Ion conductor containing Li2B12H12 and LiBH4, method for producing same, and solid electrolyte for all-solid-state batteries, which contains said ion conductor

Patent metadata

Field	Value
Publication number	US-11769873-B2
Application number	US-201916971868-A
Country	US
Kind code	B2
Filing date	Feb 22, 2019
Priority date	Feb 28, 2018
Publication date	Sep 26, 2023
Grant date	Sep 26, 2023

Abstract

The present application provides a method for producing an ion conductor containing Li2B12H12 and LiBH4, which includes obtaining a mixture by mixing LiBH4 and B10H14 at a molar ratio LiBH4/B10H14 of from 2.1 to 4.3; and subjecting the mixture to a heat treatment.

First claim

The invention claimed is:

1. A method for producing an ion conductor comprising Li 2 B 12 H 12 and LiBH 4 , which comprises:
obtaining a mixture by mixing LiBH 4 and B 10 H 14 at a molar ratio LiBH 4 /B 10 H 14 of from 2.1 to 4.3; and
subjecting the mixture to a heat treatment.

2. The method for producing an ion conductor according to claim 1 , wherein the temperature of the heat treatment is 100 to 300° C.

3. The method for producing an ion conductor according to claim 1 , which comprises subjecting the mixture to a mechanical milling treatment prior to the heat treatment.

4. The method for producing an ion conductor according to claim 3 , wherein the time for carrying out the mechanical milling treatment is 0.5 to 7 hours.

5. The method for producing an ion conductor according to claim 3 , which comprises subjecting the mixture to a second mechanical milling treatment after the heat treatment.

6. The method for producing an ion conductor according to claim 5 , wherein the time for carrying out the second mechanical milling treatment is 10 to 30 hours.

7. The method for producing an ion conductor according to claim 1 , wherein the ion conductor obtained has peaks at at least −15.6 ppm (±1 ppm), −17.6 ppm (±1 ppm), −1.7 ppm and −29.4 ppm (±1.5 ppm), and −42.0 ppm (±2 ppm) in a B 11 MAS NMR measurement, and wherein when −15.6 ppm (±1 ppm) is regarded as Peak A and −42.0 ppm (±2 ppm) is regarded as Peak B, the intensity ratio of Peak B to Peak A (B/A) is 0.1 to 2.0.

8. A method for producing an all-solid-state battery, which comprises carrying out molding using the ion conductor obtained by the method according to claim 1 under an atmosphere at a dew point of −30° C. to −80° C.

9. An ion conductor comprising L 12 B 12 H 12 and LiBH 4 , which has peaks at at least −15.6 ppm (±1 ppm), −17.6 ppm (±1 ppm), −1.7 ppm and −29.4 ppm (±1.5 ppm), and −42.0 ppm (±2 ppm) in a B 11 MAS NMR measurement, wherein when −15.6 ppm (±1 ppm) is regarded as Peak A and −42.0 ppm (±2 ppm) is regarded as Peak B, the intensity ratio of Peak B to Peak A (B/A) is 0.1 to 2.0.

10. The ion conductor according to claim 9 , which has X-ray diffraction peaks at at least 2θ=16.1±0.5 deg, 18.6±0.5 deg, 24.0±0.5 deg, 24.9±0.8 deg, 27.0±0.8 deg, 31.0±0.8 deg and 32.5±0.8 deg.

11. A solid electrolyte for all-solid-state batteries, which comprises the ion conductor according to claim 9 .

Assignees

• Mitsubishi Gas Chemical Co
• Tohoku Techno Arch Co Ltd

Inventors

• Nogami Genki
• Shimada Masahiro
• Toyama Naoki
• KIM Sangryun
• Orimo Shin-Ichi

Classifications

• H01M4/364 Primary

  as mixtures · CPC title

• C01B6/21

  Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7 · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title