Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
  • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
  • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
• • 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
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • 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
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
  • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
  • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
• • 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
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
  • Y02E60/10—Energy storage using batteries

Definitions

• This invention relates to cyano-substituted salts including cyano- substituted methides and amides.
• salts can often be useful as conductivity additives or enhancers, when dissolved or dispensed in other materials; as cationic polymerization initiators or catalysts; as anti-static additives; as surfactants; and often, in combination with other materials, can be used to conduct electrical charge, for example, as electrolytes (ionic conductors) within electrochemical cells such as batteries, fuel cells, capacitors, supercapacitors and electrochemical sensors, etc.
• these salts should exhibit specific chemical and physical properties to be useful in such applications. First of all they must exhibit good ionic conductivity. In many applications they must also exhibit thermal and electrochemical stability. They should not cause damage to other components of systems in which they are used (e.g., corrosion). They should have acceptable environmental impact; and, they preferably can be produced at an economically feasible price. When employed in electrochemical cells the salts should exhibit good cycling properties and should produce electrochemical cells that can be operated and maintained with minimal concerns for safety. With respect to the very specific application of salt compounds in electrochemical cells, there is both a current and projected future demand for high energy density, lightweight, rechargeable power sources for use in automotive, industrial, and consumer markets.
• lithium-ion battery technology which requires the use of electrolyte salts dissolved in a non-aqueous solvent to act as an electrolyte.
• This electrolyte solution acts as the medium in which ionic conduction can occur between electrodes, providing charge balance within an electrochemical cell, such as a battery.
• electrolyte salts There are currently only a small number of electrolyte salts known to be suitable for use in lithium-ion batteries, and all have identifiable drawbacks.
• the most common electrolyte salt is LiPF 6 , which exhibits good conductivity and corrosion resistance, but is thermally and hydrolytically unstable. Hydrolytically unstable means that exposure to water will cause decomposition to form fluoride ions.
• Other salts having potential uses as lithium electrolytes include LiAsF ⁇ (toxic), LiBF 4 (relatively poor conductivity), and LiClO 4 (potentially explosive).
• organofluorine lithium salts There are also a number of known organofluorine lithium salts, but each of these has its own individual short-comings.
• LiOSO 2 CF 3 and LiN(SO 2 CF 3 ) 2 are thermally very stable but can be corrosive to aluminum current collectors, and LiC(SO 2 CF 3 ) 3 is expensive to produce for most commercial scale applications.
• the battery industry is currently seeking electrolyte salts which can perform at useful conductivity levels, and that are easily handled and can be produced at a reasonable cost.
• (-CN) group and in the case of a methide salt, two cyano groups, have been found useful in applications requiring a high degree of ionic dissociation.
• the salts are especially useful as electrolyte components in electrochemical cells such as batteries, fuel cells, capacitors, supercapacitors, electrochemical sensors and electrolytic cells, by providing a means for ionic conduction and transport.
• the present invention relates to an electrolyte which includes a salt of an N-cyano-substituted amide, (e.g., an N-cyano-substituted carboxamide, or an N-cyano-substituted sulfonamide), a 1,1,1-dicyano- substituted sulfonyl methide, a 1,1,1-dicyanoacyl methide, or a mixture thereof in a matrix material.
• an N-cyano-substituted amide e.g., an N-cyano-substituted carboxamide, or an N-cyano-substituted sulfonamide
• 1,1,1-dicyano- substituted sulfonyl methide e.g., a 1,1,1-dicyanoacyl methide, or a mixture thereof in a matrix material.
• the present invention includes as an electrolyte a matrix material and a salt of the formula R-[Q-X-(CN)neig] y y/mM m+ (I)
• y is 1 or 2;
• X is C or N, which when X is C, n is 2 and when X is N, n is 1 ;
• R is a fluorine atom, a hydrocarbon or a fluorinated hydrocarbon group
• Q is a linking group
• M" 1"1" is a cation having a valence of m.
• a mixture of salts of formula I may also be included in the electrolyte.
• Another aspect of the present invention is an electrochemical cell containing the above described electrolyte, an anode and a cathode.
• a further aspect of the present invention includes certain novel methide and amide salts which are salts of an N-cyano-substituted amide, (e.g., an N- cyano-substituted carboxamide or an N-cyano-substituted sulfonamide), a 1,1,1- dicyano-substituted sulfonyl methide, or a 1,1, 1-dicyanoacyl methide.
• N-cyano-substituted amide e.g., an N- cyano-substituted carboxamide or an N-cyano-substituted sulfonamide
• 1,1,1- dicyano-substituted sulfonyl methide e.g., 1,1,1- dicyano-substituted sulfonyl methide
• 1,1, 1-dicyanoacyl methide e.g., 1,1, 1-dicyanoacy
• novel salts of the invention include methide salts of the formula
• y is 1 or 2;
• R is a fluorine atom or a perfluorinated hydrocarbon group
• M m+ is a cation having a valence of m.
• Novel salts of the invention also include amide salts of the formula
• y is 1 or 2;
• R is a fluorine atom or a perfluorinated hydrocarbon group
• Q is a linking group
• M m+ is a cation having a valence of m.
• Further salts include salts containing polymerizable groups, for example, methide salts of the formula
• y is 1 or 2;
• R is a halogenated or non-halogenated polymerizable group
• Q is a linking group
• M m+ is a cation having a valence of m; and amide salts of the formula
• y is 1 or 2;
• R is a halogenated or non-halogenated polymerizable group; and M m+ is a cation having a valence of m.
• Electrochemical cell includes all electrical energy storage devices and electrolytic cells, including capacitors, supercapacitors, electrochromic devices, electrochemical sensors, fuel cells and batteries.
• Macromolecular material refers to a homopolymer, copolymer, or combination thereof, which may or may not be cross-linked and/or plasticized.
• Gel refers to a physically or chemically cross-linked polymer swollen with solvent.
• Microx or “matrix material” refers to a medium (e.g., a solid, liquid, gel or plasticized polymer) in which electrolyte salts may be dissolved or dispersed to form an ionically conductive electrolyte.
• a medium e.g., a solid, liquid, gel or plasticized polymer
• electrolyte salts may be dissolved or dispersed to form an ionically conductive electrolyte.
• the matrix is liquid; for a “lithium polymer battery,” the matrix is a solid, gel or plasticized polymer.
• “Plasticized polymer” refers to a polymer containing a low molecular weight additive, such as an organic solvent.
• Voltages specified refer to electrical potential differences between a positive electrode measured relative to a Li/Li + reference electrode, except where otherwise noted.
• a "fluorinated hydrocarbon group” may be either a partially or fully fluorinated hydrocarbon group.
• a partially fluorinated hydrocarbon exists where only a portion of the hydrogen atoms in the hydrocarbon have been replaced with fluorine atoms, whereas in a fully fluorinated or perfluorinated hydrocarbon group, essentially all of the hydrogen atoms, e.g. at least 90 %, attached to carbon have been replaced by fluorine.
• an occasional carbon bonded hydrogen atom , bromine atom or chlorine atom may be present. Where present, however, they preferably are present not more than once for every two carbon atoms on the average.
• the non-skeletal valence bonds are preferably carbon-to-fluorine bonds.
• hydrocarbon group refers to a monovalent or divalent straight or branched aliphatic group, a cycloaliphatic group, a cycloaliphatic-aliphatic group, or an aryl, biaryl or aralkyl group. These groups are further defined below.
• a straight or branched aliphatic group refers to a hydrocarbon radical, e.g. an alkyl group, which is either in the form of a straight or branched chain and, in this case, ranging from 1 to 18 carbon atoms or as otherwise designated.
• Cycloaliphatic group is a cyclic group, e.g. a cycloalkyl group, having from 3 to 12 carbon atoms and refers to a cyclic saturated group.
• the group includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
• Alkylene refers to either straight or branched chain divalent organic groups which may join at both ends to another group or groups. Preferred alkylene groups are ethylene and propylene.
• Acyl refers to either a straight, branched or cyclic hydrocarbon group which has a carbonyl group, such as an alkanoyl group, e.g. acetyl, or aroyl, e.g. benzoyl.
• Fluorinated divalent hydrocarbon refers to either straight or branched chain divalent partially fluorinated organic groups which may join at both ends to another group or groups, such as a "fluoroalkylene” group, e.g. fluoroethylene, fluoropropylene and fluorobutylene.
• aryl refers to a substituted or unsubstituted aromatic hydrocarbon, preferably a phenyl or naphthyl group which is unsubstituted or substituted by well recognized aromatic substituents such as, for example, alkyl of 1-4 carbon atoms,
• R includes any group capable of reacting with itself or with other groups.
• R can contain a polymerizable group such as an olefinically unsaturated group (e.g., acrylate or allyl), an epoxide group, an isocyanato group and the like that would allow the amide or methide salt to react with other reactive compounds, including other molecules of the same salt or molecules of a different reactive or polymerizable compound, via grafting or polymerization (cationic, anionic or free radical mechanism) to form a homopolymer or a copolymer.
• a homopolymer or copolymer material would be useful in electrolytes, particularly as single ion conductors.
• the above polymerizable groups include halogenated or non-halogenated groups where the halogenated group preferably contains fluorine atoms as the halogen.
• a heteroatom refers to a heteroatom interrupting a carbon chain, such as for example nitrogen, oxygen, or sulfur.
• An electrolyte is defined as a salt or a combination of salts in a solvent, preferably a non-aqueous solvent.
• the invention is an electrolyte which contains a salt selected from the group consisting of N-cyano-substituted amide (e.g., a N- cyano-substituted carboxamide, or N-cyano-substituted sulfonamide), a 1,1,1- dicyano-substituted sulfomylmethide, a 1,1,1-dicyanoacyl methide and a matrix material. More generally, the invention is an electrolyte which contains a salt of the formula: R-[Q- ⁇ -(CN) n ] y y/mM m+ (I)
• y is 1 or 2
• X is C or N.
• n is 2 and the compound is a methide.
• n is 1 and the compound is an amide.
• Q is a linking group selected from - SO 2 - and -C(O)- and M" 1 ⁇ is a cation having a valence of m.
• Suitable cations, M" + include alkali metal cations (e.g., Li + , Na + , K + and Cs + ), alkaline earth metal cations (e.g., Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ ), Group LUA cations (e.g., Al 3+ ), transition metal cations (e.g., Fe 3+ , Fe 2+ , Zn 2+ , Ti 4+ and Cu 2+ ), rare earth metal cations (e.g., Ce 4+ and La 3+ ), alkylammonium cations (i.e., R 4 N + , where R is independently alkyl, preferably having from 1 to 4 carbon atoms, or hydrogen), sulfonium cations (i.e., R 3 S + ), phosphonium cations (i.e., R ⁇ P ) and protons (i.e., IT " ). Suitable cations also include organol
• Suitable monovalent or divalent organic R groups include a fluorine atom, a hydrocarbon or a fluorinated hydrocarbon group.
• R includes a monovalent or divalent nonfluorinated or fluorinated straight or branched, saturated or unsaturated aliphatic group having 1 to 18 carbon atoms, a cycloaliphatic group of 3 to 12 carbon atoms, a cycloaliphatic-aliphatic group in which the aliphatic group has 1 to 4 carbon atoms, in which the carbon chain of the aliphatic or cycloaliphatic groups are uninterrupted or interrupted by a catenary heteroatom and which the aliphatic or cycloaliphatic group is unsubstituted or substituted by a halogen atom; an aryl or arylaliphatic group, in which said aliphatic group has 1 to 4 carbon atoms, or a reactive group.
• Suitable reactive groups may include those groups containing double bonds (e.g., vinyl, allyl, vinylbenzyl, acryloyl or methacryloyl groups) or those groups containing reactive heterocyclic ring structures (e.g., oxirane (epoxy), oxetane, azetidine or aziridine groups).
• a suitable reactive group may also include those groups containing hydroxyl, amino, isocyanato or trialkylsilyl groups.
• the reactive group can be protected by reactants that are reversibly bound to it. For example, a double bond may be protected as a dihalo derivative and subsequently dehalogenated.
• Particularly preferred electrolytes of the invention include methide and amide salts of the formulae:
• R f is a perfluoroalkyl group of from 1 to 12 carbon atoms.
• the matrix material can be chosen to provide the particular conductivity, viscosity, mechanical strength, and reactivity properties desired for the electrolyte.
• Suitable matrix materials for preparing electrolyte solutions can be liquid, polymeric, or mixtures of polymer and liquid.
• solvent is preferably present in the matrix material, the solvent preferably including a nonaqueous, polar, aprotic, organic solvent.
• solvents are generally dry, having a water content of less than about 100 ppm, preferably less than about 50 ppm.
• Suitable aprotic solvents include linear ethers such as diethyl ether, diethylene glycol dimethyl ether, and 1,2-dimethoxyethane; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dioxolane, and 4-methyldioxolane; esters such as methyl formate, ethyl formate, methyl acetate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, and butyrolactones (e.g., linear ethers such as diethyl ether, diethylene glycol dimethyl ether, and 1,2-dimethoxyethane; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dioxolane, and 4-methyldioxolane; esters such as methyl formate, ethyl formate, methyl acetate
• gamma butyrolactone nitriles such as acetonitrile and benzonitrile; nitro compounds such as nitromethane or nitrobenzene; amides such as N,N- dimethylformamide, N,N-diethylformamide, and N-methylpyrrolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as dimethylsulfone, tetramethylene sulfone, and other sulfolanes; oxazolidinones such as N-methyl-2- oxazolidinone and mixtures thereof.
• nitriles such as acetonitrile and benzonitrile
• nitro compounds such as nitromethane or nitrobenzene
• amides such as N,N- dimethylformamide, N,N-diethylformamide, and N-methylpyrrolidinone
• sulfoxides such as dimethyl sulfoxide
• suitable solid matrix materials include polymers and copolymers such as polyethers like poly(ethylene oxide), polyesters, polyacrylates, polyphosphazenes, polysiloxanes, poly(propylene oxide), fluoropolymers (e.g., poly(vinylidene fluoride)), and poly(acrylonitrile), as well as the polymers and copolymers described in Armand et al., U.S. Patent No. 4,505,997, and mixtures thereof.
• the polymers may be used in cross-linked or uncross-linked form and or plasticized. When used in Li batteries, such materials are generally dry, i.e., have a water content less than about 100 ppm, preferably less than about 50 ppm.
• the matrix material may also include a separator in the case where electrolyte is imbibed in the separator.
• Salts of the invention can be useful in a number of applications that require or gain advantage from the presence of weakly coordinating anions.
• the methide and amide salts of the invention can be useful as conductivity additives, e.g., for coating processes including electrostatic spray coating processes as described in United States Serial No.
• electrolytes e.g., for use within electrochemical cells including but not limited to battery cells, fuel cells, rechargeable battery cells, capacitors, supercapacitors and electrochemical sensors.
• electrolytes e.g., for use within electrochemical cells including but not limited to battery cells, fuel cells, rechargeable battery cells, capacitors, supercapacitors and electrochemical sensors.
• electrolyte salts that can be useful, as well as the specific amount of the salt within an electrolytic composition, can depend on a number of factors, including the desired application within which the electrolyte salt will be used.
• the electrolytic salts of the invention can function as surfactants since the anions will effectively have separate hydrophobic and hydrophilic portions.
• Such surfactant salts have R groups which have 4 or more carbon atoms, preferably 8 or more carbon atoms. Specifically, surfactant salts aid in the wetting of components with the electrolyte without adversely affecting cell performance.
• Conductivities of the electrolyte salts of this invention in typical nonaqueous, polar, aprotic liquid media e.g., propylene carbonate
• the optional solvent may be present at a concentration ranging from about 1 to 95 wt-%.
• the invention is also found in an electrochemical cell utilizing an electrolyte which contains one or more salts of the formula
• y, R, Q, X, n and M m+ are as defined above, an anode, and a cathode.
• the methide or amide electrolyte salts above defined can preferably be employed in a battery electrolyte composition at a concentration such that the conductivity of the electrolyte composition is at or near its maximum value, although a wide range of other concentrations might also be useful for a range of applications.
• concentration of the electrolytic methide or amide salt within a battery electrolyte composition can range from about 0.1M to about 2.0M, and is preferably in a range from about 0.5 to 1.5M, most preferably about 1M.
• particularly useful salts, R and M m+ components thereof can be chosen to be optimal within a specific battery system.
• the salts are useful for maintaining charge balance within the battery.
• an electrolyte salt according to the invention can be mixed with a matrix material such that the electrolyte salt is at least partially dissolved or dispersed in the matrix material ("solvent" is in the class of "matrix materials”).
• solvent is in the class of "matrix materials”.
• Useful and preferred metal cations and matrix materials can depend on the entire construction of the battery, e.g., the cathode, anode, current collector, etc.
• additional salts can include, but are not limited to, alkali metal, alkaline earth metal, alkyl ammonium and Group II B metal (e.g., aluminum) salts of anions such as NO 3 ⁇ BF 4 " ; PF 6 ' ; AsF 6 " ; ClO 4 ' ; SbF 6 ' ; RfSO 3 " (in which Rf is a perfluoroalkyl group having between 1 and 12 carbons, preferably between 4 and 8 carbons); a bis-(perfluoroalkylsulfonyl)imide anion of the formula -N(SO2Rf) (SO 2 R ) in which Rf and Rp 1 are independently perfluoroalkyl groups having between 1 and 12 carbon atoms, inclusive; an (arylsulfonyl) perfluoroalkylsulfony
• R is alkyl or aryl and R f is as previously described;
• Z is -CF 2 -, -O-,
• Rn and R ⁇ independently, are -CF 3 , -CmF 2m+1 , or -(CF 2 ) q -SO 2 - M ;
• R ⁇ , R f4 , and R ⁇ independently, are -CF3, -C m F 2m+ ⁇ , -(CF ) q - SO2-XM + ,
• Rfs is -CF 3 , -C m F 2m+1 , or -(CF 2 ) q -SO 2 -XM + ;
• R f6 and R ⁇ independently, are perfluoroalkylene moieties having the formula -C r F2 r -; n is 1-4; r is 1-4; m is 1-12 preferably 1-8; and q is 1-4; (such salts are described by Waddell, et al. in U.S
• Rf-SO2-C " (R)-SO2-Rf a bis-perfluoroalkylsulfonyl methide anion Rf-SO2-C " (R)-SO2-Rf in which R f and R f , independently, are perfluoroalkyl groups having between 1 and 12 carbon atoms, inclusive, and R is H, Br, CI, I, an alkyl group having between 1 and 20 carbon atoms, inclusive, aryl, or alkylaryl; and a tris- (perfluoroalkylsulfonyl)methide anion of the formula -C(SO 2 Rf) (SO 2 R f ) (SO 2 Rf") in which Rf, R f , and R f ", independently, are perfluoroalkyl groups having between 1 and 12 carbon atoms, inclusive.
• Suitable additional salts include, LiNO 3 , LiBF 4 , LiAsF 6 , LiClO 4 , LiPF 6 , C-jFgSOs i, C 8 F 17 SO 3 Li, (CF 3 SO 2 ) NLi,
• a preferred chemical power source of the present invention relates to a battery that includes at least one cathode, at least one anode, a separator and liquid electrolyte comprising one or more amide or methide salts of the present invention and aprotic solvents.
• the electrodes (i.e., anode and cathode) of, for example, a lithium battery generally consist of a metallic foil and particles of active material blended with a conductive diluent such as carbon black or graphite bound into a plastic material binder.
• Typical binders include polytetrafluoroethylene, polyvinylidene fluoride, ethylene-propylene-diene (EPDM) terpolymer, and emulsified styrene-butadiene rubber (SBR), and the binder may be cross-linked.
• the binder may also be, for example, a solid carbon matrix formed from the thermal decomposition of an organic compound.
• the metallic foil or composite electrode material is generally applied to an expanded metal screen or metal foil (preferably aluminum, copper or nickel) current collector using a variety of processes such as coating, casting, pressing or extrusion.
• the polymer electrolyte can act as the active material binder.
• Suitable anode (negative electrode) materials include but are not limited to lithium metal, lithium metal alloys, sodium metal, carbon-based materials such as graphite, coke, carbon fiber, pitch, transition metal oxides (such as LiTi 5 O ⁇ 2 and LiWO 2 ), and lithiated tin oxide.
• the lithium may be intercalated into a host material such as carbon (i.e., to give lithiated carbon) or carbon alloyed with other elements (such as silicon, boron and nitrogen), a conductive polymer, or an inorganic host that is intercalatable (such as Li x Ti 5 O 12 .)
• a host material such as carbon (i.e., to give lithiated carbon) or carbon alloyed with other elements (such as silicon, boron and nitrogen), a conductive polymer, or an inorganic host that is intercalatable (such as Li x Ti 5 O 12 .)
• the material comprising the anode may be carried on foil (e.g., nickel and copper) backing or pressed into expanded metal screen and alloyed with various other metals.
• cathode (positive electrode) materials include but are not limited to graphite, amorphous carbon, Li x CoO 2 , Li x NiO2, Co-doped
• the cathode can be fluorinated carbon
• Lithium batteries and supercapacitors usually contain a separator to prevent short-circuiting between the cathode and anode.
• the separator usually consists of a single-ply or multi-ply sheet of microporous polymer (typically polyolefin, e.g., polyethylene, polypropylene, or combinations thereof) having a predetermined length and width and having a thickness of less than 10 mils (0.025 cm).
• microporous polymer typically polyolefin, e.g., polyethylene, polypropylene, or combinations thereof
• the pore size in these microporous membranes is sufficiently large to allow transport of ions but is sufficiently small to prevent cathode/anode contact, either directly or from particle penetration or dendrites which can form on the electrodes.
• the invention includes primary and secondary batteries.
• the cathode could be fluorinated carbon (CF x ) n , SO2, SO2CI2, or Ag 2 CrO 4 .
• the invention includes novel methide salts of the formula:
• y is 1 or 2
• R is a fluorine atom or a perfluorinated hydrocarbon group
• M m+ is a cation having a valence of m.
• Suitable cations, M" + include alkali metal cations (e.g., Li + , Na + , K + and Cs + ), alkaline earth metal cations (e.g., Mg 2+ , Ca 2+ , Sr + and Ba 2+ ), Group LIIA cations (e.g., Al 3+ ), transition metal cations (e.g., Fe 3+ , Fe 2+ , Zn 2+ , Ti 4+ and Cu 2+ ), rare earth metal cations (e.g., Ce 4+ and La 3+ ), alkylammonium cations (i.e., R-tjNT, where R is independently alkyl, preferably having from 1 to 4 carbon atoms, or hydrogen) sulfonium ions (i.e., R 3 S + ), phosphonium ions (R-tP + ) and protons (i.e., IT " ).
• alkali metal cations e.g.,
• Suitable cations also include organometallic cations such as ferrocenium cation, cyclopentadienyl (arene)M m+ , (arene)M(CO)3 m+ , (arene)2M m+ ,
• the cation is an alkali metal cation.
• the cation is a lithium cation.
• Suitable monovalent or divalent perfluorinated organic R groups include divalent perfluorinated straight or branched, saturated or unsaturated aliphatic group having 1 to 18 carbon atoms, a perfluorinated cycloaliphatic group of 3 to 12 carbon atoms, a perfluorinated cycloaliphatic-aliphatic group in which the aliphatic group has 1 to 4 carbon atoms, in which the carbon chain of the aliphatic or cycloaliphatic groups are uninterrupted or interrupted by a heteroatom and which the aliphatic or cycloaliphatic group is unsubstituted or substituted by a halogen atom or a reactive group; a perfluorinated aryl or arylaliphatic group, in which said aliphatic group has 1 to 4 carbon atoms.
• R is a perfluorinated alkyl, alkylene , cycloalkyl or aralkyl group in which alkyl, cycloalkyl or aryl group is unsubstituted or substituted by a polymerizable reactive group
• R is a perfluorinated alkyl group of 1 to 12 carbon atoms and, most preferably, a perfluorinated alkyl group of 1 to 4 carbon atoms.
• R groups are perfluorinated hydrocarbons selected from the group consisting of perfluoromethyl and perfluorobutyl.
• Suitable reactive groups may include those groups containing double bonds (e.g., vinyl, allyl, vinylbenzyl, acryloyl or methacryloyl groups) or those groups containing reactive heterocyclic ring structures (e.g., oxirane (epoxy), oxetane, azetidine or aziridine groups).
• groups containing double bonds e.g., vinyl, allyl, vinylbenzyl, acryloyl or methacryloyl groups
• groups containing reactive heterocyclic ring structures e.g., oxirane (epoxy), oxetane, azetidine or aziridine groups.
• Particularly preferred methide compounds of the invention include:
• the invention includes novel amide salts of the formula
• y is 1 or 2
• Q is a linking group selected from -SO 2 - and -C(O)-.
• R is as defined above.
• M m+ is a cation having a valence of m.
• Suitable cations, M m+ include alkali metal cations (e.g., Li + , Na + , K + and Cs*), alkaline earth metal cations (e.g., Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ ), Group IIIA cations (e.g., Al 3+ ), transition metal cations (e.g., Fe 3+ , Fe 2+ , Zn 2+ , Ti 4+ and Cu 2+ ), rare earth metal cations (e.g., Ce 4+ and La 3+ ), alkylammonium cations (i.e., R-jN*, where R is independently alkyl, preferably having from 1 to 4 carbon atoms, or hydrogen), sulfonium cations (i.e., R 3 S + ), phosphonium cations (i.e., F P + ) and protons (i.e., IT).
• alkali metal cations e.
• Suitable cations also include organometallic cations such as ferrocenium cation, cyclopentadienyl (arene)M m+ , (arene)M(CO) 3 m+ , (arene) 2 M m+ , (cyclopentadienyl) 2 M(CH 3 ) m+ , onium cations such as diaryliodium ortriarylsulfurium, wherein M is a transition metal.
• the cation is an alkali metal cation.
• the cation is a lithium cation.
• organometallic cations such as ferrocenium cation, cyclopentadienyl (arene)M m+ , (arene)M(CO) 3 m+ , (arene) 2 M m+ , (cyclopentadienyl) 2 M(CH 3 ) m+
• onium cations such as diarylio
• amide and methide salts can contain reactive moieties which allow the dimerization, trimerization, oligomerization, grafting or polymerization of such reactive amide or methide salts. These compounds can be reacted by known polymerization or grafting reactions methods to create solid, polymerized or copolymerized materials with pendant amide or methide salt groups. Moreover, certain methide and amide salts are preferred embodiments of the present invention which include polymerizable groups. These include methide salts of the formula
• y is 1 or 2;
• R is a halogenated or non-halogenated polymerizable group
• Q is a linking group
• M m+ is a cation having a valence of m; and amide salts of the formula
• y is 1 or 2;
• R is a halogenated or non-halogenated polymerizable group; and M m+ is a cation having a valence of m.
• cyano-containing methides and amides containing perfluorosulfonylalkyl groups can be prepared from the reaction of fluoroalkyl sulfonyl fluorides, RfSO 2 F, with anhydrous malononitrile and cyanamide, respectively, in the presence of a non-nucleophilic base.
• This synthetic procedure is described in Scheme 1 of United States Patent Application Serial No. 08/577,425 for making (bis)fluoroalkylsulfonylimides, wherein either the malononitrile or the cyanamide is substituted for the fluoroalkylsulfonamide.
• the intermediate non-nucleophilic base cation-containing methide or amide salt can be converted to the desired cation salt (typically lithium) via standard methods known in the art. Obvious variations of this synthetic procedure can be used to make methides and amides containing other R groups, as described in United States Patent Application Serial Number 08/937,519.
• Preferred methides can be prepared according to the procedure shown below
• Preferred amides can be prepared according to the procedure shown below:
• Y is a leaving group such as halogen or tosylate
• B is a non- nucleophilic base such as a tertiary amine, e.g. triethylamine or pyridine.
• the reaction can also use inorganic bases, such as, for example, solid anhydrous alkali metal carbonates.
• Perfluoroalkylsulfonyl fluorides can be prepared by a variety of methods known in the chemical art, and as described, for example, in United States Patent Numbers 3,542,864; 5,318,674; 3,423,299; 3,951,762; 3,623,963; 2,732,398; S. Temple, J. Org. Chem.. 33(1), 344 (1968); and D.D. DesMarteau, Inorg. Chem.. 32, 5007 (1993).
• the organic phase was separated and the solvent was removed by reduced pressure distillation.
• the acidic residue was then neutralized and solubilized by stirring for 40 minutes in 300 mL of water containing 15 g of LiOH H 2 O to form the aqueous solution of the crude lithium salt.
• Water was then removed from the lithium salt solution using reduced pressure distillation, and about 100 mL of methyl t-butyl ether (MTBE) was added to dissolve the residue. Insolubles were removed by filtration, and the filtrate was dried over anhydrous MgSO 4 for a day.
• the solution was then filtered to remove the drying agent, decolorizing carbon was added, and the solution was heated to boiling for 3 minutes followed by cooling to room temperature. The carbon was then filtered off, resulting in a pale yellow filtrate.
• MTBE methyl t-butyl ether
• a solution containing 4.0 g of cyanamide, 75 mL of anhydrous acetonitrile and 50 mL of triethylamine was prepared in a flask by stirring under a nitrogen blanket at a temperature of 0°C. Then 32 g of C 4 FgSO2F (88% pure, the remaining 12% being non-functional inert material, available from 3M Company) was added dropwise, and the reaction mixture was warmed to room temperature and stirred overnight.
• the pyridinium salt intermediate was prepared using the following procedure. To a 500 mL flask vented with nitrogen was added 200 g of anhydrous pyridine via cannula (a "cannula” is a long double-ended syringe needle for transferring liquids from a pressurized container sealed with a septum). Then 66 g of malononitrile (available from Aldrich Chem. Co.) was gently heated to past its melting point and was added to the pyridine-containing flask in a similar manner, causing a red solution to form. The red solution was transferred to an evacuated 600 mL stirred monel Parr bomb reactor.
• the reactor and its contents were chilled to a temperature of 0°C with stirring, and CF 3 SO 2 F was slowly added, controlling the addition rate so that the temperature in the reactor never exceeded 10°C.
• the addition of CF 3 SO 2 F continued until the pressure reached 50 psi (2600 torr), as measured at 5°C.
• the reactor and its contents were then heated to 50°C with stirring for 4 hours, during which time the pressure in the reactor dropped from 160 psi (8300 torr) to 120 psi (6200 torr).
• the contents of the reactor were then stirred overnight as the reactor was allowed to cool to room temperature.
• the reactor was vented and was heated to 70°C under vacuum for 45 minutes to remove the volatile products.
• the residue remaining in the reactor was extracted three times with
• the pyridinium salt intermediate was converted to the desired purified lithium salt through a cesium salt intermediate using the following procedure.
• a separatory funnel was added 56 g of pyridinium salt intermediate, 500 mL of MTBE and 500 mL of 2M aqueous H2SO 4 . After shaking, the resulting dark mixture formed two liquid phases, which were separated, and the organic phase was saved. Anhydrous K2CO3 was mixed overnight with the organic phase to dry and neutralize the contents of the phase, resulting next day in the formation of a brown sticky precipitate. The phase with precipitate was filtered and the resulting solids washed with 300 mL of acetonitrile.
• the MTBE samples were combined, stripped of solvent using reduced pressure distillation, and the residue was dissolved in 50 mL of deionized water. To this aqueous solution was added 10 g of cone. H2SO 4 and 50 mL of MTBE. The resulting two phases were mixed and the organic phase was isolated. A molar excess of Li 2 CO 3 was added to neutralize the dicyanomethide acid formed in the organic phase. The resulting lithium salt solution in MTBE was then filtered and concentrated by reduced pressure distillation. Toluene was added to azeotrope the remaining water and MTBE.
• Lithium bis(perfluoroethylsulfonyl) imide was prepared as described in Example 3 of U.S. Pat. No. 5,652,072. The structure of the product was confirmed by 1H and 19 F NMR spectroscopy, which indicated that the purity of the electrolyte salt was 99.9% by weight.
• LiN(SO 2 CF 3 ) 2 The electrolyte salt LiN(SO 2 CF 3 ) 2 used in the examples is commercially available in high purity from 3M Company, St. Paul, Minnesota, as FLUORADTM HQ-115 Lithium Trifluoromethanesulfonimide Battery Electrolyte.
• LiPF 6 electrolyte salt High purity, battery grade LiPF 6 electrolyte salt was purchased from Hashimoto Chemical Co., Ltd. through Biesterfeld Inc., a U.S. distributor.
• reaction mixture in the round bottom flask was allowed to cool in an ice bath with stirring, and 25 mL of triethylamine was added dropwise via syringe. This reaction mixture was then stirred for 48 hours after it was allowed to warm to room temperature. After removing the solvents by reduced pressure distillation using a RotovapTM rotary evaporator, a solution consisting of 5 g LiOH H 2 O in 100 mL deionized water was added to the reaction mixture. The resulting dark aqueous solution became homogeneous after stirring and periodically scraping material from the surface of the flask. Using the RotovapTM rotary evaporator, water was removed from the solution until about half of the original solution volume remained.
• the solution was acidified with 25 g concentrated sulfuric acid, and more water was added to increase the total solution volume to about 100 mL. This acidified solution was then mixed with methylene chloride to extract the organic contents. Using the RotovapTM rotary evaporator, the methylene chloride was removed from the resulting solution, and the residual brown oil was dissolved with heating in a mixture consisting of 100 mL deionized water and 6 g CsCl to form an aqueous brown solution. A spatula of carbon black was added to the solution, the mixture was filtered and filtrate was recrystallized. Solids were isolated and the recrystallization process from water was repeated two more times.
• a solution was prepared consisting of 100 mL THF, 4.0 g of and 0.038g AIBN (2,2'-azobisisobutyronitrile).
• Ionic Conductivity measurements for liquid electrolytes were generally made using a 1 molar (1M) electrolyte derived from carefully purified and dried components.
• the 1M electrolyte was made by dissolving 10 millimoles of electrolyte salt in 10 mL of a 50/50 (vol) mixture of propylene carbonate (PC)/l,2-dimethoxyethane (DME) or ethylene carbonate (EC)/dimethyl carbonate (DMC).
• the repassivation potential of the candidate salt was measured using a cyclic voltammetry test employing aluminum as a working electrode, using the technique generally described in Bard and Faulkner, Electrochemical Methods: Fundamentals and Applications, John Wiley and Sons, New York, 1980, pp. 350- 353.
• the repassivation potential is an excellent predictor of the degree of corrosion to be expected when aluminum is used in an electrode, especially as a current collector.
• a three-electrode cell was used, having aluminum as the working electrode, metallic lithium as the reference electrode and metallic lithium as the auxiliary electrode.
• the aluminum electrode consisted of a 99.9% pure aluminum rod inserted into a polytetrafluoroethylene sleeve to provide a planar electrode having an area of 0.07cm 2 .
• the native metal oxide layer was removed from the aluminum electrode by polishing the electrode with 3 ⁇ m aluminum oxide paper using heptane as a lubricant.
• a lithium wire inserted in a luggin glass capillary served as a reference electrode, and a 10 cm 2 platinum flag was used as the auxiliary electrode.
• the three electrodes and a glass cell for holding the electrolyte were all placed in an oxygen- and moisture-free dry box, and the three electrodes were connected to a potentiostat.
• Each electrolyte salt to be evaluated was dissolved at 1M concentration in a 1:1 (vol) blend of ethylene carbonate: dimethyl carbonate to form the test electrolyte (containing less than 50 ppm water, as determined by Karl Fischer titration), and 10 mL of each test electrolyte was placed in the glass cell.
• a scan at the rate of approximately lmV/sec was taken from 1 V up to at least 5 V (vs. the reference electrode), followed by gradually returning the potential to 1 V, and the current was measured as a function of voltage potential.
• the repassivation potential was defined as that voltage at which the measured current of the hysteresis loop fell precipitously back to a value close to the currents measured during the early part of the forward scan (i.e., the point of inflection on the curve).
• Redox Stability The redox potential of the candidate salt was measured using a cyclic voltammetry test employing a glassy carbon electrode.
• the redox potential is an excellent predictor of the electrochemical stability of the salt in the electrolyte - the higher the potential, the more stable the salt.
• the same three-electrode cell and test procedure was used as described in the just-described repassivation potential test procedure, except that a glassy carbon rod was substituted for the aluminum working electrode.
• the redox potential was defined as that voltage at which the measured current of the hysteresis loop fell precipitously back to a value close to the currents measured during the early part of the forward scan (i.e., the point of inflection on the curve). All electrolyte salt measurements were made at 1 M in 50/50 (vol) ethylene carbonate/dimethyl carbonate.
• the chronoamperometry test was run (1) to measure residual current density as a function of applied voltage and time and (2) to determine total charge passed during the voltage pulse. Again this test was run using the same electrode cell setup described in the repassivation test procedure, being careful to exclude both water and air from the cell. The aluminum electrode was also polished as described in this procedure. Current vs. time was measured was measured at two different voltage pulses over a period of 1 hour, with the applied voltage of 4.2 V.
• the current after the 1 hour pulse should fall to less than 5 ⁇ A cm 2 .
• Cyano-substituted perfluoroalkylsulfonyl amide and methide electrolyte salts of this invention were compared in a battery electrolyte solution to state-of-the-art electrolyte salts (Comparative Examples C1-C3) for ionic conductivity and aluminum repassivation potential.
• the battery electrolyte solution consisted of a 1M solution of the test electrolyte salt in a dry solvent blend of 50:50 (volume) propylene carbonate:dimethoxyethane. Results of these measurements are shown in Table 1.
• CF 3 SO 2 C(Li)(CN) 2 and C 4 F 9 SO 2 C(Li)(CN) 2 were measured for redox stability and were both found to be electrochemically stable against glassy carbon above the normal operating voltage of a typical lithium ion cell. CF 3 SO 2 C(Li)(CN) 2 did not oxidize below 4.6 V (vs. Li Li 4 ), while
• the ionic conductivity of a solid polymer electrolyte containing a dicyano-substituted perfluoroalkylsulfonyl methide electrolyte salt was determined.
• a formulation having a lithium: oxygen atomic ratio of 1:10 was prepared by dissolving 1.0 g of C F 9 SO 2 C(Li)(CN) 2 and 1.2 g of polyethylene oxide polymer (mol. wt. about 900,000, available from Aldrich Chemical Co.) in 25 mL of CH 3 CN.
• the resulting viscous formulation was coated onto a 3M silicone- coated polypropylene release liner using a 6 inch (15 cm) bladed coater to form a coating approximately 40 mils (1000 microns) thick.
• the wet coating was allowed to air-dry for 1 hour under ambient conditions, then was vacuumed dried for 5 hours at 100°C to form an electrolyte film having a thickness of approximately 4 to 5 mils (100 to 125 microns).
• a cell was then constructed by placing the freshly made electrolyte film between two stainless steel electrodes, each having a diameter of 2.5 cm. The cell was then inserted into a cell holder kept in a dry box, and conductivity was measured in mS/cm using the same measuring instruments as were previously described for the measurement of ionic conductivity for liquid electrolytes. The measured ionic conductivity value was
• the ionic conductivity and glass transition temperature of a solid polyethylene oxide electrolyte containing homopolymer electrolyte salt (HPES) was determined.
• An electrolyte having an Li:O ratio of 1 : 10 was prepared by combining
• the electrolyte/aluminum layer was placed in a dry-box between two stainless steel electrodes and then held under pressure by a conductivity measurement device.
• the impedance of this solid polymer electrolyte was measured using the same electrochemical instruments as described in the liquid electrolyte example.
• the bulk conductivity as calculated from the impedance was 1.10 x 10 '7 S cm -1 at room temperature.
• the DSC of this electrolyte showed that the T g was - .8°C and the T m was 15°C.

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