Electrolytes including fluorinated solvents for use in electrochemical cells

• US 9,077,046 B2
• Filed: 06/03/2013
• Issued: 07/07/2015
• Est. Priority Date: 06/19/2012
• Status: Expired due to Fees

• Current Assignee: A123 Systems Incorporated
• Original Assignee: A123 Systems Incorporated
• Inventors: Tikhonov, Konstantin, Yip, Ka Ki, Lin, Tzu-Yuan
• Primary Examiner(s): Kelly, Cynthia H
• Assistant Examiner(s): WILLS, MONIQUE M
• Application Number:
  US13/909,014
• Publication Number:
  US 20130337338A1
• Time in Patent Office: 764 Days
• US Class Current: 1/1
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0034 Fluorinated solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about −30° C. to about 80° C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF₆, fluoroalkyl-substituted LiBF₄ salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

Claims

1. An electrolyte for use in an electrochemical cell, the electrolyte comprising:

an electrolyte salt comprising at least one carbon atom and at least two fluoride atoms and is selected from the group consisting of;

i) fluoroalkyl-substituted LiPF₆ salts having a general structure LiPF_xR_1-x, wherein x is from 1 to 5 and wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8;

ii) fluoroalkyl-substituted LiBF₄ salts having a general structure LiBF_xR_1-x, wherein x is from 1 to 4 and wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8;

iii) linear imide salts having a general structure LiN(—

SO₂—

R)₂, wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8;

iv) cyclic imide salts having a general structure LiN(—

SO₂—

R—

), wherein R is fluorinated alkyl having a chain length of from 1 to 8; and

v) methide salts having a general structure LiC(—

SO₂—

R)₃, wherein at least one R is fluorinated alkyl with a chain length of from 1 to 8;

a fluorinated solvent being present at a concentration of between about 30% and 80% by weight excluding a weight of the electrolyte salt, wherein the fluorinated solvent has a general structure C_xF_yH_zO_i such that x is an integer ranging from 3 to 15, y is an integer ranging from 1 to 30, z is an integer ranging from 0 to 15, and i is an integer ranging from 1 to 5; and

a non-fluorinated solvent selected from the group consisting of an ester, an ether, and a carbonate wherein a weight ratio of the non-fluorinated solvents to the fluorinated solvent is less than 0.9,

wherein the electrolyte is a one-phase solution at a temperature ranging from about −

30°

C. to about 80°

C.

2. The electrolyte according to claim 1, wherein the fluorinated solvent is selected from a group consisting of fluorinated ethers, fluorinated esters, and fluorinated carbonates.

3. The electrolyte according to claim 1, wherein the fluorinated solvent is selected from the group consisting of 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.

4. The electrolyte according to claim 1, wherein the fluorinated solvent has the concentration of between about 50% and 75% by weight excluding the weight of the electrolyte salt.

5. The electrolyte according to claim 1, wherein the fluorinated solvent comprises 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.

6. The electrolyte according to claim 1, wherein the fluorinated solvent comprises 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane.

7. The electrolyte according to claim 6, wherein the electrolyte salt comprises LiN(SO₂CF₂CF₃)₂.

8. The electrolyte according to claim 1, wherein the electrolyte salt is selected from the group consisting of LiN(SO₂CF₂CF₃)₂, LiN(SO₂CF₃)₂, and LiN(SO₂F)₂.

9. The electrolyte according to claim 1, wherein the non-fluorinated solvent is selected from the group consisting of diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate.

10. The electrolyte according to claim 1, wherein the non-fluorinated solvent has a dynamic viscosity ranging from 0.3 cP to 2.0 cP.

11. The electrolyte according to claim 1, wherein the electrolyte has a conductivity ranging from about 0.1 mS to about 10 mS.

12. The electrolyte according to claim 1, further comprising a flame-retardant additive, the flame-retardant additive being present at a concentration ranging from about 1% to about 10% by weight.

13. The electrolyte according to claim 12, wherein the flame-retardant additive comprises one or more materials selected from the group consisting of phosphates, phosphite, phosphines, and phosphazenes.

14. The electrolyte according to claim 12, wherein the flame-retardant additive comprises P₃N₃F_x(OR)_6-x such that R is an alkyl with a number of carbon atoms from 1 to 12, or R is an aromatic hydrocarbon, and wherein x is from 1 to 6.

15. The electrolyte according to claim 12, wherein the flame-retardant additive comprises a cyclic phosphazene.

16. The electrolyte according to claim 1, further comprising an ionic liquid, wherein the ionic liquid is present at a concentration ranging from about 1% to about 25% by weight.

17. The electrolyte according to claim 16, wherein the ionic liquid comprises one or more materials selected from the group consisting of pyridinium, peperridinium, imidazolium, and phosphonium ionic liquids.

18. The electrolyte according to claim 1, wherein the fluorinated solvent has a dynamic viscosity ranging from about 0.3 cP to about 5.0 cP.

19. An electrolyte for use in an electrochemical cell, the electrolyte comprising:

LiN(SO₂CF₂CF₃)₂ being present at a concentration between about 0.6M and about 2M,

3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane being present at a concentration of between about 60% and 80% by weight excluding a weight of an electrolyte salt;

ethyl butyrate being present at a concentration of between about 10% and 30% by weight excluding a weight of the electrolyte salt; and

a cyclic phosphazene being present at a concentration of between about 5% and 15% by weight excluding a weight of the electrolyte salt.

20. An electrochemical cell comprising:

a positive electrode;

a negative electrode;

an electrolyte providing ionic exchange between the positive electrode and negative electrode and comprising;

an electrolyte salt comprising at least one carbon atom and at least two fluoride atoms and is selected from the group consisting of;

i) fluoroalkyl-substituted LiPF₆ salts having a general structure LiPF_xR_1-x, wherein x is from 1 to 5 and wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8;

ii) fluoroalkyl-substituted LiBF₄ salts having a general structure LiBF_xR_1-x, wherein x is from 1 to 4 and wherein at least one R is an fluorinated alkyl having a chain length of from 1 to 8;

iii) linear imide salts having a general structure LiN(—

SO₂—

R)₂, wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8;

iv) cyclic imide salts having a general structure LiN(—

SO₂—

R—

), wherein R is fluorinated alkyl having a chain length of from 1 to 8; and

v) methide salts having a general structure LiC(—

SO₂—

R)₃, wherein at least one R is fluorinated alkyl with a chain length of from 1 to 8;

a fluorinated solvent being present at a concentration of between about 30% and 80% by weight excluding a weight of the electrolyte salt, wherein the fluorinated solvent has a general structure C_xF_yH_zO_i such that x is an integer ranging from 3 to 15, y is an integer ranging from 1 to 30, z is an integer ranging from 0 to 15, and i is an integer ranging from 1 to 5; and

a non-fluorinated solvent selected from the group consisting of an ester, an ether, and a carbonate wherein a weight ratio of the non-fluorinated solvents to the fluorinated solvent is less than 0.9,

wherein the electrolyte is a one-phase solution at a temperature ranging from about −

30°

C. to about 80°

C.