NONAQUEOUS ELECTROLYTIC SOLUTION AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY

• US 20100035146A1
• Filed: 12/06/2007
• Published: 02/11/2010
• Est. Priority Date: 12/06/2006
• Status: Abandoned Application

• Current Assignee: Mitsubishi Chemical Corporation (Mitsubishi Chemical Group Corp.)
• Original Assignee: Mitsubishi Chemical Corporation (Mitsubishi Chemical Group Corp.)
• Inventors: Fujii, Takashi, Kinoshita, Shinichi, Ohashi, Youichi
• Application Number:
  US12/518,188
• Publication Number:
  US 20100035146A1
• Time in Patent Office: Days
• US Class Current: 429/200
• 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 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A nonaqueous electrolytic solution that can provide a high energy density nonaqueous electrolyte secondary battery having a high capacity, excellent storage characteristics, and excellent cycle characteristics and suppressing the decomposition of an electrolytic solution and the deterioration thereof when used in a high-temperature environment includes an electrolyte, a nonaqueous solvent, and a compound represented by general formula (1):

wherein R¹, R², and R³ each independently represent a hydrogen atom, a cyano group, or an optionally halogen atom-substituted hydrocarbon group having 1 to 10 carbon atoms, with the proviso that R¹ and R² do not simultaneously represent hydrogen atoms.

Claims

1. A nonaqueous electrolytic solution for use in a nonaqueous electrolyte secondary battery including a positive electrode having a positive-electrode active material capable of storing and releasing metal ions and a negative electrode having a negative-electrode active material containing at least one atom selected from the group consisting of Si, Sn, and Pb and capable of storing and releasing metal ions, the nonaqueous electrolytic solution comprising a compound represented by general formula (1) and/or a compound having 2 to 4 cyano groups in its structural formula:

wherein in general formula (1), R¹, R², and R³ each independently represent a hydrogen atom, a cyano group, or an optionally halogen atom-substituted hydrocarbon group having 1 to 10 carbon atoms.

2. The nonaqueous electrolytic solution according to claim 1, wherein in general formula (1), either or both of R¹ and R² each independently represent a cyano group or an optionally halogen atom-substituted hydrocarbon group having 1 to 10 carbon atoms.

3. The nonaqueous electrolytic solution according to claim 1, wherein the compound represented by general formula (1) is at least one compound selected from the group consisting of acrylonitrile, methacrylonitrile, crotononitrile, 3-methylcrotononitriles, 2-methyl-2-butenenitrile, 2-pentenenitrile, 2-methyl-2-pentenenitrile, 1-cyano-1-cyclopentene, 1-cyano-1-cyclohexene, geranylnitrile, cinnamonitrile, 2-furonitrile, fumaronitrile, and tetracyanoethylene.

4. The nonaqueous electrolytic solution according to claim 1, wherein the compound having 2 to 4 cyano groups in its structural formula is represented by general formula (3):

NC—

(X)_n—

CN  

 

(3)

wherein in general formula (3), X represents CH₂, CFH, CF₂, CHR, CFR, CR₂, C═

O, O, S, NH, or NR;

R represents an optionally substituted hydrocarbon group having 5 or less carbon atoms or a cyano group;

n represents an integer of 1 or more; and

n X'"'"'s may be the same or different.

5. The nonaqueous electrolytic solution according to claim 4, wherein in general formula (3), X represents one or more groups selected from the group consisting of CH₂, CFH, CF₂, CHR, CFR, CR₂, O, S, and NR, and the one or more groups may be the same or different.

6. The nonaqueous electrolytic solution according to claim 5, wherein the compound represented by general formula (3) is at least one compound selected from the group consisting of succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, azelanitrile, sebaconitrile, 3,3′

-oxydipropionitrile, 3,3′

-thiodipropionitrile, 1,2,3-propanetricarbonitrile, and 1,3,5-pentanetricarbonitrile.

7. The nonaqueous electrolytic solution according to claim 4, wherein in general formula (3), n represents an integer of 5 or more.

8. The nonaqueous electrolytic solution according to claim 7, wherein the compound represented by general formula (3) is at least one compound selected from the group consisting of pimelonitrile, suberonitrile, azelanitrile, sebaconitrile, 3,3′

-oxydipropionitrile, and 1,3,5-pentanetricarbonitrile.

9. The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous electrolytic solution contains 0.001 to 10% by weight of the compound represented by general formula (1) and/or the compound having 2 to 4 cyano groups in its structural formula.

10. The nonaqueous electrolytic solution according to claim 1, further comprising at least one compound selected from the group consisting of a halogen atom-containing cyclic carbonate, a cyclic carbonate having a carbon-carbon unsaturated bond, a monofluorophosphate, and a difluorophosphate.

11. The nonaqueous electrolytic solution according to claim 10, wherein the nonaqueous electrolytic solution contains 0.001 to 70% by weight of the halogen atom-containing cyclic carbonate.

12. The nonaqueous electrolytic solution according to claim 10, wherein the halogen atom-containing cyclic carbonate is at least one compound selected from the group consisting of fluoroethylene carbonate, difluoroethylene carbonate, fluoropropylene carbonate, trifluoromethylethylene carbonate, and fluorotrifluoromethylethylene carbonate.

13. The nonaqueous electrolytic solution according to claim 10, wherein the nonaqueous electrolytic solution contains 0.001 to 10% by weight of the cyclic carbonate having a carbon-carbon unsaturated bond.

14. The nonaqueous electrolytic solution according to claim 10, wherein the cyclic carbonate having a carbon-carbon unsaturated bond is at least one compound selected from the group consisting of vinylene carbonate, 4-methylvinylene carbonate, 4,5-dimethylvinylene carbonate, 4-vinylethylene carbonate, and 5-methyl-4-vinylethylene carbonate.

15. The nonaqueous electrolytic solution according to claim 10, wherein the nonaqueous electrolytic solution contains 0.001 to 5% by weight of at least one compound selected from the group consisting of monofluorophosphates and difluorophosphates.

27. A nonaqueous electrolyte secondary battery comprising a positive electrode having a positive-electrode active material capable of storing and releasing metal ions, a negative electrode having a negative-electrode active material containing at least one atom selected from the group consisting of Si, Sn, and Pb and capable of storing and releasing metal ions, and the nonaqueous electrolytic solution according to claim 1.

16. A nonaqueous electrolytic solution for use in a nonaqueous electrolyte secondary battery including a negative electrode, a positive electrode, and a nonaqueous electrolytic solution, the negative electrode and the positive electrode being capable of storing and releasing metal ions, the nonaqueous electrolytic solution comprising an electrolyte, a nonaqueous solvent, and a compound represented by general formula (2):

wherein in general formula (2), R⁴, R⁵, and R⁶ each independently represent a hydrogen atom, a cyano group, or an optionally halogen atom-substituted hydrocarbon group having 1 to 10 carbon atoms, with the proviso that R⁴ and R⁵ do not simultaneously represent hydrogen atoms.

17. The nonaqueous electrolytic solution according to claim 16, wherein the nonaqueous electrolytic solution contains 0.001 to 10% by weight of the compound represented by general formula (2).

18. The nonaqueous electrolytic solution according to claim 16, further comprising at least one compound selected from the group consisting of a halogen atom-containing cyclic carbonate, a cyclic carbonate having a carbon-carbon unsaturated bond, a monofluorophosphate, and a difluorophosphate.

19. The nonaqueous electrolytic solution according to claim 18, wherein the nonaqueous electrolytic solution contains 0.001 to 70% by weight of the halogen atom-containing cyclic carbonate.

20. The nonaqueous electrolytic solution according to claim 18, wherein the halogen atom-containing cyclic carbonate is at least one compound selected from the group consisting of fluoroethylene carbonate, difluoroethylene carbonate, fluoropropylene carbonate, trifluoromethylethylene carbonate, and fluorotrifluoromethylethylene carbonate.

21. The nonaqueous electrolytic solution according to claim 18, wherein the nonaqueous electrolytic solution contains 0.001 to 10% by weight of the cyclic carbonate having a carbon-carbon unsaturated bond.

22. The nonaqueous electrolytic solution according to claim 18, wherein the cyclic carbonate having a carbon-carbon unsaturated bond is at least one compound selected from the group consisting of vinylene carbonate, 4-methylvinylene carbonate, 4,5-dimethylvinylene carbonate, 4-vinylethylene carbonate, and 5-methyl-4-vinylethylene carbonate.

23. The nonaqueous electrolytic solution according to claim 18, wherein the nonaqueous electrolytic solution contains 0.001 to 5% by weight of at least one compound selected from the group consisting of monofluorophosphates and difluorophosphates.

24. The nonaqueous electrolytic solution according to claim 16, wherein the nonaqueous electrolytic solution is used in a nonaqueous electrolyte secondary battery including a negative electrode containing a carbonaceous material serving as an active material.

28. A nonaqueous electrolyte secondary battery comprising a positive electrode having a positive-electrode active material capable of storing and releasing metal ions, a negative electrode having a negative-electrode active material containing at least one atom selected from the group consisting of Si, Sn, and Pb and capable of storing and releasing metal ions, and the nonaqueous electrolytic solution according to claim 16.

29. A nonaqueous electrolyte secondary battery comprising a negative electrode, a positive electrode, and a nonaqueous electrolytic solution, the negative electrode and the positive electrode being capable of storing and releasing metal ions, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to claim 16.

30. The nonaqueous electrolyte secondary battery according to claim 29, wherein the negative electrode contains a carbonaceous material serving as an active material.

25. A nonaqueous electrolytic solution for use in a nonaqueous electrolyte secondary battery including a negative electrode, a positive electrode, and a nonaqueous electrolytic solution, the negative electrode and the positive electrode being capable of storing and releasing metal ions, the nonaqueous electrolytic solution comprising an electrolyte, a nonaqueous solvent, a compound represented by general formula (1), and at least one compound selected from the group consisting of halogen atom-containing cyclic carbonates, monofluorophosphates, and difluorophosphates:

wherein in general formula (1), R¹, R², and R³ each independently represent a hydrogen atom, a cyano group, or an optionally halogen atom-substituted hydrocarbon group having 1 to 10 carbon atoms.

26. The nonaqueous electrolytic solution according to claim 25, wherein the nonaqueous electrolytic solution is used in a nonaqueous electrolyte secondary battery including a negative electrode containing a carbonaceous material serving as an active material.

31. A nonaqueous electrolyte secondary battery comprising a negative electrode, a positive electrode, and a nonaqueous electrolytic solution, the negative electrode and the positive electrode being capable of storing and releasing metal ions, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to claim 25.

32. The nonaqueous electrolyte secondary battery according to claim 31, wherein the negative electrode contains a carbonaceous material serving as an active material.