Lithium secondary battery

• US 5,498,492 A
• Filed: 09/15/1994
• Issued: 03/12/1996
• Est. Priority Date: 09/17/1993
• Status: Expired due to Term

• Current Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Original Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Inventors: Takami, Norio, Satoh, Asako, Hara, Michikazu, Ohsaki, Takahisa
• Primary Examiner(s): Willis, Jr., Prince
• Assistant Examiner(s): CHANEY, CAROL DIANE
• Application Number:
  US08/305,336
• Time in Patent Office: 544 Days
• Field of Search: 429/212, 429/213, 429/194
• US Class Current: 429/212
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/745 Expanded metal
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A lithium secondary battery with a large capacity and a long cycle life is disclosed. This lithium secondary battery includes a case, a negative electrode accommodated in the case and containing a polymeric material which has been formed by heat-treating a polymer having a perynaphthalene structure as a main repeating unit in a non-oxidizing atmosphere at 500° to 1000° C. and which absorbs and desorbs lithium ions, a positive electrode accommodated in the case and so arranged as to oppose the negative electrode with a separator sandwiched between them, and a nonaqueous electrolyte contained in the case.

Claims

1. A lithium secondary battery comprising:

a case;

a negative electrode accommodated in said case and containing a polymeric material which absorbs and desorbs lithium ions and which has been formed by heat-treating a polymer in a non-oxidizing atmosphere at 500°

to 1000°

C., the polymer having as a main repeating unit a structure represented by formula (I) below;

##STR10## wherein R¹ to R⁴ may be the same or different and represent hydrogen, an alkyl group, a phenyl group, or a naphthyl group;

a positive electrode accommodated in said case and so arranged as to oppose said negative electrode with a separator sandwiched therebetween; and

a nonaqueous electrolyte contained in said case.

2. The secondary battery according to claim 1, wherein all of R¹ to R⁴ in formula (I) are hydrogen.

3. The secondary battery according to claim 1, wherein said polymeric material has a specific surface area not more than 500 m² /g.

4. The secondary battery according to claim 1, wherein said polymeric material has a density of 1.0 to 1.9 g/cm³.

5. The secondary battery according to claim 1, wherein said polymeric material is contained in said negative electrode in the form of particles or fibers.

6. The secondary battery according to claim 1, wherein said positive electrode contains lithium-cobalt oxide or lithium-nickel oxide as an active material.

7. The secondary battery according to claim 1, wherein said nonaqueous electrolyte has a composition prepared by dissolving lithium hexafluorophosphate (LiPF₆) as an electrolyte in a solvent mixture of ethylenecarbonate and at least one nonaqueous solvent selected from the group consisting of propylenecarbonate, 2-methyltetrahydrofuran, and 1,2-dimethoxyethane.

8. A lithium secondary battery comprising:

a case;

a negative electrode accommodated in said case and containing a polymeric material which absorbs and releases lithium ions and which comprises a heat-treated material of polymer having as a main repeating unit a structure represented by formula (I) below;

##STR11## wherein R¹ to R⁴ may be the same or different and represent hydrogen, an alkyl group, a phenyl group, or a naphthyl group, and having one aromatic ring vibrational peak at 1500 to 1700 cm^-1 in infrared photo-acoustic spectroscopy and a peak derived from aromatic ring at 100 to 150 ppm in a solid-state C₁₃ NMR spectrum;

a positive electrode accommodated in said case and so arranged as to oppose said negative electrode with a separator sandwiched therebetween; and

a nonaqueous electrolyte contained in said case.

9. The secondary battery according to claim 8, wherein said polymeric material has one aromatic ring vibrational peak with a half-width of not less than 50 cm^-1 at 1500 to 1700 cm^-1 in infrared photo-acoustic spectroscopy.

10. The secondary battery according to claim 8, wherein said polymeric material has a composition in which all of R¹ to R⁴ in formula (II) are hydrogen, has three aromatic CH bending vibrational peaks at 700 to 950 cm^-1 in infrared photo-acoustic spectroscopy, and has an element ratio (H/C) of hydrogen to carbon of not more than 0.35.

11. The secondary battery according to claim 8, wherein said polymeric material has a specific surface area not more than 500 m² /g.

12. The secondary battery according to claim 8, wherein said polymeric material has a density of 1.0 to 1.9 g/cm³.

13. The secondary battery according to claim 8, wherein said polymeric material is contained in said negative electrode in the form of particles or fibers.

14. The secondary battery according to claim 8, wherein said positive electrode contains lithium-cobalt oxide or lithium-nickel oxide as an active material.

15. The secondary battery according to claim 8, wherein said nonaqueous electrolyte has a composition prepared by dissolving lithium hexafluorophosphate (LiPF₆) as an electrolyte in a solvent mixture of ethylenecarbonate and at least one nonaqueous solvent selected from the group consisting of propylenecarbonate, 2-methyltetrahydrofuran, and 1,2-dimethoxyethane.

16. A lithium secondary battery comprising:

a case;

a negative electrode accommodated in said case and containing a polymeric material which absorbs and desorbs lithium ions, and which comprises a polymer having a structure represented by formula (II) below ##STR12## as a repeating unit in each of X and Y directions such that the repeating unit in the X direction is equal to or larger than the repeating unit in the Y direction wherein said polymeric material has one aromatic ring vibrational peak at 1500 to 1700 cm^-1 in infrared photo-acoustic spectroscopy and has a peak derived from aromatic ring at 100 to 150 ppm in a silid-state C₁₃ NMR spectrum;

a positive electrode accommodated in said case and so arranged as to oppose said negative electrode with a separator sandwiched therebetween; and

a nonaqueous electrolyte contained in said case.

17. The secondary battery according to claim 16, wherein said polymeric material has one aromatic ring vibrational peak with a half-width of not less than 50 cm^-1 at 1500 to 1700 cm^-1 in infrared photo-acoustic spectroscopy.

18. The secondary battery according to claim 16, wherein said polymeric material has two aromatic CH bending vibrational peaks at 700 to 950 cm^-1 in infrared photo-acoustic spectroscopy.

19. The secondary battery according to claim 16, wherein said polymeric material has a specific surface area not more than 500 m² /g.

20. The secondary battery according to claim 16, wherein said polymeric material has a density of 1.0 to 1.9 g/cm³.

21. The secondary battery according to claim 16, wherein said polymeric material is contained in said negative electrode in the form of particles or fibers.

22. The secondary battery according to claim 16, wherein said positive electrode contains lithium-cobalt oxide or lithium-nickel oxide as an active material.

23. The secondary battery according to claim 16, wherein said nonaqueous electrolyte has a composition prepared by dissolving lithium hexafluorophosphate (LiPF₆) as an electrolyte in a solvent mixture of ethylenecarbonate and at least one nonaqueous solvent selected from the group consisting of propylenecarbonate, 2-methyltetrahydrofuran, and 1,2-dimethoxyethane.