Electrolyte for lithium secondary battery and lithium secondary battery including the same

• US 20080131785A1
• Filed: 11/15/2007
• Published: 06/05/2008
• Est. Priority Date: 11/30/2006
• Status: Active Grant

• Current Assignee: Samsung SDI Company Limited
• Original Assignee: Samsung SDI Company Limited
• Inventors: Kim, Jin-Bum, Kim, Jin-Sung, Park, Na-Rae, Kim, Yong-Shik
• Granted Patent: US 8,257,871 B2
• Time in Patent Office: Days
• US Class Current: 429/339
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrolyte for a lithium secondary battery, and a lithium secondary battery including the same are provided. The electrolyte includes: a cyclic ester; an organic solvent including a nitrile-containing solvent represented by Formula 1 at a content ranging from 1 to 5% by volume; and a lithium salt,

R—C≡N   (1)

wherein R is selected from the group consisting of a C₁ to C₁₀ aliphatic hydrocarbon, a C₁ to C₁₀ halogenated aliphatic hydrocarbon, a C₆ to C₁₀ aromatic hydrocarbon, and a C₆ to C₁₀ halogenated aromatic hydrocarbon. The electrolyte can improve swelling characteristics and discharge capacity characteristics at a low temperature, and realize equal or better performance in characteristics such as capacity, life span and the like, as compared to a conventional carbonate-containing electrolyte.

Claims

1. An electrolyte for a lithium secondary battery, comprising:

a cyclic ester;

an organic solvent comprising a nitrile-containing solvent represented by the following Formula 1 at a content ranging from 1 to 5% by volume based on the total volume of the cyclic ester and the nitrile-containing solvent;

R—

C≡

N 

 

(1)

wherein R is selected from the group consisting of a C₁ to C₁₀ aliphatic hydrocarbon, a C₁ to C₁₀ halogenated aliphatic hydrocarbon, a C₆ to C₁₀ aromatic hydrocarbon, and a C₆ to C₁₀ halogenated aromatic hydrocarbon; and

a lithium salt.

2. The electrolyte according to claim 1, wherein the nitrile-containing solvent comprises at least one selected from the group consisting of acetonitrile, propionitrile, butyronitrile, t-butyl cyanide, valeronitrile, caprylonitrile or heptyl cyanide, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, 2-chlorobenzonitrile, 4-chlorobenzonitrile, dichlorobenzonitrile, trichlorobenzonitrile, 2-chloro-4-fluorobenzonitrile, 4-chloro-2-fluorobenzonitrile, phenylacetonitirle, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.

3. The electrolyte according to claim 1, wherein the nitrile-containing solvent comprises cyclohexane carbonitrile.

4. The electrolyte according to claim 1, wherein the electrolyte comprises the cyclic ester at a content ranging from 95 to 99% by volume, based on the total volume of the cyclic ester and the nitrile-containing solvent.

5. The electrolyte according to claim 1, wherein the nitrile-containing solvent is in the range from 1 to 4% by volume based on the total volume of the cyclic ester and the nitrile-containing solvent.

6. The electrolyte according to claim 1, wherein the cyclic ester comprises at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, γ

-butyrolactone, γ

-valerolactone, γ

-caprolactone, δ

-valerolactone, ∈

-caprolactone, and a mixture thereof.

7. The electrolyte according to claim 1, wherein the electrolyte further comprises a linear ester at a content of greater than 0 and not more than 70 parts by volume based on 100 parts by volume of the total cyclic ester and the nitrile-containing solvent.

8. The electrolyte according to claim 6, wherein the linear ester comprises at least one selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl acetate, ethyl acetate, methyl hexanoate, methyl formate, and a mixture thereof.

9. The electrolyte according to claim 1, wherein the lithium salt comprises at least one selected from the group consisting of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, LiAlO₄, LiAlCl₄, LiN(C_xF_2x+1SO₂)(C_yF_2x+1SO₂) (herein, x and y are natural numbers), LiSO₃CF₃, and a mixture thereof.

10. The electrolyte according to claim 1, further comprising:

an additive selected from the group consisting of a carbonate derivative having a substituent selected from the group consisting of halogen, a cyano (CN) group and a nitro (NO₂) group, vinylene carbonate, divinylsulfone, and ethylene sulfite.

11. The electrolyte according to claim 10, wherein the additive comprises an ethylene carbonate derivative represented by Formula 2:

12. The electrolyte according to claim 10, wherein the additive comprises fluoroethylene carbonate.

13. The electrolyte according to claim 10, wherein the additive is added at a content ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total electrolyte.

14. A lithium secondary battery, comprising:

a positive electrode containing a positive electrode active material which can intercalate and deintercalate lithium;

a negative electrode containing a negative electrode active material which can intercalate and deintercalate lithium; and

an electrolyte comprising a cyclic ester, an organic solvent containing a nitrile-containing solvent represented by the following Formula 1 at a content ranging from 1 to 5% by volume based on the total volume of the cyclic ester and the nitrile-containing solvent, and a lithium salt;

R—

C≡

N 

 

(1)

wherein R is selected from the group consisting of a C₁ to C₁₀ aliphatic hydrocarbon, a C₁ to C₁₀ halogenated aliphatic hydrocarbon, a C₆ to C₁₀ aromatic hydrocarbon, and a C₆ to C₁₀ halogenated aromatic hydrocarbon.

15. The battery according to claim 14, wherein the nitrile-containing solvent comprises at least one selected from the group consisting of acetonitrile, propionitrile, butyronitrile, t-butyl cyanide, valeronitrile, caprylonitrile or heptyl cyanide, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, 2-chlorobenzonitrile, 4-chlorobenzonitrile, dichlorobenzonitrile, trichlorobenzonitrile, 2-chloro-4-fluorobenzonitrile, 4-chloro-2-fluorobenzonitrile, phenylacetonitirle, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.

16. The battery according to claim 14, wherein the nitrile-containing solvent comprises cyclohexane carbonitrile.

17. The battery according to claim 14, wherein the electrolyte comprises the cyclic ester at a content ranging from 95 to 99% by volume, based on the total volume of the cyclic ester and the nitrile-containing solvent.

18. The battery according to claim 14, wherein the nitrile-containing solvent is in the range from 1 to 4% by volume based on the total volume of the cyclic ester and the nitrile-containing solvent.

19. The battery according to claim 14, wherein the cyclic ester comprises at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, γ

-butyrolactone, γ

-valerolactone, γ

-caprolactone, δ

-valerolactone, ∈

-caprolactone, and a mixture thereof.

20. The battery according to claim 14, wherein the electrolyte further comprises a linear ester at a content of greater than 0 and not more than 70 parts by volume based on the 100 parts by volume of the total cyclic ester and the nitrile-containing solvent.

21. The battery according to claim 20, wherein the linear ester comprises at least one selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl acetate, ethyl acetate, methyl hexanoate, methyl formate, and a mixture thereof.

22. The battery according to claim 14, wherein the lithium salt comprises at least one selected from the group consisting of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, LiAlO₄, LiAlCl₄, LiN(C_xF_2x+1SO₂)(C_yF_2x+1SO₂) (herein, x and y are natural numbers), LiSO₃CF₃, and a mixture thereof.

23. The battery according to claim 14, wherein the electrolyte further comprises an additive selected from the group consisting of a carbonate derivative with a substituent selected from the group consisting of halogen, a cyano (CN) group and a nitro (NO₂) group, vinylene carbonate, divinylsulfone, and ethylene sulfite.

24. The battery according to claim 23, wherein the additive comprises an ethylene carbonate derivative represented by Formula 2:

25. The battery according to claim 23, wherein the additive comprises fluoroethlyene carbonate.

26. The battery according to claim 23, wherein the additive is added at a content ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total electrolyte.