Nonaqueous electrolyte compositions comprising silyl oxalates

Patent metadata

Field	Value
Publication number	US-11489198-B2
Application number	US-201716326466-A
Country	US
Kind code	B2
Filing date	Jul 27, 2017
Priority date	Aug 19, 2016
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

Disclosed herein are electrolyte compositions comprising a fluorinated solvent, at least one silyl oxalate represented by the formulas RR′Si(C2O4), wherein R and R′ are each the same or different from each other and independently selected from C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, or C6-C10 aryl radical, optionally comprising at least one substituent selected from halogen, hydroxyl, alkoxy, carbonyl, and carboxyl groups; and LiPF6. Also disclosed herein are electrolyte compositions comprising a fluorinated solvent and a lithium oxalato phosphate salt represented by the formula LiPF(6-2q)(C2O4)q, wherein q is 1, 2 or 3; wherein the oxalato phosphate salt comprises at least a portion that is derived from at least one silyl oxalate as defined herein. The electrolyte compositions are useful in electrochemical cells, such as lithium ion batteries.

First claim

The invention claimed is:

1. An electrolyte composition comprising:
a) a fluorinated solvent;
b) at least one silyl oxalate represented by Formula I:
RR′Si(C 2 O 4 )  (I),

wherein R, and R′ are each the same or different from each other and independently selected from C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, or C 6 -C 10 aryl radical, optionally comprising at least one substituent selected from halogen, hydroxyl, alkoxy, carbonyl, and carboxyl groups; and
c) LiPF 6 .

2. The electrolyte composition of claim 1 , wherein the silyl oxalate comprises dimethylsilyl oxalate, vinylphenylsilyl oxalate, methylvinylsilyl oxalate, or diphenylsilyl oxalate.

3. The electrolyte composition of claim 1 , wherein the fluorinated solvent comprises:
a) a fluorinated acyclic carboxylic acid ester represented by the formula:
R 1 —COO—R 2 ,

b) a fluorinated acyclic carbonate represented by the formula:
R 3 —OCOO—R 4 ,

c) a fluorinated acyclic ether represented by the formula:
R 5 —O—R 6 ,

or mixtures thereof;
wherein
i) R 1 is H, an alkyl group, or a fluoroalkyl group;
ii) R 3 and R 5 is each independently a fluoroalkyl group and can be either the same as or different from each other;
iii) R 2 , R 4 , and R 6 is each independently an alkyl group or a fluoroalkyl group and can be either the same as or different from each other;
iv) either or both of R 1 and R 2 comprises fluorine; and
v) R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , each taken as a pair, comprise at least two carbon atoms but not more than seven carbon atoms.

4. The electrolyte composition of claim 3 , wherein the fluorinated acyclic carboxylic acid ester comprises CH 3 —COO—CH 2 CF 2 H, CH 3 CH 2 —COO—CH 2 CF 2 H, F 2 CHCH 2 —COO—CH 3 , F 2 CHCH 2 —COO—CH 2 CH 3 , CH 3 —COO—CH 2 CH 2 CF 2 H, CH 3 CH 2 —COO—CH 2 CH 2 CF 2 H, F 2 CHCH 2 CH 2 —COO—CH 2 CH 3 , CH 3 —COO—CH 2 CF 3 , CH 3 CH 2 —COO—CH 2 CF 2 H, CH 3 —COO—CH 2 CF 3 , H.COO—CH 2 CF 2 H, H—COO—CH 2 CF 3 , or mixtures thereof.

5. The electrolyte composition of claim 4 , wherein the fluorinated acyclic carboxylic acid ester comprises CH 3 —COO—CH 2 CF 2 H.

6. The electrolyte composition of claim 1 , further comprising an organic carbonate.

7. The electrolyte composition of claim 6 , wherein the organic carbonate comprises 4-fluoroethylene carbonate, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, or mixtures thereof.

8. The electrolyte composition of claim 7 , wherein the organic carbonate comprises 4-fluoroethylene carbonate.

9. An electrolyte composition comprising:
a) a fluorinated solvent; and
b) a lithium oxalato phosphate salt represented by Formula III:
LiPF (6-2q) (C 2 O 4 ) q   (III)

wherein q is 1, 2 or 3;
wherein the oxalato phosphate salt comprises at least a portion that is derived from at least one silyl oxalate represented by Formula I:
RR′Si(C 2 O 4 )  (I),

wherein R and R′ are each the same or different from each other and independently selected from C 1 -C 5 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, or C 6 -C 10 aryl radical, optionally comprising at least one substituent selected from halogen, hydroxyl, alkoxy, carbonyl, and carboxyl groups.

10. The electrolyte composition of claim 9 , wherein the silyl oxalate comprises dimethylsilyl oxalate, vinylphenylsilyl oxalate, methylvinylsilyl oxalate, or diphenylsilyl oxalate.

11. The electrolyte composition of claim 9 , wherein the fluorinated solvent comprises a fluorinated acyclic carboxylic acid ester comprising CH 3 —COO—CH 2 CF 2 H, CH 3 CH 2 —COO—CH 2 CF 2 H, F 2 CHCH 2 —COO—CH 3 , F 2 CHCH 2 —COO—CH 2 CH 3 , CH 3 —COO—CH 2 CH 2 CF 2 H, CH 3 CH 2 —COO—CH 2 CH 2 CF 2 H, F 2 CHCH 2 CH 2 —COO—CH 2 CH 3 , CH 3 —COO—CH 2 CF 3 , CH 3 CH 2 —COO—CH 2 CF 2 H, CH 3 —COO—CH 2 CF 3 , H.COO—CH 2 CF 2 H, H—COO—CH 2 CF 3 , or mixtures thereof.

12. The electrolyte composition of claim 11 , wherein the fluorinated acyclic carboxylic acid ester comprises CH 3 —COO—CH 2 CF 2 H.

13. The electrolyte composition of claim 9 , wherein the oxalato phosphate salt comprises lithium tris(oxalato)phosphate.

14. A method comprising:
a step of combining:
a) a fluorinated solvent;
b) at least one silyl oxalate represented by Formula I:
RR′Si(C 2 O 4 )  (I),

wherein R and R′ are each the same or different from each other and independently selected from C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, or C 6 -C 10 aryl radical, optionally comprising at least one substituent selected from halogen, hydroxyl, alkoxy, carbonyl, and carboxyl groups; and
c) LiPF6;
to form an electrolyte composition.

15. An electrochemical cell comprising:
(a) a housing;
(b) an anode and a cathode disposed in the housing and in ionically conductive contact with one another;
(c) the electrolyte composition of claim 9 disposed in the housing and providing an ionically conductive pathway between the anode and the cathode; and
(d) a porous separator between the anode and the cathode.

16. The electrochemical cell of claim 15 , wherein the electrochemical cell is a lithium ion battery.

17. An electronic device, transportation device, or telecommunications device, comprising an electrochemical cell according to claim 15 .

Assignees

• Solvay

Inventors

• Moloy Kenneth Gene
• Burkhardt Stephen E
• Kourtakis Kostantinos
• Levy-Polis Brian

Classifications

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M2300/0034

  Fluorinated solvents · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title