Non-aqueous electrolytes for lithium ion batteries

• US 20060210883A1
• Filed: 03/10/2006
• Published: 09/21/2006
• Est. Priority Date: 03/15/2005
• Status: Active Grant

• Current Assignee: U Chicago Argonne, LLC
• Original Assignee: University of Chicago
• Inventors: Amine, Khalil, Chen, Zonghai
• Granted Patent: US 9,184,428 B2
• Time in Patent Office: Days
• US Class Current: 429/326
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0566 Liquid materials
• 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 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1315 containing halogen atoms, e.g. LiCoOxFy
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 50/417 Polyolefins
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

Claims

1. An electrolyte comprising:

a lithium salt;

a polar aprotic solvent; and

an additive at a concentration of 0.0005 M to 0.05 M, wherein the additive is an anion receptor that assists in the dissolution of LiF on the surface of electrodes.

2. The electrolyte of claim 1, wherein the anion receptor is a Lewis acid.

3. The electrolyte of claim 1, wherein the anion receptor has the Formula I:

4. The electrolyte of claim 3, wherein the anion receptor has the Formula IA:

5. The electrolyte of claim 4, wherein L is a C_2-3 alkylene group, optionally substituted with one or more halogens.

6. The electrolyte of claim 3, wherein the anion receptor has Formula II:

7. The electrolyte of claim 6, wherein the anion receptor has Formula IIA or

8. The electrolyte of claim 7, wherein L is a C_2-3 alkylene group optionally substituted with one or more halogens, and L′

is a C_1-2 alkylene group, optionally substituted with one or more halogens.

9. The electrolyte of claim 3, wherein the anion receptor has Formula III:

10. The electrolyte of claim 9, wherein the anion receptor has the Formula IIIA or IIIB:

11. The electrolyte of claim 3, wherein the anion receptor has Formula IV:

12. The electrolyte of claim 11, wherein the anion receptor has Formula IVA:

13. The electrolyte of claim 12, wherein L″

is absent or is a methylene group, optionally substituted with one or more halogens.

14. The electrolyte of claim 3, wherein the anion receptor has Formula VA or VB:

15. The electrolyte of claim 1, wherein the additive is tris(1,1,1,3,3,3-hexafluoro-propan-2-yl)borate, tris(1,1,1,3,3,3-hexafluoro-2-phenyl-propan-2-yl)borate, tris(1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)borate, triphenylborate, tris(4-fluorophenyl)borate, tris(2,4-difluorophenyl)borate, tris(2,3,5,6-tetrafluorophenyl)borate, tris(pentafluorophenyl)borate, tris(3-(trifluoromethyl)phenyl)borate, tris(3,5-bis(trifluoromethyl)phenyl)borate, tris(pentafluorophenyl)borane, 2-(2,4-difluorophenyl)-4-fluoro-1,3,2-benzodioxaborole, 2-(3-trifluoromethylphenyl)-4-fluoro-1,3,2-benzodioxaborole, 2,5-bis(trifluoromethyl)phenyl-4-fluoro-1,3,2-benzodioxaborole, 2-(4-fluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole, 2-(2,4-difluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole, 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole, 2-(2-trifluoromethyl)phenyltetrafluoro-1,3,2-benzodioxaborole, 2,5-bis(trifluoromethyl)phenyl-tetrafluoro-1,3,2-benzodioxaborole, 2-phenyl-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2-benzodioxaborolane, 2-(3,5-difluorophenyl)-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2-dioxaborolane, 2-pentafluorophenyl-4,4,5,5-tetrakis-(trifluoromethyl)-1,3,2-dioxaborolane, bis(1,1,1,3,3,3-hexafluoroisopropyl)phenylboronate, bis(1,1,1,3,3,3-hexafluoroisopropyl)-3,5-difluorophenylboronate, bis(1,1,1,3,3,3-hexafluoro-isopropyl)(pentafluorophenyl)boronate, or a mixture of any two or more thereof.

16. The electrolyte of claim 1, wherein the lithium salt is Li[PF₂(C₂O₄)₂], Li[B(C₂O₄)₂], Li[BF₂(C₂O₄)], LiClO₄, LiBF₄, LiAsF₆, LiPF₆, LiCF₃SO₃, Li[N(CF₃SO₂)₂], Li[C(CF₃SO₂)₃], Li[N(SO₂C₂F₅)₂], lithium alkyl fluorophosphates, or a mixture of any two or more thereof.

17. The electrolyte of claim 1, wherein the lithium salt is other than Li[PF₂(C₂O₄)₂], Li[B(C₂O₄)₂], or Li[BF₂(C₂O₄)], and the electrolyte further comprises about 0.001 to about 8 wt % of an electrode stabilizing additive that is Li[PF₂(C₂O₄)₂], Li[B(C₂O₄)₂], Li[BF₂(C₂O₄)], or a mixture of any two or more thereof.

18. The electrolyte of claim 1, wherein the polar aprotic solvent is ethyl acetate, propyl acetate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diethyl ether, methyl acetate, gamma-butyrolactone, sulfolane, or a mixture of any two or more thereof.

19. The electrolyte of claim 1, further comprising an electrode stabilizing additive that can be decomposed on the surface of a negative electrode to form a passivation film on the surface of negative electrode.

20. The electrolyte of claim 1, further comprising an electrode stabilizing additive that can be decomposed on the surface of positive electrode to form a passivation film on the surface of the positive electrode.

21. The electrolyte of claim 1, further comprising an electrode stabilizing additive selected from 1,2-divinyl furoate, 1-vinylazetidin-2-one, 1-vinylaziridin-2-one, 1-vinylpiperidin-2-one, 1-vinylpyrrolidin-2-one, 2,4-divinyl-1,3-dioxane, 2-amino-4-vinylcyclobutanone, 1,3-dimethyl butadiene, 2-amino-5-vinylcyclopentanone, 2-vinyl-aminocyclopropanone, 2-vinyloxy-cyclopropanone, 3-(N-vinylamino)-cyclohexanone, 3,5-divinyl furoate, 3-vinylazetidin-2-one, 3-vinylpyrrolidin-2-one, 4,4-divinyl-3-dioxolan-2-one, 5-vinylpiperidin-3-one, allylglycidyl ether, butadiene, butadiene monoxide, butyl vinyl ether, dihydropyran-3-one, divinyl butyl carbonate, divinyl carbonate, divinyl crotonate, divinyl ether, divinyl ethylene carbonate, divinyl ethylene silicate, divinyl ethylene sulfate, divinyl ethylene sulfite, divinyl methoxypyrazine, divinyl methylphosphate, divinyl propylene carbonate, ethyl phosphate, methyl phosphate, oxetan-2-yl-vinylamine, oxiranylvinylamine, piperidine, triethanolamine, trivinylphosphate, vinyl carbonate, vinyl crotonate, vinyl cyclopentanone, vinyl ethyl-2-furoate, vinyl ethylene carbonate, vinyl ethylene silicate, vinyl ethylene sulfate, vinyl ethylene sulfite, vinyl methacrylate, vinyl phosphate, vinyl piperidine, vinyl-2-furoate, vinylcylopropanone, vinylethylene oxide, β

-vinyl-γ

-butyrolactone, alkyloxy, alkenyloxy, aryloxy, methoxy, allyloxy groups, 2-amino-3-vinylcyclohexanone, 2-vinylaminocyclohexanol, 2-vinyloxetane, 2-vinyl-[1,2]oxazetidine, 3-vinylcyclobutanone, 3-vinylcyclopentanone, 3-vinyloxaziridine, 3-vinyloxetane, 1,3-butadiene carbonate, 4-vinyltetrahydropyran, 2-amino-3-vinylcyclopropanone, 3-vinylaziridin-2-one, (divinyl)(methoxy)(trifluoro)cyclotriphosphazene compounds, (trivinyl)(difluoro)(methoxy)-cyclotriphosphazene compounds, (vinyl)(methoxy)(tetrafluoro)cyclotriphosphazene compounds, (aryloxy)(tetrafluoro)(methoxy)cyclotriphosphazene compounds, (diaryloxy)(trifluoro)(methoxy)cyclotriphosphazene compounds, 1,2-diphenyl ether, 1,2-diphenylethane, 1-divinylimidazole, 2,4-dimethyl-6-hydroxy-pyrimidine, 2,4-divinyl isooxazole, 2-aryl-cyclopropanone, 2-aryloxycyclopropanone, 2-diaryloxy-furoate, 3,4-divinyl-1-methyl pyrrole, 3-vinyltetrahydrofuran, 4-allylanisole, allylanisole, aryloxpyrrole, aryloxy ethylene sulfate, aryloxy-2-furoate, aryloxycarbazole, aryloxy-crotonate, aryloxy-cyclobutane, aryloxy-cyclopentanone, aryloxy-cyclophosphazene, aryloxy-cyclopropanone, aryloxy-ethyl-2-furoate, aryloxy-ethylene silicate, aryloxy-ethylene sulfate, aryloxy-ethylene sulfite, aryloxy-imidazole, aryloxy-methacrylate, aryloxy-o-terphenyl, aryloxyoxetane, aryloxy-phenyl carbonate, aryloxy-phosphate, aryloxy-piperidine, aryloxypyrazine, aryloxypyridazine, aryloxy-pyrrole, aryloxy-quinoline, aryloxy-tetrahydrofuran, biphenyl, butyl-aryloxy-ether, diaryloxy ethylene carbonate, diaryloxy furan, diaryloxy methyl phosphate, diaryloxy-butyl carbonate, diaryloxy-crotonate, diaryloxy-cyclotriphosphazene, diaryloxy-diphenyl ether, diaryloxy-ethyl silicate, diaryloxy-ethylene silicate, diaryloxy-ethylene sulfate, diaryloxyethylene sulfite, diaryloxy-phenyl carbonate, diaryloxy-propylene carbonate, diphenyl carbonate, diphenyl diaryloxy silicate, diphenyl divinyl silicate, diphenyl ether, diphenyl silicate, divinyl diphenyl ether, divinyl furan, divinyl methoxy furan, divinyl methoxybipyridine, divinyl methoxydiphenyl ether, divinyl phenyl carbonate, divinylpyrazine, imidazole, indole, isoquinoline, methoxy-4-vinylbiphenyl, methoxycarbazole, methoxy-o-terphenyl, naphthalene, N-methyl pyrrole, o-terphenyl, pyrazine, pyridazine, pyridine, pyrimidine, quinoline, quinoxaline, (tetrahydro-furan-2-yl)-vinylamine, vinyl imidazole, vinyl indole, vinyl isoquinoline, vinyl methoxy carbazole, vinyl methoxy imidazole, vinyl methoxy piperidine, vinyl methoxypyrazine, vinyl methoxyquinoline, vinyl methyl carbonate, vinyl pyrazine, vinyl pyridazine, vinyl pyridazine, vinyl pyridine, vinyl pyrimidine, vinyl quinoline, vinyl quinoxaline, vinylmethoxy pyrrole, vinyl-tetrahydrofuran, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-divinyl-2,4,8-trioxaspiro[5.5]undecane, 3,9-divinyl-2,4-dioxaspiro[5.5]undecane, 3,9-diethylidene-2,4,8, 10-tetraoxaspiro[5.5]undecane, 3,9-diethylidene-2,4,8-trioxaspiro[5.5]undecane, 3,9-diethylidene-2,4-dioxaspiro[5.5]undecane, 3,9-dimethylene-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-divinyl-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-dimethylene-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-diethylidene-1,5,7,11-tetraoxaspiro[5.5]undecane, or a mixture of any two or more thereof.

22. The electrolyte of claim 1, further comprising an electrode stabilizing additive that is a substituted or unsubstituted spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group, wherein the electrode stabilizing additive has Formula VI:

23. The electrolyte of claim 22, wherein the electrode stabilizing additive is 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-divinyl-2,4,8-trioxaspiro[5.5]undecane, 3,9-divinyl-2,4-dioxaspiro[5.5]undecane, 3,9-diethylidene-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-diethylidene-2,4,8-trioxaspiro[5.5]undecane, 3,9-diethylidene-2,4-dioxaspiro[5.5]undecane, 3,9-dimethylene-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-divinyl-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-dimethylene-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-diethylidene-1,5,7,11-tetraoxaspiro[5.5]undecane, or a mixture of any two or more thereof.

24. The electrolyte of claim 20, wherein the electrode stabilizing additive is present at a concentration of about 0.001 to about 8 wt %.

26. An electrochemical device comprising:

a cathode

an anode; and

an electrolyte of claim 1.

25. A method of preparing an electrolyte, comprising combining a lithium salt;

a polar aprotic solvent; and

an anion receptor additive that assists in the dissolution of LiF in an amount sufficient to provide a concentration of anion receptor additive at 0.0005 M to 0.05 M.