Electrolytes containing six membered ring cyclic sulfates

Patent metadata

Field	Value
Publication number	US-11038196-B2
Application number	US-201716333316-A
Country	US
Kind code	B2
Filing date	Sep 12, 2017
Priority date	Sep 14, 2016
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

Disclosed herein are electrolyte compositions comprising at least one electrolyte component comprising a cyclic carbonate, such as a fluoroethylene carbonate, and at least one additive comprising a 6-member ring heterocyclic sulfate, such as a 1,3 propylene sulfate. The disclosed electrolyte compositions can comprise additional electrolyte components, such as fluorinated acyclic carboxylic acid esters, and additional additives, such as lithium boron compounds, and cyclic carboxylic acid anhydrides, such as maleic anhydride. The improved battery performances, which include high temperature cycling conditions and/or room temperature stability, make these electrolyte compositions useful in electrochemical cells, such as lithium ion batteries.

First claim

The invention claimed is:

1. An electrolyte composition comprising:
at least one electrolyte component comprising a cyclic carbonate, wherein said cyclic carbonate comprises at least one fluorinated carbonate, and wherein the at least one electrolyte component further comprises a fluorinated acyclic carboxylic acid ester;
at least one additive comprising a 6-member ring heterocyclic sulfate represented by Formula (I):

wherein n=1, and R 15 to R 18 each independently represent a hydrogen or a vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl group, wherein the vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl groups may each be unsubstituted or partially or totally fluorinated; and
at least one electrolyte salt.

2. The electrolyte composition of claim 1 , wherein the 6-member ring heterocyclic sulfate comprises 1,3 propylene sulfate.

3. The electrolyte composition of claim 1 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.

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

5. The electrolyte composition of claim 1 , further comprising a non-fluorinated acyclic carbonate.

6. The electrolyte composition of claim 1 , wherein the at least one electrolyte component further comprises a fluorinated acyclic carbonate.

7. The electrolyte composition of claim 6 , wherein the fluorinated acyclic carbonate comprises CH 3 —OC(O)O—CH 2 CF 2 H, CH 3 —OC(O)O—CH 2 CF 3 , CH 3 —OC(O)O—CH 2 CF 2 CF 2 H, HCF 2 CH 2 —OCOO—CH 2 CH 3 , CF 3 CH 2 —OCOO—CH 2 CH3, or mixtures thereof.

8. The electrolyte composition of claim 7 , wherein the fluorinated acyclic carbonate comprises CH 3 —OC(O)O—CH 2 CF 2 H.

9. The electrolyte composition of claim 1 , wherein the at least one electrolyte component further comprises a fluorinated acyclic ether.

10. The electrolyte composition of claim 1 , further comprising an additive selected from a lithium boron compound, a cyclic sultone, a cyclic sulfate, a cyclic carboxylic acid anhydride, or combinations thereof.

11. The electrolyte composition of claim 1 , wherein said at least one additive comprising a 6-member ring heterocyclic sulfate is present in an amount ranging from 0.1 weight percent to about 12 weight percent of the total electrolyte composition, sufficient to improve at least one property of the electrolyte chosen from (1) battery performance during high temperature cycling conditions and (2) room temperature stability.

12. The electrolyte composition of claim 1 , wherein the electrolyte composition does not show an oxygenated product of FEC (4-hydroxy-1,3-dioxolan-2-on), above 0.01 mole % relative to the entire electrolyte formulation as determined by NMR, after aging at 25° C. for at least 200 hours.

13. The electrolyte composition of claim 12 , wherein the electrolyte composition does not show an oxygenated product of FEC above 0.01 mole % relative to the entire electrolyte formulation as determined by NMR, after aging at 25° C. for a time ranging from 200-840 hours.

14. The electrolyte composition of claim 1 , wherein the cyclic carbonate comprises fluoroethylene carbonate.

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) an electrolyte composition comprising:
at least one electrolyte component comprising a cyclic carbonate, wherein said cyclic carbonate comprises at least one fluorinated carbonate, and wherein the at least one electrolyte component further comprises a fluorinated acyclic carboxylic acid ester; and
at least one additive comprising a 6-member ring heterocyclic sulfate represented by Formula (I):

wherein n=1, and R 15 to R 18 each independently represent a hydrogen or a vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl group, wherein the vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl groups may each be unsubstituted or partially or totally fluorinated; and

at least one electrolyte salt,
wherein said electrolyte composition is disposed in the housing and provides 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. The electrochemical cell of claim 15 , 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 4.35 V versus a Li/Li + reference electrode.

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

Assignees

• Solvay

Inventors

• Burkhardt Stephen E
• Kourtakis Kostantinos
• Levy-Polis Brian

Classifications

• H01M2300/0034

  Fluorinated solvents · CPC title

• H01M4/505

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

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0525 Primary

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