Co-fired all-solid-state battery

Patent metadata

Field	Value
Publication number	US-11322776-B2
Application number	US-201916702869-A
Country	US
Kind code	B2
Filing date	Dec 4, 2019
Priority date	Aug 30, 2017
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

A co-fired all-solid-state battery that includes a negative electrode, a solid electrolyte layer, and a positive electrode. The negative electrode contains a negative electrode active material and a garnet-type solid electrolyte. The negative electrode active material contains Li, V, and O. The negative electrode active material has a mole ratio (Li/V) of a Li content to a V content of 2.0 or more. The garnet-type solid electrolyte contains Li, La, Zr, and O.

First claim

The invention claimed is:

1. A co-fired all-solid-state battery comprising:
a negative electrode containing a negative electrode active material and a garnet-type solid electrolyte, the negative electrode active material containing Li, V, and O and having a mole ratio (Li/V) of a Li content to a V content of 2.0 or more, and the garnet-type solid electrolyte containing Li, La, Zr, and O;
a positive electrode; and
a solid electrolyte layer between the negative electrode and the positive electrode.

2. The co-fired all-solid-state battery according to claim 1 , wherein the negative electrode active material is a composite oxide.

3. The co-fired all-solid-state battery according to claim 1 , wherein the negative electrode active material is represented by (Li [3−ax+(5−b)y] A x ) (V 1−y B y )O 4 , wherein A is at least one element selected from the group consisting of Mg, Al, Ga, and Zn; B is at least one element selected from the group consisting of Zn, Al, Ga, Si, Ge, P, and Ti; 0≤x≤1.0; 0≤y≤0.6; a is an average valence of A; and b is an average valence of B.

4. The co-fired all-solid-state battery according to claim 3 , wherein the Li is partially substituted with Na, K, Ca, Fe, Cr, or Co.

5. The co-fired all-solid-state battery according to claim 4 , wherein the V is partially substituted with Zn, Al, Ga, Sn, As, Mo, W, Fe, Cr, or Co.

6. The co-fired all-solid-state battery according to claim 3 , wherein the V is partially substituted with Zn, Al, Ga, Sn, As, Mo, W, Fe, Cr, or Co.

7. The co-fired all-solid-state battery according to claim 1 , wherein the negative electrode active material has a β II -Li 3 VO 4 structure or a γ II -Li 3 VO 4 structure.

8. The co-fired all-solid-state battery according to claim 1 , wherein the negative electrode active material has a γ II -Li 3 VO 4 structure.

9. The co-fired all-solid-state battery according to claim 1 , wherein the negative electrode active material is selected from Li 3 VO 4 , Li 3.2 V 0.8 Si 0.2 O 4 , Li 3.2 V 0.8 Ge 0.2 O 4 , Li 3.2 V 0.7 Ti 0.3 O 4 , Li 2.7 Al 0.1 VO 4 , Li 2.4 Al 0.2 VO 4 , Li 2.7 Ga 0.1 VO 4 , Li 2.8 Zn 0.1 VO 4 , Li 2.0 Zn 0.5 VO 4 , Li 3.0 Zn 0.1 V 0.8 Si 0.2 O 4 , and Li 3.0 V 0.7 P 0.3 O 4 .

10. The co-fired all-solid-state battery according to claim 1 , wherein a content of the negative electrode active material in the negative electrode is 20 vol % to 80 vol %.

11. The co-fired all-solid-state battery according to claim 1 , wherein the negative electrode active material is in the form of negative electrode active material grains, and the negative electrode active material grains have an average grain size of 0.005 μm to 5.0 μm.

12. The co-fired all-solid-state battery according to claim 3 , wherein the garnet-type solid electrolyte is represented by (Li [7−ax−(b−4)y] A x )La 3 (Zr 2−y B y )O 12 , wherein A is at least one element selected from the group consisting of Ga, Al, Mg, Zn, and Sc; B is at least one element selected from the group consisting of Nb, Ta, W, Te, Mo, and Bi; 0≤x≤0.5; 0≤y≤2.0; a is an average valence of A; and b is an average valence of B.

13. The co-fired all-solid-state battery according to claim 3 , wherein the garnet-type solid electrolyte is selected from (Li 6.4 Ga 0.05 Al 0.15 )La 3 Zr 2 O 12 , Li 6.6 La 3 (Zr 1.6 Ta 0.4 )O 12 , Li 6.6 La 3 (Zr 1.6 Ta 0.4 )O 12 , (Li 6.4 Al 0.2 )La 3 Zr 2 O 12 , (Li 6.4 Ga 0.15 Sc 0.05 )La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 Zr 2 O 12 , (Li 6.45 Al 0.1 )La 3 (Zr 1.75 Nb 0.25 )O 12 , and (Li 6.45 Al 0.1 )La 3 (Zr 1.75 Bi 0.25 )O 12 .

14. The co-fired all-solid-state battery according to claim 1 , wherein the garnet-type solid electrolyte is represented by (Li [7−ax−(b−4)y] A x )La 3 (Zr 2−y B y )O 12 , wherein A is at least one element selected from the group consisting of Ga, Al, Mg, Zn, and Sc; B is at least one element selected from the group consisting of Nb, Ta, W, Te, Mo, and Bi; 0≤x≤0.5; 0≤y≤2.0; a is an average valence of A; and b is an average valence of B.

15. The co-fired all-solid-state battery according to claim 1 , wherein the garnet-type solid electrolyte is selected from (Li 6.4 Ga 0.05 Al 0.15 )La 3 Zr 2 O 12 , Li 6.6 La 3 (Zr 1.6 Ta 0.4 )O 12 , Li 6.6 La 3 (Zr 1.6 Ta 0.4 )O 12 , (Li 6.4 Al 0.2 )La 3 Zr 2 O 12 , (Li 6.4 Ga 0.15 Sc 0.05 )La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 Zr 2 O 12 , (Li 6.45 Al 0.1 )La 3 (Zr 1.75 Nb 0.25 )O 12 , and (Li 6.45 Al 0.1 )La 3 (Zr 1.75 Bi 0.25 )O 12 .

16. The co-fired all-solid-state battery according to claim 1 , wherein a content of the garnet-type solid electrolyte in the negative electrode is 5 vol % to 60 vol %.

17. The co-fired all-solid-state battery according to claim 1 , wherein
the negative electrode further contains a conductive auxiliary agent, and
the negative electrode has a volume proportion of the conductive auxiliary agent ((volume of conductive auxiliary agent/volume of negative electrode)×100) of 0.1% to 35%.

18. The co-fired all-solid-state battery according to claim 1 , wherein
the negative electrode further contains a sintering additive, and
the sintering additive contains Li, M, and O, with M being at least one element other than Li and O.

19. The co-fired all-solid-state battery according to claim 18 , wherein
the sintering additive contains Li, B, and O, and
the sintering additive has a mole ratio (Li/B) of a Li content to a B content of 2.0 or more.

20. The co-fired all-solid-state battery according to claim 1 , wherein the solid electrolyte layer contains the garnet-type solid electrolyte contained in the negative electrode.

Assignees

• Murata Manufacturing Co

Inventors

• TAKANO Ryohei
• Yoshioka Makoto
• Ishikura Takeo
• Ito Akisuke

Classifications

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title

• H01M10/058 Primary

  Construction or manufacture · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• Y02E60/10

  Energy storage using batteries · 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