FLUORIDE ION BATTERY COMPOSITIONS

• US 20120164541A1
• Filed: 10/14/2011
• Published: 06/28/2012
• Est. Priority Date: 12/22/2010
• Status: Active Grant

• Current Assignee: California Institute of Technology
• Original Assignee: Contour Energy Systems, Inc.
• Inventors: Darolles, Isabelle, Weiss, Cedric M., Alam, Maksudul M., Tiruvannamalai, Arunkumar, Jones, Simon Christopher
• Granted Patent: US 9,166,249 B2
• Time in Patent Office: Days
• US Class Current: 429/326
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/0045 Room temperature molten salts comprising at least one organic ion
• CPC Class Codes: H01M 6/164 by the solvent
• CPC Class Codes: H01M 6/166 by the solute
• CPC Class Codes: H01M 6/168 by additives
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A lithium-free, anion based charge transport electrochemical system that uses fluoride ion transporting electrolytes, including ionic liquids, with and without various additives to improve performance, is described. The fluoride ion transporting electrolyte can be wholly or partly an ionic liquid that is typically liquid at temperatures less than 200 degrees Celsius. In other embodiments, electrolytes that remain liquid at less than 100 degrees Celsius are useful.

Claims

1. A fluoride ion battery comprising:

an anode

a cathode,

an electrolyte comprising an ionic liquid solvent, and a dissolved fluoride salt that is liquid at a temperature less than 200 degrees Celsius.

2. The fluoride ion battery of claim 1, wherein the electrolyte further comprises an additive that reduces viscosity of the ionic liquid solvent.

3. The fluoride ion battery of claim 1, wherein the electrolyte is liquid at a temperature of less than 100 degrees Celsius.

4. The fluoride ion battery of claim 1, wherein the electrolyte further comprises a fluoride complexing species comprising at least one of boron, aluminum, ammonium, aza ether, or an H-bond donor.

5. The fluoride ion battery of claim 4, wherein the fluoride complexing species comprises at least one of:

tris(hexafluoroisopropyl)borate;

tris(pentafluorophenyl)borane;

difluorophenyl boroxin, and regioisomers thereof;

trifluorophenyl boroxin;

bis(trifluoromethyl)phenyl boroxin;

trifluoromethyl)phenyl boroxin; and

, fluoro(trifluoromethyl)phenyl boroxin.

6. The fluoride ion battery of claim 1, wherein the ionic liquid solvent comprises at least one of 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide;

butyltrimethylammonium bis(trifluoromethanesulfonyl)imide;

1-butyl,1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide;

or fluoroalkylphosphate anion derivatives thereof, optionally comprising a hydrophobic anion.

7. The fluoride ion battery of claim 1, wherein electrochemical reactions between the anode and the cathode are reversible to allow a rechargeable battery.

8. The fluoride ion battery of claim 1, wherein electrochemical reactions between the anode and the cathode are substantially irreversible to form a primary battery.

9. A fluoride ion battery comprising:

an anode

a cathode,

an electrolyte comprising a dissolved fluoride salt at least partially dissolved in a solvent, and

an additive comprising a fluoride ion complexing species.

10. The fluoride ion battery of claim 9, wherein the fluoride complexing species comprises at least one of boron, aluminum, ammonium, aza ether, or an H-bond donor.

11. The fluoride ion battery of claim 9, wherein the fluoride complexing species comprises at least one of tris(hexafluoroisopropyl)borate, tris(pentafluorophenyl)borane, regioisomers of difluorophenyl boroxin, trifluorophenyl boroxin, bis(trifluoromethyl)phenyl boroxin, trifluoromethyl)phenyl boroxin or fluoro(trifluoromethyl)phenyl boroxin.

12. The fluoride ion battery of claim 9, wherein the solvent further comprises an ionic liquid comprising at least one of 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl,1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, or fluoroalkylphosphate anion derivatives thereof.

13. The fluoride ion battery of claim 9, wherein the solvent further comprises an organic liquid comprising one ore more members of a group consisting of nitriles, amines, ethers, carbonates, nitro-containing compounds, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated compounds, sulfoxides, sulfones, amides, esters, alcohols, heterocyclic compound, linear and cyclic alkyls optionally substituted with one or more of these functional groups.

14. A fluoride ion battery comprising:

a substantially lithium-free anode and cathode, with at least one of the anode or cathode containing fluorine, and

a substantially lithium-free liquid electrolyte comprising an ionic liquid, wherein the electrolyte is liquid at some temperature less than 200 degrees Celsius.

15. The fluoride ion battery of claim 14, wherein the solvent comprises at least one of acetone, acetonitrile, benzonitrile, 4-fluorobenzonitrile, pentafluorobenzonitrile, triethylamine, diisopropylethylamine, 1,2-dimethoxyethane, ethylene carbonate, propylene carbonate, γ

-butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl methyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, nitromethane, benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, dimethylsulfoxide, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, carbon disulfide, ethyl acetate, methyl butyrate, n-propyl acetate, methyl propionate, methyl formate, 4-methyl-1,3,-dioxolane, pyridine, methyl isobutyl ketone, methyl ethyl ketone, hexamethylphosphoramide, hexamethylphosphorus triamide, 1-methyl-2-pyrrolidinone, 2-methoxyethyl acetate, trimethyl borate, triethylborate and substituted derivatives thereof, ethylmethylsulfone, trimethylene sulfone, 1-methyltrimethylene sulfone, ethyl-sec-butyl sulfone, ethyl isopropyl sulfone, 3,3,3-trifluoropropylmethyl sulfone, and 2,2,2-trifluoroethyl sulfone.

16. The fluoride ion battery of claim 14, wherein the organic-soluble fluoride salt comprises at least one of:

1,2-bis(dimethylamino)-1,2-bis(dimethylammonium)ethene difluoride;

hexamethylguanidinium fluoride;

1-propyl, 1-methyl-piperidinium fluoride;

1,3,3,6,6,-hexamethylpiperidinium fluoride;

1-methylhexamethylenetetramine fluoride;

tetramethylphosphonium fluoride;

tetraphenylphosphonium fluoride;

phenyltrimethylphosphonium fluoride;

trimethylsulfonium fluoride;

tetramethylammonium fluoride;

neopentyltrimethylammonium fluoride;

cobaltocenium fluoride;

poly(1,1-dimethyl-3,5-dimethylene piperidinium)fluoride;

dimethylpropyltrimethylammonium fluoride;

1-adamantyltrimethylammonium fluoride;

phenyltrimethylammonium fluoride;

cobaltocenium fluoride;

poly(1,1-dimethyl-3,5-dimethylene piperidinium)fluoride;

an alkylammonium or substituted alkylammonium cation R¹R²R³S⁺ F⁻

, wherein R¹, R² and R³ are independently and optionally substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group;

an alkylammonium or substituted alkylammonium cation, wherein one or more R-groups is joined to two or more alkylammonium cations to provide a dimer, oligomer or polymer (R¹R²R³R⁴N⁺)_x(F⁻

)_x , wherein R¹, R², R³ and R⁴ are independently and optionally substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group, and wherein x is 2 to 50;

an alkylguanidinium and substituted alkylguanidinium cation (R¹R²N)₃—

C⁺ F⁻

, wherein R¹, R², R³ and R⁴ are independently and optionally substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group;

a fluoride salt in the form of X+ F—

wherein X is a heterocyclic cation, in the heterocyclic ring comprises 4 to 7 atoms;

optionally benzoannelated, polycyclic, and substituted at one or more positions with a substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group;

a phosphazene or phosphazenium-containing compound, optionally selected from 1,1,1,3,3,3 -hexakis(dimethylamino)diphosphazenium fluoride and tetrakis[tris(dimethylamino)-phosphoranylidenamino]phosphonium fluoride;

an alkylphosphonium or substituted alkylphosphonium cation R¹R²R³R⁴P+ F—

wherein R¹, R², R³ and R⁴ may each be separately a substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group;

alkylsulfonium or substituted alkylsulfonium cation R¹R²R³S+ F—

, wherein R¹, R² and R³ are optionally and independently substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group; and

,

a cation polymer compound comprising —

[Z-Het+-X-Het+-]-n, wherein Het is a heterocyclic cation comprising 4-7 atoms;

optionally benzoannelated, polycyclic and substituted at one or more positions with a substituted or unsubstituted, linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl groups;

wherein Z and X are spacer groups comprising at least one of CH₂, CMe₂, SiMe₂, SO₂, P═

O, C₂ to C₅₀, aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or a substituted aryl group, and n is 1 to 8.

17. The fluoride ion battery of claim 14, wherein the organic-soluble fluoride salt comprises a metal-organic, substituted metal-organic or metal-coordination complex species

[R¹,R²,R³R^N . . . M]ⁿ⁺F_n⁻

wherein R¹, R²,R³,R^N comprise a ligand species selected from at least one of a carbocyclic or heterocyclic organometallic ligand, n is independently 1 to 8 for each occurrence, N is 1 to 8, and M is metal species.

18. The fluoride ion battery of claim 17, wherein the carbocyclic or heterocyclic organometallic ligand comprises at least one of a cyclopentadienyl, benzene, cyclobutadiene, pyridine, phenanthroline or phosphacyclopentadienyl, isolobal analogues thereof, optionally substituted with a linear or branched, C₁ to C₅₀ aliphatic or cyclic aliphatic, fluoroalkyl, oligo(ethyleneglycol), aryl or substituted aryl group, alkyl, alkene, alkyne, alkynyl, carbonyl, amine, phosphine, halide, hydride, nitrile, or isonitrile.

19. The fluoride ion battery of claim 17, wherein the metal species comprises a main-group metal, transition metal or lanthanide metal.

22. The fluoride ion battery of claim 14, wherein the solvent is an ionic liquid solvent comprising at least one of 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide;

butyltrimethylammonium bis(trifluoromethanesulfonyl)imide;

1 -butyl, 1 -methylpyrrolidinium bis(trifluoromethanesulfonyl)imide;

or fluoroalkylphosphate anion derivatives thereof.

20. A fluoride ion battery comprising

an anode

a cathode, and

an electrolyte comprising at least one of a room temperature ionic liquid fluoride or acidic ionic liquid fluoride.

21. The fluoride ion battery of claim 20, wherein the room temperature ionic liquid fluoride or acidic ionic liquid fluoride comprises

X⁺ F⁻

(HF)_n,

wherein X⁺ comprises at least one of an organic-soluble cation, wherein n is 0 to 5;

acidic 1-ethyl-3-methylimidazolium fluoride (EMIF.(HF)_2.3);

or acidic 1-methyl-1-propylpiperidinium fluoride (MPPF.(HF)_n) wherein n is about 2.3.