Negative electrode material for lithium secondary battery and its manufacturing method, and negative electrode for lithium secondary battery, and lithium secondary battery

Patent metadata

Field	Value
Publication number	US-9070941-B2
Application number	US-201113391811-A
Country	US
Kind code	B2
Filing date	Dec 9, 2011
Priority date	Mar 2, 2011
Publication date	Jun 30, 2015
Grant date	Jun 30, 2015

Abstract

[Object] The object is to provide a negative electrode material for a lithium secondary battery, wherein a sulfide-based negative electrode with water-resistant properties can exert excellent cycle characteristics and high output performance while maintaining a high discharge capacity and there is no precipitation of lithium dendrites during charge at low temperature.
[Means for Solving Problems] A negative electrode material for a lithium secondary battery comprising sulfur and sulfide glass including the following components (i) and (ii):
(i) at least one or more elements selected from a group consisting of Sb, As, Bi, Ge, Si, Cu, Zn, Pd, In and Zr; and
(ii) at least one or more elements selected from a group consisting of Se, Te, Ga, Sn, Pb, Cd, Al, Fe, Mg, Ca, Co, Ag, Sr, P and Ba,

wherein the ratio of the above components is sulfur: 40-80 mol %, (i): 1-50 mol % and (ii): 1-50 mol %, respectively.

First claim

The invention claimed is:

1. A negative electrode material for a lithium secondary battery comprising sulfide glass, including sulfur and the following components (i) and (ii):
(i) at least one or more elements selected from a group consisting of Sb, Bi, Ge, Cu, and Zn; and
(ii) the element Sn,
wherein the ratio in said sulfide glass is sulfur: 40-80 mol %, (i): 1-50 mol % and (ii) 1-50 mol %, respectively.

2. The negative electrode material for a lithium secondary battery according to claim 1 , wherein said sulfide glass includes 0.5-40 mol % of Ge.

3. A negative electrode material for a lithium secondary battery comprising a composite powder of component A and component B,
wherein (1) said component A is a material capable of electrochemically absorbing and releasing lithium; and
(2) said component B is the sulfide glass according to claim 1 .

4. The negative electrode material for a lithium secondary battery according to claim 3 , wherein said composite powder is a composite powder with component B coated on the surface of component A.

5. The negative electrode material for a lithium secondary battery according to claim 3 , wherein regarding the ratio of component A and component B of all said composite powder, component A is 5-80 mass % and component B is 95-20 mass %, given that the total amount of both is 100 mass %.

6. A negative electrode for a lithium secondary battery using the negative electrode material according to claim 1 .

7. A negative electrode for a lithium secondary battery using the negative electrode material according to claim 3 .

8. The negative electrode for a lithium secondary battery according to claim 6 including a water-based binder.

9. The negative electrode for a lithium secondary battery according to claim 7 including a water-based binder.

10. The negative electrode for a lithium secondary battery according to claim 6 including a polyimide binder.

11. The negative electrode for a lithium secondary battery according to claim 7 including a polyimide binder.

12. A lithium secondary battery using the negative electrode according to claim 6 .

13. A lithium secondary battery using the negative electrode according to claim 7 .

14. A manufacturing method of the negative electrode material for a lithium secondary battery according to claim 3 , the method comprising:
(A) obtaining component B by preparing the material of component B and by vitrifying the prepared material through heat treatment (temperature: 400-1100° C. and treatment time: 1-30 hours); and
(B) making a composite of component A and component B.

15. The manufacturing method of the negative electrode material for a lithium secondary battery according to claim 14 , wherein said step (B) is a step of making a composite of component A and component B through mechanical milling.

16. The manufacturing method of the negative electrode material for a lithium secondary battery according to claim 14 , wherein said step (B) is a step of dispersing component A in melted component B and crushing it after cooling.

17. The manufacturing method of the negative electrode material for a lithium secondary battery according to claim 14 , wherein a conductive aid and/or binder is added during said step (A) and/or step (B) and thus the conductive aid and/or binder is included in the composite powder.

18. A negative electrode material for a lithium secondary battery comprising sulfide glass, including sulfur and the following components (i) and (ii):
i. the element Ge
ii. at least one or more elements selected from a group consisting of Te, Ga, Sn, Al, Mg, Ca, Sr, P and Ba, wherein the ratio in said sulfide glass is sulfur: 40-80 mol %, (i): 1-50 mol % and (ii) 1-50 mol %, respectively.

19. The negative electrode material for a lithium secondary battery according to claim 18 , wherein said sulfide glass includes 0.5-40 mol % of Ge.

20. A negative electrode material for a lithium secondary battery comprising a composite powder of component A and component B, wherein (1) said component A is a material capable of electrochemically absorbing and releasing lithium; and (2) said component B is the sulfide glass according to claim 18 .

21. The negative electrode material for a lithium secondary battery according to claim 20 , wherein said composite powder is a composite powder with component B coated on the surface of component A.

22. The negative electrode material for a lithium secondary battery according to claim 21 , wherein regarding the ratio of component A and component B of all said composite powder, component A is 5-80 mass % and component B is 95-20 mass %, given that the total amount of both is 100 mass %.

23. A negative electrode for a lithium secondary battery using the negative electrode material according to claim 18 .

24. A negative electrode for a lithium secondary battery using the negative electrode material according to claim 21 .

25. The negative electrode for a lithium secondary battery according to claim 24 including a water-based binder.

26. The negative electrode for a lithium secondary battery according to claim 25 including a water-based binder.

27. The negative electrode for a lithium secondary battery according to claim 24 including a polyimide binder.

28. The negative electrode for a lithium secondary battery according to claim 25 including a polyimide binder.

29. A lithium secondary battery using the negative electrode according to claim 24 .

30. A lithium secondary battery using the negative electrode according to claim 25 .

31. A manufacturing method of the negative electrode material for a lithium secondary battery according to claim 21 , the method comprising:
a. obtaining component B by preparing the material of component B and by vitrifying the prepared material through heat treatment (temperature: 400-1100° C. and treatment time: 1-30 hours); and
b. making a composite of component A and component B.

32. The manufacturing method of the negative electrode material for a lithium secondary battery according to claim 31 , wherein said step (B) is a step of making a composite of component A and component B through mechanical milling.

33. The manufacturing method of the negative electrode material for a lithium secondary battery according to claim 31 , wherein said step (B) is a step of dispersing component A in melted component B and crushing it after cooling.

34. The manufacturing method of the negative electrode material for a lithium secondary battery according to claim 31 , wherein a conductive aid and/or binder is added during said step (A) and/or step (B) and thus the conductive aid and/or binder is included in the composite powder.

Assignees

• Mukai Takashi
• Sakamoto Taichi
• Sakai Tetsuo
• Tani Kunihiko
• Yamashita Naoto
• Ikeda Koichiro
• Nat Inst Of Advanced Ind Scien
• Isuzu Glass Company Ltd

Inventors

• Mukai Takashi
• Sakamoto Taichi
• Sakai Tetsuo
• Tani Kunihiko
• Yamashita Naoto
• Ikeda Koichiro

Classifications

• H01M4/622

  being polymers · CPC title

• H01M4/136 Primary

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/664

  Ceramic materials · CPC title

• H01M4/5815

  Sulfides · CPC title

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title