SOLID ELECTROLYTE

• US 20140302382A1
• Filed: 11/02/2012
• Published: 10/09/2014
• Est. Priority Date: 11/07/2011
• Status: Active Grant

• Current Assignee: Idemitsu Kosan Company Limited
• Original Assignee: Idemitsu Kosan Company Limited
• Inventors: Junke, Tadanori, Aburatani, Ryo, Higuchi, Hiroyuki, Ota, Tsuyoshi, Seino, Yoshikatsu, Kambara, Takayoshi, Nakagawa, Masaru
• Granted Patent: US 9,620,811 B2
• Time in Patent Office: Days
• US Class Current: 429/162
• CPC Class Codes: C03C 10/16 Halogen containing crystalline phase
• CPC Class Codes: C03C 2205/00 Compositions applicable for the manufacture of vitreous enamels or glazes
• CPC Class Codes: H01B 1/122 Ionic conductors
• 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 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/008 Halides
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A solid electrolyte including an alkali metal element, phosphorous, sulfur and halogen as constituent components.

Claims

1. A solid electrolyte, comprising:

an alkali metal element,

phosphorous,

sulfur, and

halogen,

wherein the solid electrolyte has a peak in a peak region of 75.0 ppm or more and 80.0 ppm or less in a ³¹P-NMR spectrum.

5. The solid electrolyte according to claim 1, wherein

the solid electrolyte has a first peak I₁ in a first peak region of 75.0 ppm or more and 80.0 ppm or less in the ³¹P-NMR spectrum, and

an intensity ratio of a peak in a region other than the first peak region and a second peak region of 86.0 ppm or more and 92.0 ppm or less is 0.5 or less relative to the first peak I₁.

6. The solid electrolyte according to claim 5, wherein the solid electrolyte has a peak in the first peak region and a peak in the second peak region.

7. The solid electrolyte according to claim 6, wherein an intensity ratio I₂/I₁ of a second peak I₂ in the second peak region relative to the first peak I₁ is from 1 to 10.

8. The solid electrolyte according to claim 1, wherein the solid electrolyte has a composition represented by formula (A′

);

L_aM_bP_cS_dX_e 

 

(A′

)

where L is an alkali metal;

M is B, Al, Si, Ge, As, Se, Sn, Sb, Te, Pb or Bi or a combination thereof;

X is I, Cl, Br or F or a combination thereof; and

a, b, c, d and e satisfy 0<

a≦

12, 0≦

b≦

0.2, c=1, 0<

d≦

9 and 0<

e≦

9.

9. The solid electrolyte according to claim 8, wherein b is 0.

10. The solid electrolyte according to claim 8, wherein d is 4.

11. The solid electrolyte according to claim 8, wherein X is I, Br or Cl.

12. The solid electrolyte according to claim 8, wherein the solid electrolyte has a crystalline structure.

13. The solid electrolyte according to claim 8, wherein

the solid electrolyte is amorphous, and

X is Br or Cl.

14. The solid electrolyte according to claim 8, wherein the solid electrolyte is obtained from raw materials of lithium sulfide and phosphorous sulfide;

sulfur and phosphorous;

phosphorous sulfide and sulfur;

or phosphorous sulfide, sulfur and phosphorous; and

a compound represented by formula (E′

);

M_wX_x 

 

(E′

)

where M is Li, B, Al, Si, P, S, Ge, As, Se, Sn, Sb, Te, Pb or Bi;

X is F, Cl, Br or I; and

w is an integer of 1 or 2 and x is an integer of from 1 to 10.

15. The solid electrolyte according to claim 14, wherein M is P and X is Br, I or Cl.

16. The solid electrolyte according to claim 14, wherein M is Li and X is Br, I or Cl.

17. The solid electrolyte according to claim 8, wherein the solid electrolyte is amorphous and has two crystallization peaks in a thermo gravimetric-differential thermal measurement.

18. The solid electrolyte according to claim 17, wherein the two crystallization peaks appear in a range of 150°

C. or higher and 360°

C. or lower.

19. The solid electrolyte according to claim 17, wherein a distance between the two crystallization peaks is 20 to 100°

C.

20. A solid electrolyte obtained by a process comprising heating at a temperature of 150°

C. or higher and 360°

C. or lower the solid electrolyte according to claim 8 that is amorphous.

21. A solid electrolyte obtained by a process comprising heating the solid electrolyte according to claim 17 at a temperature between temperatures indicated by the two crystallization peaks.

28. The solid electrolyte according to claim 1, wherein the alkali metal element is lithium.

29. The solid electrolyte according to claim 1, wherein the solid electrolyte has an ionic conductivity of 5×

10<sup>−

4</sup> S/cm or more.

30. The solid electrolyte according to claim 1, wherein the solid electrolyte has an average hydrogen sulfide concentration measured by a hydrolysis test of 200 ppm or less.

33. An electrolyte layer, comprising the solid electrolyte according to claim 1.

34. A battery, comprising:

a cathode layer,

an electrolyte layer, and

an anode layer,

wherein at least one of the cathode layer, the electrolyte layer and the anode layer comprises the solid electrolyte according to claim 1.

35. The solid electrolyte according to claim 5, wherein the alkali metal element is lithium and the halogen is Br.

36. The solid electrolyte according to claim 35, wherein an intensity ratio I₂/I₁ of a second peak I₂ in the second peak region relative to the first peak I₁ is 1 or more and 10 or less.

37. The solid electrolyte according to claim 35, wherein an intensity ratio I_c/I₁ of a peak I_c appearing in regions other than the first peak region and the second peak region relative to the first peak I₁ is 0.25 or less.

38. The solid electrolyte according to claim 35, wherein the solid electrolyte has an ionic conductivity of 5×

10<sup>−

4</sup> S/cm or more.

39. The solid electrolyte according to claim 35, wherein the solid electrolyte has an average hydrogen sulfide concentration measured by a hydrolysis test of 200 ppm or less.

40. The solid electrolyte according to claim 35, wherein the solid electrolyte has a crystalline structure.

2-3. -3. (canceled)

4. A solid electrolyte, comprising:

an alkali metal element,

phosphorous,

sulfur, and

halogen,

wherein the solid electrolyte has a peak in a peak region of 86.0 ppm or more and 92.0 ppm or less in a ³¹P-NMR spectrum.

22-27. -27. (canceled)

31-32. -32. (canceled)