Nonaqueous electrolyte compositions comprising sultone and fluorinated solvent

Patent metadata

Field	Value
Publication number	US-10673096-B2
Application number	US-201515503794-A
Country	US
Kind code	B2
Filing date	Aug 12, 2015
Priority date	Aug 14, 2014
Publication date	Jun 2, 2020
Grant date	Jun 2, 2020

Abstract

Described are electrolyte compositions comprising a fluorinated solvent, an organic carbonate, a sultone, and optionally a borate. The fluorinated solvent may be a fluorinated acyclic carboxylic acid ester, a fluorinated acyclic carbonate, a fluorinated acyclic ether, or mixtures thereof. The organic carbonate may be fluorinated or non-fluorinated. The electrolyte compositions are useful in electrochemical cells, such as lithium ion batteries.

First claim

What is claimed is:

1. An electrochemical cell comprising:
(a) a housing;
(b) an anode and a cathode disposed in said housing and in ionically conductive contact with one another;
(c) an electrolyte composition comprising:
i) from about 10 to about 80 weight percent, based on the total weight of the electrolyte composition, of a fluorinated acyclic carboxylic acid ester represented by the formula R 1 —COO—R 2 , wherein R 1 is H, an alkyl group, or a fluoroalkyl group, R 2 is an alkyl group or a fluoroalkyl group, either or both of R 1 and R 2 comprises fluorine, and R 1 and R 2 , taken as a pair, comprises at least two carbon atoms but not more than seven carbon atoms;
ii) from about 10 to about 80 weight percent, based on the total weight of the electrolyte composition, of an organic carbonate, selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, propylene carbonate, fluoroethylene carbonate, or mixtures thereof;
iii) from about 0.01 to about 10 weight percent, based on the total weight of the electrolyte composition, of a sultone represented by the formula

wherein each A is independently a hydrogen, fluorine, or an optionally fluorinated alkyl, vinyl, allyl, acetylenic, or propargyl group; and

iv) at least one electrolyte salt;

wherein the composition is disposed in said housing and providing an ionically conductive pathway between said anode and said cathode; and
(d) a porous separator between said anode and said cathode,
wherein the electrochemical cell is a liquid electrolyte chemical cell.

2. The electrolyte composition of claim 1 , wherein R 1 and R 2 taken as a pair, further comprises at least two fluorine atoms, with the proviso that none of R 1 or R 2 contains a —CH 2 F or —CHF— group.

3. The electrolyte composition of claim 1 , wherein the fluorinated solvent comprises 2,2-difluoroethyl acetate.

4. The electrolyte composition of claim 1 , wherein the sultone comprises 1,3-propane sultone.

5. The electrolyte composition of claim 1 , further comprising a borate selected from the group consisting of lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium tetrafluoroborate, and mixtures thereof.

6. The electrolyte composition of claim 1 comprising 2,2-difluoroethyl acetate, ethylene carbonate, and 1,3-propane sultone, and further comprising lithium bis(oxalato)borate.

7. The electrolyte composition of claim 1 comprising 2,2-difluoroethyl acetate, 4-fluoroethylene carbonate, and 1,3-propane sultone.

8. The electrolyte composition of claim 7 , further comprising 2,2-difluoroethyl methyl carbonate.

9. The electrolyte composition of claim 1 comprising 2,2-difluoroethyl methyl carbonate, 4-fluoroethylene carbonate, and 1,3-propane sultone.

10. The electrolyte composition of claim 1 comprising 2,2-difluoroethyl methyl carbonate, ethylene carbonate, and 1,3-propane sultone.

11. The electrochemical cell of claim 1 , wherein said electrochemical cell is a lithium ion battery.

12. The electrochemical cell of claim 11 wherein the anode active material is lithium titanate, graphite, lithium alloys, silicon, or combinations thereof.

13. The electrochemical cell of claim 11 , wherein the cathode comprises a cathode active material exhibiting greater than 30 mAh/g capacity in the potential range greater than 4.6 V versus a Li/Li + reference electrode, or a cathode active material which is charged to a potential greater than or equal to 4.1 V versus a Li/Li + reference electrode.

14. The electrochemical cell of claim 11 , wherein the cathode comprises
Li a Ni b Mn c Co d R e O 2-f Z f ,
wherein:
R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, a rare earth element, or a combination thereof;
Z is F, S, P, or a combination thereof; and
0.8≤a≤1.2, 0.1≤b≤0.9, 0.0≤c≤0.7, 0.05≤d≤0.4, 0≤e≤0.2; wherein the sum of b+c+d+e is about 1; and 0≤f≤0.08.

15. The electrochemical cell of claim 11 , wherein the cathode comprises a composite material represented by the structure of Formula:
x(Li 2-w A 1-v Q w+v O 3-e )·(1-x)(Li y Mn 2-z M z O 4-d )

wherein:
x is about 0 to about 0.1;
A comprises one or more of Mn or Ti;
Q comprises one or more of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr or Y;
e is 0 to about 0.3;
v is 0 to about 0.5;
w is 0 to about 0.6;
M comprises one or more of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr or Y;
d is 0 to about 0.5;
y is about 0 to about 1; and
z is about 0.3 to about 1; and
wherein the Li y Mn 2-z M z O 4-d component has a spinel structure and the Li 2-w Q w+v A 1-v O 3-e component has a layered structure.

16. The electrochemical cell of claim 11 , wherein the cathode comprises:
Li a A 1-b R b D 2 ,
wherein:
A is Ni, Co, Mn, or a combination thereof;
R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, a rare earth element, or a combination thereof;
D is O, F, S, P, or a combination thereof; and
0.90≤a≤1.8 and 0≤b≤0.5.

17. The electrochemical cell of claim 11 , wherein the cathode comprises:
Li a A 1-x R x DO 4-f Z f ,
wherein:
A is Fe, Mn, Ni, Co, V, or a combination thereof;
R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, a rare earth element, or a combination thereof;
D is P, S, Si, or a combination thereof;
Z is F, Cl, S, or a combination thereof;
0.8≤a≤2.2;
0≤x≤0.3; and
0≤f≤0.1.

18. An electronic device, transportation device, or telecommunications device, comprising an electrochemical cell according to claim 1 .

19. A method for reducing gas formation in a lithium ion battery, the method comprising:
(a) preparing an electrolyte composition comprising:
i) from about 10 to about 80 weight percent, based on the total weight of the electrolyte composition, of a fluorinated acyclic carboxylic acid ester represented by the formula R 1 —COO—R 2 , wherein R 1 is H, an alkyl group, or a fluoroalkyl group, R 2 is an alkyl group or a fluoroalkyl group, either or both of R 1 and R 2 comprises fluorine, and R 1 and R 2 , taken as a pair, comprises at least two carbon atoms but not more than seven carbon atoms;
ii) from about 10 to about 80 weight percent, based on the total weight of the electrolyte composition, of an organic carbonate, selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, propylene carbonate, fluoroethylene carbonate, or mixtures thereof;
iii) from about 0.01 to about 10 weight percent, based on the total weight of the electrolyte composition, of a sultone represented by the formula

wherein each A is independently a hydrogen, fluorine, or an optionally fluorinated alkyl, vinyl, allyl, acetylenic, or propargyl group; and

iv) at least one electrolyte salt;

(b) placing the electrolyte composition in a liquid electrolyte lithium ion battery comprising
(i) a housing;
(ii) an anode and a cathode disposed in said housing and in ionically conductive contact with one another; and
(iii) a porous separator between said anode and said cathode;

whereby the electrolyte composition provides an ionically conductive pathway between sai

Assignees

• Solvay

Inventors

• Burkhardt Stephen E
• Kourtakis Kostantinos
• Liu Jun J
• Roelofs Mark Gerrit
• Kim Sang-Hwan

Classifications

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M6/164 Primary

  by the solvent · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title

• H01M10/0569 Primary

  characterised by the solvents · CPC title