Lithium secondary battery

• US 6,365,300 B1
• Filed: 09/15/2000
• Issued: 04/02/2002
• Est. Priority Date: 12/03/1998
• Status: Expired due to Term

• Current Assignee: Sumitomo Electric Industries Limited (Sumitomo Corporation)
• Original Assignee: Sumitomo Electric Industries Limited (Sumitomo Corporation)
• Inventors: Yamanaka, Shosaku, Ota, Nobuhiro
• Primary Examiner(s): Chaney, Carol
• Assistant Examiner(s): YUAN, DAH WEI D
• Application Number:
  US09/601,498
• Time in Patent Office: 564 Days
• Field of Search: 429/188, 429/303, 429/304, 429/307, 429/322, 429/324
• US Class Current: 429/304
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• 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 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/621 Binders
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 6/182 with halogenide as solid electrolyte
• CPC Class Codes: H01M 6/187 Solid electrolyte characterised by the form
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A lithium secondary battery that can suppress short circuits caused by the generation of dendrites from the negative electrode, that has high energy density, and that is excellent in charge and discharge-cycle performance. The lithium secondary battery comprises an electrolytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material. The electrolytic layer is made of an inorganic solid electrolyte. The positive electrode contains an organic high polymer. It is desirable that the electrolytic layer contain at least one type selected from the group consisting of oxygen, sulfur, nitrogen, sulfide, and oxynitride. It is also desirable that the organic electrolysis solution contained in the positive electrode have a lithium ion-conductivity lower than that of the inorganic solid electrolyte constituting the electrolytic layer.

Claims

1. A lithium secondary battery comprising an electrolytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the electrolytic layer contains;

(a) an Li constituent not less than 30 atm. % and not more than 65 atm. %;

(b) at least one type of element selected from the group consisting of phosphorous, silicon, boron, germanium, and gallium; and

(c) sulfur.

2. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer has a lithium-ion conductivity of 1×

10<sup>−

5</sup> S/cm or more at 25°

C.

3. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer has a lithium-ion conductivity of 5×

10<sup>−

5</sup> S/cm or more at 25°

C.

4. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer is made of an amorphous body.

5. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer contains at least one type selected from the group consisting of oxygen, nitrogen, sulfide, and oxynitride.

6. The lithium secondary battery as defined in claim 1, wherein the electrolytic layer contains at least one element selected from the group consisting of oxygen and nitrogen.

7. The lithium secondary battery as defined in claim 1, wherein the organic high polymer contained in the positive electrode is a disulfide-family high polymer containing polyaniline.

8. The lithium secondary battery as defined in claim 1, wherein the organic high polymer contained in the positive electrode contains one type of lithium salt selected from the group consisting of LiPF₆ and LiCF₃SO₃.

9. The lithium secondary battery as defined in claim 1, wherein the positive electrode contains an organic electrolyte solution.

10. The lithium secondary battery as defined in claim 9, wherein the organic electrolyte solution contained in the positive electrode has a lithium ion-conductivity lower than that of the inorganic solid electrolyte that constitutes the electrolytic layer.

11. The lithium secondary battery as defined in claim 9, wherein the organic electrolyte solution contained in the positive electrode:

(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and

(b) thereby reduces the ionic conductivity of the organic electrolyte solution in the vicinity of the contact portion to a value lower than that of the inorganic solid electrolyte.

12. The lithium secondary battery as defined in claim 9, wherein the organic solvent contained in the organic electrolyte solution contained in the positive electrode:

(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and

(b) thereby increases the viscosity of the organic electrolyte solution in the vicinity of the contact portion.

13. The lithium secondary battery as defined in claim 9, wherein the organic solvent contained in the organic electrolyte solution contained in the positive electrode contains a sulfolane-family compound.

14. The lithium secondary battery as defined in claim 9, wherein the organic solvent contained in the organic electrolyte solution contained in the positive electrode contains a chain carboxylic ester family.

15. The lithium secondary battery as defined in claim 1, wherein the negative electrode has a surface roughness not less than 0.01 μ

m and not more than 5 μ

m in the value of Rmax.

16. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the electrolytic layer contains at least one type selected from the group consisting of oxygen, nitrogen, sulfide, and oxynitride; and

(a) the sulfide is composed of at least one type selected from the group consisting of Li₂S, a compound between Li₂S and SiS₂, a compound between Li₂S and GeS₂, and a compound between

(b) the oxynitiride is composed of at least one type selected from the group consisting of Li₃PO_4-xN_2x/3, Li₄SiO_4-xN_2x/3, Li₄GeO_4-xN_2x/3 (where 0<

X<

4), and Li₃BO_3-xN_2x/3 (where 0<

X<

3).

17. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the electrolytic layer has a thickness not less than 50 nm and not more than 50 μ

m.

18. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the electrolytic layer consists of two layers that are a positive electrode-side layer and a negative electrode-side layer.

19. The lithium secondary battery as defined in claim 18, wherein:

(a) the negative electrode-side layer is a film made of a lithium ion-conductive compound containing sulfide; and

(b) the positive electrode-side layer is a film made of a lithium ion-conductive compound containing oxide.

20. The lithium secondary battery as defined in claim 18, wherein:

(a) the electrolytic layer consisting of two layers has a total thickness not less than 2 μ

m and not more than 22 μ

m; and

(b) the positive electrode-side layer has a thickness not less than 0.1 μ

m and not more than 2 μ

m.

21. The lithium secondary battery as defined in claim 18, wherein:

(a) the negative electrode-side layer contains lithium sulfide and silicon sulfide; and

(b) the positive electrode-side layer contains at least one type selected from the group consisting of a phosphate compound and a titanate compound.

22. The lithium secondary battery as defined in claim 18, wherein the positive electrode-side layer contains:

(a) an Li constituent not less than 30 atm. % and not more than 50 atm. %;

(b) phosphorus; and

(c) at least one element selected from the group consisting of oxygen and nitrogen.

23. The lithium secondary battery as defined in claim 18, wherein the positive electrode-side layer has a thickness not less than 1% and not more than 50% of the thickness of the negative electrode-side layer.

24. The lithium secondary battery as defined in claim 18, wherein the positive electrode-side layer has a thickness not less than 10 nm and not more than 25 μ

m.

25. The lithium secondary battery as defined in claim 18, wherein:

(a) the positive electrode contains inorganic solid electrolytic particles having lithium-ion conductivity; and

(b) the inorganic solid electrolytic particles have an ion-conductivity of 10<sup>−

3</sup> S/cm or more.

26. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the positive electrode contains an organic electrolyte solution, and the organic solvent contained in the organic electrolyte solution contained in the positive electrode;

(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and

(b) thereby gasifies in the vicinity of the contact portion.

27. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrode; and

(b) the positive electrode contains an organic high polymer, wherein the positive electrode contains an organic electrolyte solution, and the organic solvent contained in the organic electrolyte solution contained in the positive electrode;

(a) comes into contact with the lithium-containing material that constitutes the negative electrode; and

(b) thereby solidifies in the vicinity of the contact portion.

28. A lithium secondary battery comprising an electrolytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the positive electrode contains an organic electrolyte solution, and the organic solvent contained in the organic electrolyte solution contained in the positive electrode contains at least one type of compound selected from the group consisting of compounds having a nitrile group and compounds having olefinic linkage.

29. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the negative electrode;

(a) has at its electrolytic-layer side a layer of a metal that forms an alloy or intermetallic compound with lithium; and

(b) has a multilayer or a graded structure in composition.

30. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the negative electrode;

(a) has no oxide layer on its surface; and

(b) has a sulfide or nitride layer on its surface.

31. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein the electrolytic layer is formed directly on the surface of the negative electrode without the medium of an oxide layer.

32. A lithium secondary battery comprising an electroytic layer, a positive electrode, and a negative electrode that is made of a lithium-containing material, in which battery:

(a) the electrolytic layer is made of an inorganic solid electrolyte; and

(b) the positive electrode contains an organic high polymer, wherein;

(a) the positive and negative electrodes are each provided with a collector; and

(b) the electrolytic layer is formed directly on the negative electrode-side collector without providing a lithium-containing material as the negative electrode.