Lithium ion conducting sulfide based crystallized glass and method for production thereof

• US 20070160911A1
• Filed: 01/31/2005
• Published: 07/12/2007
• Est. Priority Date: 02/12/2004
• Status: Active Grant

• Current Assignee: Public University Corporation Osaka City University
• Original Assignee: Idemitsu Kosan Company Limited, Masahiro Tatsumisago
• Inventors: Tatsumisago, Masahiro, Senga, Minoru, Seino, Yoshikatsu, Hayashi, Akitoshi
• Granted Patent: US 8,962,194 B2
• Time in Patent Office: Days
• US Class Current: 429/322
• CPC Class Codes: C03C 10/00 Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
• CPC Class Codes: C03C 4/18 for ion-sensitive glass
• CPC Class Codes: H01B 1/10 sulfides
• CPC Class Codes: H01B 1/122 Ionic conductors
• 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: Y02E 60/10 Energy storage using batteries

Abstract

A lithium-ion-conducting sulfide-based crystallized glass including: lithium (Li), phosphorus (P), and sulfur (S) elements, wherein the glass has diffraction peaks at 2θ=17.8±0.3 deg, 18.2±0.3 deg, 19.8±0.3 deg, 21.8±0.3 deg, 23.8±0.3 deg, 25.9±0.3 deg, 29.5±0.3 deg and 30.0±0.3 deg in X-ray diffraction (CuKα: λ=1.5418 Å).

Claims

1. A lithium-ion-conducting sulfide-based crystallized glass comprising:

lithium (Li), phosphorus (P), and sulfur (S) elements, wherein the glass has diffraction peaks at 2θ

=17.8±

0.3 deg, 18.2±

0.3 deg, 19.8±

0.3 deg, 21.8±

0.3 deg, 23.8±

0.3 deg, 25.9±

0.3 deg, 29.5±

0.3 deg and 30.0±

0.3 deg in X-ray diffraction (CuKα

;

λ

=1.5418 Å

).

8. A solid electrolyte for a lithium rechargeable battery comprising the lithium-ion-conducting sulfide-based crystallized glass according to claim 1 as a material.

10. An all-solid battery comprising the solid electrolyte according to claim 8.

2. A method of producing a lithium-ion-conducting sulfide-based crystallized glass comprising heat-treating a sulfide-based glass comprising 68 to 74 mol % of Li₂S and 26 to 32 mol % of P₂S₅ at 150 to 360°

C.

3. The method according to claim 2, wherein the Li₂S is prepared by reacting lithium hydroxide with hydrogen sulfide in an aprotic organic solvent to produce crude Li₂S and purifying the crude Li₂S by cleaning with an organic solvent at 100°

C. or more.

4. The method according to claim 2, wherein the total amount of sulfur oxides contained in the Li₂S is 0.15 mass % or less and the amount of lithium N-methylaminobutyrate (LMAB) is 0.1 mass % or less.

5. The method according to claim 2, wherein phosphorus (P) and sulfur (S) at a molar ratio corresponding to P₂S₅ are used instead of the P₂S₅.

6. The method according to claim 2, wherein the sulfide-based glass is produced from Li₂S and P₂S₅ or phosphorus (P) and sulfur (S) by a mechanical milling process.

7. A lithium-ion-conducting sulfide-based crystallized glass produced by the method according to claim 2.

9. A solid electrolyte for a lithium rechargeable battery comprising the lithium-ion-conducting sulfide-based crystallized glass according to claim 7 as a material.

11. An all-solid battery comprising the solid electrolyte according to claim 9.

12. A lithium-ion-conducting sulfide-based crystallized glass produced by the method according to claim 5.