Additives to improve electrolyte performance in lithium ion batteries

• US 10,074,874 B2
• Filed: 03/08/2013
• Issued: 09/11/2018
• Est. Priority Date: 06/01/2012
• Status: Active Grant

• Current Assignee: Syensqo SA
• Original Assignee: Solvay SA (Solvac SA)
• Inventors: Dubois, Charles J., Petrov, Viacheslav A., Roelofs, Mark Gerrit
• Primary Examiner(s): Weiner, Laura S
• Application Number:
  US14/404,169
• Publication Number:
  US 20150140444A1
• Time in Patent Office: 2,013 Days
• 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 comprising;

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;

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 fluorine-containing carboxylic acid ester 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 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 electrolyte composition further comprises 4-fluoroethylene carbonate at a concentration of about 0.5% to about 2% by weight.

3. 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.

4. 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.

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

6. The lithium ion battery of claim 1, wherein y is 0.38 to 0.48, z is 0.03 to 0.12, and d is 0 to 0.1.

7. The lithium ion battery of claim 1, wherein M is one or more of Li, Cr, Fe, Co, and Ga.

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

9. A lithium ion battery comprising:

a) a stabilized manganese cathode comprising;

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;

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 15% to about 40% by weight;

(B) at least one fluorine-containing carboxylic acid ester 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 at about 40% to about 80% by weight; and

(C) at least one phosphate additive at about 0.5% to about 5% by weight, said at least one phosphate additive represented by the formula;

10. The lithium ion battery of claim 9, wherein the electrolyte composition further comprises 4-fluoroethylene carbonate at a concentration of about 0.5% to about 2% by weight.

11. The lithium ion battery of claim 9, 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.

12. The lithium ion battery of claim 9, 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.

13. The lithium ion battery of claim 9, wherein the anode is lithium titanate or graphite.

14. 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.

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

16. An electronic device that comprises a lithium ion battery according to claim 9.