# US 2006/0134527 A1 · Long life lithium batteries with stabilized electrodes

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- Number: US 2006/0134527 A1
- Document ID: US20060134527A1
- Status: Published application
- Kind: A1
- Application number: 11/297,120
- Filed: 2005-12-08
- Published: 2006-06-22
- Earliest claimed: 2004-12-16
- Assignees: The University of Chicago
- Inventors: Khalil Amine; Jun Liu; Donald Vissers; Wenquan Lu
- Web page: https://patentgrep.com/patent/US20060134527A1

## CPC

- H01M 10/0567: characterised by the additives
- H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M 4/366: {as layered products}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0568: characterised by the solutes
- H01M 10/0569: characterised by the solvents
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

## Claims

### Claim 1

An electrolyte comprising:
an alkali metal salt;
a polar aprotic solvent; and
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 electrolyte is substantially non-aqueous.

### Claim 2 (depends on 1)

The electrolyte of claim 1, wherein the electrode stabilizing additive contains 1, 2, 3, 4, 5, or 6 oxygen atoms.

### Claim 3 (depends on 1)

The electrolyte of claim 1, wherein the electrode stabilizing additive has 1 or 2 alkenyl groups.

### Claim 4 (depends on 1)

The electrolyte of claim 1, wherein the electrode stabilizing additive has the Formula I:
wherein
X1, X2, X3, and X4 are independently O or CR3R4; provided that X1 is not O when Y1 is O, X2 is not O when Y2 is O, X3 is not O when Y3 is O, and X4 is not O when Y4 is O;
Y1, Y2, Y3, and Y4 are independently O or CR3R4; provided that Y1 is not O when X1 is O, Y2 is not O when X2 is O, Y3 is not O when X3 is O, and Y4 is not O when X4 is O;
R1 and R2 are independently a substituted or unsubstituted divalent alkenyl or alkynyl group; and
R3 and R4 at each occurrence are independently H, F, Cl, a substituted or an unsubstituted alkyl, alkenyl, or alkynyl group.

### Claim 5 (depends on 4)

The electrolyte of claim 4, wherein at least one of X1, X2, X3, and X4 is O.

### Claim 6 (depends on 4)

The electrolyte of claim 4, wherein X1 is O.

### Claim 7 (depends on 4)

The electrolyte of claim 4, wherein each of X1, X2, X3, and X4 is O.

### Claim 8 (depends on 4)

The electrolyte of claim 4, wherein R1 and R2 are the same.

### Claim 9 (depends on 8)

The electrolyte of claim 8, wherein R1 and R2 are each CH—CH═CH2, C═CH2, or C═CHCH3.

### Claim 10 (depends on 4)

The electrolyte of claim 4, wherein at each occurrence R3 and R4 are each H.

### Claim 11 (depends on 4)

The electrolyte of claim 4, wherein the 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.

### Claim 12 (depends on 1)

The electrolyte of claim 1, wherein the stabilizing additive is present in an amount of about 0.0005 to about 15 wt %.

### Claim 13 (depends on 1)

The electrolyte of claim 1, wherein the stabilizing additive is present in an amount of about 0.0005 to about 2 wt %.

### Claim 14 (depends on 1)

The electrolyte of claim 1, wherein the alkali metal salt is a lithium salt.

### Claim 15 (depends on 1)

The electrolyte of claim 1, wherein the alkali metal salt is Li[(C2O4)2B], Li(C2O4)BF2, LiPF2C4O8, LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, Li(CF3SO2)2N, Li(CF3SO2)3C, LiN(SO2C2F5)2, lithium alkyl fluorophosphates, or a mixture of any two or more thereof.

### Claim 16 (depends on 1)

The electrolyte of claim 1, wherein the alkali metal salt is lithium(chelato)borate.

### Claim 17 (depends on 1)

The electrolyte of claim 1, wherein the alkali metal salt is Li(C2O4)BF2, Li[(C2O4)2B], or a mixture of any two or more thereof.

### Claim 18 (depends on 1)

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, dimethyl ether, diethyl ether, methyl-acetate, gamma-butyrolactone, or a mixture of any two or more thereof.

### Claim 19

An electrolyte comprising:
an alkali metal salt;
a polar aprotic solvent; and
an electrode stabilizing additive having Formula II:
wherein,
X1 and X2 are independently O, CHR3, CHR4, or CR3R4; provided that X1 is not O when Y1 is O, and X2 is not O when Y2 is O;
Y1 and Y2 are independently O, CHR3, CHR4, or CR3R4; provided that Y1 is not O when X1 is O and Y2 is not O when X2 is O;
R1 and R2 are independently a substituted or unsubstituted divalent alkenyl or alkynyl group;
R3 and R4 at each occurrence are independently H, F, Cl, a substituted or an unsubstituted alkyl, alkenyl, or alkynyl group; and
wherein the electrolyte is substantially non-aqueous.

### Claim 20 (depends on 19)

The electrolyte of claim 19, wherein the electrode stabilizing additive is 2,4-divinyl-tetrahydropyran, 2,5-divinyl-tetrahydropyran, 2,6-divinyl-tetrahydropyran, 2,5-divinyl-[1,4]dioxane, 2,5-divinyl-[1,3]dioxane, 2-ethylidene-5-vinyl-[1,3]dioxane or a mixture of any two or more thereof.

### Claim 21 (depends on 1)

A method of making the electrolyte of claim 1, the method comprising combining
an alkali metal salt;
a polar aprotic solvent; and
an electrode stabilizing additive that is a spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group.

### Claim 22

An electrolyte comprising:
an alkali metal salt;
a polar aprotic solvent;
a first 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; and
a second electrode stabilizing additive that is capable of stabilizing the anode;
wherein the electrolyte is substantially non-aqueous.

### Claim 23 (depends on 22)

The electrolyte of claim 22 wherein the second electrode stabilizing additive is selected from vinyl ethylene carbonate, vinyl carbonate, a lithium(chelato)borate, a lithium(chelato)phosphate, a cyclotriphosphazene, or a mixture of any two or more thereof.

### Claim 24 (depends on 23)

The electrolyte of claim 23, wherein the lithium(chelato)borate is selected from Li(C2O4)2B, Li(C2O4)BF2, or a mixture thereof.

### Claim 25 (depends on 23)

The electrolyte of claim 23, wherein the lithium(chelato)phosphate is LiPF2C4O8.

### Claim 26 (depends on 23)

The electrolyte of claim 23, wherein the cyclotriphosphazene is selected from P-ethoxy-P,P′,P″-pentafluorocyclotriphosphazene, P,P′-diethoxy-P,P′,P″-tetrafluorocyclotriphosphazene, P-phenoxy-P,P′,P″-pentafluorocyclotriphosphazene, P,P′,P″-hexamethoxycyclotriphosphazene, P-phenoxy-P′-(prop-2-ene-oxy)-P,P′,P″-pentafluorocyclotriphosphazene, or mixtures of any two or more thereof.

### Claim 27 (depends on 22)

The electrolyte of claim 22, wherein the second electrode stabilizing additive is present between about 0.01 wt % and about 15 wt %.

### Claim 28 (depends on 22)

The electrolyte of claim 22, wherein the alkali metal salt is other than Li(C2O4)2B, Li(C2O4)BF2, or LiPF2C4O8.