Lithium secondary battery

• US 5,686,138 A
• Filed: 01/24/1994
• Issued: 11/11/1997
• Est. Priority Date: 11/12/1991
• Status: Expired due to Term

• Current Assignee: Sanyo Electric Company Limited (Panasonic Holdings Corporation)
• Original Assignee: Sanyo Electric Company Limited (Panasonic Holdings Corporation)
• Inventors: Fujimoto, Masahisa, Nohma, Toshiyuki, Ueno, Koji, Takahashi, Masatoshi, Furukawa, Nobuhiro, Yoshinaga, Noriyuki
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/188,609
• Time in Patent Office: 1,387 Days
• Field of Search: 429/194, 429/196, 429/197, 429/218, 429/213, 429/223, 429/224, 429/57, 423/445 R, 423/448, 420/900
• US Class Current: 429/326
• 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 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• 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 4/1315 containing halogen atoms, e.g. LiCoOxFy
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• 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: H01M 6/10 with wound or folded electrodes
• CPC Class Codes: H01M 6/162 characterised by the electrolyte
• CPC Class Codes: H01M 6/164 by the solvent
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Provided is a novel lithium secondary battery including a positive electrode including a compound capable of occluding and discharging lithium, a negative electrode composed mainly of a carbon material which includes a graphite as an only or as a principal component, a separator between the positive electrode and the negative electrode; and an electrolyte solution of an electrolyte solute dissolved in a solvent including at least one specific cyclic compound.

The lithium secondary battery has a large capacity, small self-discharge rate and excellent cycle characteristics and high charge-discharge efficiency.

Claims

1. A lithium secondary battery comprising:

a negative electrode composed mainly of a carbon material consisting essentially of a graphite having

(a) a d-value of the lattice plane (002) obtained by X-ray diffraction thereof of 3,354 to 3,370 and

(b) a crystallite size in the c-axis direction obtained by X-ray diffraction thereof of at least 200 Å

;

a positive electrode composed mainly of a compound capable of occluding and discharging lithium and which is different from the graphite of the negative electrode;

a separator between said positive electrode and said negative electrode; and

an electrolyte solution of an electrolyte solute dissolved in a solvent, said solvent comprising ethylene carbonate in an amount of 20% to 80% by volume based on the volume of the solvent.

2. The lithium secondary battery according to claim 1, wherein said compound capable of occluding and discharging lithium is represented by the formula Li_x MO₂ or Li_y M₂ O₄, wherein M is a transition element, and 0≦

×

≦

1 and 0≦

y≦

2.

3. The lithium secondary battery according to claim 1, wherein said electrolyte solute is selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃ SO₃, LiC₄ F₉ SO₃, LiN(CF₃ SO₂)₂ and LiAsF₆.

4. The lithium secondary battery according to claim 1, wherein said solvent further comprises at least one cyclic compound selected from the group consisting of ethylene thiocarbonate, γ

-thiobutyrolactone, α

-pyrrolidone, γ

-butyrolactone, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, γ

-valerolactone, γ

-ethyl-γ

-butyrolactone, β

-methyl-γ

-butyrolactone, thiolane, pyrazolidine, pyrrolidine, tetrahydrofuran, 3-methyltetrahydrofuran, sulfolane, 3-methylsulfolane, 2-methylsulfolane, 3-ethylsulfolane and 2-ethylsulfolane.

5. The lithium secondary battery according to claim 1, wherein said solvent further comprises at least one low-boiling point solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-diethoxymethoxyethane.

6. A lithium secondary battery comprising:

a negative electrode composed mainly of a carbon material consisting essentially of a graphite having

(a) a d-value of the lattice plane (002) obtained by X-ray diffraction thereof of 3.354 to 3,370,

(b) a crystallite size in the c-axis direction obtained by X-ray diffraction thereof of at least 200 Å and

(c) an average particle diameter of 1 μ

m to 30 μ

m;

a positive electrode composed mainly of a compound capable of occluding and discharging lithium and which is different from the graphite of the negative electrode;

a separator between said positive electrode and said negative electrode; and

an electrolyte solution of an electrolyte solute dissolved in a solvent, said solvent comprising ethylene carbonate in an amount of 20% to 80% by volume based on the volume of the solvent.

7. The lithium secondary battery according to claim 6, wherein said compound capable of occluding and discharging lithium is represented by the formula Li_x MO₂ or Li _y M₂ O₄, wherein M is a transition element, and 0≦

×

≦

1 and 0≦

y≦

2.

8. The lithium secondary battery according to claim 6, wherein said electrolyte solute is selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃ SO₃, LiC₄ F₉ SO₃, LiN(CF₃ SO₂)₂ and LiAsF₆.

9. The lithium secondary battery according to claim 6, wherein said solvent further comprises at least one cyclic compound selected from the group consisting of ethylene thiocarbonate, γ

-thiobutyrolactone, α

-pyrrolidone, γ

-butyrolactone, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, γ

-valerolactone, γ

-ethyl-γ

-butyrolactone, β

-methyl-γ

butyrolactone, thiolane, pyrazolidine, pyrrolidine, tetrahydrofuran, 3-methyltetrahydrofuran, sulfolane, 3-methylsulfolane, 2-methylsulfolane, 3-ethylsulfolane and 2-ethylsulfolane.

10. The lithium secondary battery according to claim 6, wherein said solvent further comprises at least one low-boiling point solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-diethoxymethoxyethane.

11. A lithium secondary battery comprising:

a negative electrode composed mainly of a carbon material consisting essentially of a graphite having

(a) a d-value of the lattice plane (002) obtained by X-ray diffraction thereof of 3.354 to 3.370,

(b) a crystallite size in the c-axis direction obtained by X-ray diffraction thereof of at least 200 Å and

(c) a specific surface area of 0.5 m² /g to 50 m² /g;

a positive electrode composed mainly of a compound capable of occluding and discharging lithium and which is different from the graphite of the negative electrode;

a separator between said positive electrode and said negative electrode; and

an electrolyte solution of an electrolyte solute dissolved in a solvent, said solvent comprising ethylene carbonate in an amount of 20% to 80% by volume based on the volume of the solvent.

12. The lithium secondary battery according to claim 11, wherein said compound capable of occluding and discharging lithium is represented by the formula Li_x MO₂ or Li _y M₂ O₄, wherein M is a transition element, and 0≦

×

≦

1 and 0≦

y≦

2.

13. The lithium secondary battery according to claim 11, wherein said electrolyte solute is selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃ SO₃, LiC₄ F₉ SO₃, LiN(CF₃ SO₂)₂ and LiAsF₆.

14. The lithium secondary battery according to claim 11, wherein said solvent further comprises at least one cyclic compound selected from the group consisting of ethylene thiocarbonate, γ

-thiobutyrolactone , α

-pyrrolidone, γ

-butyrolactone, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, γ

-valerolactone, γ

-ethyl-γ

-butyrolactone, β

-methyl-γ

-butyrolactone, thiolane, pyrazolidine, pyrrolidine, tetrahydrofuran, 3-methyltetrahydrofuran, sulfolane, 3-methylsulfolane, 2-methylsulfolane, 3-ethylsulfolane and 2-ethylsulfolane.

15. The lithium secondary battery according to claim 11, wherein said solvent further comprises at least one low-boiling point solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-diethoxymethoxyethane.

16. A lithium secondary battery comprising:

a negative electrode composed mainly of a carbon material consisting essentially of a graphite having

(a) a d-value of the lattice plane (002) obtained by X-ray diffraction thereof of 3.354 to 3,370,

(b) a crystallite size in the c-axis direction obtained by X-ray diffraction thereof of at least 200 Å

,

(c) an average particle diameter of 1 μ

m to 30 μ

m and

(d) a specific surface area of 0.5 m² /g to 50 m² /g;

a positive electrode composed mainly of a compound capable of occluding and discharging lithium and which is different from the graphite of the negative electrode;

a separator between said positive electrode and said negative electrode; and

an electrolyte solution of an electrolyte solute dissolved in a solvent, said solvent comprising ethylene carbonate in an amount of 20% to 80% by volume based on the volume of the solvent.

17. The lithium secondary battery according to claim 16, wherein said compound capable of occluding and discharging lithium is represented by the formula Li_x MO₂ or Li _y M₂ O₄, wherein M is a transition element, and 0≦

×

≦

1 and 0≦

y≦

2.

18. The lithium secondary battery according to claim 16, wherein said electrolyte solute is selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃ SO₃, LiC₄ F₉ SO₃, LiN(CF₃ SO₂)₂ and LiAsF₆.

19. The lithium secondary battery according to claim 16, wherein said solvent further comprises at least one cyclic compound selected from the group consisting of ethylene thiocarbonate, γ

-thiobutyrolactone , α

-pyrrolidone, γ

butyrolactone, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, γ

-valerolactone, γ

-ethyl-γ

butyrolactone, β

-methyl-γ

-butyrolactone, thiolane, pyrazolidine, pyrrolidine, tetrahydrofuran, 3-methyltetrahydrofuran, sulfolane, 3-methylsulfolane, 2-methylsulfolane, 3-ethylsulfolane and 2-ethylsulfolane.

20. The lithium secondary battery according to claim 16, wherein said solvent further comprises at least one low-boiling point solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-diethoxymethoxyethane.

21. A lithium secondary battery comprising:

a negative electrode composed mainly of a carbon material consisting essentially of a graphite having

(a) a d-value of the lattice plane (002) obtained by X-ray diffraction thereof of 3.354 to 3.370,

(b) a crystallite size in the c-axis direction obtained by X-ray diffraction thereof of at least 200 Å

,

(c) an average particle diameter of 1 μ

m to 30 μ

m,

(d) a specific surface area of 0.5 m² /g to 50 m² /g and

(e) a true density of 1.9 g/cm³ to 2.25 g/cm³ ;

a positive electrode composed mainly of a compound capable of occluding and discharging lithium and which is different from the graphite of the negative electrode;

a separator between said positive electrode and said negative electrode; and

an electrolyte solution of an electrolyte solute dissolved in a solvent, said solvent comprising ethylene carbonate in an amount of 20% to 80% by volume based on the volume of the solvent.

22. The lithium secondary battery according to claim 21, wherein said compound capable of occluding and discharging lithium is represented by the formula Li_x MO₂ or Li _y M₂ O₄, wherein M is a transition element, and 0≦

×

≦

1 and 0≦

y≦

2.

23. The lithium secondary battery according to claim 21, wherein said electrolyte solute is selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃ SO₃, LiC₄ F₉ SO₃, LiN(CF₃ SO₂)₂ and LiAsF₆.

24. The lithium secondary battery according to claim 21, wherein said solvent further comprises at least one cyclic compound selected from the group consisting of ethylene thiocarbonate, γ

-thiobutyrolactone , α

-pyrrolidone, γ

-butyrolactone, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, γ

-valerolactone, γ

-ethyl-γ

-butyrolactone, β

-methyl-γ

butyrolactone, thiolane, pyrazolidine, pyrrolidine, tetrahydrofuran, 3-methyltetrahydrofuran, sulfolane, 3-methylsulfolane, 2-methylsulfolane, 3-ethylsulfolane and 2-ethylsulfolane.

25. The lithium secondary battery according to claim 21, wherein said solvent further comprises at least one low-boiling point solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-diethoxymethoxyethane.

29. The lithium secondary battery according to claim 22 or 27, wherein said compound capable of occluding and discharging lithium is selected from the group consisting of LiCoO₂, LiMnO₂, LiNiO₂, LiCrO₂ and LiMn₂ O₄.

30. The lithium secondary battery according to claim 21 or 26, wherein said d-value is 3.355 or more and less than 3.360.

31. The lithium secondary battery according to claim 21 or 26, wherein said d-value is 3.360 or more and less than 3.365.

32. The lithium secondary battery according to claim 21 or 26, wherein said d-value is 3.365 or more and less than 3.370.

33. The lithium secondary battery according to claim 21 or 26, wherein said solvent consists essentially of 20% to 80% by volume of ethylene carbonate and 80% to 20% by volume of dimethyl carbonate.

34. The lithium secondary battery according to claim 21 or 26, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

35. The lithium secondary battery according to claim 22 or 27, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

36. The lithium secondary battery according to claim 23 or 28, wherein said crystallite size in c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

37. The lithium secondary battery according to claim 29, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

38. The lithium secondary battery according to claim 30, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

39. The lithium secondary battery according to claim 31, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

40. The lithium secondary battery according to claim 32, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

41. The lithium secondary battery according to claim 33, wherein said crystallite size in the c-axis direction obtained by X-ray diffraction is greater than 220 Å

.

26. A lithium secondary battery comprising:

a negative electrode composed mainly of, a carbon material consisting essentially of a graphite having

(a) a d-value of the lattice plane (002) obtained by X-ray diffraction thereof of 3.354 to 3.370,

(b) a crystallite size in the c-axis direction obtained by X-ray diffraction thereof of at least 200 Å

,

(c) an average particle diameter of 1 μ

m to 30 μ

m,.

(d) a specific surface area of 0.5 m² /g to 50 m² /g and

(e) a true density of 1.9 g/cm³ to 2.25 g/cm³ ;

a positive electrode composed mainly of a compound capable of occluding and discharging lithium and which is different from the graphite of the negative electrode;

a separator between said positive electrode and said negative electrode; and

an electrolyte solution of an electrolyte solute dissolved in a solvent, said solvent consisting essentially of 20% to 80% by volume of ethylene carbonate and 80% to 20% by volume of an least one of dimethyl carbonate and diethyl carbonate.

27. The lithium secondary battery according to claim 26, wherein said compound capable of occluding and discharging lithium is represented by the formula Li_x MO₂ or Li_y M₂ O₄, wherein M is a transition element, and 0≦

×

≦

1 and 0≦

y≦

2.

28. The lithium secondary battery according to claim 26, wherein said electrolyte solute is selected from the group consisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃ SO₃, LiC₄ F₉ SO₃, LiN(CF₃ SO₂)₂ and LiAsF₆.