LITHIUM ION BATTERY

• US 20150140444A1
• Filed: 03/08/2013
• Published: 05/21/2015
• Est. Priority Date: 06/01/2012
• Status: Active Grant

• Current Assignee: Syensqo SA
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Dubois, Charles J., Petrov, Viacheslav A.
• Granted Patent: US 10,074,874 B2
• Time in Patent Office: Days
• US Class Current: 429/331
• 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 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/0034 Fluorinated solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• 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 4/485 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 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A lithium ion battery that has a 5 V stabilized manganese cathode and a nonaqueous electrolyte comprising a phosphate additive is described. The lithium ion battery operates with a high voltage cathode (i.e. up to about 5 V) and has improved cycling performance at high temperature.

Claims

1. A lithium ion battery comprising:

a) a stabilized manganese cathode;

b) an anode;

c) a porous separator between said anode and said cathode;

d) a nonaqueous electrolyte composition providing an ionically conductive pathway between said anode and said cathode, wherein said electrolyte comprises;

(i) a solvent mixture comprising;

(A) ethylene carbonate at about 10% to about 40% by weight;

(B) at least one co-solvent at about 20% to about 80% by weight; and

(C) at least one phosphate additive at about 0.2% to about 10% by weight, said at least one phosphate additive represented by the formula;

2. The lithium ion battery of claim 1, wherein the co-solvent is a fluorine-containing carboxylic acid ester represented by the formula:

R₄—

COO—

R₅, where R₄ and R₅ independently represent an alkyl group, the sum of carbon atoms in R₄ and R₅ is 2 to 7, at least two hydrogens in R₄ and/or R₅ are replaced by fluorines and neither R₄ nor R₅ contains a FCH₂ or FCH group.

3. The lithium ion battery of claim 2, wherein the fluorine-containing carboxylic acid ester is selected from the group consisting of CH₃—

COO—

CH₂CF₂H, CH₃CH₂—

COO—

CH₂CF₂H, F₂CHCH₂—

COO—

CH₃, F₂CHCH₂—

COO—

CH₂CH₃, CH₃—

COO—

CH₂CH₂CF₂H, CH₃CH₂—

COO—

CH₂CH₂CF₂H, and F₂CHCH₂CH₂—

COO—

CH₂CH₃.

4. The lithium ion battery of claim 1, wherein the electrolyte composition further comprises 4-fluoroethylene carbonate at a concentration of about 0.5% to about 2% by weight.

5. The lithium ion battery of claim 1, wherein the solvent mixture comprises ethylene carbonate and CH₃—

COO—

CH₂CF₂H, or CH₃CH₂—

COO—

CH₂CF₂H at a weight ratio of about 30;

70 and the phosphate additive at about 1% by weight.

6. The lithium ion battery of claim 1, wherein the co-solvent is selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and propylene carbonate.

7. The lithium ion battery of claim 1, wherein the phosphate additive is selected from the group consisting of tris(1,1,1,3,3,3-hexafluoropropan-2yl) phosphate, tris(2,2,2-trifluoroethyl) phosphate, tri(2,2,3,3,3-pentafluoropropyl) phosphate, tris(2,2,3,3-tetrafluoropropyl) phosphate, triethyl phosphate, trimethyl phosphate, tripropyl phosphate, triphenyl phosphate, triisopropyl phosphate, tris(2,2,3,3,4,4,5,5,6,6-decafluorohexyl) phosphate, and tris(2,2-difluoroethyl) phosphate.

8. The lithium ion battery of claim 1, wherein the anode is lithium titanate or graphite.

9. The lithium ion battery of claim 1, wherein the stabilized manganese cathode comprises a lithium-containing manganese composite oxide having a spinel structure as active material, the lithium-containing manganese composite oxide being represented by the formula:

Li_xNi_yM_zMn_2-y-zO_4-d,

wherein x is 0.03 to 1.0;

x changes in accordance with release and uptake of lithium ions and electrons during charge and discharge;

y is 0.3 to 0.6;

M comprises one or more of Cr, Fe, Co, Li, Al, Ga, Nb, Mo, Ti, Zr, Mg, Zn, V, and Cu;

z is 0.01 to 0.18, and d is 0 to 0.3.

10. The lithium ion battery of claim 9, wherein y is 0.38 to 0.48, z is 0.03 to 0.12, and d is 0 to 0.1.

11. The lithium ion battery of claim 9, wherein M is one or more of Li, Cr, Fe, Co, and Ga.

12. An electronic device that comprises a lithium ion battery according to claim 1.

13. A lithium ion battery comprising:

a) a stabilized manganese cathode;

b) an anode;

c) a porous separator between said anode and said cathode;

d) a nonaqueous electrolyte composition providing an ionically conductive pathway between said anode and said cathode, wherein said electrolyte comprises;

(i) a solvent mixture comprising;

(A) ethylene carbonate;

(B) at least one co-solvent; and

(C) at least one phosphate additive represented by the formula;