WO2012146525A1 - Lithium air battery cell - Google Patents

Lithium air battery cell Download PDF

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Publication number
WO2012146525A1
WO2012146525A1 PCT/EP2012/057169 EP2012057169W WO2012146525A1 WO 2012146525 A1 WO2012146525 A1 WO 2012146525A1 EP 2012057169 W EP2012057169 W EP 2012057169W WO 2012146525 A1 WO2012146525 A1 WO 2012146525A1
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WO
WIPO (PCT)
Prior art keywords
lithium
carbonate
fluorosubstituted
battery cell
air battery
Prior art date
Application number
PCT/EP2012/057169
Other languages
French (fr)
Inventor
Johannes Eicher
Jens Olschimke
Martin Bomkamp
Placido Garcia-Juan
Original Assignee
Solvay Sa
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Filing date
Publication date
Application filed by Solvay Sa filed Critical Solvay Sa
Priority to JP2014506824A priority Critical patent/JP2014515168A/en
Priority to KR1020137030901A priority patent/KR20140037850A/en
Priority to US14/113,436 priority patent/US20140045078A1/en
Priority to EP12714720.5A priority patent/EP2702631A1/en
Priority to CN201280031539.2A priority patent/CN103636052A/en
Publication of WO2012146525A1 publication Critical patent/WO2012146525A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention concerns a lithium-air battery cell and a lithium-air battery which contain L1PO2F2 as additive.
  • Lithium-air batteries are suitable as storage media for electrical energy and useful for household items, e.g. cell phones or laptops, and they are especially suitable as car batteries.
  • Lithium-air batteries shortly, “Li-0 batteries”, comprise one or more lithium-air battery cells containing lithium anodes electrochemically coupled to atmospheric oxygen. The oxygen is usually taken from the atmosphere and thus is an unlimited cathode reactant.
  • the lithium-air battery has a much higher energy density than the currently existing lithium ion batteries, and is rechargeable.
  • the battery cell comprises a metal anode in an anode compartment and a cathode (for example, porous carbon), with a gel-polymer electrolyte membrane or a nonaqueous solvent which serve as ion-transporting medium.
  • a membrane - for example, a Lisicon membrane or a Nasicon membrane - which is permeable for the metal cation, but impermeable for other compounds like water or solvent, serves to effectively separate anode and cathode compartments. If discharged, the respective metal is oxidized to the respective metal cation, the formed cation is transported via membrane and solvent to the cathode compartment and forms there the metal oxide.
  • the metal ions are migrating back to the anode compartment and are reduced to the respective metal, while the oxide is oxidized to oxygen.
  • the cathode compartment may be separated from the surrounding air by a water-repelling membrane, e.g. a Teflon ® membrane.
  • the object of the present invention is to provide a lithium-air battery cell with improved additives and solvents and a battery, especially a car battery, constituted from a multitude of such lithium-air cells.
  • a lithium-air battery cell comprising an electrolyte composition which comprises L1PO2F2.
  • Li In a lithium-air battery, during discharge, on the anode, Li is oxidized forming Li + . On the cathode, oxygen is reduced to form the O2 2" ion and the 0 2 ⁇ ion. Upon charging of the lithium-air battery cell, the reverse reactions happen. Li 2 0 or Li 2 0 2 , respectively, which have formed during discharge, are split at the cathode to finally produce elemental oxygen.
  • Figure 1 shows an example of a Li-air battery cell.
  • a lithium-air battery cell comprising an electrolyte solvent which comprises L1PO2F2 as electrolyte salt or as additive.
  • the term “battery cell” denotes a cell for a battery or a battery comprising a single battery cell.
  • the terms “battery” denotes an item comprising a single cell or a multitude of cells.
  • a battery comprising a single cell may be denoted “battery” or “battery cell” in the present description. In a battery with a multitude of cells, these cells are usually assembled in line to achieve a higher voltage than a single cell has.
  • Figure 1 presents a battery cell for car battery according to the present invention.
  • the cell is covered by a battery housing which is omitted from figure 1.
  • the anode a is formed by lithium metal.
  • an organic electrolyte solvent is contained in the anode compartment b. Suitable electrolyte solvents are described in more detail below.
  • the membrane c (a solid state electrolyte) separates the anode compartment b which is in contact with the lithium metal of anode a, and the cathode compartment d which is in contact with the air electrode e. It is made from material which is permeable for Li ions, but not for other components present in the anode compartment b and anode compartment d.
  • Lisicon membranes are suitable here.
  • the cathode compartment may comprise, in the embodiment of figure 1 , an aqueous electrolyte
  • the organic electrolyte composition of the cathode compartment d is preferably essentially identical to the organic electrolyte composition in the anode compartment b.
  • the lithium-air battery cell of the invention may comprise an electrolyte salt which is selected among salts known to the expert to be suitable for this purpose.
  • Such salts have the general formula M a A ⁇ .
  • M is a metal cation, and A is an anion.
  • M is preferably selected from Li + , and NR4 + .
  • Preferred anions are PF 6 “ , AsF 6 " , BF 4 " , CIO4-.
  • M is Li + .
  • M is Li + and the solution comprises an electrolyte salt selected from the group consisting of LiBF 4 , L1CIO4, LiAsFg, LiPF 6 , Li (CF 3 S0 2 ) 2 and LiN(i-C 3 F 7 S0 2 ) 2 .
  • Lithium bis(oxalato)borate can be applied as an additional additive.
  • the concentration of the electrolyte salt is preferably 1 ⁇ 0.1 molar.
  • LiP0 2 F 2 is the only electrolyte salt, its concentration in the electrolyte solution is, as mentioned, preferably 1 ⁇ 0.1 molar. If LiP0 2 F 2 is applied as an additive together with another electrolyte salt, the electrolyte solution is a composition comprising the electrolyte solvent, the electrolyte salt and additives, notably the LiP0 2 F 2 ,the concentration of LiP0 2 F 2 in the electrolyte solution (i.e.
  • the electrolyte composition preferably is equal to or greater than 0.1 % by weight, more preferably equal to or greater than 0.5 % by weight ; preferably, its concentration is equal to or lower than 10 % by weight, more preferably, equal to or lower than 5 % by weight when the total electrolyte composition including electrolyte salt, solvent and additives is set as 100 % by weight.
  • the content of LiP0 2 F 2 is 1 to 10 % by weight, more preferably 1 to 5 % by weight, relative to the electrolyte composition set as 100 % by weight.
  • the solvent used in the electrolyte may comprise any non-fluorinated and/or fluorinated solvent or solvent mixture known to be useful for rechargeable battery cells, especially, known to be useful for rechargeable battery cells based in Li salts.
  • fluorinated denotes partial or total substitution of hydrogen atoms in the solvent.
  • the fluorosubstituted compounds may be contained in lower amounts, e.g. in an amount of 0.1 % by weight respective to the total content of solvent, up to about 10 % by weight respective to the total amount of solvent. They might then be considered rather as solvent additive than solvent.
  • the content of fluorosubstituted compound may even be higher than 10 % by weight, and in this case, they may be considered rather as solvent.
  • Suitable solvents for the electrolyte composition may be selected from the group consisting of with linear or cyclic ethers, linear and cyclic esters, linear and cyclic ketones, saturated and unsaturated linear and cyclic alkanes, aromatic hydrocarbons and especially linear and cyclic organic carbonates.
  • Alkyl carbonates and alkylene carbonates are the preferred solvent.
  • alkyl preferably denotes a CI to C3 group.
  • alkylene preferably denotes an alkylene group with a C2, C3 or C4 chain which is arranged between the oxygen atoms of an 0-C(0)-0 group.
  • the alkylene group may be substituted by one or more CI to C3 alkyl groups, e.g. by one or two methyl groups and/or one or two ethyl groups.
  • ethylene carbonate (EC) is comprised in the solvent.
  • Propylene carbonate and butylene carbonate are other solvents which may be a suitable constituent of the electrolyte solution.
  • the solvent may instead or additionally contain low viscosity agents, e.g. ethers like 1 ,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyldioxolane, dimethylcarbonate, ethylmethyl carbonate, diethyl carbonate and any mixtures thereof.
  • ethers like 1 ,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyldioxolane, dimethylcarbonate, ethylmethyl carbonate, diethyl carbonate and any mixtures thereof.
  • Nitriles with a CI to C20 alkyl group e.g.
  • acetonitrile, dinitriles with a CI to C20 alkylene group, t-amyl benzene, and thiosubstituted compounds for example, ethylene- 1,3-dioxolane- 2-thione (ethylene thiocarbonate) are also highly suitable non-fluorinated solvents or additives.
  • the solvent or solvent mixture contained in the electrolyte solution may also comprise or consist of one or more
  • fluorosubstituted organic compound which contains at least one heteroatom selected from the group consisting of oxygen, nitrogen, phosphorous, sulfur and silicon may be comprised or constitute the only solvent.
  • the electrolyte solvent or solvent mixture (be it fluorosubstituted or not) is selected such that it is liquid at the temperature at which the battery is intended to be used. If the melting point of the respective fluorosubstituted organic compound (just as any respective non-fluorinated compound) is low enough it can be used neat.
  • the melting point of monofluoroethylene carbonate (“F1EC”) for example, is at about 22°C. Thus, it is preferred to apply this compound with a co-solvent with a lower melting point, e.g.
  • the solvent is a solvent mixture.
  • the electrolyte solvent or solvent mixture is liquid at a temperature equal to or above -20°C.
  • fluorinated organic compounds are selected from the group consisting of monofluorinated, difluorinated, trifluorinated, polyfluormated and perfluorinated organic compounds.
  • polyfluormated denotes compounds which are substituted by four or more fluorine atoms, but contain at least one hydrogen atom, or at least one chlorine atom, or at least one hydrogen atom and at least one chlorine atom.
  • the monofluorinated, difluorinated, trifluorinated, polyfluorinated and perfluorinated organic compounds are not substituted by chlorine atoms.
  • Perfluorinated are those compounds in which all hydrogen atoms are substituted by fluorine atoms.
  • Suitable compounds are those described in WO2007/042471. That document discloses compounds useful to be applied the present invention selected from the group of aromatic compounds consisting of l-acetoxy-2- fluorobenzene, 1 -acetoxy-3-fluorobenzene, 1 -acetoxy-4-fluorobenzene,
  • the solvent may also additionally contain benzene, fluorobenzene, toluene, trifluorotoluene, xylene or cyclohexane.
  • difluoroacetophenone encompasses the isomers with the fluorine substitution in the 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-position on the aromatic ring.
  • fluorobenzophenone encompasses in particular the isomers 2-fluorobenzophenone and 4-fluorobenzophenone.
  • difluorobenzophenone encompasses the isomers with the fluorine substitution in the 2,3'-, 2,3-, 2,4'-, 2,4-, 2,5-, 2,6-, 3,3'-, 3,4'-, 3,4-, 3,5- and 4,4'-position.
  • fluorophenylacetonitrile encompasses the isomers with the fluorine substitution in the 2-, 3- and 4-position.
  • the compounds can be synthesized in a known manner and are also commercially available, for example from ABCR GmbH & Co.KG, Düsseldorf, Germany.
  • Preferred fluorinated organic compounds are selected from the group of fluorosubstituted carboxylic acid esters, fluorosubstituted carboxylic acid amides, fluorosubstituted fluorinated ethers, fluorosubstituted carbamates, fluorosubstituted cyclic carbonates, fluorosubstituted acyclic carbonates, fluorosubstituted phosphites, fluorosubstituted phosphoranes, fluorosubstituted phosphoric acid esters, fluorosubstituted phosphonic acid esters and saturated or unsaturated fluorosubstituted heterocycles.
  • Suitable fluorinated ethers applicable as solvent or solvent additive are for example those as described in US 5,916,708, namely partially fluorinated ethers of formula (I)
  • R is a linear alkyl group with 1 to 10 C atoms or a branched alkyl group with 3 to 10 C atoms,
  • X is fluorine, chlorine or a perfluoroalkyl group with 1 to 6 C atoms which groups may include ether oxygen,
  • n is an integer of 2 to 6 and
  • n is an integer of 1 to 8
  • X, m and n have the meaning given above.
  • Partially fluorinated carbamates suitable as solvent additives are for example those described in US 6,159,640, namely compounds of the
  • R 1 R 2 N-C(0)OR 3 wherein R 1 and R 2 independently are the same or different, and are linear Cl-C6-alkyl, branched C3-C6-alkyl, C3-C7-cycloalkyl, or R 1 and R 2 are connected directly or via one or more additional N and/or O atoms forming a ring with 3 to 7 members.
  • additional N atoms in the ring are saturated with CI to C3 alkyl groups, and additionally, the carbon atoms of the ring may be substituted by CI to C3 alkyl groups.
  • one or more hydrogen atoms may be substituted by fluorine atoms.
  • R 3 is a partially fluorinated or perfluorinated linear or branched alkyl group with 1 to 6 or, respectively, 3 to 6 carbon atoms, or a partially or perfluorinated cycloalkyl group with 3 to 7 C atoms, which may be substituted by one or more CI to C6 alkyl groups.
  • Fluorinated acetamides suitble as solvent additive are for example those described US 6,489,064, namely partially fluorinated amide corresponding to formula (I)R 1 CO-NR 2 R 3 (III) wherein R 1 is a linear CI - C6 alkyl group in which at least one hydrogen atom is replaced by fluorine, or a branched C3 - C6 alkyl group in which at least one hydrogen atom is replaced by fluorine, or a C3 - C7 cycloalkyl group optionally substituted one or more times by a linear CI - C6 alkyl group or branched C3 - C6 alkyl group or both in which at least one hydrogen atom of the cycloalkyl group or the optional linear or branched alkyl substituent or both is replaced by fluorine, and R 2 and R 3 independently represent an identical or different linear CI - C6 alkyl group, a branched C3 - C6 alkyl group or a C3
  • Partially fluorinated esters suitable as solvent or solvent additive are for example those described in US 6,677,085 partially fluorinated compound derived from a diol corresponding to formula (IV) : R ⁇ CO-O-tCHR ⁇ CH 2 ) m -0 ]n -R 2 (IV) wherein R 1 is a (CI - C8) alkyl group or a (C3 - C8) cycloalkyl group, wherein each of said groups is partially fluorinated or perfluorinated so that at least one hydrogen atom of the group is replaced by fluorine ;R 2 is a (CI - C8) alkyl carbonyl or (C3 - C8) cycloalkyl carbonyl group, wherein said alkylcarbonyl or cycloalkylcarbonyl group may optionally be partially fluorinated or
  • R 3 is a hydrogen atom or a (CI - C8) alkyl or (C3 - C8) cycloalkyl group ; m is 0, 1, 2 or 3, and n is 1, 2 or 3.
  • linear or branched fluorosubstituted dialkyl carbonates and fluorosubstituted alkylene carbonates are especially preferred.
  • Fluorinated dialkyl carbonates suitable as solvent or solvent additive are those of formula (V)
  • R 1 -0-C(0)-0-R 2 (V)
  • R 1 and R 2 can be the same or different with the proviso that at least one of R 1 and R 2 are substituted by at least one fluorine atom.
  • R 1 and R 2 are preferably linear alkyl groups with 1 to 8 carbon atoms, preferably, 1 to 4 carbons, more preferably, with 1 to 3 carbon atoms ; branched alkyl groups with 3 to 8 carbon atoms, preferably with 3 carbon atoms ; or cyclic alkyl groups with 5 to 7 carbon atoms, preferably, 5 or 6 carbon atoms ; with the proviso that at least one of R 1 and R 2 is substituted by at least one fluorine atom.
  • R 1 and R 2 denote linear alkyl groups with 1 to 3 carbon atoms, with the proviso that at least one of R 1 and R 2 is substituted by at least one fluorine atom.
  • R 1 and R 2 are selected from the group consisting of methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1 ,2-difluoroethyl, 2,2,2-trifluoroethyl and 1-fluoro-l-methylethyl.
  • Most preferred compounds of formula (V) are methyl fluoromethyl carbonate, fluoromethyl ethyl carbonate, methyl
  • 2,2,2-trifluoroethyl carbonate fluoromethyl 2,2,2-trifluoroethyl carbonate and bis-2,2,2-trifluoroethyl carbonate.
  • Such compounds can be manufactured from phosgene, COFC1 or COF 2 , and the respective alcohols, or as described in unpublished EP patent application No. 09155665.2.
  • the manufacture of fluoroalkyl (fluoro)alkyl carbonates of the general formula (Vi), FCHR-OC(0)-OR' wherein R denotes linear or branched alkyl with 1 to 5 C atoms or H and R' denotes linear or branched alkyl with 1 to 7 carbon atoms ; linear or branched alkyl with 2 to 7 carbon atoms, substituted by at least one fluorine atom ; phenyl ; phenyl, substituted by 1 or more C 1 to C3 alkyl groups atoms or phenyl substituted by 1 or more chlorine or fluorine atoms ; or benzyl includes a step of reacting a fluoroalkyl fluoroformate of formula (VII), FCHROC(0)F, or a fluoroalkyl chloroformate of formula (VIF), FCHROC(0)Cl, with an alcohol of formula (VIII), R'OH, wherein R and R' have the meanings given
  • fluorosubstituted alkylene carbonates of formula (X) are applied.
  • R 1 , R 2 , R 3 and R 4 are independently selected from H, linear alkyl groups with 1 to 3 carbon atoms and alkenyl groups with 2 or 3 carbon atom ; linear alkyl groups with 1 to 3 carbon atoms or an alkenyle group with 2 or 3 carbon atoms, substituted by at least one fluorine atom ; and fluorine, with the proviso that at least one of R 1 , R 2 , R 3 and R 4 is fluorine or an alkyl group substituted by at least one fluorine atom.
  • R 1 , R 2 , R 3 and R 4 are selected from H and F, with the proviso that at least one of R 1 , R 2 , R 3 and R 4 is fluorine.
  • fluoroethylene carbonate but also cis- and trans- 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, trifluoroethylene carbonate and tetrafluoroethylene carbonate are very suitable.
  • These compounds can be manufactured by direct fluorination of ethylene carbonate. In the case of difluorosubstituted ethylene carbonate, cis and trans-4,5-difluoroethylene carbonate and 4,4-difluoroethylene carbonate are obtained. These isomers can be separated by fractionated distillation.
  • R J is a CI to C3 alkyl group or a CI to C3 alkyl group, substituted by at least one fluorine atom ; and R 2 , R 3 and R 4 are H or F, with the proviso that at least one ofR 2 , R 3 and R 4 are F, or R J is a CI to C3 alkyl group, substituted by at least one fluorine atom.
  • R 1 is methyl, ethyl or vinyl.
  • Especially preferred compounds of this type are 4-fluoro-4-methyl-l,3- dioxolane-2-one, 4-fluoro-5-methyl- 1 ,3-dioxolane-2-one, 4-ethyl-4-fluoro- 1 ,3- dioxolane-2one, 5-ethyl-4-fluor-4-ethyl-l,3-dioxolan-2-one and 4,5-dimethyl-4- fluoro- 1 ,3-dioxolane-2-one.
  • the compounds are known and can be manufactured by fluorination of the respective non-fluorinated compounds or by chlorine- fluorine exchange of the respective chlorosubstituted compounds.
  • the cyclization reaction is preferably catalyzed by a heterocyclic compound containing nitrogen, or by fluoride ions.
  • the heterocyclic compound is an aromatic compound.
  • pyridine or 2-methylimidazole can be used as catalyst.
  • pyridines substituted by at least one dialkylamino group are very suitable.
  • Other 4-dialkylaminopyridines, for example, those wherein alkyl denotes a CI to C3 alkyl group, are also considered to be suitable.
  • R 1 and R 2 are CI to C3 alkyl groups or CI to C3 alkyl groups, substituted by at least one fluorine atom ;
  • R 3 and R 4 are H or F, with the proviso that at least one of R 3 and R 4 are F, or at least one of R 1 and R 2 is a CI to C3 alkyl group, substituted by at least one fluorine atom.
  • Especially preferred compounds of this type are 4-fluoro-5-(l-fluoroethyl)- l,3-dioxolan-2-one, 4-fluoro-5-(2-fluoroethyl)-l,3-dioxolan-2-one,
  • Tris-(2,2,2- trifluoroethyl) phosphate is the preferred compound. It can be prepared from PCI3 and trifluoroethanol, optionally in the presence of a base, e.g. an amine.
  • Still another group of compounds are perfluoroalkyl phosphoranes of formula (XII), (CnF 2n+m )5P wherein n is 1, 2, 3, 4, 5, 6, 7 or 8, and m is +1 or -1. They can be prepared from pentaalkyl phosphanes via electro fluorination analogously to the process described in US 6,264,818.
  • R-P ⁇ RiR 2 are also suitable.
  • R is a CI to C4 alkyl group ; a CI to C4 alkyl group, substituted by at least 1 fluorine atom ; or a fluorosubstituted C2 to C4 alkoxy group ;
  • R 1 and R 2 are the same or different and represent C2 to C4 alkoxy groups, substituted by at least one fluorine atom.
  • Preferred compounds of this type are methyl bis-(2,2,2- trifluoroethyl) phosphonate, ethyl bis-(2,2,2-trifluoroethyl) phosphonate, and tris-(2,2,2-trifluoroethyl) phosphate.
  • Fluorosubstituted carbonic acid esters of formula (XIV), R-C(0)OR 1 are also suitable.
  • R denotes preferably CI to C3 and R 1 preferably denotes a CI to C3 alkyl group with the proviso that at least one of R and R 1 are substituted by at least one fluorine atom.
  • R-C(0)-C(H) C(H)-OR 1 .
  • R is a
  • R 1 is CI to C4 alkyl ; CI to C4 alkyl, substituted by one or more fluorine atoms ; or phenyl.
  • R is preferably CF 3 , CHF 2 , or C 2 F 5 ; and R 1 is preferably methyl or ethyl.
  • the most preferred compound is 4-Ethoxy- 1,1,1 -trifluoro-3-buten-2-one (ETFBO). These compounds can be prepared by the addition of the respective carboxylic acid chlorides to the respective vinyl ether and subsequent dehydrochlorination.
  • ETFBO for example, can be prepared from trifluoroacetyl chloride and ethyl vinyl ether. ETFBO is also available e.g. from Solvay Fluor GmbH, Hannover, Germany.
  • perfluorinated ethers Suitable perfluorinated polyethers are described, for example, in WO 02/38718. These perfluorinated polyethers consist essentially of carbon, fluorine and oxygen atoms and comprise at least two, preferably three, C-O-C ether linkages, or a mixture of several compounds satisfying that definition. Often, the oxygen atoms in the perf uoropolyether are exclusively present within the C-O-C ether linkages.
  • the perfluoropolyethers generally have a molecular weight of about 200 or more. Generally they have a molecular weight of less than about 1500. If the polyether is a mixture of several substances, the molecular weight is the weight-average molecular weight.
  • the perfluoropolyether has a boiling point greater than or equal to 40°C at 101.3 kPa.
  • the perfluoropolyether generally has a boiling point less or equal to about 200°C at 101.3 kPa.
  • these perfluoropolyethers often are a mixture of individual substances.
  • the kinematic viscosity of the perfluoropolyether is less than or equal to 1 cSt (Centistoke) at 25°C.
  • the kinematic viscosity is at least 0.3 cSt at 25°C.
  • the preferred perfluoro polyethers are the products marketed by Solvay
  • Examples include :
  • GALDEN HT 55 boiling point 57°C at 101.3 kPA ; average molecular weight 340
  • GALDEN HT 70 boiling point 66°C at 101.3 kPa ; average molecular weight 410
  • FOMBLIN PFS1 boiling point 90°C at 101.3 kPa ; average molecular weight 460
  • Partially fluorinated polyethers are the hydrofluoro ethers marketed by 3M under the name NOVEC ® .
  • the GALDEN ® and FOMBLIN ® systems are usually multicomponent systems having a boiling point in the range from 40 to 76°C.
  • fluorosubstituted compounds which are suitable as fluorosubstituted compound are lithium fluoro(oxalate)borate and lithium difluoro(oxalato)borate. They are no solvents but an electrolyte salt additive.
  • fluorinated heterocyclic compounds are suitable as solvent additives, especially, fluorinated dioxolanes, fluorinated oxazolidines, fluorinated imidazolindines, fluorinated dihydroimidazoles, fluorinated
  • Suitable fluorinated dioxo lanes are for example 2,2-difluoro-l,3-dioxolane (US 5,750,730) and 2-f uoro-4,4,5,5-tetramethyl-l,3-dioxolane, available from chemstep, France.
  • Suitable fluorinated oxazolidines are for example 2,2-difluoro-3- methyloxazolidine and 4,5-difluoro-3-methyloxazolidine-2-one, available from chemstep.
  • Suitable fluorinated imidazolidines are for example 2,2-difluoro-l,3- dimethylimidazolidine, available from abcr, and l,3-dibutyl-2,2- dif uoroimidazolidineavailable from Apollo.
  • Suitable fluorinated 2,3-dihydroimidazoles are for example 2,2-difluoro- 1 ,3-dimethyl-2,3-dihydro- lH-imidazole and 1 -ethyl-2-fluoro-3-methyl-2,3- dihydro-lH-imidazole, available from chemstep.
  • Suitable fluorinated imidazoles are for example l-(trif uoromethyl)-lH- imidazole, available from selectlab, and 2-fluoro-l-(methoxymethyl)-lH- imidazole, available from chemstep.
  • a suitable fluorinated pyrrole is for example 2-ethyl-5-fluoro-l-methyl- lH-pyrrole, available from chemstep.
  • a suitable fluorinated thiophene is for example 2-f uorothiophene, available from apacpharma.
  • a suitable fluorinated thiazole is for example 4-f uorothiazole, available from chemstep.
  • f uorosubstituted organic liquids e.g. 4,5-dimethyl-3-perfluorooctyl-
  • the fluorinated organic compounds mentioned above can be used as the only solvent, or they are applied in admixture with one or more organic solvents which are not fluorosubstituted.
  • Preferred mixtures comprise at least one compound selected from the group consisting of monofluoroethylene carbonate, cis-dif uoroethylene carbonate, trans-difluoroethylene carbonate, 4,4- difluoroethylene carbonate, 4-fluoro-4-methyl- 1 ,3-dioxolane-2-one, 4-fluoro-4-ethyl- 1 ,3-dioxolane-2-one, 4-trifluoromethyl- 1 ,3-dioxolane-2-one, 2,2,2-trif uoroethyl-methyl carbonate, 2,2,2-trifluoroethyl-fluoromethyl carbonate, and at least one non- fluorinated organic compound selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
  • the electrolyte solvent contains 0.1 to 100 % by weight of the
  • the fluorinated organic compound is contained in the electrolyte solvent in an amount of equal to or more than 1 % by weight, preferably equal to or more than 3 % by weight. Often, the content is preferably equal to or lower than 20 % by weight relative to the electrolyte solvent set as 100 % by weight, and more preferably, equal to or lower than 10 % by weight.
  • ionic liquids can be applied in a mixture with any of the fluorosubstituted compounds mentioned above.
  • Very suitable ionic liquids are those based on imidazolium, and pyridinium
  • phosphonium or tetraalkylammonium compounds can also be applied.
  • Representative ionic liquids are tosylate, triflate, hexafluorophosphate, bis-(fluorosulfonyl)amide, bis-(trifluoromethylsulfonyl)amide and
  • the Li-air battery cell of the present invention preferably comprises a membrane permeable for lithium ions.
  • a suitable Li-air battery cell is disclosed in US-A 5,510,209.
  • the battery cell described therein, for example, in fig. 1 of US-A 5,510,209, comprises a lithium foil anode, a polymer electrolyte (comprising polyacrylnitrile, a solvent, e.g. propylene carbonate or ethylene carbonate, and an electrolyte salt, e.g. LiPF 6 ), a composite positive electrode current collector and an oxygen permeable membrane through which oxygen (from the surrounding air) is transported to the porous carbon electrode.
  • a polymer electrolyte comprising polyacrylnitrile, a solvent, e.g. propylene carbonate or ethylene carbonate, and an electrolyte salt, e.g. LiPF 6
  • a composite positive electrode current collector e.g. LiPF 6
  • oxygen permeable membrane through which oxygen (from the surrounding air) is transported to the porous carbon electrode.
  • the battery cell (which, in fact, is a battery comprising one cell) described therein is said to have a favorable cycle characteristic.
  • the cell described therein comprises : an positive electrode which is an air electrode (also called "air pole") having an air electrode layer containing a conductive material and an air electrode power collector for collecting electric power from the air electrode layer ; a negative electrode having a negative electrode layer containing a negative electrode active material that adsorbs and releases Li ions and a negative electrode power collector for collecting electric power from the negative electrode layer ; a separator provided between the air electrode layer and the negative electrode layer ; and a fluorosubstituted electrolyte with which at least the separator is impregnated.
  • the cell also contains a discharge controller that terminates the discharge of the air battery cell.
  • the discharge final voltage of the discharge controller is 2.3 V or higher based on Li metal.
  • the cell also has provisions to handle the volume changes of the electrolyte if the battery charges or discharges.
  • the discharge controller serves to prevent the formation of LiF from LiPF 6 (the commonly applied electrolyte salt) which occurs if the voltage during discharge drops beyond a 2.3V level relative to Li metal.
  • the negative electrode may be constructed from materials commonly used in Li ion battery cells, e.g. from metallic lithium or carbon.
  • the collector of the negative pole may be made from metals, e.g. copper, stainless steel, or nickel.
  • the air pole may be made from carbon which is preferably porous.
  • the air pole charge collector may be made from metals, e.g. stainless steel, nickel, aluminium, iron, or titanium. It may have the form of a foil, a grid, or a mesh to provide a high surface.
  • the air pole is separated from the ambient atmosphere by a thin porous membrane to filter dust etc.
  • the electrolyte may comprise methyl difluoroacetate, ethyl difluoroacetate, dimethyl difluoromalonate, methyl pentafluoropropionate as fluorosubstituted solvent and fluoroethylene carbonate, fluorobenzene, trifluoromethyl propylene carbonate as fluorosubstituted solvent additive.
  • the battery cell according to the present invention can be used in a battery comprising a single battery cell or two or more battery cells wherein the electrolyte salt comprises or even consists of LiP0 2 F 2 ; if desired, the solvent of the electrolyte composition may comprise or consist of a non-fluorinated organic electrolyte solvent as described above, a fluorinated organic electrolyte solvent as described above and any mixtures thereof.
  • a polymer gel can be present in the electrolyte, but it is not necessarily present in the battery of the current invention ; it is sufficient to provide the lithium ion transporting solvent or solvent mixture which contains or consist of a fluorosubstituted organic compound.
  • the chemical processes in the Li-air cell include lithium dissolution from the anode surface during discharge, and lithium plating back on to the nominal anode while charging.
  • Li + 0 2 - Li + 0 2 -
  • the Li + ions pass to the anode to be reduced to Li metal.
  • the Li-air battery cell is of the type which contains a membrane between the anode and the cathode compartment ; this is mandatory if the anode compartment comprises an organic electrolyte composition while the cathode compartment comprises an aqueous electrolyte composition.
  • the membrane must be permeable for Li ions but not for water or organic liquids. Suitable membranes are described below.
  • the rechargeability of the Li-air battery cell is improved if the cathode - which often is made from carbon - contains catalysts derived from metal complexes, for example, cobalt phthalocyanine, or oxides of metals such as the oxides of cobalt or mananese. It is assumed that the catalyst lowers the overvoltage for the oxidation of Li 2 0 2 or Li 2 0 to form metallic Li and oxygen.
  • catalysts derived from metal complexes for example, cobalt phthalocyanine, or oxides of metals such as the oxides of cobalt or mananese. It is assumed that the catalyst lowers the overvoltage for the oxidation of Li 2 0 2 or Li 2 0 to form metallic Li and oxygen.
  • electrolyte salt was always comprised in an amount of approximately 1 mol/liter electrolyte composition
  • solvent or solvent mixture is the balance to 100 % by weight of the respective composition.
  • Electrolyte salt LiP0 2 F 2 Non- Fluorinated Additive
  • F1EC monofluoroethylene carbonate
  • F2EC difluoroethylene carbonate (mixture containing cis-4,5, trans-4,5 and 4,4-isomers)
  • F3EC trifluoroethylene carbonate
  • F4EC tetrafluoro ethylene carbonate
  • F1DMC fluoromethyl methyl carbonate
  • FMTFEC fluoromethyl 2,2,2-trifiuoroethyl carbonate
  • the electrolyte compositions can be applied in batteries with liquid electrolytes and in battery cells with gel state electrolytes.
  • gel state electrolytes the non-aqueous solvents are gelled through the use of a gelling agent such as polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride.
  • Polymerizable monomers that are added to the non-aqueous solvent system and polymerized in situ by the use of heat or radiation may also be used.
  • a preferred battery cell of the present invention comprises a membrane between the anode and cathode compartments.
  • Highly suitable membranes are described in US 7,390,591 which is incorporated herein by reference in its entirety for all purposes. These membranes, are highly conductive for ions of the active metal, but are otherwise substantially impervious. They are chemically stable and protect the active metal anode from deleterious reactions with other battery components and decouple the chemical environments of the anode and the cathode. They may be monolithic or be composed of two or more layers.
  • a first layer for example, which is in contact with the active metal, may be partially or completely composed of L13N, L13P, Lil, LiBr, LiCl, LiF and LiPON.
  • a second layer may be composed of material that is substantially impervious, ionically conductive and chemically compatible with the first material (or its precursor).
  • suitable materials include glassy or amorphous metal ion conductors, for example, phosphorus-based or oxide based glasses, phosphorus-oxynitride-based glass, selenide-based glass, gallium-based glass, germanium-based glass and boracite glass.
  • Ceramic active metal ion conductors such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON) and the like, and glass- ceramic active metal ion conductors are also suitable. Specific examples, e.g. LiPON, are found in US 7,390,591 in column 4, lines 1 to 39.
  • the layers may further comprise additional components, e.g. polymers, for example, polymer-iodine complexes like polyethylene-iodine, or polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite.
  • polymers for example, polymer-iodine complexes like polyethylene-iodine, or polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite.
  • polymers for example, polymer-iodine complexes like polyethylene-iodine, or polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite.
  • polymers for example, polymer-iodine complexes like polyethylene-iodine, or polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite.
  • the cathode is preferably one of those described in column 15 of
  • Suitable cathodes include Li x Co0 2 , Li x 0 2 , Li x Mn 2 0 4 , LiFeP0 4 , Ag x V 2 0 5 , Cu x V 2 0 5 , V 2 0 5 , V 6 0 13 , FeS 2 and TiS 2 .
  • the advantage of the battery cells and consequently of batteries composed of a multitude of cells of the present invention is a high energy density per volume.
  • LiP0 2 F 2 can be manufactured from L1 3 PO 4 and POF 3 as described in unpublished patent application EP 10188108.4 filed in the name of Solvay SA on October 19, 2010 corresponding to WO 2012016924.
  • LiP0 2 F 2 is manufactured in a gas-solid type reaction preferably at a temperature in the range of 0°C t o 100°C and a pressure preferably higher than 5 bar (abs) by the reaction of phosphoryl fluoride (POF 3 ) and lithium orthophosphate (Li 3 P0 4 ) according to the equation 2POF 3 + L13PO4 -> 3 LiP0 2 F 2
  • EP-A-2 065 339 discloses how to manufacture a mixture of LiPF 6 and L1PO 2 F 2 from a halide other than a fluoride, LiPF 6 and water. The resulting salt mixture, dissolved in aprotic solvents, is used as an electrolyte solution for lithium ion batteries.
  • EP-A-2 061 115 describes the manufacture of L1PO 2 F 2 from P 2 O 3 F 4 and Li compounds, and the manufacture of L1PO 2 F 2 from LiPF 6 and compounds with a Si-O-Si bond, e.g. siloxanes.
  • US-A 2008/305402 discloses preparation of L1PO 2 F 2 from LiPF 6 with a carbonate compound.
  • a further aspect of the invention concerns a vehicle battery, especially preferably a car battery, constituted of a multitude of lithium-air battery cells of the present invention.
  • vehicle includes cars, motor cycles, planes, trains, lorries and electrically driven bicycles.
  • the battery of the invention is not only suitable as a battery in a vehicle with an internal combustion engine, but also in vehicles with hybrid drive, i.e. vehicles which may be driven by electric power and internal combustion engine, but also in vehicles which are driven only by electric power supplied from the battery.
  • a coin cell type lithium-air battery which corresponds to the battery type of figure la and lb of JP-A 2009/032415. It comprises a negative pole which may be made from metal, e.g. copper, stainless steel or nickel and may be present, for example, in the form of a foil, a mesh or a grid, a positive pole ("air pole") which may be made, for example, from a porous carbon material supporting the catalyst mentioned above, e.g. manganese oxide, and respective current collectors.
  • the anode contains a layer of lithium.
  • the cathode is in contact with the surrounding air ; to protect it against dust, an air- permeable membrane separates the air pole from the ambient space.
  • the battery further contains as a separator a substantially non-porous lithium- ion conductive membrane between the anode compartment and the cathode compartment. It may be, for example, a porous membrane made from polyethylene or
  • the membrane may also be for example a LISICON membrane as available from Ceramatec Inc., Salt Lake City, USA, e.g. a membrane based on Li 1+x Al x Ti 2-x (P0 4 )3 wherein x is between 0.0 and 0.5.
  • the membrane can be infused with a lithium salt, e.g. LiPF 6 , to conduct lithium ions between anode and the membrane.
  • the electrolyte composition is in contact with both the anode and the cathode is selected from one of the mixtures compiled in table 1 ; for example, composition N° 9 is very suitable.
  • lithium metal is oxidized at the anode to produce lithium ions.
  • the electrons pass through a power consuming equipment, and the lithium ions are conducted through the membrane to the cathode where they react with oxygen from surrounding air gradually forming Li 2 0 2 and Li 2 0.
  • the voltage may drop from approximately 3 V a lower value ; it is preferred to stop the discharge before 2.3 V are reached.
  • the battery cell When the battery cell is connected to a power source, it will be recharged.
  • the lithium ions from the cathode compartment migrate through the membrane to the anode compartment and are combined with electrons to form elemental lithium.
  • elemental oxygen forms from the O " and 0 2 ⁇ ions, respectively (depending on the status of discharge).
  • Example 2 Li-air type car battery
  • the car battery comprises 20 cells which are assembled in line thus providing a voltage which is the sum of the respective voltage of the cells.
  • a shut-off installation shuts the current off if the voltage is lower than 46 V during discharge.
  • Each cell is arranged in a cell housing.
  • the cell housing comprises an anode made of Li metal which is in contact with an electrolyte solution comprising 1 mol/liter of LiPF 6 , 2 % by weight of LiP0 2 F 2 , 3 % by weight of monofluoroethylene carbonate (“F1EC”) and as balance to 100 % by weight of the total electrolyte composition, a mixture of ethylene carbonate and propylene carbonate in a weight ratio of 1 : 1.
  • the same electrolyte composition is in the cathode compartment.
  • the anode compartment and the anode compartment are separated by a Lisicon membrane which comprises LiPF 6 as electrolyte salt.
  • the air electrode made from Ni is in contact with the electrolyte solvent in the cathode compartment.
  • An electric consumer e.g., an electric motor driving the vehicle, or a conventional consumer of electric current, for example, the car radio
  • the plus pole which is formed from a carbon electrode being in contact with the Li metal, and the Ni made minus pole. If the electric consumer is operating, electric current flows from the minus pole to the plus pole.
  • voltage is applied (e.g. from the generator of the motor or a battery charger), and electric current flows from the plus pole to the minus pole thus charging the battery again.
  • the car battery as described in this example comprises an electrolyte based on water in the cathode compartment.

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Abstract

A lithium-air battery cell with an electrolyte composition comprising LiPO2F2 is described. The electrolyte composition comprises an electrolyte solvent, for example, one or more non-fluorinated solvents, e.g. ethylene carbonate, a dialkyl carbonate or propylene carbonate, and/or one or more fluorinated organic solvents, e.g. fluoroethylene carbonate, cis-difluoroethylene carbonate, trans-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, 4-fluoro-4-methyl-1,3-dioxolane-2-one, 4-fluoro-4-ethyl-1,3-dioxolane-2-one, 2,2,2-trifluoroethyl-methyl carbonate, 2,2,2-trifluoroethyl-fluoromethyl carbonate are preferred. The solvent may further comprise other additives. Also described is a vehicle battery, especially a car battery constituted of a multitude of lithium-air battery cells of the invention. The battery can be used to provide electrical energy to consumers for electric current including an electric motor driving the vehicle.

Description

Lithium air battery cell
The present invention concerns a lithium-air battery cell and a lithium-air battery which contain L1PO2F2 as additive.
Rechargeable lithium-air batteries are suitable as storage media for electrical energy and useful for household items, e.g. cell phones or laptops, and they are especially suitable as car batteries. Lithium-air batteries, shortly, "Li-0 batteries", comprise one or more lithium-air battery cells containing lithium anodes electrochemically coupled to atmospheric oxygen. The oxygen is usually taken from the atmosphere and thus is an unlimited cathode reactant. The lithium-air battery has a much higher energy density than the currently existing lithium ion batteries, and is rechargeable. The underlying principle is that the battery cell comprises a metal anode in an anode compartment and a cathode (for example, porous carbon), with a gel-polymer electrolyte membrane or a nonaqueous solvent which serve as ion-transporting medium. Often, a membrane - for example, a Lisicon membrane or a Nasicon membrane - which is permeable for the metal cation, but impermeable for other compounds like water or solvent, serves to effectively separate anode and cathode compartments. If discharged, the respective metal is oxidized to the respective metal cation, the formed cation is transported via membrane and solvent to the cathode compartment and forms there the metal oxide. If rechargeable, the metal ions are migrating back to the anode compartment and are reduced to the respective metal, while the oxide is oxidized to oxygen. To prevent the intrusion of water the cathode compartment may be separated from the surrounding air by a water-repelling membrane, e.g. a Teflon® membrane.
The object of the present invention is to provide a lithium-air battery cell with improved additives and solvents and a battery, especially a car battery, constituted from a multitude of such lithium-air cells. These and other objects are achieved by the lithium-air battery cell and the battery for vehicles, especially for cars, as stated in the claims.
According to the present invention, a lithium-air battery cell is provided comprising an electrolyte composition which comprises L1PO2F2.
In a lithium-air battery, during discharge, on the anode, Li is oxidized forming Li+. On the cathode, oxygen is reduced to form the O22" ion and the 02~ ion. Upon charging of the lithium-air battery cell, the reverse reactions happen. Li20 or Li202, respectively, which have formed during discharge, are split at the cathode to finally produce elemental oxygen.
Brief description of the drawing
Figure 1 shows an example of a Li-air battery cell.
Detailed description of the invention
A lithium-air battery cell is provided comprising an electrolyte solvent which comprises L1PO2F2 as electrolyte salt or as additive. The term "battery cell" denotes a cell for a battery or a battery comprising a single battery cell. The terms "battery" denotes an item comprising a single cell or a multitude of cells. Thus, a battery comprising a single cell may be denoted "battery" or "battery cell" in the present description. In a battery with a multitude of cells, these cells are usually assembled in line to achieve a higher voltage than a single cell has.
Description of the drawing
Figure 1 presents a battery cell for car battery according to the present invention.
The cell is covered by a battery housing which is omitted from figure 1. The anode a is formed by lithium metal. In the anode compartment b, an organic electrolyte solvent is contained. Suitable electrolyte solvents are described in more detail below. The membrane c (a solid state electrolyte) separates the anode compartment b which is in contact with the lithium metal of anode a, and the cathode compartment d which is in contact with the air electrode e. It is made from material which is permeable for Li ions, but not for other components present in the anode compartment b and anode compartment d. For example, Lisicon membranes are suitable here. The cathode compartment may comprise, in the embodiment of figure 1 , an aqueous electrolyte
composition or an organic electrolyte composition. If present, the organic electrolyte composition of the cathode compartment d is preferably essentially identical to the organic electrolyte composition in the anode compartment b.
To provide a battery with higher voltage than the voltage provided by a single Li-air battery cell, several battery cells can be assembled to achieve the desired combined voltage of, for example, twelve or more Li-air cells.
The lithium-air battery cell of the invention may comprise an electrolyte salt which is selected among salts known to the expert to be suitable for this purpose. Such salts have the general formula MaA^. M is a metal cation, and A is an anion. M is preferably selected from Li+, and NR4+. Preferred anions are PF6 ", AsF6 ", BF4 ", CIO4-.
Preferably, M is Li+. Especially preferably, M is Li+ and the solution comprises an electrolyte salt selected from the group consisting of LiBF4, L1CIO4, LiAsFg, LiPF6 , Li (CF3S02)2 and LiN(i-C3F7S02)2. Lithium bis(oxalato)borate can be applied as an additional additive. The concentration of the electrolyte salt is preferably 1 ± 0.1 molar.
If LiP02F2 is the only electrolyte salt, its concentration in the electrolyte solution is, as mentioned, preferably 1 ± 0.1 molar. If LiP02F2 is applied as an additive together with another electrolyte salt, the electrolyte solution is a composition comprising the electrolyte solvent, the electrolyte salt and additives, notably the LiP02F2,the concentration of LiP02F2 in the electrolyte solution (i.e. the electrolyte composition) preferably is equal to or greater than 0.1 % by weight, more preferably equal to or greater than 0.5 % by weight ; preferably, its concentration is equal to or lower than 10 % by weight, more preferably, equal to or lower than 5 % by weight when the total electrolyte composition including electrolyte salt, solvent and additives is set as 100 % by weight. Preferably, the content of LiP02F2 is 1 to 10 % by weight, more preferably 1 to 5 % by weight, relative to the electrolyte composition set as 100 % by weight.
The solvent used in the electrolyte may comprise any non-fluorinated and/or fluorinated solvent or solvent mixture known to be useful for rechargeable battery cells, especially, known to be useful for rechargeable battery cells based in Li salts. The term "fluorinated" denotes partial or total substitution of hydrogen atoms in the solvent. The fluorosubstituted compounds may be contained in lower amounts, e.g. in an amount of 0.1 % by weight respective to the total content of solvent, up to about 10 % by weight respective to the total amount of solvent. They might then be considered rather as solvent additive than solvent. The content of fluorosubstituted compound may even be higher than 10 % by weight, and in this case, they may be considered rather as solvent.
Suitable solvents for the electrolyte composition may be selected from the group consisting of with linear or cyclic ethers, linear and cyclic esters, linear and cyclic ketones, saturated and unsaturated linear and cyclic alkanes, aromatic hydrocarbons and especially linear and cyclic organic carbonates. Alkyl carbonates and alkylene carbonates are the preferred solvent. The term "alkyl" preferably denotes a CI to C3 group. The term "alkylene" preferably denotes an alkylene group with a C2, C3 or C4 chain which is arranged between the oxygen atoms of an 0-C(0)-0 group. The alkylene group may be substituted by one or more CI to C3 alkyl groups, e.g. by one or two methyl groups and/or one or two ethyl groups. Often, ethylene carbonate (EC) is comprised in the solvent.
Propylene carbonate and butylene carbonate are other solvents which may be a suitable constituent of the electrolyte solution. The solvent may instead or additionally contain low viscosity agents, e.g. ethers like 1 ,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyldioxolane, dimethylcarbonate, ethylmethyl carbonate, diethyl carbonate and any mixtures thereof. Nitriles with a CI to C20 alkyl group, e.g. acetonitrile, dinitriles with a CI to C20 alkylene group, t-amyl benzene, and thiosubstituted compounds, for example, ethylene- 1,3-dioxolane- 2-thione (ethylene thiocarbonate) are also highly suitable non-fluorinated solvents or additives.
As indicated above, the solvent or solvent mixture contained in the electrolyte solution may also comprise or consist of one or more
fluorosubstituted organic compounds. For example, at least one
fluorosubstituted organic compound which contains at least one heteroatom selected from the group consisting of oxygen, nitrogen, phosphorous, sulfur and silicon may be comprised or constitute the only solvent. The electrolyte solvent or solvent mixture (be it fluorosubstituted or not) is selected such that it is liquid at the temperature at which the battery is intended to be used. If the melting point of the respective fluorosubstituted organic compound (just as any respective non-fluorinated compound) is low enough it can be used neat. The melting point of monofluoroethylene carbonate ("F1EC"), for example, is at about 22°C. Thus, it is preferred to apply this compound with a co-solvent with a lower melting point, e.g. with dimethyl carbonate or diethyl carbonate which have a melting point of about 2 to 4°C, with ethyl methyl carbonate having a melting point of -14.5°C, or with propylene carbonate with a melting point in the range of -50°C. Accordingly, in this case, the solvent is a solvent mixture. Preferably, the electrolyte solvent or solvent mixture is liquid at a temperature equal to or above -20°C.
In the following, highly suitable fluorosubstituted organic compounds are mentioned which are suitable as solvents or additional solvents. Preferred fluorinated organic compounds are selected from the group consisting of monofluorinated, difluorinated, trifluorinated, polyfluormated and perfluorinated organic compounds. Here, the term "polyfluormated" denotes compounds which are substituted by four or more fluorine atoms, but contain at least one hydrogen atom, or at least one chlorine atom, or at least one hydrogen atom and at least one chlorine atom. Preferably, the monofluorinated, difluorinated, trifluorinated, polyfluorinated and perfluorinated organic compounds are not substituted by chlorine atoms. "Perfluorinated" are those compounds in which all hydrogen atoms are substituted by fluorine atoms.
Suitable compounds are those described in WO2007/042471. That document discloses compounds useful to be applied the present invention selected from the group of aromatic compounds consisting of l-acetoxy-2- fluorobenzene, 1 -acetoxy-3-fluorobenzene, 1 -acetoxy-4-fluorobenzene,
2-acetoxy-5-f uorobenzyl acetate, 4-acetyl-2,2-difluoro-l,3-benzodioxole, 6-acetyl-2,2,3,3-tetrafluorobenzo-l,4-dioxin,
1 -acetyl-3 -trifluoromethyl-5 -phenylpyrazo le,
1 -acetyl-5 -trifluoromethyl-3 -phenylpyrazo le, benzotrif uoride,
benzoyltrifluoroacetone, 1 -benzoyl-3 -trifluoromethyl-5 -methylpyrazo le, 1 -benzoyl-5 -trifluoromethyl-3 -methylpyrazo le,
l-benzoyloxy-4-(2,2,2-trifluoroethoxy)benzene,
1 -benzoyl-4-trifluoromethylbenzene, 1 ,4-bis(t-butoxy)tetrafluorobenzene,
2,2-bis(4-methylphenyl)hexafluoropropane, bis(pentafluorophenyl) carbonate,
1 ,4-bis( 1 , 1 ,2,2-tetrafluoroethoxy)benzene, 2,4-bis(trifluoromethyl)benzaldehyde, 2,6-bis(trifluoromethyl)benzonitrile, dif uoroacetophenone,
2,2-dif uorobenzodioxole, 2,2-dif uoro- 1 ,3-benzodioxole-4-carbaldehyde,
1 - [4-(difluoromethoxy)phenyl] ethanone, 3 -(3 ,5 -difluorophenyl)- 1 -propene, fluorobenzophenone, dif uorobenzophenone,
1 -(2'-fluoro[ 1 , 1 '-biphenyl]-4-yl)propan- 1 -one,
6-fluoro-3,4-dihydro-2H-l-benzothiin-4-one, 4-fluorodiphenyl ether,
5-fluoro- 1 -indanone, 1 -(3-fluoro-4-methoxyphenyl)ethanone,
fluorophenylacetonitrile,
the group of compounds having an Si-C bond consisting of
bis(pentafluorophenyl)dimethylsilane, l,2-bis[difluoro(methyl)silyl]ethane, N,0-bis(trimethylsilyl)trifiuoroacetamide,
N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide, t-butyldimethylsilyl trifluoromethanesulphonate, 2-dimethylamino- 1 ,3-dimethylimidazolium trimethyldifluorosiliconate, diphenyldifluorosilane,
the group of compounds having a C=0 bond consisting of
bis(l,l,l,3,3,3-hexafluoroprop-2-yl) 2-methylenesuccinate,
bis(l,l,l,3,3,3-hexafluoroprop-2-yl) maleate, bis(2,2,2-trifluoroethyl) maleate, bis(perfluorooctyl) fumarate, bis(perfluoroisopropyl) ketone,
2,6-bis(2,2,2-trifluoroacetyl)cyclohexanone, butyl 2,2-difluoroacetate, cyclopropyl 4-fluorophenyl ketone, diethyl perfluoroadipate,
N,N-diethy 1-2 ,3,3,3 -tetrafluoropropionamide,
the group of compounds having a C=C bond consisting of allyl
1 H, 1 H-heptafluorobutyl ether, trans- 1 ,2-bis(perfluorohexyl)ethylene,
(E)-5 ,6-difluoroocta-3 ,7-diene-2-one,
the group of amines consisting of
N,N-diethyl- 1,1,2,3 ,3 ,3-hexafluoropropylamine
These compounds are applicable as additive or additives for electrolyte solvents in lithium-air batteries. The solvent may also additionally contain benzene, fluorobenzene, toluene, trifluorotoluene, xylene or cyclohexane.
The term "difluoroacetophenone" encompasses the isomers with the fluorine substitution in the 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-position on the aromatic ring.
The term "fluorobenzophenone" encompasses in particular the isomers 2-fluorobenzophenone and 4-fluorobenzophenone.
The term "difluorobenzophenone" encompasses the isomers with the fluorine substitution in the 2,3'-, 2,3-, 2,4'-, 2,4-, 2,5-, 2,6-, 3,3'-, 3,4'-, 3,4-, 3,5- and 4,4'-position.
The term "fluorophenylacetonitrile" encompasses the isomers with the fluorine substitution in the 2-, 3- and 4-position.
The compounds can be synthesized in a known manner and are also commercially available, for example from ABCR GmbH & Co.KG, Karlsruhe, Germany.
Preferred fluorinated organic compounds are selected from the group of fluorosubstituted carboxylic acid esters, fluorosubstituted carboxylic acid amides, fluorosubstituted fluorinated ethers, fluorosubstituted carbamates, fluorosubstituted cyclic carbonates, fluorosubstituted acyclic carbonates, fluorosubstituted phosphites, fluorosubstituted phosphoranes, fluorosubstituted phosphoric acid esters, fluorosubstituted phosphonic acid esters and saturated or unsaturated fluorosubstituted heterocycles.
Suitable fluorinated ethers applicable as solvent or solvent additive are for example those as described in US 5,916,708, namely partially fluorinated ethers of formula (I)
RO-[(CH2)mO]n-CF2-CFH-X (I) wherein
R is a linear alkyl group with 1 to 10 C atoms or a branched alkyl group with 3 to 10 C atoms,
X is fluorine, chlorine or a perfluoroalkyl group with 1 to 6 C atoms which groups may include ether oxygen,
m is an integer of 2 to 6 and
n is an integer of 1 to 8,
and/or of formula (II)
X-CFH-CF20-[(CH2)mO]n-CF2-CFH-X (II) wherein
X, m and n have the meaning given above.
Partially fluorinated carbamates suitable as solvent additives are for example those described in US 6,159,640, namely compounds of the
formula R1R2N-C(0)OR3 wherein R1 and R2 independently are the same or different, and are linear Cl-C6-alkyl, branched C3-C6-alkyl, C3-C7-cycloalkyl, or R1 and R2 are connected directly or via one or more additional N and/or O atoms forming a ring with 3 to 7 members. Optionally, additional N atoms in the ring are saturated with CI to C3 alkyl groups, and additionally, the carbon atoms of the ring may be substituted by CI to C3 alkyl groups. In the groups R1 and R2, one or more hydrogen atoms may be substituted by fluorine atoms. R3 is a partially fluorinated or perfluorinated linear or branched alkyl group with 1 to 6 or, respectively, 3 to 6 carbon atoms, or a partially or perfluorinated cycloalkyl group with 3 to 7 C atoms, which may be substituted by one or more CI to C6 alkyl groups.
Fluorinated acetamides suitble as solvent additive are for example those described US 6,489,064, namely partially fluorinated amide corresponding to formula (I)R1CO-NR2R3 (III) wherein R1 is a linear CI - C6 alkyl group in which at least one hydrogen atom is replaced by fluorine, or a branched C3 - C6 alkyl group in which at least one hydrogen atom is replaced by fluorine, or a C3 - C7 cycloalkyl group optionally substituted one or more times by a linear CI - C6 alkyl group or branched C3 - C6 alkyl group or both in which at least one hydrogen atom of the cycloalkyl group or the optional linear or branched alkyl substituent or both is replaced by fluorine, and R2 and R3 independently represent an identical or different linear CI - C6 alkyl group, a branched C3 - C6 alkyl group or a C3 - C7 cycloalkyl group, or together with the amide nitrogen form a saturated five or six-membered nitrogen-containing ring, or are joined with one or more additional N and/or O atom(s) to form a 4 to 7-membered ring in which the additional N atoms present in the ring are optionally saturated with CI - C3 alkyl groups and the ring carbon atoms may also carry CI - C3 alkyl groups.
Partially fluorinated esters suitable as solvent or solvent additive are for example those described in US 6,677,085 partially fluorinated compound derived from a diol corresponding to formula (IV) : R^CO-O-tCHR^CH 2) m-0]n -R2 (IV) wherein R1 is a (CI - C8) alkyl group or a (C3 - C8) cycloalkyl group, wherein each of said groups is partially fluorinated or perfluorinated so that at least one hydrogen atom of the group is replaced by fluorine ;R2 is a (CI - C8) alkyl carbonyl or (C3 - C8) cycloalkyl carbonyl group, wherein said alkylcarbonyl or cycloalkylcarbonyl group may optionally be partially fluorinated or
perfluorinated ;R3 is a hydrogen atom or a (CI - C8) alkyl or (C3 - C8) cycloalkyl group ; m is 0, 1, 2 or 3, and n is 1, 2 or 3.
Especially preferred are linear or branched fluorosubstituted dialkyl carbonates and fluorosubstituted alkylene carbonates.
Fluorinated dialkyl carbonates suitable as solvent or solvent additive are those of formula (V)
R1-0-C(0)-0-R2 (V) In the compounds of formula (V), R1 and R2 can be the same or different with the proviso that at least one of R1 and R2 are substituted by at least one fluorine atom. R1 and R2 are preferably linear alkyl groups with 1 to 8 carbon atoms, preferably, 1 to 4 carbons, more preferably, with 1 to 3 carbon atoms ; branched alkyl groups with 3 to 8 carbon atoms, preferably with 3 carbon atoms ; or cyclic alkyl groups with 5 to 7 carbon atoms, preferably, 5 or 6 carbon atoms ; with the proviso that at least one of R1 and R2 is substituted by at least one fluorine atom.
Highly preferably, R1 and R2 denote linear alkyl groups with 1 to 3 carbon atoms, with the proviso that at least one of R1 and R2 is substituted by at least one fluorine atom. Most preferably, R1 and R2 are selected from the group consisting of methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1 ,2-difluoroethyl, 2,2,2-trifluoroethyl and 1-fluoro-l-methylethyl. Most preferred compounds of formula (V) are methyl fluoromethyl carbonate, fluoromethyl ethyl carbonate, methyl
2,2,2-trifluoroethyl carbonate, fluoromethyl 2,2,2-trifluoroethyl carbonate and bis-2,2,2-trifluoroethyl carbonate. Such compounds can be manufactured from phosgene, COFC1 or COF2, and the respective alcohols, or as described in unpublished EP patent application No. 09155665.2. According to that process, the manufacture of fluoroalkyl (fluoro)alkyl carbonates of the general formula (Vi), FCHR-OC(0)-OR' wherein R denotes linear or branched alkyl with 1 to 5 C atoms or H and R' denotes linear or branched alkyl with 1 to 7 carbon atoms ; linear or branched alkyl with 2 to 7 carbon atoms, substituted by at least one fluorine atom ; phenyl ; phenyl, substituted by 1 or more C 1 to C3 alkyl groups atoms or phenyl substituted by 1 or more chlorine or fluorine atoms ; or benzyl includes a step of reacting a fluoroalkyl fluoroformate of formula (VII), FCHROC(0)F, or a fluoroalkyl chloroformate of formula (VIF), FCHROC(0)Cl, with an alcohol of formula (VIII), R'OH, wherein R and R' have the meanings given above, or includes a step of reacting a chloroalkyl fluoroformate of formula (IX), C1CHR0C(0)F, or a chloroalkyl chloroformate of formula (IX'), C1CHR0C(0)C1, wherein R has the meaning given above, with an alcohol of formula (VIII), R'OH wherein R' has the meaning given above, and a subsequent chlorine- fluorine exchange. The term "fluoro)alkyl" denotes alkyl and fluorosubstituted alkyl.
According to another embodiment, fluorosubstituted alkylene carbonates of formula (X) are applied
Figure imgf000011_0001
Here, R1, R2, R3 and R4 are independently selected from H, linear alkyl groups with 1 to 3 carbon atoms and alkenyl groups with 2 or 3 carbon atom ; linear alkyl groups with 1 to 3 carbon atoms or an alkenyle group with 2 or 3 carbon atoms, substituted by at least one fluorine atom ; and fluorine, with the proviso that at least one of R1, R2, R3 and R4 is fluorine or an alkyl group substituted by at least one fluorine atom.
According to one embodiment, in compounds of formula (X), R1, R2, R3 and R4 are selected from H and F, with the proviso that at least one of R1, R2, R3 and R4 is fluorine. Especially fluoroethylene carbonate, but also cis- and trans- 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, trifluoroethylene carbonate and tetrafluoroethylene carbonate are very suitable. These compounds can be manufactured by direct fluorination of ethylene carbonate. In the case of difluorosubstituted ethylene carbonate, cis and trans-4,5-difluoroethylene carbonate and 4,4-difluoroethylene carbonate are obtained. These isomers can be separated by fractionated distillation.
According to another preferred embodiment, in compounds of formula (X), RJis a CI to C3 alkyl group or a CI to C3 alkyl group, substituted by at least one fluorine atom ; and R2, R3 and R4 are H or F, with the proviso that at least one ofR2, R3 and R4 are F, or RJis a CI to C3 alkyl group, substituted by at least one fluorine atom. Preferably, R1 is methyl, ethyl or vinyl.
Especially preferred compounds of this type are 4-fluoro-4-methyl-l,3- dioxolane-2-one, 4-fluoro-5-methyl- 1 ,3-dioxolane-2-one, 4-ethyl-4-fluoro- 1 ,3- dioxolane-2one, 5-ethyl-4-fluor-4-ethyl-l,3-dioxolan-2-one and 4,5-dimethyl-4- fluoro- 1 ,3-dioxolane-2-one.
The compounds are known and can be manufactured by fluorination of the respective non-fluorinated compounds or by chlorine- fluorine exchange of the respective chlorosubstituted compounds. 4-Alkyl-4-fluorosubstituted
compounds can be manufactured as described in 09161429.7 : 4-fluoro-4-R-5- R'-l,3-dioxolane-2-ones are prepared by cyclization of compounds of formula (XI), FC(0)OCHR'C(0)R, wherein R is alkyl and R' is H or CI to C3 alkyl. R denotes preferably CI to C5 alkyl, more preferably, CI to C3 alkyl. Most preferably, R denotes methyl, ethyl, i-propyl and n-propyl. R' preferably is H. Especially preferably, R is methyl and R' is H.
The cyclization reaction is preferably catalyzed by a heterocyclic compound containing nitrogen, or by fluoride ions. In a preferred embodiment, the heterocyclic compound is an aromatic compound. For example, pyridine or 2-methylimidazole can be used as catalyst. Especially preferred are pyridines substituted by at least one dialkylamino group. 4-Dimethylaminopyridine is very suitable. Other 4-dialkylaminopyridines, for example, those wherein alkyl denotes a CI to C3 alkyl group, are also considered to be suitable.
According to a further preferred embodiment, R1 and R2 are CI to C3 alkyl groups or CI to C3 alkyl groups, substituted by at least one fluorine atom ; R3 and R4 are H or F, with the proviso that at least one of R3 and R4 are F, or at least one of R1 and R2 is a CI to C3 alkyl group, substituted by at least one fluorine atom.
Especially preferred compounds of this type are 4-fluoro-5-(l-fluoroethyl)- l,3-dioxolan-2-one, 4-fluoro-5-(2-fluoroethyl)-l,3-dioxolan-2-one,
4-trifluoromethyl-4-methyl- 1 ,3-dioxolan-2-one, 4-trifluoromethyl-4-methyl-5- fluoro- 1 ,3-dioxolan-2-one and 4-(2,2,2-trifluoroethyl)-4-methyl-5-fluoro- 1 ,3- dioxolan-2-one.
Another group of compounds are trialkyl phosphites wherein at least one alkyl group is substituted by at least one fluorine atom. Tris-(2,2,2- trifluoroethyl) phosphate is the preferred compound. It can be prepared from PCI3 and trifluoroethanol, optionally in the presence of a base, e.g. an amine.
Still another group of compounds are perfluoroalkyl phosphoranes of formula (XII), (CnF2n+m)5P wherein n is 1, 2, 3, 4, 5, 6, 7 or 8, and m is +1 or -1. They can be prepared from pentaalkyl phosphanes via electro fluorination analogously to the process described in US 6,264,818.
Fluorosubstituted phosphonate esters and phosphate esters of
formula (XIII), R-P^RiR2, are also suitable. In formula (XIII), R is a CI to C4 alkyl group ; a CI to C4 alkyl group, substituted by at least 1 fluorine atom ; or a fluorosubstituted C2 to C4 alkoxy group ; R1 and R2 are the same or different and represent C2 to C4 alkoxy groups, substituted by at least one fluorine atom. Preferred compounds of this type are methyl bis-(2,2,2- trifluoroethyl) phosphonate, ethyl bis-(2,2,2-trifluoroethyl) phosphonate, and tris-(2,2,2-trifluoroethyl) phosphate.
Fluorosubstituted carbonic acid esters of formula (XIV), R-C(0)OR1 are also suitable. In the formula (XIV), R denotes preferably CI to C3 and R1 preferably denotes a CI to C3 alkyl group with the proviso that at least one of R and R1 are substituted by at least one fluorine atom. Preferred compounds are 2,2,2-trifluoroethyl butyrate (R = C3H7, R1 = C2H2F3), ethyl trifluoroacetate (R = CF3, R1 = C2H5), 2,2,2-trifluoroethyl acetate (R = CH3, R1 = C2H2F3) and methyl pentafluoropropionate (R = C2F5, R1 = CH3). These compounds are suitable for batteries which are operated at low temperatures as described in US patent application publication 2008/0305401.
Another group of suitable compounds are those of formula (XV),
R-C(0)-C(H)=C(H)-OR1. In compounds of formula (XV), R is a
polyfluorinated or perfluorinated alkyl group, and R1 is CI to C4 alkyl ; CI to C4 alkyl, substituted by one or more fluorine atoms ; or phenyl. R is preferably CF3, CHF2, or C2F5 ; and R1 is preferably methyl or ethyl. The most preferred compound is 4-Ethoxy- 1,1,1 -trifluoro-3-buten-2-one (ETFBO). These compounds can be prepared by the addition of the respective carboxylic acid chlorides to the respective vinyl ether and subsequent dehydrochlorination. ETFBO, for example, can be prepared from trifluoroacetyl chloride and ethyl vinyl ether. ETFBO is also available e.g. from Solvay Fluor GmbH, Hannover, Germany.
Another group of suitable compounds are polyfluorinated and
perfluorinated ethers. Suitable perfluorinated polyethers are described, for example, in WO 02/38718. These perfluorinated polyethers consist essentially of carbon, fluorine and oxygen atoms and comprise at least two, preferably three, C-O-C ether linkages, or a mixture of several compounds satisfying that definition. Often, the oxygen atoms in the perf uoropolyether are exclusively present within the C-O-C ether linkages. The perfluoropolyethers generally have a molecular weight of about 200 or more. Generally they have a molecular weight of less than about 1500. If the polyether is a mixture of several substances, the molecular weight is the weight-average molecular weight.
Generally, the perfluoropolyether has a boiling point greater than or equal to 40°C at 101.3 kPa. The perfluoropolyether generally has a boiling point less or equal to about 200°C at 101.3 kPa. As a result of the preparation, these perfluoropolyethers often are a mixture of individual substances. Generally, the kinematic viscosity of the perfluoropolyether is less than or equal to 1 cSt (Centistoke) at 25°C. Generally, the kinematic viscosity is at least 0.3 cSt at 25°C.
The preferred perfluoro polyethers are the products marketed by Solvay
Solexis under the names GALDEN® and FOMBLIN®.
Examples include :
GALDEN HT 55 : boiling point 57°C at 101.3 kPA ; average molecular weight 340
GALDEN HT 70 : boiling point 66°C at 101.3 kPa ; average molecular weight 410
FOMBLIN PFS1 : boiling point 90°C at 101.3 kPa ; average molecular weight 460
Partially fluorinated polyethers are the hydrofluoro ethers marketed by 3M under the name NOVEC®. The GALDEN® and FOMBLIN® systems are usually multicomponent systems having a boiling point in the range from 40 to 76°C.
Other fluorosubstituted compounds which are suitable as fluorosubstituted compound are lithium fluoro(oxalate)borate and lithium difluoro(oxalato)borate. They are no solvents but an electrolyte salt additive.
Also, fluorinated heterocyclic compounds are suitable as solvent additives, especially, fluorinated dioxolanes, fluorinated oxazolidines, fluorinated imidazolindines, fluorinated dihydroimidazoles, fluorinated
2,3-dihydroimidazoles, fluorinated pyrroles, fluorinated thiophenes, fluorinated thiazoles and fluorinated imidazoles.
Suitable fluorinated dioxo lanes are for example 2,2-difluoro-l,3-dioxolane (US 5,750,730) and 2-f uoro-4,4,5,5-tetramethyl-l,3-dioxolane, available from chemstep, France.
Suitable fluorinated oxazolidines are for example 2,2-difluoro-3- methyloxazolidine and 4,5-difluoro-3-methyloxazolidine-2-one, available from chemstep.
Suitable fluorinated imidazolidines are for example 2,2-difluoro-l,3- dimethylimidazolidine, available from abcr, and l,3-dibutyl-2,2- dif uoroimidazolidineavailable from Apollo.
Suitable fluorinated 2,3-dihydroimidazoles are for example 2,2-difluoro- 1 ,3-dimethyl-2,3-dihydro- lH-imidazole and 1 -ethyl-2-fluoro-3-methyl-2,3- dihydro-lH-imidazole, available from chemstep.
Suitable fluorinated imidazoles are for example l-(trif uoromethyl)-lH- imidazole, available from selectlab, and 2-fluoro-l-(methoxymethyl)-lH- imidazole, available from chemstep.
A suitable fluorinated pyrrole is for example 2-ethyl-5-fluoro-l-methyl- lH-pyrrole, available from chemstep.
A suitable fluorinated thiophene is for example 2-f uorothiophene, available from apacpharma.
A suitable fluorinated thiazole is for example 4-f uorothiazole, available from chemstep.
Also, f uorosubstituted organic liquids, e.g. 4,5-dimethyl-3-perfluorooctyl-
1 ,2,4-triazolium tetrafluoroborate.
The fluorinated organic compounds mentioned above can be used as the only solvent, or they are applied in admixture with one or more organic solvents which are not fluorosubstituted.
Preferred mixtures comprise at least one compound selected from the group consisting of monofluoroethylene carbonate, cis-dif uoroethylene carbonate, trans-difluoroethylene carbonate, 4,4- difluoroethylene carbonate, 4-fluoro-4-methyl- 1 ,3-dioxolane-2-one, 4-fluoro-4-ethyl- 1 ,3-dioxolane-2-one, 4-trifluoromethyl- 1 ,3-dioxolane-2-one, 2,2,2-trif uoroethyl-methyl carbonate, 2,2,2-trifluoroethyl-fluoromethyl carbonate, and at least one non- fluorinated organic compound selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
The electrolyte solvent contains 0.1 to 100 % by weight of the
fluorosubstituted organic compound, if such a compound or compounds is or are contained. Often, the fluorinated organic compound is contained in the electrolyte solvent in an amount of equal to or more than 1 % by weight, preferably equal to or more than 3 % by weight. Often, the content is preferably equal to or lower than 20 % by weight relative to the electrolyte solvent set as 100 % by weight, and more preferably, equal to or lower than 10 % by weight.
In battery cells which comprise membranes to separate the metallic lithium from the solvent in the cathode compartment, ionic liquids can be applied in a mixture with any of the fluorosubstituted compounds mentioned above. Very suitable ionic liquids are those based on imidazolium, and pyridinium
derivatives, but phosphonium or tetraalkylammonium compounds can also be applied. Representative ionic liquids are tosylate, triflate, hexafluorophosphate, bis-(fluorosulfonyl)amide, bis-(trifluoromethylsulfonyl)amide and
tetrafluoroborate of l-ethyl-3-methylimidazolium, and the octyl sulfate of 1 -butyl-3 -methylimidazolium.
The Li-air battery cell of the present invention preferably comprises a membrane permeable for lithium ions.
A suitable Li-air battery cell is disclosed in US-A 5,510,209. The battery cell described therein, for example, in fig. 1 of US-A 5,510,209, comprises a lithium foil anode, a polymer electrolyte (comprising polyacrylnitrile, a solvent, e.g. propylene carbonate or ethylene carbonate, and an electrolyte salt, e.g. LiPF6), a composite positive electrode current collector and an oxygen permeable membrane through which oxygen (from the surrounding air) is transported to the porous carbon electrode.
Another Li-air battery cell is described in JP patent application
2009/032415. The battery cell (which, in fact, is a battery comprising one cell) described therein is said to have a favorable cycle characteristic. The cell described therein comprises : an positive electrode which is an air electrode (also called "air pole") having an air electrode layer containing a conductive material and an air electrode power collector for collecting electric power from the air electrode layer ; a negative electrode having a negative electrode layer containing a negative electrode active material that adsorbs and releases Li ions and a negative electrode power collector for collecting electric power from the negative electrode layer ; a separator provided between the air electrode layer and the negative electrode layer ; and a fluorosubstituted electrolyte with which at least the separator is impregnated. It also contains a discharge controller that terminates the discharge of the air battery cell. The discharge final voltage of the discharge controller is 2.3 V or higher based on Li metal. The cell also has provisions to handle the volume changes of the electrolyte if the battery charges or discharges. The discharge controller serves to prevent the formation of LiF from LiPF6 (the commonly applied electrolyte salt) which occurs if the voltage during discharge drops beyond a 2.3V level relative to Li metal.
The negative electrode may be constructed from materials commonly used in Li ion battery cells, e.g. from metallic lithium or carbon. The collector of the negative pole may be made from metals, e.g. copper, stainless steel, or nickel. The air pole may be made from carbon which is preferably porous. The air pole charge collector may be made from metals, e.g. stainless steel, nickel, aluminium, iron, or titanium. It may have the form of a foil, a grid, or a mesh to provide a high surface. The air pole is separated from the ambient atmosphere by a thin porous membrane to filter dust etc. The electrolyte may comprise methyl difluoroacetate, ethyl difluoroacetate, dimethyl difluoromalonate, methyl pentafluoropropionate as fluorosubstituted solvent and fluoroethylene carbonate, fluorobenzene, trifluoromethyl propylene carbonate as fluorosubstituted solvent additive.
The battery cell according to the present invention can be used in a battery comprising a single battery cell or two or more battery cells wherein the electrolyte salt comprises or even consists of LiP02F2 ; if desired, the solvent of the electrolyte composition may comprise or consist of a non-fluorinated organic electrolyte solvent as described above, a fluorinated organic electrolyte solvent as described above and any mixtures thereof. A polymer gel can be present in the electrolyte, but it is not necessarily present in the battery of the current invention ; it is sufficient to provide the lithium ion transporting solvent or solvent mixture which contains or consist of a fluorosubstituted organic compound.
The chemical processes in the Li-air cell include lithium dissolution from the anode surface during discharge, and lithium plating back on to the nominal anode while charging.
During discharge, on the anode, Li is oxidized forming Li+. On the cathode, oxygen is reduced to form the 02 2~ ion and the 0 ~ ion : 2 Li + 02 -» Li202
4 Li + 02 -> 2 Li20
Upon charging the lithium-air battery cell, the reverse reactions happen. The Li20 or Li202, respectively, is broken at the cathode to produce finally elemental oxygen :
2 Li20 -» Li202 -» 02.
The Li+ ions pass to the anode to be reduced to Li metal.
According to a preferred embodiment, the Li-air battery cell is of the type which contains a membrane between the anode and the cathode compartment ; this is mandatory if the anode compartment comprises an organic electrolyte composition while the cathode compartment comprises an aqueous electrolyte composition. Here, the membrane must be permeable for Li ions but not for water or organic liquids. Suitable membranes are described below.
The rechargeability of the Li-air battery cell is improved if the cathode - which often is made from carbon - contains catalysts derived from metal complexes, for example, cobalt phthalocyanine, or oxides of metals such as the oxides of cobalt or mananese. It is assumed that the catalyst lowers the overvoltage for the oxidation of Li202 or Li20 to form metallic Li and oxygen.
In the following, preferred electrolyte compositions are listed. The electrolyte salt was always comprised in an amount of approximately 1 mol/liter electrolyte composition The indicated solvent or solvent mixture is the balance to 100 % by weight of the respective composition.
Table 1 : Electrolyte compositions
Composition Electrolyte salt LiP02F2 Non- Fluorinated Additive
N° [% weight] [% fluorinated solvent [% [% wt] weight] solvent weight,
[weight weight ratio] ratio]
1 LiAsFfi 1 EC/PC; 1:1 F1EC;5
2 LiC104 1 EC/PC; 1:1 F1EC;5 AND ;
2.5
3 LiN(CF3S02)2. 1 EC/PC; 1:1 F1EC
2.5/F2EC - 2.5 ; 1:1
4 LiPFfi 1 EC/PC; 1:1 F1EC;5
5 LiPFfi 2 EC/PC; 1:1
6 LiPFfi 2 EC/PC; 1:1
7 LiPFfi 2 EC/PC; 1:1 PN;2
8 LiPFfi 2 EC/PC; 1:1 SN;2
9 LiPF6 2 EC/DEC ; F1EC;5 GN;2
1:1.25
10 LiPFfi 2 EC/DEC ; F1DMC ; 5 1 : 1.25
11 LiPF6 5 EC/DEC ; 4-FPC ; 5
1 : 1.25
12 LiPFfi 5 EC:PC ; 1 : 1 FMTFEC ; 3
13 LiPF6 8 EC/DEC ; F3EC ; 3 PNG ; 2
1 : 1.25
14 LiPFfi 8 EC:TG ; 1 : 1 F1EC ; 5
15 LiPF6 8 EC/DEC ; F4EC ; 5
1 : 1.25
Abbreviations :
DEC = diethyl carbonate
EC = ethylene carbonate
PC = propylene carbonate
TG = tetraglyme
F1EC = monofluoroethylene carbonate
F2EC = difluoroethylene carbonate (mixture containing cis-4,5, trans-4,5 and 4,4-isomers)
F3EC = trifluoroethylene carbonate
F4EC = tetrafluoro ethylene carbonate
F1DMC = fluoromethyl methyl carbonate
4FPC = 4-fluoro-4-methyl-l,3-dioxolane-2-one
FMTFEC = fluoromethyl 2,2,2-trifiuoroethyl carbonate
ADN = adiponitrile
SN = succinonitrle
GN = glutaronitrile
PN = propionitrile
The electrolyte compositions can be applied in batteries with liquid electrolytes and in battery cells with gel state electrolytes. In gel state electrolytes, the non-aqueous solvents are gelled through the use of a gelling agent such as polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride. Polymerizable monomers that are added to the non-aqueous solvent system and polymerized in situ by the use of heat or radiation may also be used.
As mentioned above, a preferred battery cell of the present invention comprises a membrane between the anode and cathode compartments. Highly suitable membranes are described in US 7,390,591 which is incorporated herein by reference in its entirety for all purposes. These membranes, are highly conductive for ions of the active metal, but are otherwise substantially impervious. They are chemically stable and protect the active metal anode from deleterious reactions with other battery components and decouple the chemical environments of the anode and the cathode. They may be monolithic or be composed of two or more layers.
A first layer, for example, which is in contact with the active metal, may be partially or completely composed of L13N, L13P, Lil, LiBr, LiCl, LiF and LiPON.
A second layer may be composed of material that is substantially impervious, ionically conductive and chemically compatible with the first material (or its precursor). Suitable materials include glassy or amorphous metal ion conductors, for example, phosphorus-based or oxide based glasses, phosphorus-oxynitride-based glass, selenide-based glass, gallium-based glass, germanium-based glass and boracite glass. Ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON) and the like, and glass- ceramic active metal ion conductors are also suitable. Specific examples, e.g. LiPON, are found in US 7,390,591 in column 4, lines 1 to 39.
The layers may further comprise additional components, e.g. polymers, for example, polymer-iodine complexes like polyethylene-iodine, or polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite. For example, a composite of a Li-ion conducting glass-ceramic material and a solid polymer electrolyte based on polyethyleneoxide-Li salt complexes. Such a material is available from the company Ohara Corp.
The cathode is preferably one of those described in column 15 of
US 7,390,591. Suitable cathodes include LixCo02, Lix 02, LixMn204, LiFeP04, AgxV205, CuxV205, V205, V6013, FeS2 and TiS2.
The manufacture of the battery cells is known in the art as indicated in
US 7,390,591 in column 15, line 33 to column 16, line 2.
The advantage of the battery cells and consequently of batteries composed of a multitude of cells of the present invention is a high energy density per volume.
LiP02F2 can be manufactured from L13PO4 and POF3 as described in unpublished patent application EP 10188108.4 filed in the name of Solvay SA on October 19, 2010 corresponding to WO 2012016924. LiP02F2 is manufactured in a gas-solid type reaction preferably at a temperature in the range of 0°C t o 100°C and a pressure preferably higher than 5 bar (abs) by the reaction of phosphoryl fluoride (POF3) and lithium orthophosphate (Li3P04) according to the equation 2POF3 + L13PO4 -> 3 LiP02F2
Since no byproduct is ideally produced from the reaction, the purity of L1PO2F2 is very high.
EP-A-2 065 339 discloses how to manufacture a mixture of LiPF6 and L1PO2F2 from a halide other than a fluoride, LiPF6 and water. The resulting salt mixture, dissolved in aprotic solvents, is used as an electrolyte solution for lithium ion batteries. EP-A-2 061 115 describes the manufacture of L1PO2F2 from P2O3F4 and Li compounds, and the manufacture of L1PO2F2 from LiPF6 and compounds with a Si-O-Si bond, e.g. siloxanes. US-A 2008/305402 discloses preparation of L1PO2F2 from LiPF6 with a carbonate compound.
A further aspect of the invention concerns a vehicle battery, especially preferably a car battery, constituted of a multitude of lithium-air battery cells of the present invention. The term "vehicle" includes cars, motor cycles, planes, trains, lorries and electrically driven bicycles.
The battery of the invention is not only suitable as a battery in a vehicle with an internal combustion engine, but also in vehicles with hybrid drive, i.e. vehicles which may be driven by electric power and internal combustion engine, but also in vehicles which are driven only by electric power supplied from the battery.
Should the disclosure of any patents, patent applications, and
publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
The following examples are intended to explain the invention without limiting it.
Example
A coin cell type lithium-air battery is provided which corresponds to the battery type of figure la and lb of JP-A 2009/032415. It comprises a negative pole which may be made from metal, e.g. copper, stainless steel or nickel and may be present, for example, in the form of a foil, a mesh or a grid, a positive pole ("air pole") which may be made, for example, from a porous carbon material supporting the catalyst mentioned above, e.g. manganese oxide, and respective current collectors. The anode contains a layer of lithium. The cathode is in contact with the surrounding air ; to protect it against dust, an air- permeable membrane separates the air pole from the ambient space. The battery further contains as a separator a substantially non-porous lithium- ion conductive membrane between the anode compartment and the cathode compartment. It may be, for example, a porous membrane made from polyethylene or
polypropylene. The membrane may also be for example a LISICON membrane as available from Ceramatec Inc., Salt Lake City, USA, e.g. a membrane based on Li1+xAlxTi2-x(P04)3 wherein x is between 0.0 and 0.5. If desired, the membrane can be infused with a lithium salt, e.g. LiPF6, to conduct lithium ions between anode and the membrane.
The electrolyte composition is in contact with both the anode and the cathode is selected from one of the mixtures compiled in table 1 ; for example, composition N° 9 is very suitable.
Operation of the battery :
If the battery cell described above is discharged, lithium metal is oxidized at the anode to produce lithium ions. The electrons pass through a power consuming equipment, and the lithium ions are conducted through the membrane to the cathode where they react with oxygen from surrounding air gradually forming Li202 and Li20. The voltage may drop from approximately 3 V a lower value ; it is preferred to stop the discharge before 2.3 V are reached.
When the battery cell is connected to a power source, it will be recharged. Here, the lithium ions from the cathode compartment migrate through the membrane to the anode compartment and are combined with electrons to form elemental lithium. In the cathode compartment, elemental oxygen forms from the O" and 02~ ions, respectively (depending on the status of discharge).
Example 2 : Li-air type car battery
The car battery comprises 20 cells which are assembled in line thus providing a voltage which is the sum of the respective voltage of the cells. A shut-off installation shuts the current off if the voltage is lower than 46 V during discharge. Each cell is arranged in a cell housing. The cell housing comprises an anode made of Li metal which is in contact with an electrolyte solution comprising 1 mol/liter of LiPF6, 2 % by weight of LiP02F2, 3 % by weight of monofluoroethylene carbonate ("F1EC") and as balance to 100 % by weight of the total electrolyte composition, a mixture of ethylene carbonate and propylene carbonate in a weight ratio of 1 : 1. The same electrolyte composition is in the cathode compartment. The anode compartment and the anode compartment are separated by a Lisicon membrane which comprises LiPF6 as electrolyte salt. The air electrode made from Ni is in contact with the electrolyte solvent in the cathode compartment. An electric consumer (e.g., an electric motor driving the vehicle, or a conventional consumer of electric current, for example, the car radio) is arranged between the plus pole which is formed from a carbon electrode being in contact with the Li metal, and the Ni made minus pole. If the electric consumer is operating, electric current flows from the minus pole to the plus pole. For charging, voltage is applied (e.g. from the generator of the motor or a battery charger), and electric current flows from the plus pole to the minus pole thus charging the battery again.
In another alternative, the car battery as described in this example comprises an electrolyte based on water in the cathode compartment.

Claims

C L A I M S
1. A lithium-air battery cell comprising an electrolyte composition which comprises LiP02F2.
2. The lithium-air battery cell of claim 1 wherein the content of L1PO2F2 is 1 to 10 % by weight.
3. The lithium-air battery cell of anyone of claims 1 to 2 wherein the electrolyte composition comprises at least one electrolyte solvent selected from the group consisting of non-fluorinated aprotic organic compounds and fluorinated aprotic organic compounds.
4. The lithium-air battery cell of anyone of claims 1 to 3 wherein the electrolyte composition comprises an electrolyte solvent which comprises or consists of at least one fluorosubstituted organic compound which contains at least one heteroatom selected from the group consisting of oxygen, nitrogen, phosphorous, sulfur and silicon.
5. The lithium-air battery cell of claim 4 wherein the fluorosubstituted electrolyte solvent is selected from the group consisting of fluorosubstituted carboxylic acid esters, fluorosubstituted carboxylic acid amides,
fluorosubstituted fluorinated ethers, fluorosubstituted carbamates,
fluorosubstituted cyclic carbonates, fluorosubstituted acyclic carbonates, fluorosubstituted ethers, perf uoroalkyl phosphoranes, fluorosubstituted phosphites, fluorosubstituted phosphates, fluorosubstituted phosphonates and fluorosubstituted heterocycles.
6. The lithium-air battery cell of claim 5 wherein the fluorosubstituted solvent is selected from the group consisting of monofluoroethylene carbonate, cis-difluoroethylene carbonate, trans-difluoroethylene carbonate,
4,4-dif uoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, 4-fluoro-4-methyl- 1 ,3-dioxolane-2-one, 4-fluoro-4-ethyl- 1,3- dioxolane-2-one, 2,2,2-trifluoroethyl-methyl carbonate, and 2,2,2-trifluoroethyl- fluoromethyl carbonate.
7. The lithium-air battery cell of anyone of claims 3 to 6 wherein the non-fluorinated electrolyte solvent is selected from the group consisting of alkyl carbonates, alkylene carbonates, and ethers.
8. The lithium-air battery cell of claim 7 wherein the non-fluorinated solvent is at least one solvent selected from the group consisting of
1.2- dimethoxyethane, tetraglyme, tetrahydrofuran, 2-methyltetrahydrofuran,
1.3- dioxolane, 4-methyldioxolane, dimethylcarbonate, ethylmethyl carbonate, diethyl carbonate and any mixtures thereof.
9. The lithium-air battery cell of anyone of claims 1 to 8 which further comprises a membrane which is selectively conductive for lithium ions.
10. The lithium-air battery cell of anyone of claims 1 to 9 wherein the electrolyte composition comprises LiPF6 as electrolyte salt.
11. The lithium-air battery cell of claim 10 wherein the concentration of LiPF6 in the electrolyte composition is 1 ± 0.1 mol.
12. The lithium-air battery cell of anyone of claims 1 to 11 wherein the electrolyte composition further comprises a mononitrile with a CI to C20 alkyl chain or a dinitrile with a CI to C20 alkylene chain.
13. The lithium-air battery cell of anyone of claims 1 to 12 wherein the electrolyte composition of the anode compartment and the electrolyte composition of the cathode compartment are identical.
14. The lithium-air battery cell of anyone of claims 1 to 12 wherein the electrolyte composition of the anode compartment is based on an aprotic organic solvent, and the electrolyte composition in the cathode compartment is based on water as solvent.
15. A battery constituted of a multitude of lithium-air battery cells according to anyone of claims 1 to 14.
PCT/EP2012/057169 2011-04-26 2012-04-19 Lithium air battery cell WO2012146525A1 (en)

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US14/113,436 US20140045078A1 (en) 2011-04-26 2012-04-19 Lithium air battery cell
EP12714720.5A EP2702631A1 (en) 2011-04-26 2012-04-19 Lithium air battery cell
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KR20140037850A (en) 2014-03-27
US20140045078A1 (en) 2014-02-13

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