Lithium secondary battery

• US 5,244,757 A
• Filed: 01/13/1992
• Issued: 09/14/1993
• Est. Priority Date: 01/14/1991
• Status: Expired due to Term

• Current Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Original Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Inventors: Ohasaki, Takahisa, Takami, Norio
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US07/819,224
• Time in Patent Office: 610 Days
• Field of Search: 429/194, 429/218, 429/196, 429/197, 423/435
• US Class Current: 429/336
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• 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 10/0569 characterised by the solvents
• CPC Class Codes: H01M 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 6/10 with wound or folded electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A lithium secondary battery which comprises a vessel, a positive electrode, a negative electrode and an electrolyte. Both of the electrodes are placed in the vessel and the vessel is filled with the electrolyte. The negative electrode includes carbonaceous material spherical particles or carbonaceous fibers which absorb and discharge lithium ions. The carbonaceous material has a graphite-like layered structure part and a turbulence-layered structure part. Fine structures of the carbonaceous material spherical particles are arranged in point-orientation.

Claims

1. A lithium secondary battery, comprising:

a vessel;

a positive electrode containing an active material housed in the vessel;

a lithium ion conductive electrolyte in the vessel; and

a negative electrode arranged in the vessel containing carbonaceous material spherical particles as active materials that absorb and discharge lithium ions, the carbonaceous material spherical particles containing a graphitoid layered structure part and a turbulence-layered structure part, fine structures of the carbonaceous material spherical particle being arranged in point-orientation.

2. The battery of claim 1, wherein the mean value of the (002) face distance (d₀₀₂) in the carbonaceous material spherical particle is 0.337 nm to 0.380 nm.

3. The battery of claim 1, wherein the mean size of the crystal lattice (LC) along the C-axis in the spherical particle is 1 nm to 25 nm.

4. The battery of claim 1, wherein the Raman spectrum ratio R₁ /R₂ of the spherical particles is in the range of 0.5 to 1.5 where:

R₁ is a peak value at 1,360^-1 cm, and

R₂ is a peak value at 1,580^-1 cm.

5. The battery of claim 1, wherein the atomic ratio of hydrogen to carbon (H/C) in the spherical particles is less than 0.15.

6. The battery of claim 1, wherein the average size of the spherical particles is in the range of 0.5 μ

m to 100 μ

m.

7. The battery of claim 1, wherein the ratio of the minor radius and the major radius of the spherical particles is at least 1/10.

8. The battery of claim 1, wherein the spherical particles have an exothermic peak at 900°

C. or less measured by differential thermal analysis.

16. The battery of claim 1 or claim 9 alternatively, wherein the lithium ion conductive electrolyte contains a solvent including ethylene carbonate, propylene carbonate and at least one compound selected from the group consisting of 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl carbonate, dimethoxymethane, γ

-butyrolactone and tetrahydrofuran, and an electrolytic salt selected from the group consisting of lithium borofluoride, lithium phosphate hexafluoride and lithium trifluorometasulfonate.

17. The battery of claim 16, wherein the ratio of at least one compound in the solvent is 40 volume % or less.

18. The battery of either of claims 1 or 9, wherein the lithium ion conductive electrolyte contains at least one nonaqueous solvent selected from a group consisting of ethylene carbonate, propylene carbonate, diethyl carbonate γ

-butyrolactone, sulpholan, acetonitrile, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,3-dimethoxypropane, dimethylether, tetrahydrofuran and 2-methyltetrahydrofuran.

9. A lithium secondary battery, comprising:

a vessel;

a positive electrode containing an active material housed in the vessel;

a lithium ion conductive electrolyte in the vessel; and

,

a negative electrode arranged in the vessel containing carbonaceous material fibers as active materials that absorb and discharge lithium ions, the carbonaceous material fibers containing a graphitoid layered structure part and a turbulence-layered structure part both having fine structures arranged in at least one of (a) a lamellar type structure and (b) a Brooks-Taylor type structure defined by a combination of lamellar and radiant type structures or by a radial crystallite orientation surface property and a random central structure.

10. The battery of claim 9, wherein the mean value of the (002) face distance (d₀₀₂) in the carbonaceous material fibers is 0.337 nm to 0.380 nm.

11. The battery of claim 9, wherein the mean size of the crystal lattice (Lc) along the C-axis direction in the fibers is 1 nm to 25 nm.

12. The battery of claim 9, wherein the Raman spectrum ratio R₁ /R₂ of the fibers is in the range of 0.5 to 1.5 where;

R₁ is a peak value at 1,360^-1 cm, and

R² is a peak value at 1,580^-1 cm.

13. The battery of claim 9, wherein the atomic ratio of hydrogen/carbon (H/C) of the fibers is less than 0.15.

14. The battery of claim 9, wherein the average size of the diameter of the fibers is in the range of 1 μ

m to 100 μ

m and the average size of the length of the fibers is in the range of 1 μ

m to 200 μ

m.

15. The battery of claim 9, wherein the fibers have an exothermic peak at 900°

C. or less measured by differential thermal analysis.