Nonaqueous electrolyte compositions comprising cyclic sulfates

Patent metadata

Field	Value
Publication number	US-10559850-B2
Application number	US-201515311330-A
Country	US
Kind code	B2
Filing date	May 14, 2015
Priority date	May 23, 2014
Publication date	Feb 11, 2020
Grant date	Feb 11, 2020

Abstract

Described herein are electrolyte compositions containing an organic carbonate, a fluorinated solvent, a cyclic sulfate, and at least one electrolyte salt. The cyclic sulfate can be represented by the formula:

wherein each A is independently a hydrogen or an optionally fluorinated vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl group. The electrolyte compositions are useful in electrochemical cells, such as lithium ion batteries.

First claim

What is claimed is:

1. An electrolyte composition comprising:
a) an organic carbonate selected from ethylene carbonate and/or propylene carbonate;
b) a fluorinated acyclic carboxylic acid ester selected from CH 3 —COO—CH 2 CF 2 H;
c) a cyclic sulfate selected from one of ethylene sulfate or propylene sulfate; and
d) at least one electrolyte salt;
wherein the electrolyte composition comprises about 0.5 weight percent to about 3 weight percent of the cyclic sulfate.

2. The electrolyte composition of claim 1 , further comprising lithium bis(oxalate)borate or fluoroethylene carbonate.

3. The electrolyte composition of claim 1 , wherein the organic carbonate is ethylene carbonate, and the cyclic sulfate is ethylene sulfate.

4. 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) the electrolyte composition of claim 1 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.

5. The electrochemical cell of claim 4 , wherein said electrochemical cell is a lithium ion battery.

6. The electrochemical cell of claim 4 , wherein the anode is lithium titanate or graphite.

7. The electrochemical cell of claim 4 , 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.

8. The electrochemical cell of claim 4 , wherein the cathode comprises a cathode active material which is charged to a potential greater than or equal to 4.35 V versus a Li/Li+ reference electrode.

9. The electrochemical cell of claim 4 , wherein the 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 x Ni y M z Mn 2-y-z O 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 electrochemical cell of claim 4 , wherein the cathode comprises
Li a Ni b Mn c CO d R c 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, and Z is F, S, P, or a combination thereof; and
0.8≤a≤1.2, 0.1≤b≤0.5, 0.2≤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.

11. The electrochemical cell of claim 4 , wherein the cathode comprises
L ia 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, and D is 0, F, S, P, or a combination thereof; and
0.90≤a≤1.8 and 0≤b≤0.5.

12. The electrochemical cell of claim 4 , wherein the cathode comprises a composite material represented by the structure of Formula:
x (Li 2-w A 1-v Q w+y O 3-θ )*(1 −x )(Li y Mn 2-z M z O 4-d )
wherein:
x is about 0.005 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 -vO 3-e component has a layered structure.

13. An electronic device, transportation device, or telecommunications device, comprising an electrochemical cell according to claim 4 .

14. A method comprising:
combining:
a) an organic carbonate selected from ethylene carbonate and/or propylene carbonate;
b) a fluorinated acyclic carboxylic acid ester selected from CH 3 —COO—CH 2 CF 2 H;
c) a cyclic sulfate selected from ethylene sulfate or propylene sulfate; and
d) at least one electrolyte salt;

to form an electrolyte composition;
wherein the electrolyte composition comprises about 0.5 weight percent to about 3 weight percent of the cyclic sulfate.

15. The method of claim 14 , wherein the organic carbonate is ethylene carbonate, and the cyclic sulfate is ethylene sulfate.

16. The electrolyte composition of claim 1 , wherein the organic carbonate is ethylene carbonate.

17. The method of claim 14 , wherein the organic carbonate is ethylene carbonate.

Assignees

• Solvay

Inventors

• Dubois Charles J
• Kourtakis Kostantinos
• Liu Jun J
• Roelofs Mark Gerrit

Classifications

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M2300/0034

  Fluorinated solvents · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M2300/0037

  Mixture of 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