Oxide all-solid-state battery

• US 10,461,337 B2
• Filed: 02/23/2018
• Issued: 10/29/2019
• Est. Priority Date: 02/27/2017
• Status: Active Grant

• Current Assignee: Japan Advanced Institute Of Science And Technology, Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Original Assignee: Japan Advanced Institute Of Science And Technology
• Inventors: Shimoda, Tatsuya, Masuda, Takashi, Saito, Toshiya, Ohta, Shingo
• Primary Examiner(s): Ruddock, Ula C
• Assistant Examiner(s): Rosenbaum, Amanda
• Application Number:
  US15/903,092
• Publication Number:
  US 20180248201A1
• Time in Patent Office: 613 Days
• Field of Search: None
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 4/0407 by coating on an electrolyte layer
• CPC Class Codes: H01M 4/0426 Sputtering
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/0497 Chemical precipitation
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

An oxide all-solid-state battery excellent in lithium ion conductivity and joint strength between an anode active material layer and solid electrolyte layer thereof. In the oxide all-solid-state battery, the solid electrolyte layer is a layer mainly containing a garnet-type oxide solid electrolyte sintered body represented by the following formula (1): (Li_x-3y-z, E_y, H_z)L_αM_βO_γ; a solid electrolyte interface layer is disposed between the anode active material layer and the solid electrolyte layer; the solid electrolyte interface layer contains at least a Si element and an O element; and a laminate containing at least the anode active material layer, the solid electrolyte interface layer and the solid electrolyte layer has peaks at positions where 2θ=32.3°±0.5°, 37.6°±0.5°, 43.8°±0.5°, and 57.7°±0.5° in a XRD spectrum obtained by XRD measurement using CuKα irradiation.

Claims

1. An oxide all-solid-state battery comprising a cathode active material layer, an anode active material layer mainly comprising silicon, and a solid electrolyte layer disposed between the cathode active material layer and the anode active material layer,

wherein the solid electrolyte layer is a layer mainly comprising a garnet-type oxide solid electrolyte sintered body represented by the following formula (1):

(Li_x-3y-z, E_y, H_z)L_α

M_β

O_γ

 

 

Formula (1)

where E is at least one kind of element selected from the group consisting of Al and Ga;

L is at least one kind of element selected from the group consisting of an alkaline-earth metal element and a lanthanoid element;

M is at least one kind of element selected from a transition element that can be six-coordinated with oxygen and typical elements in the Groups 12 to 15;

x, y and z are real numbers that satisfy 5≤

x-3y-z≤

7, 0≤

y<

0.22 and 0≤

z<

2.0, respectively; and

α

, β and

γ

are real numbers that satisfy 2.5≤

α

≤

3.5, 1.5≤

β

≤

2.5 and 11≤

γ

≤

13, respectively;

wherein a solid electrolyte interface layer is disposed between the anode active material layer and the solid electrolyte layer;

wherein the solid electrolyte interface layer comprises at least a Si element and an O element; and

wherein a laminate comprising at least the anode active material layer, the solid electrolyte interface layer and the solid electrolyte layer has peaks at positions where 2θ

=32.3°

±

0.5°

, 37.6°

±

0.5°

, 43.8°

±

0.5°

, and 57.7°

±

0.5°

in a XRD spectrum obtained by XRD measurement using CuKα

irradiation.

2. The oxide all-solid-state battery according to claim 1, wherein the solid electrolyte interface layer comprises a Si element, an O element and a Li element.

3. The oxide all-solid-state battery according to claim 1, wherein the peaks at the positions where 2θ

=32.3°

±

0.5°

, 37.6°

±

0.5°

, 43.8°

±

0.5°

, and 57.7°

±

0.5°

in the XRD spectrum, are assigned to the solid electrolyte interface layer.

4. The oxide all-solid-state battery according to claim 1, wherein an average thickness of the solid electrolyte interface layer is 1 nm or more and 800 nm or less.

5. The oxide all-solid-state battery according to claim 1, wherein the anode active material layer is an amorphous layer mainly comprising silicon.