Nonaqueous electrolyte compositions

• US 10,686,220 B2
• Filed: 04/04/2014
• Issued: 06/16/2020
• Est. Priority Date: 04/04/2013
• Status: Active Grant

• Current Assignee: Syensqo SA
• Original Assignee: Solvay SA (Solvac SA)
• Inventors: Burkhardt, Stephen E., Chen, Xudong, Dubois, Charles J., Holstein, William L., Kourtakis, Kostantinos, Roelofs, Mark Gerrit
• Primary Examiner(s): White, Sadie
• Application Number:
  US14/244,968
• Publication Number:
  US 20140302401A1
• Time in Patent Office: 2,265 Days
• 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 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0034 Fluorinated solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 2300/004 Three solvents
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Electrolyte compositions comprising fluorinated acyclic carboxylic acid esters, fluorinated acyclic carbonates, and/or fluorinated acyclic ethers; co-solvents; and certain film-forming chemical compounds are described. The electrolyte compositions are useful in electrochemical cells, such as lithium ion batteries where they provide the improved performance of a combination of high capacity and high cycle life.

Claims

1. An electrolyte composition comprising:

a) a fluorinated acyclic carboxylic acid ester represented by the formula;

R¹—

COO—

R²,

wherein R¹ and R² independently represent a linear or branched alkyl group;

the sum of carbon atoms in R¹ and R² is 2 to 7;

at least two hydrogens in R¹ and/or R² are replaced by fluorines; and

neither R¹ nor R² contains a FCH₂ or FCH group;

b) at least one co-solvent selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, and propylene carbonate, and further comprising one or more members of the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, and ethyl methyl sulfone;

c) at least one film-forming chemical compound which is present in the electrolyte composition at a concentration at which said film-forming chemical compound decomposes at a potential of less than +1.0 V versus a Li/Li⁺ reference electrode, such that the electrolyte composition forms a film and wherein the electrolyte composition does not form a film at a potential of 1.0 V or above versus a Li/Li⁺ reference electrode; and

d) at least one electrolyte salt;

with the proviso that b) and c) are different.

2. The electrolyte composition of claim 1, wherein the fluorinated solvent is a fluorinated acyclic carboxylic ester and the number of carbon atoms in R¹ is 1, 3, 4, or 5.

3. The electrolyte composition of claim 1, wherein the fluorinated solvent is a fluorinated acyclic carboxylic ester and the number of carbon atoms in R¹ is 1.

4. The electrolyte composition of claim 1, wherein the fluorinated solvent is a fluorinated acyclic carboxylic ester, R¹ does not contain fluorine, and R² contains fluorine.

5. The electrolyte composition of claim 1, wherein the fluorinated acyclic carboxylic acid ester is selected from one or more members of the group consisting of CH₃—

COO—

CH₂CF₂H, CH₃CH₂—

COOCH₂CF₂H, F₂CHCH₂—

COO—

CH₃, F₂CHCH₂—

COO—

CH₂CH₃, CH₃—

COO—

CH₂CH₂CF₂H, CH₃CH₂—

COO—

CH₂CH₂CF₂H, F₂CHCH₂CH₂—

COO—

CH₂CH₃, and CH₃—

COO—

CH₂CF₃.

6. The electrolyte composition of claim 5, wherein the fluorinated acyclic carboxylic acid ester is 2,2-difluoroethyl acetate.

7. The electrolyte composition of claim 1, wherein the electrolyte composition further comprises a fluorinated acyclic carbonate selected from one or more members of the group consisting of CH₃—

OC(O)O—

CH₂CF₂H, CH₃—

OC(O)O—

CH₂CF₃, CH₃—

OC(O)O—

CH₂CF₂CF₂H, HCF₂CH₂—

OCOO—

CH₂CH₃, and CF₃CH₂—

OCOO—

CH₂CH₃.

8. The electrolyte composition of claim 1, wherein the electrolyte composition further comprises a fluorinated acyclic ether selected from one or more members of the group consisting of HCF₂CF₂CH₂—

O—

CF₂CF₂H and HCF₂CH₂—

O—

CF₂CF₂H.

9. The electrolyte composition of claim 1, wherein the at least one film-forming compound is present in an amount of about 0.01% to about 10% by weight of the total electrolyte composition.

10. The electrolyte composition of claim 1, wherein the electrolyte composition comprises 2,2-difluoroethyl acetate, ethylene carbonate and/or fluoroethylene carbonate, and maleic anhydride.

11. The electrolyte composition of claim 10, wherein the electrolyte composition comprises about 50% to about 80% of 2,2-difluoroethyl acetate by weight of the total electrolyte composition, about 10% to about 40% of ethylene carbonate, fluoroethylene carbonate, or a mixture thereof by weight of the total electrolyte composition;

and about 0.25% to about 5.0% of maleic anhydride by weight of the total electrolyte composition.

12. The electrolyte composition of claim 10, wherein the electrolyte composition comprises about 50% to about 80% of 2,2-difluoroethyl acetate by weight of the total electrolyte composition, about 20% to about 30% of ethylene carbonate by weight of the total electrolyte composition, about 0.25% to about 5.0% of fluoroethylene carbonate by weight of the total electrolyte composition, and about 0.25% to about 5.0% of maleic anhydride by weight of the total electrolyte composition.

13. The electrolyte composition of claim 1, wherein the electrolyte composition comprises 2,2-difluoroethyl acetate and lithium bis(oxalate)borate, and one or more of ethylene carbonate, 2,2-difluoroethyl methyl carbonate, dimethyl carbonate, and fluoroethylene carbonate.

14. 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.

15. The electrochemical cell of claim 14, wherein said electrochemical cell is a lithium ion battery.

16. The lithium ion battery of claim 14, wherein the anode is lithium titanate or graphite.

17. The lithium ion battery of claim 14, 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.

18. The lithium ion battery of claim 14, 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.

19. The lithium ion battery of claim 14, 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_xNi_yM_zMn_2-y-zO_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.

20. The lithium ion battery of claim 14, wherein the cathode comprises Li_aNi_bMn_cCo_dR_eO_2-fZ_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.

21. An electronic device, transportation device, telecommunications device, comprising an electrochemical cell according to claim 14.

23. The electrolyte composition of claim 1, wherein the electrolyte composition consists essentially of:

a) a fluorinated acyclic carboxylic acid ester represented by the formula;

R¹—

COO—

R²,

wherein R¹ and R², independently represent a linear or branched alkyl group;

the sum of carbon atoms in any of R¹ and R² is 2 to 7;

at least two hydrogens in R¹ and/or R² are replaced by fluorines; and

neither R¹ nor R² contains a FCH₂ or FCH group;

b) at least one co-solvent selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, and propylene carbonate, and further comprising one or more members of the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, and ethyl methyl sulfone;

c) at least one film-forming chemical compound which is present in the electrolyte composition at a concentration at which said film-forming chemical compound decomposes at a potential of less than +1.0 V versus a Li/Li⁺ reference electrode, such that the electrolyte composition forms a film and wherein the electrolyte composition does not form a film at a potential of 1.0 V or above versus a Li/Li⁺ reference electrode; and

d) at least one electrolyte salt;

with the proviso that b) and c) are different,

wherein the at least one film-forming chemical compound is at least one selected from the group consisting of maleic anhydride, glutaric anhydride, 2,3-dimethylmaleic anhydride, citraconic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, 2,3-diphenylmaleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 2,3-dihydro-1,4-dithiono-[2,3-c]furan-5,7 dione, phenylmaleic anhydride.

22. A method comprising combining:

a) a fluorinated acyclic carboxylic acid ester represented by the formula;

R¹—

COO—

R²,

wherein R¹ and R² independently represent a linear or branched alkyl group;

the sum of carbon atoms in R¹ and R² is 2 to 7;

at least two hydrogens in R¹ and/or R² are replaced by fluorines; and

neither R¹ nor R² contains a FCH₂ or FCH group;

b) at least one co-solvent selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, and propylene carbonate, and further comprising one or more members of the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, and ethyl methyl sulfone;

c) at least one film-forming chemical compound which is present in the electrolyte composition at a concentration at which said film-forming chemical compound decomposes at a potential of less than +1.0 V versus a Li/Li⁺ reference electrode, such that the electrolyte composition forms a film and wherein the electrolyte composition does not form a film at a potential of 1.0 V or above versus a Li/Li⁺ reference electrode; and

d) at least one electrolyte salt;

with the proviso that b) and c) are different;

to form an electrolyte composition.

24. An electrolyte composition comprising:

a) a fluorinated acyclic carboxylic acid ester represented by the formula;

R¹—

COO—

R²,

wherein R¹ and R² independently represent a linear or branched alkyl group;

the sum of carbon atoms in R¹ and R² is 2 to 7;

at least two hydrogens in R¹ and/or R² are replaced by fluorines; and

neither R¹ nor R² contains a FCH₂ or FCH group;

b) at least one co-solvent selected from the group consisting of ethylene carbonate;

fluoroethylene carbonate, and propylene carbonate, and further comprising one or more members of the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, and ethyl methyl sulfone;

c) at least one film-forming chemical compound which is not lithium bis(oxalate)borate and which is present in the electrolyte composition at a concentration at which said film-forming chemical compound decomposes at a potential of less than +1.0 V versus a Li/Li⁺ reference electrode, such that the electrolyte composition forms a film and wherein the electrolyte composition does not form a film at a potential of 1.0 V or above versus a Li/Li⁺ reference electrode; and

d) at least one electrolyte salt;

with the proviso that b) and c) are different.