageously comprises water and an organic solvent, such as a polyalkylene glycol. Alternatively, the solvent may consist of only an organic solvent.
Certain embodiments of the present invention include electrolyte compositions comprising:
a) protic acid/water and/or an organic solvent,
b) protic ammonium compound/water and/or organic solvent,
c) ionic liquids (protic or aprotic, ammonium or
Figure BDA0001292960300000232
A compound),
d) ionic liquid/water and/or an organic solvent,
e) alkali metal alkoxide/alcohol or glycol or polyalkylene glycol solvents,
f) an alkali metal hydroxide/organic solvent (e.g. PEG),
g) alkali metal hydroxide/water and organic solvents (e.g. PEG),
h) an alkali metal carboxylate/carboxylic acid,
i) a carboxylic acid/water and/or an organic solvent,
j) alkali metal carboxylate/water and/or organic solvent,
k) an ionic compound of highly non-coordinating ions/water and/or an organic solvent,
l) a mixture of at least two different ionic liquids,
m) mixtures of ionic liquids and protic or aprotic salts, and
n) a mixture of an ionic liquid and a carboxylate compound and/or a carboxylic acid.
The electrolyte compositions of the invention are, for example, liquid at room temperature (25 ℃). The liquid comprises a syrupy high viscosity liquid. For example, the viscosity of the electrolyte composition is from about 0.2cP to about 100cP at 25 ℃. For example, the electrolyte composition has a viscosity of less than or equal to 100cP, less than or equal to 90cP, less than or equal to 80cP, less than or equal to 70cP, less than or equal to 50cP, less than or equal to 40cP, less than or equal to 30cP, less than or equal to 20cP, less than or equal to 10cP, or less than or equal to 5cP at 25 ℃.
The viscosity can be measured, for example, by a rotational rheometer or using a mini-viscometer using a rolling steel ball in a glass capillary that is timed and calibrated against a control liquid. The viscosity can also be measured with a DVI or DVII Brookfield viscometer, a plate viscometer or an oscillation type viscometer.
The subject of the invention is also an electrolyte composition.
The half-cell charge/discharge electrochemical reaction at the anode in 30 wt% aqueous KOH electrolyte solution was (MH is metal hydride):
Figure BDA0001292960300000231
many of the electrolyte compositions of the present invention are neutral or acidic, i.e., have a pH of less than or equal to about 7.
The invention also relates to a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein the pH of said electrolyte composition is less than or equal to about 7.
When using the neutral or acidic electrolyte composition of the present invention, the half-cell charge/discharge electrochemical reaction at the anode when a potential is applied across the cell is:
Figure BDA0001292960300000241
the invention also relates to a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein the half-cell charge/discharge electrochemical reaction at the anode upon application of an electrical potential across the battery is
Figure BDA0001292960300000242
All values herein, such as voltage, viscosity, pH, pKa, etc., are determined at 25 ℃ and atmospheric pressure.
The terms "a" or "an" relating to elements of an embodiment may be "one" or may be "one or more".
The term "about" means, for example, by typical measurement and processing procedures; inadvertent errors through these procedures; by differences in the manufacture, source or purity of the ingredients used; differences by the method of use; and so on, as may occur. The term "about" also includes amounts that differ due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether or not modified by the term "about," the embodiments and claims include equivalents to the amounts described.
All numerical values herein are modified by the term "about", whether or not explicitly indicated. The term "about" generally refers to a range of numbers that one of ordinary skill in the art would consider equivalent to the recited value (i.e., having the same function and/or result). In many cases, the term "about" may include numbers that are rounded to the nearest significant figure.
The term "about" modified values naturally include the specified values. For example, "about 5.0" must include 5.0.
The term "consisting essentially of" means that the composition, method or structure may include additional ingredients, steps and/or components, but only if the additional ingredients, steps and/or components do not materially alter the basic and novel characteristics of the claimed composition, method or structure.
U.S. patents, U.S. published patent applications, and U.S. patent applications discussed herein are each incorporated by reference herein.
The following are some embodiments of the invention.
E1. A metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein
The electrolyte composition comprises one or more ionic compounds, wherein
If the electrolyte composition comprises KOH and water, the composition comprises one or more other components.
E2. The cell according to embodiment 1, wherein the ionic compound is selected from the group consisting of a protic acid, a protic ammonium compound and a protic oxygen
Figure BDA0001292960300000251
A compound is provided.
E3. The battery according to embodiment 1, wherein the ionic compound is selected from the group consisting of an aprotic ammonium compound, an aprotic oxygen
Figure BDA0001292960300000252
Compound, aprotic
Figure BDA0001292960300000253
A compound and an alkali metal or alkaline earth metal salt.
E4. The battery according to embodiment 1, wherein the one or more ionic compounds comprise a compound selected from H+Alkali metal ions, alkaline earth metal ions, ammonium, methylammonium, ethylammonium, dimethylammonium, diethylammonium, trimethylammonium, triethylammonium, tributylammonium, diethylmethylammonium, hydroxyethylammonium, methoxymethylammonium, dibutylammonium, methylbutylammonium, anilinium, pyridine
Figure BDA0001292960300000254
2-methylpyridine
Figure BDA0001292960300000255
Imidazole
Figure BDA0001292960300000256
1-methylimidazole
Figure BDA0001292960300000258
1, 2-dimethylimidazole
Figure BDA00012929603000002510
Imidazoline
Figure BDA00012929603000002511
1-ethylimidazole
Figure BDA00012929603000002512
1- (4-sulfobutyl) -3-methylimidazole
Figure BDA0001292960300000259
1-allylimidazole
Figure BDA00012929603000002516
Quinolines
Figure BDA00012929603000002515
Isoquinoline derivatives
Figure BDA00012929603000002514
Pyrrolines
Figure BDA00012929603000002513
Pyrrolines
Figure BDA0001292960300000257
(Pyrrolinium), pyrrolidine
Figure BDA00012929603000002517
Hydroxylammonium, H3O+，H+O(Et)2，H2EtO+，H2MeO+，H+O(Me)2Protonated tetrahydrofuran and protonated cations of 2-methyl-tetrahydrofuran.
E5. The battery according to embodiment 1, wherein the one or more ionic compounds comprise a compound selected from H+Ammonium, diethylmethylammonium, triethylammonium, hydroxyethylammonium, 2-methylpyridine
Figure BDA00012929603000002518
1,2, 4-trimethylpyrazoles
Figure BDA00012929603000002519
And 1-ethyl-3-methylimidazole
Figure BDA00012929603000002520
A cation of (2).
E6. The cell according to embodiment 1 wherein said one or more ionic compounds comprise a compound selected from the group consisting of tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tri-n-butylmethylammonium, n-butyl-triethylammonium, benzyltrimethylammonium, benzyltriethylammonium, 1-methylpyridine
Figure BDA00012929603000002521
1-butyl-3, 5-dimethylpyridine
Figure BDA00012929603000002522
1,2, 3-trimethylimidazole
Figure BDA00012929603000002523
1-ethyl-3-methylimidazole
Figure BDA00012929603000002524
1-butyl-3-methylimidazole
Figure BDA00012929603000002525
1-ethyl-2, 3-dimethylimidazole
Figure BDA00012929603000002526
1-allyl-3-methylimidazole
Figure BDA00012929603000002527
1-hydroxyethyl-3-methylimidazole
Figure BDA00012929603000002528
Trimethylhydroxyethylammonium (choline), tris (hydroxyethyl) methylammonium, dimethyl-di (polyoxyethylene) ammonium, 1-ethyl-1-methylpiperidine
Figure BDA00012929603000002529
4-ethyl-4-methylmorpholine
Figure BDA00012929603000002530
1- (cyanomethyl) -3-methylimidazole
Figure BDA00012929603000002531
1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000261
1, 3-bis (cyanomethyl) imidazoles
Figure BDA0001292960300000262
+O(Me)3，+O(Et)3tetrahydrofuran-Me+tetrahydrofuran-Et+2-Methyltetrahydrofuran-Me+2-Methyltetrahydrofuran-Et+Methyl triphenyl radical
Figure BDA0001292960300000263
Tetraphenyl radical
Figure BDA0001292960300000264
Tetra butyl
Figure BDA0001292960300000266
Tributyl methyl group
Figure BDA0001292960300000268
Triethyl methyl group
Figure BDA0001292960300000269
Trihexyltetradecyl
Figure BDA00012929603000002610
Triphenylpropyl radical
Figure BDA0001292960300000265
And tetra (hydroxymethyl)
Figure BDA0001292960300000267
A cation of (2).
E7. A cell according to any one of the preceding embodiments, wherein the one or more ionic compounds comprise an anion selected from the group consisting of hydroxide, nitrate, perchlorate, bifluoride, alkoxide, halide, phosphate, phosphinate, phosphonate, borate, carboxylate, sulfite, sulfate, sulfonate, carbonate, imide, aluminate, cyanate, methide, arsenate, silicate and antimonate.
E8. The battery according to any of embodiments 1-6, wherein the one or more ionic compounds comprise a compound selected from the group consisting of chloride, bromide, H2PO4 -，BF4 -Dibutyl phosphate, HPO3F-Bisulfate, thiocyanate, difluoride, perchlorate, dicyanamide, Al (OC (CF)3)3)4 -，B(C6F5)4 -，[N(SO2CF3)2]- (bis)Trifluoromethanesulfonimide), bis (pentafluoroethylsulfonyl) imide, trifluoromethanesulfonate (trifluoromethanesulfonate), p-toluenesulfonate (toluenesulfonate), methanesulfonate (methanesulfonate), tetraphenylborate, [ B (3,5- (CF) CF3)2C6H3)4]-，Al(OC(CF3)3)4 -，B(C6F5)4 -，[N(SO2CF3)2]-，N(SO2F)2 -Tris (pentafluoroethyl) trifluorophosphate, B (C)2O4)2 -Difluoro (oxalato) borate, tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate, tetrabromoaluminate, AsF6 -，PF6 -，SbF6 -And SiF6 -2The anion of (4).
E9. The battery according to any of embodiments 1-6, wherein the one or more ionic compounds comprise an ionic compound selected from BF4 -Hydrogen sulfate, thiocyanate, perchlorate, dicyanamide, bis (pentafluoroethylsulfonyl) imide, trifluoromethanesulfonate, tetraphenylborate, [ B (3,5- (CF) F3)2C6H3)4]-，Al(OC(CF3)3)4 -，B(C6F5)4 -，[N(SO2CF3)2]-Tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate, tetrabromoaluminate, AsF6 -And PF6 -The anion of (4).
E10. The battery according to embodiment 1, wherein the one or more ionic compounds are selected from H3PO4，NH4SO3CF3，NH4OH，NH4BF4，NH4Cl，NH4Br，NH4I，NH4F，NH4H2PO4，(NH4)2HPO4Methyl ammonium phosphonate, pyridine
Figure BDA00012929603000002612
Tosylate, pyridine
Figure BDA00012929603000002611
Chloride, chlorophenylammonium, hydroxylammonium chloride, (NH)4)2SO4Sulfuric acid, sulfuric acid
Figure BDA00012929603000002613
(N2H6SO4)，(NH4)HSO4，NaHSO4，NH4BF4，H2SO4，KH2PO4，K2HPO4，NaH2PO4，Na2HPO4，HBF4，H(OEt2)BF4，HPF6，HAsF6，HClO4，HSO3CF3，H[N(SO2CF3)2]，H[N(SO2CF2CF3)2]，[H(OEt2)2][B[3,5-(CF3)2C6H3]4]，[H(OEt2)][B(C6F5)4](oxygen)
Figure BDA0001292960300000271
Acid) and [ H (OEt)2)2][Al(OC(CF3)3)4]。
E11. The cell according to embodiment 1, wherein the one or more ionic compounds are selected from NMe4 +SO3CF3 –，NEt4 +BF4 –，NMe4 +OH–，NMe4 +Cl–，NEt4 +Br–，NnBu4 +I–，NnBu4 +F–，NEt4 +H2PO4 –，(NMe4)2HPO4Methyl triphenyl radical
Figure BDA0001292960300000272
Iodide, tetrakis (hydroxymethyl)
Figure BDA0001292960300000273
Chloride, tetraphenyl
Figure BDA0001292960300000274
Bromide, 1-methylpyridine
Figure BDA0001292960300000275
Chloride, benzalkonium chloride, Me3OBF4，Et3OBF4，NEt4PF6，NMe4AsF6，NMe4ClO4，NEt4SO3CF3，NMe4[N(SO2CF3)2]，NEt4[N(SO2CF2CF3)2]，Na+B[3,5-(CF3)2C6H3]4]–，K+B(C6F5)4 –And K+Al(OC(CF3)3)4 –。
E12. The battery according to any of embodiments 1-9, wherein the one or more ionic compounds are selected from ionic liquids.
E13. The battery according to embodiment 1, wherein the one or more ionic compounds are selected from zwitterions.
E14. The cell according to embodiment 1 wherein said one or more ionic compounds is selected from the group consisting of ethylammonium nitrate, diethylmethylammonium trifluoromethanesulfonate (DEMA TfO), triethylammonium methanesulfonate, 2-methylpyridine
Figure BDA0001292960300000276
Triflate, ammonium fluoride, methylammonium nitrate, hydroxyethylammonium nitrate, ethylammonium nitrate, dimethylammonium nitrate, 1-methylimidazole
Figure BDA0001292960300000277
Chloride, 1-methylimidazole
Figure BDA0001292960300000278
Nitrate, 1-ethylimidazole
Figure BDA0001292960300000279
Nitrate, tert-butylammonium tetrafluoroborate, hydroxyethylammonium tetrafluoroborate, methylbutylammonium tetrafluoroborate, triethylammonium tetrafluoroborate, imidazole
Figure BDA00012929603000002710
Tetrafluoroborate, 1-methylimidazole
Figure BDA00012929603000002711
Bisulfate, 1-methylimidazole
Figure BDA00012929603000002712
Tetrafluoroborate, 1, 2-dimethylimidazole
Figure BDA00012929603000002713
Tetrafluoroborate, tert-butylammonium triflate, 2-fluoropyridine
Figure BDA00012929603000002714
Triflate, hydroxyethylammonium triflate, 1, 2-dimethylimidazole
Figure BDA00012929603000002715
Triflate, imidazole
Figure BDA00012929603000002716
Triflate, 1-methylimidazole
Figure BDA00012929603000002717
Trifluoromethanesulfonate, hydronium trifluoromethanesulfonate, methylammonium methanesulfonate, ethylammonium methanesulfonate, butylammonium methanesulfonate, methoxyethylammonium methanesulfonate, dimethylammonium methanesulfonate, dibutylammonium methanesulfonate,triethylammonium methanesulfonate, dimethylethylammonium methanesulfonate, hydrogensulfate hydrate, ammonium bisulfate, methylammonium hydrogensulfate, ethylammonium hydrogensulfate, propylammonium hydrogensulfate, n-butylammonium hydrogensulfate, tert-butylammonium hydrogensulfate, dimethylammonium hydrogensulfate, diethylammonium hydrogensulfate, di-n-butylammonium hydrogensulfate, methylbutylammonium hydrogensulfate, ethylbutylammonium hydrogensulfate, trimethylammonium hydrogensulfate, triethylammonium hydrogensulfate, tributylammonium hydrogensulfate, dimethylethylammonium hydrogensulfate, dibutylammonium hydrogenfluorophosphate, triethylammonium hydrogenfluorophosphate, tributylammonium hydrogenfluorophosphate, dihydrogenphosphate hydrate, methylammonium dihydrogenphosphate, ethylammonium dihydrogenphosphate, propylammonium dihydrogenphosphate, n-butylammonium dihydrogenphosphate, methoxyethylammonium dihydrogenphosphate, dimethylammonium dihydrogenphosphate, dibutylammonium dihydrogen phosphate, methylbutylammonium dihydrogen phosphate, ammonium bifluoride, ethyl ammonium bifluoride and dimethyl ammonium bifluoride.
E15. The cell according to embodiment 1, wherein the one or more ionic compounds are selected from the group consisting of tri-n-butyl methylammonium methylsulfate, 1-ethyl-2, 3-dimethylimidazole
Figure BDA0001292960300000281
Ethyl sulfate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000282
Thiocyanate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000283
Tetrachloroaluminate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000284
Methyl sulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000285
Methanesulfonic acid salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000286
Bisulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000287
Bicarbonate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000288
Chloride, 1,2, 3-trimethylimidazole
Figure BDA0001292960300000289
Methyl sulfate, 1,2, 4-trimethylpyrazole
Figure BDA00012929603000002810
Methylsulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002811
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002812
Thiocyanate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002813
Methanesulfonic acid salt, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002814
Tetrachloroaluminate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002815
Bisulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002816
Ethyl sulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002817
Nitrate salt, 1-butylpyridine
Figure BDA00012929603000002818
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002819
Dicyandiamide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002820
Tetrafluoroborate, 1, 3-dimethylimidazole
Figure BDA00012929603000002821
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002822
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002823
Hexafluorophosphate, 1-butyl-3, 5-dimethylpyridine
Figure BDA00012929603000002824
Bromide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002825
Bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002826
Bis (pentafluoroethylsulfonyl) imide, 1-ethyl-2, 3-dimethylimidazole
Figure BDA00012929603000002827
Methyl carbonate, carboxymethyl tributyl
Figure BDA00012929603000002828
Bis (trifluoromethylsulfonyl) imide, N-carboxyethyl-methylpyrrolidine
Figure BDA00012929603000002829
Bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-trimethylammonium bis (trifluoromethylsulfonyl)) Imide, N-carboxymethyl-methylpyridine
Figure BDA00012929603000002830
Bis (trifluoromethylsulfonyl) imide, hexyltrimethylammonium bis (trifluoromethylsulfonyl) imide, tetrabutylphosphonium imide
Figure BDA00012929603000002831
Methanesulfonic acid salt, tetrabutyl
Figure BDA00012929603000002832
Tetrafluoroborate, tetrabutyl
Figure BDA00012929603000002833
P-toluenesulfonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002834
Bicarbonate, triethylmethylammonium methylcarbonate, tributylmethylammonium methylcarbonate, 1-ethyl-1-methylpiperidine
Figure BDA00012929603000002835
Methyl carbonate, 4-ethyl-4-methylmorpholine
Figure BDA00012929603000002836
Methylcarbonate, 1-butyl-1-methylpyrrolidine
Figure BDA00012929603000002837
Methyl carbonate, triethylmethylammonium dibutyl phosphate, tributylmethylammonium dibutyl phosphate, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000291
Dibutyl phosphate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000292
Dibutyl phosphate, 1- (cyanomethyl) -3-methylimidazole
Figure BDA0001292960300000293
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000294
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000295
Bis (trifluoromethylsulfonyl) imide, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000296
Dicyandiamide, 1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000297
Chloride, 1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000298
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (cyanomethyl) imidazole
Figure BDA0001292960300000299
Chloride, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000002910
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000002911
Chloride, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000002912
Bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazole
Figure BDA00012929603000002913
Hexafluorophosphate, 1-butyl-3-methylimidazole
Figure BDA00012929603000002914
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002915
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002916
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000002917
Bromide, 1-butyl-3-methylimidazole
Figure BDA00012929603000002918
Bromide, 1-hexyl-3-methylimidazole
Figure BDA00012929603000002919
Chloride, tributylmethyl
Figure BDA00012929603000002920
Dibutyl phosphate, triethyl methyl
Figure BDA00012929603000002921
Dibutylphosphate, tributylmethyl
Figure BDA00012929603000002922
Methyl carbonate, tributylmethyl
Figure BDA00012929603000002923
Methylsulfates, triethylmethyl
Figure BDA00012929603000002924
Dibutyl phosphate trihexyltetradecyl
Figure BDA00012929603000002925
Bis (trifluoromethylsulfonyl) imide, trihexyltetradecyl
Figure BDA00012929603000002926
Bis (2,4, 4-trimethylphenyl) phosphinic acid salt trihexyldecaTetra alkyl radical
Figure BDA00012929603000002927
Bromide, trihexyltetradecyl
Figure BDA00012929603000002928
Chloride, trihexyltetradecyl
Figure BDA00012929603000002929
Decanoate, trihexyltetradecyl
Figure BDA00012929603000002930
Dicyandiamide, 3- (triphenylphosphonium)
Figure BDA00012929603000002931
Yl) propane-1-sulfonate and 3- (triphenylphosphonium)
Figure BDA00012929603000002932
Yl) propane-1-sulfonic acid tosylate.
E16. The battery according to embodiment 1, wherein the electrolyte composition comprises at least two different ionic compounds.
E17. The battery according to embodiment 16, wherein the electrolyte composition comprises a protic ionic compound and an aprotic ionic compound.
E18. The battery according to embodiment 16, wherein the electrolyte composition comprises two different protic ionic compounds.
E19. The battery according to embodiment 16, wherein the electrolyte composition comprises two different aprotic ionic compounds.
E20. The battery according to any of embodiments 16-19, wherein the electrolyte composition comprises two different salts.
E21. A battery according to any of embodiments 16-19, wherein the electrolyte composition comprises two different ionic liquids.
E22. A battery according to any of embodiments 16 to 19, wherein the electrolyte composition comprises a salt and an ionic liquid, for example a protic or aprotic ammonium salt or an alkali metal salt such as an alkali metal halide.
E23. The battery of any of embodiments 16-18,21, and 22, wherein the electrolyte composition comprises a protic acid, a protic ammonium compound, or a protic oxygen
Figure BDA0001292960300000301
Compounds and ionic liquids.
E24. A battery according to any of embodiments 16 to 23, wherein the electrolyte composition comprises two different ionic compounds comprising the same cation or the same anion.
E25. The battery according to any of embodiments 16-24, wherein the weight to weight ratio of the two different ionic compounds is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E26. A battery according to any one of the preceding embodiments, wherein the electrolyte composition does not comprise an organic solvent, comprising less than or equal to 1000ppm, less than or equal to 100ppm, or less than or equal to 10ppm of water, based on the total weight of the electrolyte composition.
E27. The battery of any of embodiments 1-25, wherein the electrolyte composition comprises a solvent.
E28. The battery of embodiment 27, wherein the solvent consists essentially of water.
E29. The battery of embodiment 27, wherein the solvent consists essentially of an organic solvent.
E30. The battery of embodiment 27, wherein the solvent comprises water and an organic solvent.
E31. The battery of embodiment 30, wherein the weight to weight ratio of water to organic solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to 40: 60.
E32. A cell according to any of embodiments 29-31, wherein said organic solvent comprises one or more solvents selected from the group consisting of organic carbonates, ethers, glymes, orthoesters, polyalkylene glycols, esters, lactones, glycols, formates, sulfones, sulfoxides, amides, alcohols, amines, ketones, nitro solvents, and nitrile solvents.
E33. The cell according to embodiment 32 wherein the organic solvent comprises a solvent selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), trimethylene carbonate, 1, 2-Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (EMC), vinylene carbonate, difluoroethylene carbonate, monofluoroethylene carbonate, Dimethoxymethane (DMM), diethoxymethane, 1, 2-dimethoxyethane (DME or ethylene glycol dimethyl ether or glyme), diglyme, triglyme, tetraglyme, ethylene glycol diethyl ether (DEE), ethylene glycol dibutyl ether, diethylene glycol diethyl ether, Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1, 3-dibutylether, Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), and mixtures thereof
Figure BDA0001292960300000311
Alkane, 1, 3-Dioxolane (DIOX), 4-methyl-1, 3-dioxolane (4-MeDIOX), 2-methyl-1, 3-dioxolane (2-MeDIOX), 1, 4-dioxolane
Figure BDA0001292960300000312
Alkane, dimethyl ether, ethyl methyl ether, diethyl ether, di-n-butyl ether, di-tert-butyl ether, di-isopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2]]Octane, 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, polyethylene glycol, dimethyl polyethylene glycol, diethyl polyethylene glycol, gamma-butyrolactone (GBL), gamma-valerolactone, delta-valerolactone, Ethyl Acetate (EA), 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate (diethylene glycol butyl ether acetate, DBA), Ethylene Glycol Diacetate (EGDA), 3-ethoxyethyl propionate (EEP), Methyl Butyrate (MB), n-pentyl acetate (NAAC), propylene glycol methyl ether acetate (PMA), Ethyl Butyrate (EB), diethyl malonate, dimethyl malonate, dibasic ester mixture (DBE), ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol,2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol (ethylene glycol butyl ether, EB), 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol (diethylene glycol butyl ether, DB), propylene glycol butyl ether (PB), propylene glycol methyl ether (PM), triethylene glycol (TEG), dipropylene glycol methyl ether (DPM), diethylene glycol methyl ether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diethylene glycol methyl ether, fluorinated triethylene glycol methyl ether and fluorinated diethylene glycol butyl ether, methyl formate, ethyl formate, isobutyl formate, tert-butyl formate, methylsulfonylmethane (MSM or dimethylsulfone), ethylmethylsulfonylmethane, sulfolane, dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), N-methylpyrrolidone (NMP), 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone (DMI), Hexamethylphosphoramide (HMPA), N, N ' -dimethyl-N, N ' -trimethyleneurea (1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone (DMPU)), Benzyl Alcohol (BA), ethanol, trifluoroethanol (2,2' -trifluoroethanol), methanol, isopropanol, tert-butanol, N-butanol, Methyl Ethyl Ketone (MEK), methyl-isoamyl ketone (MIAK), triethylamine, tributylamine, diethylenetriamine, ethylenediamine, morpholine, piperidine, pyridine, nitrobenzene, nitromethane, nitroethane, acetonitrile, propionitrile, butyronitrile and adiponitrile.
E34. The battery according to any of embodiments 27-33, wherein the weight to weight ratio of the total amount of ionic compound to solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E35. A battery according to any one of the preceding embodiments, wherein the electrolyte composition further comprises one or more additives selected from the group consisting of corrosion inhibitors, Solid Electrolyte Interface (SEI) improvers, proton evolution improvers, self-discharge inhibitors, gas repellents, viscosity modifiers, cathodic protectants, salt stabilizers, conductivity improvers, and solvating agents.
E36. The metal hydride battery according to embodiment 1, wherein the electrolyte composition comprises one or more ionic compounds selected from alkali or alkaline earth metal hydroxides and alkoxides and an organic solvent.
E37. The battery of embodiment 36, wherein the one or more ionic compounds are selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
E38. The battery of embodiment 36, wherein the one or more ionic compounds are selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides.
E39. The cell according to embodiment 36 wherein said one or more ionic compounds is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide, and the methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, tert-butoxide, 2-methylbutoxide or phenoxide of sodium, potassium, calcium or magnesium.
E40. The cell according to embodiment 36, wherein the one or more ionic compounds are selected from the group consisting of sodium hydroxide or potassium hydroxide and sodium or potassium methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, tert-butoxide, methylbutanol or phenoxide.
E41. The cell according to embodiment 36, wherein the one or more ionic compounds are selected from the group consisting of potassium hydroxide, potassium methoxide and potassium ethoxide.
E42. The cell according to embodiment 36, wherein said one or more ionic compounds is selected from the group consisting of sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide.
E43. The cell according to any one of embodiments 36-42, wherein said organic solvent comprises one or more solvents selected from the group consisting of organic carbonate, ether, glyme, orthoester, polyalkylene glycol, alcohol, sulfone, sulfoxide, amide, and nitrile solvents.
E44. The cell according to any of embodiments 36-42 wherein the organic solvent comprises one or more organic solvents selected from the group consisting of ethylene carbonate, propylene carbonate, trimethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dimethoxymethane, 1, 2-dimethoxyethane, diglyme, triglyme, tetraglyme, ethylene glycol diethyl ether, ethylene glycol dibutyl etherEthers, diethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, 1, 4-dioxolane
Figure BDA0001292960300000331
Alkane, diethyl ether, di-tert-butyl ether, diisopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, polyethylene glycol, dimethyl polyethylene glycol, diethyl polyethylene glycol, propylene glycol butyl ether, propylene glycol methyl ether, triethylene glycol, dipropylene glycol methyl ether, diethylene glycol methyl ether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diethylene glycol methyl ether, fluorinated triethylene glycol methyl ether and fluorinated diethylene glycol butyl ether, ethylene glycol, propylene glycol, benzyl alcohol, ethanol, trifluoroethanol, methanol, isopropanol, tert-butanol, N-butanol, acetonitrile, propionitrile, butyronitrile, methylsulfonylmethane, sulfolane, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide and N, a solvent for N '-dimethyl-N, N' -trimethylene urea.
E45. The cell according to any one of embodiments 36-42, wherein the organic solvent comprises one or more solvents selected from the group consisting of 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, propylene glycol butyl ether, propylene glycol methyl ether, triethylene glycol, dipropylene glycol methyl ether, benzyl alcohol, ethanol, trifluoroethanol, ethylene glycol, propylene glycol, methanol, isopropanol, tert-butanol, and n-butanol.
E46. The cell according to embodiment 36 wherein the one or more ionic compounds is selected from the group consisting of KOH, NaOH, KOMe, NaOMe, KOEt and NaOEt and the solvent comprises one or more ionic compounds selected from the group consisting of 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, propylene glycol butyl ether, propylene glycol methyl ether, triethylene glycol, dipropylene glycol methyl ether, benzyl alcohol, ethanol, trifluoroethanol, ethylene glycol, propylene glycol, methanol, isopropanol, tert-butanol and n-butanol.
E47. The battery of any of embodiments 36-46, wherein the weight to weight ratio of the total weight of ionic compound to organic solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E48. A battery according to any of embodiments 36-47, wherein the electrolyte composition comprises 1000ppm or less, 100ppm or less, or 10ppm by weight of water, based on the total weight of the electrolyte composition.
E49. The battery of any of embodiments 36-48, wherein the electrolyte composition further comprises one or more additives selected from the group consisting of corrosion inhibitors, Solid Electrolyte Interface (SEI) modifiers, proton evolution modifiers, self-discharge inhibitors, gas repellents, viscosity modifiers, cathodic protectants, salt stabilizers, conductivity modifiers, and solvating agents.
E50. A battery according to embodiment 1, wherein the electrolyte composition comprises one or more ionic compounds selected from alkali metal hydroxides, water and one or more further components selected from organic solvents, further ionic compounds and additives.
E51. The battery of embodiment 50, wherein the electrolyte composition comprises an organic solvent.
E52. The battery of embodiment 51, wherein the organic solvent comprises one or more solvents selected from the group consisting of organic carbonate, ether, glyme, orthoester, polyalkylene glycol, alcohol, sulfone, sulfoxide, amide, and nitrile solvents.
E53. The cell of embodiment 51 wherein the organic solvent comprises one or more solvents selected from the group consisting of ethylene carbonate, propylene carbonate, trimethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dimethoxymethane, 1, 2-dimethoxyethane, diglyme, triglyme, tetraglyme, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, 1, 4-diethylene glycol dimethyl ether
Figure BDA0001292960300000351
Alkane, diethyl ether, di-tert-butyl ether, diisopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, polyethylene glycol, dimethyl polyethylene glycol, diethyl polyethylene glycol, propylene glycol butyl ether, propylene glycol methyl ether, triethylene glycol, dipropylene glycol methyl ether, diethylene glycol methyl ether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diethylene glycol methyl ether, fluorinated triethylene glycol methyl ether and fluorinated diethylene glycol butyl ether, ethylene glycol, propylene glycol, benzyl alcohol, ethanol, trifluoroethanol, methanol, isopropanol, tert-butanol, N-butanol, acetonitrile, propionitrile, butyronitrile, methylsulfonylmethane, sulfolane, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide and N, N '-dimethyl-N, N' -trimethylene urea.
E54. The battery of embodiment 51, wherein the electrolyte composition comprises polyethylene glycol, dimethyl polyethylene glycol, or diethyl polyethylene glycol.
E55. The battery of any of embodiments 51-54, wherein the weight to weight ratio of water to organic solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E56. The battery of any of embodiments 51-55, wherein the weight to weight ratio of alkali metal hydroxide to organic solvent plus water is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E57. A battery according to any of embodiments 50 to 56, wherein the electrolyte composition comprises one or more further ionic compounds.
E58. The battery of embodiment 57, wherein the electrolyte composition comprises KOH and one or more additives selected from the group consisting of NaOH, LiOH, mg (oh)2And Ca (OH)2Other ionic compounds of (a).
E59. The cell according to embodiment 57, wherein said other ionic compound is selected from ionic liquids.
E60. The battery according to any of embodiments 57-59, wherein the weight to weight ratio of alkali metal hydroxide to total weight of the other ionic compound is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E61. The battery according to any of embodiments 50-60, wherein the electrolyte composition comprises one or more additives.
E62. The battery of embodiment 61, wherein the electrolyte composition comprises one or more additives selected from the group consisting of corrosion inhibitors, Solid Electrolyte Interface (SEI) modifiers, proton evolution modifiers, self-discharge inhibitors, gas repellents, viscosity modifiers, cathodic protectants, salt stabilizers, conductivity modifiers, and solvating agents.
E63. The battery according to embodiment 1, wherein the electrolyte composition comprises one or more ionic compounds selected from the group consisting of carboxylate compounds and carboxylic acids.
E64. The battery of embodiment 63, wherein the electrolyte composition comprises one or more carboxylate compounds.
E65. The battery of embodiment 64, wherein the one or more carboxylate compounds are selected from the group consisting of alkali metal, alkaline earth metal, and ammonium carboxylates.
E66. The battery of embodiment 64, wherein the one or more carboxylate compounds are selected from the group consisting of alkali metal and alkaline earth metal carboxylates.
E67. The battery of embodiment 64, wherein the one or more carboxylate compounds are selected from the group consisting of ammonium and
Figure BDA0001292960300000361
a carboxylate salt.
E68. The battery according to embodiment 64, wherein the one or more carboxylate compounds comprise a compound selected from the group consisting of Na+，K+，Ca++，Mg++，NH4 +Methylammonium, ethylammonium, dimethylammonium, diethylammonium, trimethylammonium (NMe)3H+) Triethylammonium, tributylammonium, diethylmethylammonium, hydroxyethylammonium, methoxymethylammonium, dibutylammonium, methylbutylammonium, anilinium, pyridine
Figure BDA0001292960300000362
2-methylpyridine
Figure BDA0001292960300000363
Imidazole
Figure BDA0001292960300000364
1-methylimidazole
Figure BDA0001292960300000365
1, 2-dimethylimidazole
Figure BDA0001292960300000366
Imidazoline
Figure BDA0001292960300000367
Quinolines
Figure BDA0001292960300000368
Isoquinoline derivatives
Figure BDA0001292960300000369
Pyrrolines
Figure BDA0001292960300000371
Pyrrolines
Figure BDA0001292960300000372
(Pyrrolinium), pyrrolidine
Figure BDA0001292960300000373
Tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, n-butyltriethylammonium, benzyltrimethylammonium, tri-n-butylmethylammonium, benzyltriethylammonium, 1-methylpyridine
Figure BDA0001292960300000374
1-butyl-3, 5-dimethylpyridine
Figure BDA0001292960300000375
1,2, 4-trimethylpyrazoles
Figure BDA0001292960300000376
Trimethylhydroxyethylammonium (choline), dimethyldi (polyoxyethylene) ammonium, tris (hydroxyethyl) methylammonium, 1,2, 3-trimethylimidazole
Figure BDA0001292960300000377
1-butyl-3-methylimidazole
Figure BDA0001292960300000378
1-ethyl-2, 3-dimethylimidazole
Figure BDA0001292960300000379
1, 3-dimethylimidazole
Figure BDA00012929603000003710
1-ethyl-1-methylpiperidine
Figure BDA00012929603000003711
4-ethyl-4-methylmorpholine
Figure BDA00012929603000003712
1- (cyanomethyl) -3-methylimidazole
Figure BDA00012929603000003713
1- (3-cyanopropyl) pyridine
Figure BDA00012929603000003714
1, 3-bis (cyanomethyl) imidazoles
Figure BDA00012929603000003715
1-ethyl-3-methylimidazole
Figure BDA00012929603000003716
Methyl triphenyl
Figure BDA00012929603000003717
Tetraphenyl radical
Figure BDA00012929603000003718
Tetra butyl
Figure BDA00012929603000003719
Tributyl methyl group
Figure BDA00012929603000003720
Triethyl methyl group
Figure BDA00012929603000003721
Trihexyltetradecyl
Figure BDA00012929603000003722
Triphenylpropyl radical
Figure BDA00012929603000003723
And tetra (hydroxymethyl)
Figure BDA00012929603000003724
A cation of (2).
E69. The cell according to any one of embodiments 64-68, wherein the one or more carboxylate compounds comprise a compound selected from formate, acetate, monofluoroacetate, difluoroacetate, trifluoroacetate, monochloroacetate, dichloroacetate, trichloroacetate, propionate, n-butyrate, isobutyrate, n-valerate, isovalerate, octanoate, decanoate, benzoate, salicylate, thiosalicylate, 2-,3-, or 4-nitrobenzoate; citrate, oxalate, tartrate, glycolate, gluconate, malate, mandelate, carboxylate of nitrilotriacetic acid, carboxylate of N- (2-hydroxyethyl) -ethylenediaminetriacetic acid, carboxylate of ethylenediaminetetraacetic acid and carboxylate of diethylenetriaminepentaacetic acid.
E70. The cell according to embodiment 64, wherein the one or more carboxylate compounds are selected from the group consisting of sodium, potassium, calcium, and magnesium formates, acetates (acetates), propionates, n-butyrates, isobutyrates, n-valerates, or isovalerates.
E71. The cell according to embodiment 64 wherein said one or more carboxylate compounds are selected from the group consisting of sodium and potassium formates, acetates, propionates, n-butyrates, isobutyrates, n-valerates or isovalerates.
E72. The cell according to embodiment 64 wherein said one or more carboxylate compounds are selected from the group consisting of tetramethylammonium benzoate, tetraethylammonium oxalate, tetrabutylammonium tartrate, sodium tartrate, potassium formate, tetramethylammonium acetate, 1-methylpyridine
Figure BDA00012929603000003725
Chloride, tri-tert-trimethylammonium citrate, tetramethylammonium 2-, 3-or 4-nitrobenzoate, ammonium benzoate, ammonium salicylate, ammonium oxalate, ammonium tartrate, methyltriphenylammonium
Figure BDA00012929603000003726
Acetate salt, tetrakis (hydroxymethyl)
Figure BDA00012929603000003727
Benzoate, tetrakis (hydroxymethyl)
Figure BDA00012929603000003728
Formate, monopotassium tartrate or dipotassium tartrate, mono-, di-or tri-generation ammonium citrate; ammonium 2-nitrobenzoate, ammonium 3-nitrobenzoate, ammonium 4-nitrobenzoate, potassium trifluoroacetate and potassium chloroacetate.
E73. The battery according to any of embodiments 64-69, wherein the one or more carboxylate compounds are selected from ionic liquids.
E74. The battery according to embodiment 64, wherein the one or more carboxylate compounds are selected from trihexyltetradecyl
Figure BDA0001292960300000381
Decanoate salt, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000382
Acetate, choline salicylate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000383
Acetate salt, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000384
Lactate, 2-hydroxyethyl trimethylammonium acetate and methyltrioctylammonium thiosalicylate.
E75. The battery of embodiment 63, wherein the electrolyte composition comprises one or more carboxylic acids.
E76. The cell according to embodiment 75 wherein said one or more carboxylic acids is selected from the group consisting of formic acid, acetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, butyric acid, 3-methylbutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, benzoic acid, salicylic acid, 2-, 3-or 4-nitrobenzoic acid; citric acid, oxalic acid, tartaric acid, glycolic acid, gluconic acid, malic acid, mandelic acid, nitrilotriacetic acid, N- (2-hydroxyethyl) -ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid and diethyleneaminepentaacetic acid.
E77. The cell according to embodiment 75 wherein said one or more carboxylic acids is selected from the group consisting of acetic acid, propionic acid, butyric acid, 3-methylbutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, and pelargonic acid.
E78. A battery according to embodiment 63, wherein the electrolyte composition comprises at least two different ionic compounds as defined in any one of embodiments 63-77.
E79. The battery according to embodiment 78, wherein the electrolyte composition comprises a protic ionic compound and an aprotic ionic compound.
E80. The battery according to embodiment 78, wherein the electrolyte composition comprises two different protic ionic compounds.
E81. The battery according to embodiment 78, wherein the electrolyte composition comprises two different aprotic ionic compounds.
E82. The battery according to any of embodiments 78-81, wherein the electrolyte composition comprises two different salts.
E83. A battery according to any of embodiments 78-81, wherein the electrolyte composition comprises two different ionic liquids.
E84. A battery according to any of embodiments 78-81, wherein the electrolyte composition comprises a salt and an ionic liquid.
E85. The battery according to any of embodiments 78-81, wherein the electrolyte composition comprises a carboxylate compound and a carboxylic acid.
E86. A battery according to any of embodiments 78-80, 83, and 85, wherein the electrolyte composition comprises a carboxylic acid and an ionic liquid.
E87. A battery according to any of embodiments 78-86, wherein the electrolyte composition comprises two different ionic compounds comprising the same cation or the same anion.
E88. The battery according to any of embodiments 78-87, wherein the weight to weight ratio of the two different ionic compounds is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E89. The battery of any of embodiments 63-88 wherein the electrolyte composition does not comprise an organic solvent and comprises 1000ppm or less, 100ppm or less, or 10ppm of water based on the total weight of the electrolyte composition.
E90. A battery according to any of embodiments 63-88, wherein the electrolyte composition comprises a solvent.
E91. The battery of embodiment 90, wherein the solvent consists essentially of water.
E92. The battery of embodiment 90, wherein the solvent consists essentially of an organic solvent.
E93. The battery of embodiment 90, wherein the solvent comprises water and an organic solvent.
E94. The cell according to any of embodiments 92-93, wherein said organic solvent comprises one or more solvents selected from the group consisting of organic carbonates, ethers, glymes, orthoesters, polyalkylene glycols, esters, lactones, glycols, formates, sulfones, sulfoxides, amides, alcohols, amines, ketones, nitro solvents, and nitrile solvents.
E95. The cell according to embodiment 94 wherein the organic solvent comprises one or more solvents selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), trimethylene carbonate, 1, 2-Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (EMC), vinylene carbonate, difluoroethylene carbonate, monofluoroethylene carbonate, Dimethoxymethane (DMM), diethoxymethane, 1, 2-dimethoxyethane (DME or ethylene glycol dimethyl ether or glyme), diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol diethyl ether (DEE), ethylene glycol dibutyl ether, diethylene glycol diethyl ether, Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1, 3-Dimethyltetrahydrofuran (DMM), and mixtures thereof
Figure BDA0001292960300000401
Alkane, 1, 3-Dioxolane (DIOX), 4-methyl-1, 3-dioxolane (4-MeDIOX), 2-methyl-1, 3-dioxolane (2-MeDIOX), 1, 4-dioxolane
Figure BDA0001292960300000402
Alkane, dimethyl ether, ethyl methyl ether, diethyl ether, di-n-butyl ether, di-tert-butyl ether, di-isopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2]]Octane, 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, polyethylene glycol, dimethyl polyethylene glycol or diethyl polyethylene glycol, gamma-butyrolactone (GBL), gamma-valerolactone, delta-valerolactone, Ethyl Acetate (EA), 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate (butyl carbitol acetate, DBA), Ethylene Glycol Diacetate (EGDA), 3-ethoxyethyl propionate (EEP), Methyl Butyrate (MB), n-pentyl acetate (NAAC), propylene glycol methyl ether acetate (PMA), Ethyl Butyrate (EB), diethyl malonate, dimethyl malonate, dibasic ester mixture (DBE), ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol (ethylene glycol butyl ether, EB), 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol (diethylene glycol butyl ether, DB), propylene glycol butyl ether (PB), propylene glycol methyl ether (PM), triethylene glycol (TEG), dipropylene glycol methyl ether (DPM), diethylene glycol methyl ether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diethylene glycol methyl ether, fluorinated triethylene glycol methyl ether and fluorinated diethylene glycol butyl ether, methyl formate, ethyl formate, isobutyl formate, tert-butyl formate, methylsulfonylmethane (MSM or dimethylsulfone), ethylmethylsulfonylmethane, sulfolane, Dimethylsulfoxide (DMSO), Dimethylformamide (DMF), N-methylpyrrolidone (NMP), 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone (DMI), Hexamethylphosphoramide (HMPA), N, N' -dimethylphosphoramideSolvents based on N, N' -trimethyleneurea (1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone (DMPU)), Benzyl Alcohol (BA), ethanol, trifluoroethanol (2,2, -trifluoroethanol), methanol, isopropanol, tert-butanol, N-butanol, Methyl Ethyl Ketone (MEK), methyl isoamyl ketone (MIAK), triethylamine, tributylamine, diethylenetriamine, ethylenediamine, morpholine, piperidine, pyridine, nitrobenzene, nitromethane, nitroethane, acetonitrile, propionitrile, butyronitrile and adiponitrile.
E96. The battery according to any of embodiments 93-95, wherein the weight to weight ratio of water to organic solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 99:1 to about 1:99, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E97. The battery according to any of embodiments 90-96, wherein the weight to weight ratio of the total weight of ionic compound to solvent is from about 99.9:0.1 to about 0.1:99.9, from about 99.5:0.5 to about 0.5:99.5, from about 95:5 to about 5:95, from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40: 60.
E98. The battery of any of embodiments 63-97, wherein the electrolyte composition further comprises one or more additives selected from the group consisting of corrosion inhibitors, Solid Electrolyte Interface (SEI) modifiers, proton evolution modifiers, self-discharge inhibitors, gas repellents, viscosity modifiers, cathodic protectants, salt stabilizers, conductivity modifiers, and solvating agents.
E99. A battery according to any of the preceding embodiments, wherein the viscosity of the electrolyte composition is less than or equal to 100cP, less than or equal to 90cP, less than or equal to 80cP, less than or equal to 70cP, less than or equal to 50cP, less than or equal to 40cP, less than or equal to 30cP, less than or equal to 20cP, less than or equal to 10cP, or less than or equal to 5cP at 25 ℃.
E100. A battery according to any of the preceding embodiments, exhibiting a nominal open circuit voltage of from about 1.2 to about 5.0V, from about 1.3 to about 5.0V, from about 1.4 to about 5.0V, or from about 1.5 to about 5.0V.
E101. The electrolyte composition of any one of embodiments 1 to 99.
E102. A metal hydride battery comprising at least one negative electrode, at least one positive electrode, a housing having said electrodes located therein, and an electrolyte composition, wherein the battery has a nominal open circuit voltage of from about 1.5 to about 5.0V.
E103. The battery of embodiment 102 wherein the electrolyte composition comprises one or more electrolyte compounds selected from the group consisting of alkali or alkaline earth metal salts, protic acids, protic ammonium compounds, protons
Figure BDA0001292960300000411
Compounds, aprotic ammonium compounds, aprotic oxygen
Figure BDA0001292960300000412
Compound and aprotic
Figure BDA0001292960300000413
Ionic compounds of the compound.
E104. The cell of embodiment 103 wherein the one or more ionic compounds comprise an anion selected from the group consisting of hydroxide, nitrate, perchlorate, bifluoride, alkoxide, halide, phosphate, phosphinate, phosphonate, borate, carboxylate, sulfite, sulfate, sulfonate, carbonate, imide, aluminate, cyanate, methide, arsenate, silicate and antimonate.
E105. The battery of embodiment 103, wherein the one or more ionic compounds comprise a compound selected from the group consisting of chloride, bromide, H2PO4 -，BF4 -Dibutyl phosphate, HPO3F-Bisulfate, thiocyanate, difluoride, perchlorate, dicyanamide, Al (OC (CF)3)3)4 -，B(C6F5)4 -，[N(SO2CF3)2]-(bis-trifluorosulfonylimide), bis (pentafluoroethylsulfonyl) imide, trifluoromethanesulfonate (trifluoromethanesulfonate), p-toluenesulfonate (toluenesulfonate), methanesulfonate (methanesulfonate), tetraphenylborate, [ B (3,5- (CF) F3)2C6H3)4]–，Al(OC(CF3)3)4 –，B(C6F5)4 –，[N(SO2CF3)2]–，N(SO2F)2 –Tris (pentafluoroethyl) trifluorophosphate, B (C)2O4)2 -Difluoro (oxalato) borate, tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate, tetrabromoaluminate, AsF6 -，PF6 -，SbF6 -And SiF6 -2The anion of (4).
E106. The cell according to any one of embodiments 103-105, wherein the one or more ionic compounds are selected from ionic liquids.
E107. The cell according to embodiment 103 wherein said one or more ionic compounds is selected from the group consisting of ethylammonium nitrate, diethylmethylammonium trifluoromethanesulfonate, triethylammonium methanesulfonate, 2-methylpyridine
Figure BDA0001292960300000421
Triflate, ammonium fluoride, methylammonium nitrate, hydroxyethylammonium nitrate, ethylammonium nitrate, dimethylammonium nitrate, 1-methylimidazole
Figure BDA0001292960300000422
Chloride, 1-methylimidazole
Figure BDA0001292960300000423
Nitrate, 1-ethylimidazole
Figure BDA0001292960300000424
Nitrate, tert-butylammonium tetrafluoroborate, hydroxyethylammonium tetrafluoroborate, methylbutylammonium tetrafluoroborate, triethylammonium tetrafluoroborate, imidazole
Figure BDA0001292960300000425
Tetrafluoroborate, 1-methylimidazole
Figure BDA0001292960300000426
Bisulfate, 1-methylimidazole
Figure BDA0001292960300000427
Tetrafluoroborate, 1, 2-dimethylimidazole
Figure BDA0001292960300000428
Tetrafluoroborate, tert-butylammonium triflate, 2-fluoropyridine
Figure BDA0001292960300000429
Triflate, hydroxyethylammonium triflate, 1, 2-dimethylimidazole
Figure BDA00012929603000004210
Triflate, imidazole
Figure BDA00012929603000004211
Triflate, 1-methylimidazole
Figure BDA00012929603000004212
Trifluoromethanesulfonate, hydrotrifluoromethane hydrochloride, methylammonium methanesulfonate, ethylammonium methanesulfonate, butylammonium methanesulfonate, methoxyethylammonium methanesulfonate, dimethylammonium methanesulfonate, dibutylammonium methanesulfonate, triethylammonium methanesulfonate, dimethylethylammonium methanesulfonate, hydronium bisulfate, ammonium bisulfate, methylammonium bisulfate, ethylammonium bisulfate, propylammonium bisulfate, n-butylammonium bisulfate, tert-butylammonium bisulfate, dimethylammonium bisulfate, diethylammonium bisulfate, di-n-butylammonium bisulfate, methylbutylammonium bisulfate, ethylbutylammonium bisulfate, trimethylammonium bisulfate, triethylammonium bisulfate, tributylammonium bisulfate, dimethylethylammonium bisulfate, dibutylammonium fluorophosphate, triethylammonium fluorophosphate, tributylammonium fluorophosphate, dihydrogenphosphate hydrate, methylammonium dihydrogenphosphate, ethylammonium dihydrogenphosphate, propylammonium dihydrogenphosphate, n-butylammonium dihydrogenphosphate, methoxyethylammonium dihydrogenphosphate, dimethylammonium dihydrogenphosphate, dibutylammoniumDihydrogen phosphate, methylbutylammonium phosphate, ammonium bifluoride, methyl ammonium bifluoride, ethyl ammonium bifluoride, and dimethyl ammonium bifluoride.
E108. The cell according to embodiment 103, wherein the one or more ionic compounds are selected from the group consisting of tri-n-butyl methylammonium methylsulfate, 1-ethyl-2, 3-dimethylimidazole
Figure BDA0001292960300000431
Ethyl sulfate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000432
Thiocyanate, 1-butyl-3-methylimidazol tetrachloroaluminate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000433
Methyl sulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000434
Methanesulfonic acid salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000435
Bisulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000436
Bicarbonate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000437
Chloride 1,2, 3-trimethylimidazole
Figure BDA0001292960300000438
Methyl sulfate, 1,2, 4-trimethylpyrazole
Figure BDA0001292960300000439
Methylsulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004310
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004311
Thiocyanate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004312
Methanesulfonic acid salt, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004313
Tetrachloroaluminate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004314
Bisulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004315
Ethyl sulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004316
Nitrate salt, 1-butylpyridine
Figure BDA00012929603000004317
Chloride, 1-ethyl-3-methylimidazolidinedicyanamide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004318
Tetrafluoroborate, 1, 3-dimethylimidazole
Figure BDA00012929603000004319
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004320
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004321
Hexafluorophosphate, 1-butyl-3, 5-dimethylpyridine
Figure BDA00012929603000004322
Bromide, 1-Ethyl-3-methylimidazole
Figure BDA00012929603000004323
Bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004324
Bis (pentafluoroethylsulfonyl) imide, 1-ethyl-2, 3-dimethylimidazole
Figure BDA00012929603000004325
Methyl carbonate, carboxymethyl tributyl
Figure BDA00012929603000004326
Bis (trifluoromethylsulfonyl) imide, N-carboxyethyl-methylpyrrolidine
Figure BDA00012929603000004327
Bis (trifluoromethylsulfonyl) imide, N-carboxymethyltrimethylammonium bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-methylpyridine
Figure BDA00012929603000004328
Bis (trifluoromethylsulfonyl) imide, hexyltrimethylammonium bis (trifluoromethylsulfonyl) imide, tetrabutylphosphonium imide
Figure BDA00012929603000004329
Methanesulfonic acid salt, tetrabutyl
Figure BDA00012929603000004330
Tetrafluoroborate, tetrabutyl
Figure BDA00012929603000004331
P-toluenesulfonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004332
Bicarbonate, triethylmethylammonium methylcarbonate, tributylmethylammonium methylcarbonate, 1-ethyl-1-methylpiperidine
Figure BDA00012929603000004333
Methyl carbonate, 4-ethyl-4-methylmorpholine
Figure BDA00012929603000004334
Methylcarbonate, 1-butyl-1-methylpyrrolidine
Figure BDA0001292960300000441
Methyl carbonate, triethylmethylammonium dibutyl phosphate, tributylmethylammonium dibutyl phosphate, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000442
Dibutyl phosphate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000443
Dibutyl phosphate, 1- (cyanomethyl) -3-methylimidazole
Figure BDA0001292960300000444
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000445
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000446
Bis (trifluoromethylsulfonyl) imide, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000447
Dicyandiamide, 1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000448
Chloride, 1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000449
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000004410
Chloride, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000004411
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000004412
Chloride, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000004413
Bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazole
Figure BDA00012929603000004414
Hexafluorophosphate, 1-butyl-3-methylimidazole
Figure BDA00012929603000004415
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004416
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004417
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004418
Bromide, 1-butyl-3-methylimidazole
Figure BDA00012929603000004419
Bromide, 1-hexyl-3-methylimidazole
Figure BDA00012929603000004420
Chloride, tributylmethyl
Figure BDA00012929603000004421
Dibutyl phosphate, triethyl methyl
Figure BDA00012929603000004422
Dibutylphosphate, tributylmethyl
Figure BDA00012929603000004423
Methyl carbonate, tributylmethyl
Figure BDA00012929603000004424
Methylsulfates, triethylmethyl
Figure BDA00012929603000004425
Dibutyl phosphate trihexyltetradecyl
Figure BDA00012929603000004426
Bis (trifluoromethylsulfonyl) imide, trihexyltetradecyl
Figure BDA00012929603000004427
Bis (2,4, 4-trimethylphenyl) hypophosphite, trihexyltetradecyl
Figure BDA00012929603000004428
Bromide, trihexyltetradecyl
Figure BDA00012929603000004429
Chloride, trihexyltetradecyl
Figure BDA00012929603000004430
Decanoate, trihexyltetradecyl
Figure BDA00012929603000004431
Dicyandiamide, 3- (triphenylphosphonium)
Figure BDA00012929603000004432
Yl) propane-1-sulfonate and 3- (triphenylphosphonium)
Figure BDA00012929603000004433
Yl) propane-1-sulfonic acid tosylate.
E109. The battery of embodiment 103, wherein the electrolyte composition comprises at least two different ionic compounds.
E110. The battery of embodiment 109, wherein the electrolyte composition comprises two different salts.
E111. The battery of embodiment 109, wherein the electrolyte composition comprises two different ionic liquids.
E112. The battery of embodiment 109, wherein the electrolyte composition comprises an ionic liquid and a salt.
E113. The battery according to embodiment 102, wherein the electrolyte composition comprises an ionic liquid and one or more salts selected from protic or aprotic ammonium salts and alkali metal salts.
E114. The battery of embodiment 102, wherein the electrolyte composition comprises an ionic liquid and a protic acid, a protic ammonium compound or a protic oxygen
Figure BDA0001292960300000451
A compound is provided.
E115. The battery according to embodiment 102, wherein the electrolyte composition comprises two different ionic compounds comprising the same cation or the same anion.
E116. The battery according to embodiment 102, wherein the electrolyte composition does not include an organic solvent, comprising 1000ppm or less of water based on the total weight of the electrolyte composition.
E117. The battery according to any one of embodiments 102-116, wherein the electrolyte composition comprises a solvent.
E118. The battery of embodiment 117, wherein the solvent consists essentially of water.
E119. The battery of embodiment 117, wherein the solvent consists essentially of an organic solvent.
E120. The battery of embodiment 117, wherein the solvent comprises water and an organic solvent.
E121. The cell according to embodiment 117, wherein the solvent comprises one or more solvents selected from the group consisting of organic carbonates, ethers, glymes, orthoesters, polyalkylene glycols, esters, lactones, glycols, formates, sulfones, sulfoxides, amides, alcohols, amines, ketones, nitro solvents, and nitrile solvents.
E122. The cell according to embodiment 117 wherein the solvent comprises one or more solvents selected from the group consisting of ethylene carbonate, propylene carbonate, trimethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, vinylene carbonate, difluoroethylene carbonate, monofluoroethylene carbonate, dimethoxymethane, diethoxymethane, 1, 2-dimethoxyethane, diglyme, triglyme, tetraglyme, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dibutylene glycol
Figure BDA0001292960300000452
Alkane, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, 1, 4-dioxolane
Figure BDA0001292960300000453
Alkane, dimethyl ether, ethyl methyl ether, diethyl ether, di-n-butyl ether, di-tert-butyl ether, di-isopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2]]Octane, 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, polyethylene glycol, dimethyl polyethylene glycol, diethyl polyethylene glycol, γ -butyrolactone, γ -valerolactone, δ -valerolactone, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, ethylene glycol diacetate, 3-ethoxyethyl propionate, methyl butyrate, n-pentyl acetate, propylene glycol methyl ether acetate, ethyl butyrate, diethyl malonate, dimethyl malonate, a dibasic ester mixture, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, propylene glycol butyl ether, propylene glycol methyl ether, triethylene glycol, dipropylene glycolGlycolmethylether, diglycolmethylether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diglycolmethylether, fluorinated triethylene glycol methylether and fluorinated diethylene glycol butylether, methyl formate, ethyl formate, isobutyl formate, tert-butyl formate, methylsulfonylmethane, ethylmethylsulfonylmethane, sulfolane, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, N, N '-dimethyl-N, N' -trimethyleneurea (1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone), benzyl Alcohol (BA), ethanol, trifluoroethanol (2,2' -trifluoroethanol), methanol, isopropanol, tert-butanol, n-butanol, methyl ethyl ketone, methyl-isoamyl ketone, triethylamine, tributylamine, diethylenetriamine, ethylenediamine, morpholine, piperidine, pyridine, nitrobenzene, nitromethane, nitroethane, acetonitrile, propionitrile, butyronitrile and adiponitrile.
E125. The battery according to embodiment 102, wherein the electrolyte composition comprises one or more ionic compounds selected from alkali or alkaline earth metal hydroxides and alkoxides and an organic solvent.
E126. The battery according to embodiment 102, wherein the electrolyte composition comprises one or more ionic compounds selected from alkali metal hydroxides, water and one or more further components selected from organic solvents, further ionic compounds and additives.
E127. The battery of embodiment 126, wherein the electrolyte composition comprises an organic solvent.
E128. The battery according to embodiment 126, wherein the electrolyte composition comprises one or more other ionic compounds.
E129. The battery of embodiment 128, wherein the one or more other ionic compounds are selected from ionic liquids.
E130. The battery of embodiment 126, wherein the electrolyte composition comprises one or more additives.
E131. The battery according to embodiment 102, wherein the electrolyte composition comprises one or more ionic compounds selected from carboxylate compounds and carboxylic acids.
E132. The battery according to embodiment 102, wherein the electrolyte composition comprises one or more ionic compounds selected from carboxylate compounds.
E133 the battery of embodiment 132, wherein the one or more carboxylate compounds are selected from the group consisting of alkali metal, alkaline earth metal carboxylates, and ammonium carboxylates.
E134. The battery according to embodiment 102, wherein the electrolyte composition comprises one or more ionic compounds selected from carboxylic acids.
E135. The battery of embodiment 131 wherein the electrolyte composition comprises a carboxylate compound and a carboxylic acid.
E136. The battery of embodiment 131, wherein the electrolyte composition comprises a solvent.
E137. The battery of embodiment 136, wherein the solvent consists essentially of water.
E138. The battery of embodiment 136, wherein the solvent consists essentially of an organic solvent.
E139. The battery of embodiment 136, wherein the solvent comprises water and an organic solvent.
E140. A cell according to any one of the preceding embodiments, wherein the half-cell charge/discharge electrochemical reaction at the anode when a potential is applied across the cell is:
Figure BDA0001292960300000472
E141. a battery according to any of the preceding embodiments, wherein the pH of the electrolyte composition is less than or equal to about 7.
E142. A metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein the half-cell charge/discharge electrochemical reaction at the positive electrode upon application of a potential across the battery is:
Figure BDA0001292960300000471
E143. a metal hydride battery comprising at least one negative electrode, at least one positive electrode, a housing having the electrodes positioned therein, and an electrolyte composition, wherein the electrolyte composition has a pH of less than or equal to about 7.
E144. The cell according to embodiment 142 or 143, wherein said electrolyte composition comprises one or more selected from the group consisting of alkali or alkaline earth metal salts, protic acids, protic ammonium compounds, protic oxygen
Figure BDA0001292960300000473
Compounds, aprotic ammonium compounds, aprotic oxygen
Figure BDA0001292960300000474
Compound and aprotic
Figure BDA0001292960300000475
Ionic compounds of the compound.
E145. The cell of embodiment 144 wherein the one or more ionic compounds comprise an anion selected from the group consisting of hydroxide, nitrate, perchlorate, bifluoride, alkoxide, halide, phosphate, phosphinate, phosphonate, borate, carboxylate, sulfite, sulfate, sulfonate, carbonate, imide, aluminate, cyanate, methide, arsenate, silicate and antimonate.
E146. The battery of embodiment 144, wherein the one or more ionic compounds comprise a compound selected from the group consisting of chloride, bromide, H2PO4 -，BF4 -Dibutyl phosphate, HPO3F-Bisulfate, thiocyanate, difluoride, perchlorate, dicyanamide, Al (OC (CF)3)3)4 -，B(C6F5)4 -，[N(SO2CF3)2]- (bis (trifluorosulfonylimide), bis (pentafluoroethylsulfonyl) imide, trifluoromethanesulfonate (trifluoromethanesulfonate), p-toluenesulfonate (toluenesulfonate), methanesulfonateAcid salts (methanesulfonate), tetraphenylborate, [ B (3,5- (CF)3)2C6H3)4]-，Al(OC(CF3)3)4 -，B(C6F5)4 -，[N(SO2CF3)2]-，N(SO2F)2 -Tris (pentafluoroethyl) trifluorophosphate, B (C)2O4)2 -Difluoro (oxalato) borate, tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate, tetrabromoaluminate, AsF6 -，PF6 -，SbF6 -And SiF6 -2The anion of (4).
E147. The cell according to any one of embodiments 144-146 wherein the one or more ionic compounds are selected from ionic liquids.
E148. The cell according to embodiment 144 wherein said one or more ionic compounds is selected from the group consisting of ethylammonium nitrate, diethylmethylammonium trifluoromethanesulfonate, triethylammonium methanesulfonate, 2-methylpyridine
Figure BDA0001292960300000481
Triflate, ammonium fluoride, methylammonium nitrate, hydroxyethylammonium nitrate, ethylammonium nitrate, dimethylammonium nitrate, 1-methylimidazole
Figure BDA0001292960300000482
Chloride, 1-methylimidazole
Figure BDA0001292960300000483
Nitrate, 1-ethylimidazole
Figure BDA0001292960300000484
Nitrate, tert-butylammonium tetrafluoroborate, hydroxyethylammonium tetrafluoroborate, methylbutylammonium tetrafluoroborate, triethylammonium tetrafluoroborate, imidazole
Figure BDA0001292960300000485
Tetrafluoroborate salt, 1-methylimidazole
Figure BDA0001292960300000486
Bisulfate, 1-methylimidazole
Figure BDA0001292960300000487
Tetrafluoroborate, 1, 2-dimethylimidazole
Figure BDA0001292960300000488
Tetrafluoroborate, tert-butylammonium triflate, 2-fluoropyridine
Figure BDA0001292960300000489
Triflate, hydroxyethylammonium triflate, 1, 2-dimethylimidazole
Figure BDA00012929603000004810
Triflate, imidazole
Figure BDA00012929603000004811
Triflate, 1-methylimidazole
Figure BDA00012929603000004812
Trifluoromethanesulfonate, hydrotrifluoromethane hydrochloride, methylammonium methanesulfonate, ethylammonium methanesulfonate, butylammonium methanesulfonate, methoxyethylammonium methanesulfonate, dimethylammonium methanesulfonate, dibutylammonium methanesulfonate, triethylammonium methanesulfonate, dimethylethylammonium methanesulfonate, hydronium bisulfate, ammonium bisulfate, methylammonium bisulfate, ethylammonium bisulfate, propylammonium bisulfate, n-butylammonium bisulfate, tert-butylammonium bisulfate, dimethylammonium bisulfate, diethylammonium bisulfate, di-n-butylammonium bisulfate, methylbutylammonium bisulfate, ethylbutylammonium bisulfate, trimethylammonium bisulfate, triethylammonium bisulfate, tributylammonium bisulfate, dimethylethylammonium bisulfate, dibutylammonium fluorophosphate, triethylammonium fluorophosphate, tributylammonium fluorophosphate, dihydrogen hydrogenhydrogenhydrogenhydrogenphosphate, dihydrogen methylammonium phosphate, and ethylammonium phosphateDihydrogen salts, propyl ammonium dihydrogen phosphate, n-butyl ammonium dihydrogen phosphate, methoxyethyl ammonium dihydrogen phosphate, dimethyl ammonium dihydrogen phosphate, dibutyl ammonium dihydrogen phosphate, methyl butyl ammonium dihydrogen phosphate, ammonium bifluoride, methyl ammonium bifluoride, ethyl ammonium bifluoride and dimethyl ammonium bifluoride.
E149. The cell according to embodiment 144, wherein the one or more ionic compounds are selected from the group consisting of tri-n-butyl methylammonium methylsulfate, 1-ethyl-2, 3-dimethylimidazole
Figure BDA0001292960300000491
Ethyl sulfate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000492
Thiocyanate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000493
Tetrachloroaluminate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000494
Methyl sulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000495
Methanesulfonic acid salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000496
Bisulfate salt, 1-butyl-3-methylimidazole
Figure BDA0001292960300000497
Bicarbonate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000498
Chloride 1,2, 3-trimethylimidazole
Figure BDA0001292960300000499
Methyl sulfate, 1,2, 4-trimethylpyrazole
Figure BDA00012929603000004910
Methylsulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004911
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004912
Thiocyanate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004913
Methanesulfonic acid salt, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004914
Tetrachloroaluminate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004915
Bisulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004916
Ethyl sulfate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004917
Nitrate salt, 1-butylpyridine
Figure BDA00012929603000004918
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004919
Dicyandiamide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004920
Tetrafluoroborate, 1, 3-dimethylimidazole
Figure BDA00012929603000004921
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004922
Bicarbonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004923
Hexafluorophosphate, 1-butyl-3, 5-dimethylpyridine
Figure BDA00012929603000004924
Bromide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004925
Bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004926
Bis (pentafluoroethylsulfonyl) imide, 1-ethyl-2, 3-dimethylimidazole
Figure BDA00012929603000004927
Methyl carbonate, carboxymethyl tributyl
Figure BDA00012929603000004928
Bis (trifluoromethylsulfonyl) imide, N-carboxyethyl-methylpyrrolidine
Figure BDA00012929603000004929
Bis (trifluoromethylsulfonyl) imide, N-carboxymethyltrimethylammonium bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-methylpyridine
Figure BDA00012929603000004930
Bis (trifluoromethylsulfonyl) imide, hexyltrimethylammonium bis (trifluoromethylsulfonyl) imide, tetrabutylphosphonium imide
Figure BDA00012929603000004931
Methanesulfonic acid salt, tetrabutyl
Figure BDA00012929603000004932
Tetrafluoroborate, tetrabutyl
Figure BDA00012929603000004933
P-toluenesulfonate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000004934
Bicarbonate, triethylmethylammonium methylcarbonate, tributylmethylammonium methylcarbonate, 1-ethyl-1-methylpiperidine
Figure BDA00012929603000004935
Methyl carbonate, 4-ethyl-4-methylmorpholine
Figure BDA00012929603000004936
Methylcarbonate, 1-butyl-1-methylpyrrolidine
Figure BDA0001292960300000501
Methyl carbonate, triethylmethylammonium dibutyl phosphate, tributylmethylammonium dibutyl phosphate, 1-ethyl-3-methylimidazole
Figure BDA0001292960300000502
Dibutyl phosphate, 1-butyl-3-methylimidazole
Figure BDA0001292960300000503
Dibutyl phosphate, 1- (cyanomethyl) -3-methylimidazole
Figure BDA0001292960300000504
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000505
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000506
Bis (trifluoromethylsulfonyl) imide, 1- (3-cyanopropyl) -3-methylimidazole
Figure BDA0001292960300000507
Dicyandiamide, 1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000508
Chloride, 1- (3-cyanopropyl) pyridine
Figure BDA0001292960300000509
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000005010
Chloride, 1, 3-bis (cyanomethyl) imidazole
Figure BDA00012929603000005011
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000005012
Chloride, 1, 3-bis (3-cyanopropyl) imidazole
Figure BDA00012929603000005013
Bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazole
Figure BDA00012929603000005014
Hexafluorophosphate, 1-butyl-3-methylimidazole
Figure BDA00012929603000005015
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000005016
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure BDA00012929603000005017
Chloride, 1-ethyl-3-methylimidazole
Figure BDA00012929603000005018
Bromide, 1-butyl-3-methylimidazole
Figure BDA00012929603000005019
Bromide, 1-hexyl-3-methylimidazole
Figure BDA00012929603000005020
Chloride, tributylmethyl
Figure BDA00012929603000005021
Dibutyl phosphate, triethyl methyl
Figure BDA00012929603000005022
Dibutylphosphate, tributylmethyl
Figure BDA00012929603000005023
Methyl carbonate, tributylmethyl
Figure BDA00012929603000005024
Methylsulfates, triethylmethyl
Figure BDA00012929603000005025
Dibutyl phosphate trihexyltetradecyl
Figure BDA00012929603000005026
Bis (trifluoromethylsulfonyl) imide, trihexyltetradecyl
Figure BDA00012929603000005027
Bis (2,4, 4-trimethylphenyl) hypophosphite, trihexyltetradecyl
Figure BDA00012929603000005028
Bromide, trihexyltetradecyl
Figure BDA00012929603000005029
Chloride, trihexyltetradecyl
Figure BDA00012929603000005030
Decanoate, trihexyltetradecyl
Figure BDA00012929603000005031
Dicyandiamide, 3- (triphenylphosphonium)
Figure BDA00012929603000005032
Yl) propane-1-sulfonate and 3- (triphenylphosphonium)
Figure BDA00012929603000005033
Yl) propane-1-sulfonic acid tosylate.
E150. The battery of embodiment 144 wherein the electrolyte composition comprises one or more ionic compounds selected from carboxylate compounds and carboxylic acids.
E151. The battery of embodiment 144, wherein the electrolyte composition comprises one or more ionic compounds selected from carboxylate compounds.
E152. The battery of embodiment 151, wherein the one or more carboxylate compounds are selected from the group consisting of alkali metal, alkaline earth metal, and ammonium carboxylates.
E153. The battery of embodiment 144 wherein the electrolyte composition comprises one or more ionic compounds selected from carboxylic acids.
E154. The battery of embodiment 150, wherein the electrolyte composition comprises a carboxylate compound and a carboxylic acid.
E155. The battery according to any one of embodiments 144-154, wherein the electrolyte composition comprises at least two different ionic compounds.
E156. The battery of embodiment 155, wherein the electrolyte composition comprises two different salts.
E157. The battery of embodiment 155, wherein the electrolyte composition comprises two different ionic liquids.
E158. The battery of embodiment 155, wherein the electrolyte composition comprises an ionic liquid and a salt.
E159. The battery of embodiment 144, wherein the electrolyte composition comprises an ionic liquid and one or more salts selected from protic or aprotic ammonium and alkali metal salts.
E160. The battery of embodiment 144, wherein the electrolyte composition comprisesContaining ionic liquid and protic acid, protic ammonium compound or protic oxygen
Figure BDA0001292960300000511
A compound is provided.
E161. The battery according to embodiment 144, wherein the electrolyte composition comprises two different ionic compounds comprising the same cation or the same anion.
E162. The battery according to embodiment 144, wherein the electrolyte composition does not include an organic solvent, comprising 1000ppm or less of water based on the total weight of the electrolyte composition.
E163. The battery of embodiment 144, wherein the electrolyte composition comprises a solvent.
E164. The battery of embodiment 163, wherein the solvent consists essentially of water.
E165. The battery of embodiment 163, wherein the solvent consists essentially of an organic solvent.
E166. The battery of embodiment 163, wherein the solvent comprises water and an organic solvent.
E167. The cell according to embodiment 163 wherein said solvent comprises one or more solvents selected from the group consisting of organic carbonates, ethers, glymes, orthoesters, polyalkylene glycols, esters, lactones, glycols, formates, sulfones, sulfoxides, amides, alcohols, amines, ketones, nitro solvents and nitrile solvents.
E168. The cell according to embodiment 163 wherein said solvent comprises one or more solvents selected from the group consisting of ethylene carbonate, propylene carbonate, trimethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, vinylene carbonate, difluoroethylene carbonate, monofluoroethylene carbonate, dimethoxymethane, diethoxymethane, 1, 2-dimethoxyethane, diglyme, triglyme, tetraglyme, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-diethylene glycol diethyl ether
Figure BDA0001292960300000512
Alkane, 1, 3-dioxolane4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, 1, 4-dioxolane
Figure BDA0001292960300000521
Alkane, dimethyl ether, ethyl methyl ether, diethyl ether, di-n-butyl ether, di-tert-butyl ether, di-isopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, trimethoxymethane, triethoxymethane, 1, 4-dimethyl-3, 5, 8-trioxabicyclo [2.2.2]]Octane, 4-ethyl-1-methyl-3, 5, 8-trioxabicyclo [2.2.2]Octane, polyethylene glycol, dimethyl polyethylene glycol, diethyl polyethylene glycol, γ -butyrolactone, γ -valerolactone, δ -valerolactone, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, ethylene glycol diacetate, 3-ethoxyethyl propionate, methyl butyrate, n-pentyl acetate, propylene glycol methyl ether acetate, ethyl butyrate, diethyl malonate, dimethyl malonate, a dibasic ester mixture, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, propylene glycol butyl ether, propylene glycol methyl ether, triethylene glycol, dipropylene glycol methyl ether, diethylene glycol methyl ether, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, perfluoro-1, 4-butanediol, perfluoro-1, 5-butanediol, fluorinated diethylene glycol methyl ether, fluorinated triethylene glycol methyl ether and fluorinated diethylene glycol butyl ether, methyl formate, ethyl formate, isobutyl formate, tert-butyl formate, methylsulfonylmethane, ethylmethylsulfone, sulfolane, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, n, N ' -dimethyl-N, N ' -trimethyleneurea (1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone), Benzyl Alcohol (BA), ethanol, trifluoroethanol (2,2' -trifluoroethanol), methanol, isopropanol, tert-butanol, N-butanol, methyl ethyl ketone, methyl-isoamyl ketone, triethylamine, tributylamine, diethylenetriamine, ethylenediamine, morpholine, piperidine, pyridine, nitrobenzene, nitreMethyl hydride, nitroethane, acetonitrile, propionitrile, butyronitrile and adiponitrile.
E169. The battery of embodiment 144, wherein the electrolyte composition comprises one or more additives selected from the group consisting of corrosion inhibitors, solid electrolyte interface improvers, proton evolution improvers, self-discharge inhibitors, gas resistance agents, viscosity modifiers, cathodic protection agents, salt stabilizers, conductivity improvers, and solvating agents.
E170. The battery according to any one of embodiments 144-169, wherein the viscosity of the electrolyte composition is at 25℃The lower is less than or equal to 100cP, less than or equal to 90cP, less than or equal to 80cP, less than or equal to 70cP, less than or equal to 50cP, less than or equal to 40cP, less than or equal to 30cP, less than or equal to 20cP, less than or equal to 10cP or less than or equal to 5 cP.
E171. The cell according to any one of embodiments 144 and 170, exhibiting a nominal open circuit voltage of from about 1.2 to about 5.0V, from about 1.3 to about 5.0V, from about 1.4 to about 5.0V, or from about 1.5 to about 5.0V.
Example 1
Preparation HN (Me)3BF41mol/L of an electrolyte composition in propylene carbonate. The electrolyte composition is used for preparing a rare earth nickel-based AB5The hydrogen storage material is used as a negative electrode, and the slurried nickel hydroxide positive electrode and the polypropylene/polyethylene grafted non-woven fabric spacer are arranged in the battery.
Or, NH4BF4Quilt H3PO4、NH4CF3SO3、N2H6SO4、HN(Me)3Cl、NH4H2PO4、KH2PO4Or pyridine
Figure BDA0001292960300000531
Chloride is substituted.
Alternatively, the Propylene Carbonate (PC) is replaced by Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), DMF, DMSO, dimethyl carbonate (DMC), diethyl carbonate (DEC), 1, 2-Dimethoxyethane (DME), Ethyl Acetate (EA) or mixtures thereof such as EC/DMC, EC/DEC, EC/EMC, EC/DMC/DEC or EC/DMC/EA.
Example 2
Is repeatedly carried outExample 1 Using pure Diethylmethylammonium triflate, triethylammonium methanesulfonate or 2-methylpyridine
Figure BDA0001292960300000532
Triflate salts replace the electrolyte compositions. Alternatively, diethylmethylammonium trifluoromethanesulfonate, triethylammonium methanesulfonate or 2-methylpyridine is used
Figure BDA0001292960300000533
80:20 weight: weight mixture of triflate to glyme.
Example 3
Electrolyte composition for use with rare earth nickel-based AB5The hydrogen storage material is used as a negative electrode, and the slurried nickel hydroxide positive electrode and the polypropylene/polyethylene grafted non-woven fabric spacer are arranged in the battery. The electrolyte composition is pure 1-ethyl-3-methylimidazole
Figure BDA0001292960300000534
Dicyandiamide. Alternatively, 1-ethyl-3-methylimidazole is used
Figure BDA0001292960300000535
A tetrafluoroborate salt. Alternatively, tetrabutyl radicals are used
Figure BDA0001292960300000536
Mixture of mesylate to glyme 80:20 wt./wt.
Example 4
Electrolyte composition for use in battery having rare earth nickel-based AB as negative electrode5Hydrogen storage material, slurried nickel hydroxide positive electrode and polypropylene/polyethylene grafted non-woven fabric spacer. The electrolyte composition was 30 wt% potassium ethoxide in trifluoroethanol. Alternatively, a 30% by weight mixture of sodium methoxide in methanol, a 30% by weight mixture of potassium ethoxide in ethylene glycol or a 30% by weight mixture of potassium ethoxide in ethanol is used.
Example 5
Electrolyte composition for use with rare earth nickel-based AB5Hydrogen storage materialThe material is used as a negative electrode, a slurried nickel hydroxide positive electrode and a polypropylene/polyethylene grafted non-woven fabric separator. The electrolyte composition was 25 wt% potassium hydroxide in propylene carbonate.
Example 6
Electrolyte composition for use with rare earth nickel-based AB5The hydrogen storage material is used as a negative electrode, a slurried nickel hydroxide positive electrode and a polypropylene/polyethylene grafted non-woven fabric spacer. The electrolyte composition was 25 wt% KOH in a 1:1 weight mixture of water and polyethylene glycol (PEG 600). This example was repeated, replacing the electrolyte composition with a 30 wt% KOH mixture in PEG 300.
Example 7
Electrolyte composition for use with rare earth nickel-based AB5The hydrogen storage material is used as a negative electrode, a slurried nickel hydroxide positive electrode and a polypropylene/polyethylene grafted non-woven fabric spacer. The electrolyte composition was 30 wt% potassium acetate in acetic acid. Alternatively, the electrolyte composition is 30 wt% octanoic acid in glyme, or 30 wt% potassium acetate in glyme, or 30 wt% sodium acetate in butyric acid.
Example 8
1mol/L of the electrolyte composition (triethylammonium 2-nitrobenzoate in propylene carbonate) was prepared. The composition was used in a battery according to example 1.
Example 9
Preparation of 6mol/L electrolyte composition (1-ethyl-3-methylimidazole)
Figure BDA0001292960300000541
Acetate in glacial acetic acid). The composition was used in a battery according to example 1.
Example 10
An electrolyte mixture of diethylmethylammonium triflate (DEMA TfO, ionic liquid) and trimethylammonium chloride (salt) was prepared. Ionic liquid salt mixtures were prepared at weight: weight levels of 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, and 5: 1. Alternatively, the salts tetraethylammonium bromide or diethylmethylammonium chloride are used in the mixture as the salt. Alternatively, sodium or potassium salts are used as salts, for example, NaCl or KCl. Alternatively, a carboxylate is used as the salt. The mixture was used in a battery according to example 1.
Example 11
An electrolyte mixture of diethylmethylammonium triflate (DEMA TfO, ionic liquid) and ethylammonium nitrate was prepared. Ionic liquid mixtures were prepared at weight: weight levels of 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, and 5: 1. The mixture was used in a battery as in example 1. Or the ionic liquid is composed of triethylammonium methanesulfonate and 2-methylpyridine
Figure BDA0001292960300000551
Triflate, tri-n-butyl methyl ammonium methyl sulfate, 1-ethyl-2, 3-dimethyl imidazole
Figure BDA0001292960300000552
Ethyl sulfate or 1-butyl-3-methylimidazole
Figure BDA0001292960300000553
One or more of the thiocyanates.

Claims (19)

1. A metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein
The electrolyte composition comprises a proton-free acid, a protic ammonium compound, a protic oxygen
Figure FDA0003001131570000011
Compound, aprotic ammonium compound, aprotic oxygen
Figure FDA0003001131570000012
Compound, aprotic
Figure FDA0003001131570000013
One or more of the group consisting of compounds and alkali metal or alkaline earth metal saltsA plurality of ionic compounds; and
if the electrolyte composition comprises an alkali metal salt, the composition further comprises one or more organic solvents selected from the group consisting of glymes, orthoesters, polyalkylene glycols, lactones, glycols, formates, sulfones, sulfoxides, amides, alcohols, amines, nitro solvents, and nitrile solvents.
2. A metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes located therein and an electrolyte composition, wherein
The electrolyte composition comprises a proton-free acid, a protic ammonium compound, a protic oxygen
Figure FDA0003001131570000014
Compound, aprotic ammonium compound, aprotic oxygen
Figure FDA0003001131570000015
Compound, and aprotic
Figure FDA0003001131570000016
One or more ionic compounds of the group of compounds; and
one or more organic solvents.
3. The cell according to claim 1 or 2, wherein the one or more ionic compounds comprise a compound selected from the group consisting of H+Alkali metal ion, alkaline earth metal ion, ammonium, methylammonium, ethylammonium, dimethylammonium, diethylammonium, trimethylammonium, triethylammonium, tributylammonium, diethylmethylammonium, hydroxyethylammonium, methoxymethylammonium, dibutylammonium, methylbutylammonium, anilinium, pyridine
Figure FDA0003001131570000017
2-methylpyridine
Figure FDA0003001131570000018
Imidazole
Figure FDA0003001131570000019
1-methylimidazole
Figure FDA00030011315700000110
1, 2-dimethylimidazole
Figure FDA00030011315700000111
Imidazoline
Figure FDA00030011315700000112
1-ethylimidazole
Figure FDA00030011315700000113
1- (4-sulfobutyl) -3-methylimidazole
Figure FDA00030011315700000114
1-allylimidazole
Figure FDA00030011315700000115
Quinolines
Figure FDA00030011315700000116
Isoquinoline derivatives
Figure FDA00030011315700000117
Pyrrolines
Figure FDA00030011315700000118
Pyrrolinium, pyrrolidine
Figure FDA00030011315700000128
Hydroxylammonium, H3O+、H+O(Et)2、H2EtO+、H2MeO+、H+O(Me)2Protonated tetrahydrofuran, protonated 2-methyl-tetrahydrofuran, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tri-n-butylammoniumButyl methylammonium, n-butyl-triethylammonium, benzyl-trimethylammonium, benzyl-triethylammonium, 1-methylpyridine
Figure FDA00030011315700000120
1-butyl-3, 5-dimethylpyridine
Figure FDA00030011315700000121
1,2, 3-trimethylimidazole
Figure FDA00030011315700000122
1-ethyl-3-methylimidazole
Figure FDA00030011315700000123
1-butyl-3-methylimidazole
Figure FDA00030011315700000124
1-ethyl-2, 3-dimethylimidazole
Figure FDA00030011315700000125
1-allyl-3-methylimidazole
Figure FDA00030011315700000126
1-hydroxyethyl-3-methylimidazole
Figure FDA00030011315700000127
Trimethylhydroxyethylammonium (choline), tris (hydroxyethyl) methylammonium, dimethyl-di (polyoxyethylene) ammonium, 1-ethyl-1-methylpiperidine
Figure FDA0003001131570000021
4-ethyl-4-methylmorpholine
Figure FDA0003001131570000022
1- (cyanomethyl) -3-methylimidazole
Figure FDA0003001131570000023
1- (3-cyanopropyl radical)) Pyridine compound
Figure FDA0003001131570000024
1, 3-bis (cyanomethyl) imidazoles
Figure FDA0003001131570000025
+O(Me)3、+O(Et)3tetrahydrofuran-Me+tetrahydrofuran-Et+2-methyltetrahydrofuran-Me+2-methyltetrahydrofuran-Et+Methyl triphenyl (methyl triphenyl)
Figure FDA0003001131570000026
Tetraphenyl radical
Figure FDA0003001131570000027
Tetra butyl
Figure FDA0003001131570000028
Tributyl methyl group
Figure FDA0003001131570000029
Triethyl methyl group
Figure FDA00030011315700000210
Trihexyltetradecyl
Figure FDA00030011315700000211
Triphenylpropyl radical
Figure FDA00030011315700000212
And tetra (hydroxymethyl)
Figure FDA00030011315700000213
A cation of the group consisting of.
4. The cell according to any one of claims 1 to 3, wherein the one or more ionic compounds comprise an anion selected from the group consisting of hydroxide, nitrate, perchlorate, difluoride, alkoxide, halide, phosphate, phosphinate, phosphonate, borate, carboxylate, sulfite, sulfate, sulfonate, carbonate, imide, aluminate, cyanate, methide, arsenate, silicate, and antimonate.
5. A cell according to any of claims 1 to 3, wherein the one or more ionic compounds comprise a compound selected from the group consisting of chloride, bromide, H2PO4 -、BF4 -Dibutyl phosphate, HPO3F-Hydrogen sulfate, thiocyanate, difluoride, perchlorate, dicyandiamide, Al (OC (CF)3)3)4 -、B(C6F5)4 -、[N(SO2CF3)2]-(bis-trifluoroimide), bis (pentafluoroethylsulfonyl) imide, trifluoromethanesulfonate (trifluoromethanesulfonate), p-toluenesulfonate (toluenesulfonate), methanesulfonate (methanesulfonate), tetraphenylborate, [ B (3,5- (CF) s3)2C6H3)4]-、Al(OC(CF3)3)4 -、B(C6F5)4 -、[N(SO2CF3)2]-、N(SO2F)2 -Tris (pentafluoroethyl) trifluorophosphate, B (C)2O4)2 -Difluoro (oxalato) borate, tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate, tetrabromoaluminate, AsF6 -、PF6-、SbF6 -And SiF6 -2Anions of the group.
6. A battery according to claim 1 or 2, wherein the electrolyte composition comprises one or more ionic compounds selected from the group consisting of ionic liquids.
7. A battery according to claim 1 or 2, wherein the electrolyte composition comprises aOne or more compounds selected from the group consisting of ethylammonium nitrate, diethylmethylammonium trifluoromethanesulfonate, triethylammonium methanesulfonate, 2-methylpyridine
Figure FDA00030011315700000214
Triflate, ammonium fluoride, methylammonium nitrate, hydroxyethylammonium nitrate, ethylammonium nitrate, dimethylammonium nitrate, 1-methylimidazole
Figure FDA00030011315700000215
Chloride, 1-methylimidazole
Figure FDA00030011315700000216
Nitrate salt, 1-ethylimidazole
Figure FDA00030011315700000217
Nitrate, tert-butylammonium tetrafluoroborate, hydroxyethylammonium tetrafluoroborate, methylbutylammonium tetrafluoroborate, triethylammonium tetrafluoroborate, imidazole
Figure FDA00030011315700000218
Tetrafluoroborate, 1-methylimidazole
Figure FDA00030011315700000219
Bisulfate salt, 1-methylimidazole
Figure FDA00030011315700000220
Tetrafluoroborate, 1, 2-dimethylimidazole
Figure FDA00030011315700000221
Tetrafluoroborate, tert-butylammonium triflate, 2-fluoropyridine
Figure FDA00030011315700000222
Triflate, hydroxyethylammonium triflate, 1, 2-dimethylimidazole
Figure FDA0003001131570000031
Triflate, imidazole
Figure FDA0003001131570000032
Triflate, 1-methylimidazole
Figure FDA0003001131570000033
Triflate, hydrotrifluoromethane sulfonate, methylammonium methanesulfonate, ethylammonium methanesulfonate, butylammonium methanesulfonate, methoxyethylammonium methanesulfonate, dimethylammonium methanesulfonate, dibutylammonium methanesulfonate, triethylammonium methanesulfonate, dimethylethylammonium methanesulfonate, hydronium bisulfate, ammonium bisulfate, methylammonium bisulfate, ethylammonium bisulfate, propylammonium bisulfate, n-butylammonium bisulfate, tert-butylammonium bisulfate, dimethylammonium bisulfate, diethylammonium bisulfate, di-n-butylammonium bisulfate, methylbutylammonium bisulfate, ethylbutylammonium bisulfate, trimethylammonium bisulfate, triethylammonium bisulfate, tributylammonium bisulfate, dimethylethylammonium bisulfate, dibutylammonium fluorophosphate, triethylammonium fluorophosphate, tributylammonium fluorophosphate, tetrabutylammonium fluorophosphate, ammonium fluorophosphate, and the like, Dihydrogenphosphate hydrate, methylammonium dihydrogenphosphate, ethylammonium dihydrogenphosphate, propylammonium dihydrogenphosphate, n-butylammonium dihydrogenphosphate, methoxyethylammonium dihydrogenphosphate, dimethylammonium dihydrogenphosphate, dibutylammonium dihydrogenphosphate, methylbutylammonium dihydrogenphosphate, ammonium bifluoride, methylammonium bifluoride, ethylammonium bifluoride, dimethylammonium bifluoride, tri-n-butylmethylammonium methylsulfate, 1-ethyl-2, 3-dimethylimidazole
Figure FDA0003001131570000034
Ethyl sulfate, 1-butyl-3-methylimidazole
Figure FDA0003001131570000035
Thiocyanate, 1-butyl-3-methylimidazole
Figure FDA0003001131570000036
Tetrachloroaluminate, 1-butyl-3-methylimidazole
Figure FDA0003001131570000037
Methyl sulfate, 1-butyl-3-methylimidazole
Figure FDA0003001131570000038
Methanesulfonic acid salt, 1-butyl-3-methylimidazole
Figure FDA0003001131570000039
Bisulfate salt, 1-butyl-3-methylimidazole
Figure FDA00030011315700000310
Bicarbonate, 1-butyl-3-methylimidazole
Figure FDA00030011315700000311
Chloride, 1,2, 3-trimethylimidazole
Figure FDA00030011315700000312
Methyl sulfate, 1,2, 4-trimethylpyrazole
Figure FDA00030011315700000313
Methyl sulfate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000314
Chloride, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000315
Thiocyanate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000316
Methanesulfonic acid salt, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000317
Tetrachloroaluminate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000318
Bisulfate salt, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000319
Ethyl sulfate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000320
Nitrate salt, 1-butylpyridine
Figure FDA00030011315700000321
Chloride, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000322
Dicyandiamide, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000323
Tetrafluoroborate, 1, 3-dimethylimidazole
Figure FDA00030011315700000324
Bicarbonate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000325
Bicarbonate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000326
Hexafluorophosphate, 1-butyl-3, 5-dimethylpyridine
Figure FDA00030011315700000327
Bromide, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000328
Bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000329
Bis (pentafluoroethylsulfonyl) imide, 1-ethyl-2, 3-dimethylimidazole
Figure FDA00030011315700000330
Methyl carbonate, carboxymethyl-tributyl
Figure FDA00030011315700000331
Bis (trifluoromethylsulfonyl) imide, N-carboxyethyl-methylpyrrolidine
Figure FDA00030011315700000332
Bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-trimethylammonium bis (trifluoromethylsulfonyl) imide, N-carboxymethyl-methylpyridine
Figure FDA00030011315700000333
Bis (trifluoromethylsulfonyl) imide, hexyltrimethylammonium bis (trifluoromethylsulfonyl) imide, tetrabutylphosphonium imide
Figure FDA0003001131570000041
Methanesulfonic acid salt, tetrabutyl
Figure FDA0003001131570000042
Tetrafluoroborate, tetrabutyl
Figure FDA0003001131570000043
P-toluenesulfonate salt, 1-ethyl-3-methylimidazole
Figure FDA0003001131570000044
Bicarbonate, triethylmethylammonium methylcarbonate, tributylmethylammonium methylcarbonate, 1-ethyl-1-methylpiperidine
Figure FDA0003001131570000045
Methyl carbonate, 4-ethyl-4-methylmorpholine
Figure FDA0003001131570000046
Methyl carbonate, 1-butyl-1-methylpyrrolidine
Figure FDA0003001131570000047
Methyl carbonate, triethylmethylammonium dibutyl phosphate, tributylmethylammonium dibutyl phosphate, 1-ethyl-3-methylimidazole
Figure FDA0003001131570000048
Dibutyl phosphate, 1-butyl-3-methylimidazole
Figure FDA0003001131570000049
Dibutyl phosphate, 1- (cyanomethyl) -3-methylimidazole
Figure FDA00030011315700000410
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure FDA00030011315700000411
Chloride, 1- (3-cyanopropyl) -3-methylimidazole
Figure FDA00030011315700000412
Bis (trifluoromethylsulfonyl) imide, 1- (3-cyanopropyl) -3-methylimidazole
Figure FDA00030011315700000413
Dicyandiamide, 1- (3-cyanopropyl) pyridine
Figure FDA00030011315700000414
Chloride, 1- (3-cyanopropyl) pyridine
Figure FDA00030011315700000415
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (cyanomethyl) imidazole
Figure FDA00030011315700000416
Chloride, 1, 3-bis (cyanomethyl) imidazole
Figure FDA00030011315700000417
Bis (trifluoromethylsulfonyl) imide, 1, 3-bis (3-cyanopropyl) imidazole
Figure FDA00030011315700000418
Chloride, 1, 3-bis (3-cyanopropyl) imidazole
Figure FDA00030011315700000419
Bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazole
Figure FDA00030011315700000420
Hexafluorophosphate, 1-butyl-3-methylimidazole
Figure FDA00030011315700000421
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000422
Tetrafluoroborate, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000423
Chloride, 1-ethyl-3-methylimidazole
Figure FDA00030011315700000424
Bromide, 1-butyl-3-methylimidazole
Figure FDA00030011315700000425
Bromide, 1-hexyl-3-methylimidazole
Figure FDA00030011315700000426
Chloride, tributylmethyl
Figure FDA00030011315700000427
Dibutyl phosphate, triethyl methyl
Figure FDA00030011315700000428
Dibutyl phosphate, tributylmethyl
Figure FDA00030011315700000429
Methyl carbonate, tributylmethyl
Figure FDA00030011315700000430
Methyl sulfate, triethyl methyl
Figure FDA00030011315700000431
Dibutyl phosphate trihexyltetradecyl
Figure FDA00030011315700000432
Bis (trifluoromethylsulfonyl) imide, trihexyltetradecyl
Figure FDA00030011315700000433
Bis (2,4, 4-trimethylphenyl) phosphonate, trihexyltetradecyl
Figure FDA00030011315700000434
Bromide, trihexyltetradecyl
Figure FDA00030011315700000435
Chloride, trihexyltetradecyl
Figure FDA00030011315700000436
Decanoate, trihexyltetradecyl
Figure FDA00030011315700000437
Dicyandiamide, 3- (triphenyl phosphine)
Figure FDA00030011315700000438
Yl) propane-1-sulfonate and 3- (triphenylphosphonium)
Figure FDA00030011315700000439
Alkyl) propane-1-sulfonic acid tosylate.
8. A battery according to any of claims 1 to 7, wherein the electrolyte composition comprises at least two different ionic compounds.
9. A battery according to any of claims 1 to 7, wherein the electrolyte composition comprises an ionic liquid and a salt or comprises two different ionic liquids.
10. A battery according to any of claims 1 to 7, wherein the electrolyte composition comprises a solvent selected from the group consisting of water and organic solvents and exhibits a viscosity of 100cP or less at 25 ℃.
11. A battery according to any of claims 1 to 7, wherein the electrolyte composition comprises one or more organic solvents selected from the group consisting of ethers, esters, sulfones, sulfoxides, amides, alcohols, amines, ketones, nitro solvents and nitrile solvents.
12. The metal hydride battery of claim 11 wherein the ether is selected from glyme, the alcohol is selected from a glycol, and/or the ester is selected from an organic carbonate, a lactone, a formate.
13. The metal hydride battery of claim 12 wherein the glycol is selected from the group consisting of polyalkylene glycols.
14. The metal hydride battery of claim 11 wherein the ester is selected from orthoesters.
15. The metal hydride battery of claim 11 wherein the organic solvent is propylene carbonate or polyethylene glycol.
16. A metal hydride battery according to claim 1 or 2 wherein the electrolyte composition comprises one or more alkoxides and an organic solvent.
17. A metal hydride battery according to claim 1 or 2, wherein the electrolyte composition comprises one or more ionic compounds selected from the group consisting of carboxylate compounds and carboxylic acids.
18. A battery according to claim 1 or 2, wherein the electrolyte composition comprises one or more ionic compounds selected from the group consisting of alkali metal hydroxides, water and one or more further components selected from the group consisting of organic solvents, further ionic compounds and additives.
19. A metal hydride battery according to any preceding claim which exhibits a nominal open circuit voltage of from 1.5V to 5.0V.
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