Catalyst for air electrode for metal-air secondary battery and air electrode

Patent metadata

Field	Value
Publication number	US-10693145-B2
Application number	US-201515114608-A
Country	US
Kind code	B2
Filing date	Jan 30, 2015
Priority date	Jan 31, 2014
Publication date	Jun 23, 2020
Grant date	Jun 23, 2020

Abstract

A novel transition metal oxide catalyst that is equivalent to precious metal catalysts, and an air electrode and an air secondary battery using this catalyst are provided. The catalyst is a catalyst for an air electrode including a brownmillerite-type transition metal oxide and represented by General Formula (1) below:

A 2 B 1 B 2 O 5   (1)

where A represents Ca, Sr, Ba, or a rare earth element(RE), B 1 is a metal atom that forms a tetrahedral structure together with oxygen atoms, and B 2 is a metal atom that forms an octahedral structure together with oxygen atoms. Disclosed are an air electrode for a metal-air secondary battery that includes the catalyst, and a metal-air secondary battery that includes an air electrode including the catalyst, a negative electrode including a negative electrode active material, and an electrolyte intervening between the air electrode and the negative electrode.

First claim

The invention claimed is:

1. A zinc-air secondary battery comprising:
an air electrode including an oxygen evolution catalyst containing a brownmillerite-type transition metal oxide, said oxygen evolution catalyst causing an oxygen evolution reaction represented by Formula below:
4OH − →O 2 +4 e − ;

a negative electrode containing zinc as a negative electrode active material; and
an electrolyte intervening between said air electrode and said negative electrode, said electrolyte being selected from the group consisting of an alkali aqueous solution and an aqueous solution containing zinc chloride or zinc perchlorate and in contact with said air electrode,
wherein said brownmillerite-type transition metal oxide is represented by General Formula (1) below:
A 2 B 1 B 2 O 5   (1)

where A represents Ca, Sr, Ba, or a rare earth element (RE),
B 1 is a metal atom that forms a tetrahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Ni, and Zn,
B 2 is a metal atom that forms an octahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Cr, Ni, Ti, and Cu, and
one of said B 1 and B 2 contains Co.

2. The zinc-air secondary battery according to claim 1 ,
wherein a chemical reaction for charging and discharging in the air electrode is represented by Formula below:

3. The zinc-air secondary battery according to claim 1 ,
wherein said brownmillerite-type transition metal oxide is Ca 2 FeCoO 5 or Sr 2 Co 2 O 5 .

4. The zinc-air secondary battery according to claim 1 ,
wherein a surface area of said catalyst is in a range from 0.1 to 100 m 2 /g.

5. The zinc-air secondary battery according to claim 1 ,
wherein said air electrode contains said brownmillerite-type transition metal oxide as a catalyst for oxygen evolution, the air electrode further comprising a catalyst for oxygen reduction.

6. The zinc-air secondary battery according to claim 1 , further comprising an air electrode for oxygen reduction including a catalyst for oxygen reduction.

7. A zinc-air secondary battery comprising:
an air electrode including an oxygen evolution catalyst containing a brownmillerite-type transition metal oxide, said oxygen evolution catalyst causing an oxygen evolution reaction represented by Formula below:
4OH − →O 2 +2H 2 O+4 e − ;

a negative electrode containing zinc as a negative electrode active material; and
an electrolyte intervening between said air electrode and said negative electrode, said electrolyte being selected from the group consisting of an alkali aqueous solution and an aqueous solution containing zinc chloride or zinc perchlorate and in contact with said air electrode,
wherein said brownmillerite-type transition metal oxide is represented by General Formula (1) below:
A 2 B 1 B 2 O 5   (1)

where A represents Ca, Sr, Ba, or a rare earth element (RE),
B 1 is a metal atom that forms a tetrahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Ni, and Zn,
B 2 is a metal atom that forms an octahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Cr, Ni, Ti, and Cu, and
said B 1 and B 2 represent different elements.

8. The zinc-air secondary battery according to claim 7 ,
wherein one of said B 1 and B 2 contains Co.

9. The zinc-air secondary battery according to claim 7 ,
wherein a chemical reaction for charging and discharging in the air electrode is represented by Formula below:

10. The zinc-air secondary battery according to claim 7 ,
wherein said brownmillerite-type transition metal oxide is Ca 2 FeCoO 5 .

11. The zinc-air secondary battery according to claim 7 ,
wherein a surface area of said catalyst is in a range from 0.1 to 100 m 2 /g.

12. The zinc-air secondary battery according to claim 7 ,
wherein said air electrode contains said brownmillerite-type transition metal oxide as a catalyst for oxygen evolution, the air electrode further comprising a catalyst for oxygen reduction.

13. The zinc-air secondary battery according to claim 7 , further comprising an air electrode for oxygen reduction including a catalyst for oxygen reduction.

14. An electrolytic method comprising:
preparing an electrode comprising an oxygen evolution catalyst which contains a brownmillerite-type transition metal oxide, said oxygen evolution catalyst causing an oxygen evolution reaction represented by Formula below:
4OH − →O 2 +2H 2 O+4e − ; and

putting said electrode in an electrolytic solution selected from the group consisting of an alkali aqueous solution and an aqueous solution containing zinc chloride or zinc perchlorate,
wherein said brownmillerite-type transition metal oxide is represented by General Formula (1) below:
A 2 B 1 B 2 O 5   (1)

where A represents Ca, Sr, Ba, or a rare earth element (RE),
B 1 is a metal atom that forms a tetrahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Ni, and Zn,
B 2 is a metal atom that forms an octahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Cr, Ni, Ti, and Cu, and
one of said B 1 and B 2 contains Co.

15. The electrolytic method according to claim 14 ,
wherein said brownmillerite-type transition metal oxide is Ca 2 FeCoO 5 or Sr 2 Co 2 O 5 .

16. An electrolytic method comprising:
preparing an electrode comprising an oxygen evolution catalyst which contains a brownmillerite-type transition metal oxide, said oxygen evolution catalyst causing an oxygen evolution reaction represented by Formula below:
4OH − →O 2 +2H 2 O+4 e − ; and

putting said electrode in an electrolytic solution selected from the group consisting of an alkali aqueous solution and an aqueous solution containing zinc chloride or zinc perchlorate,
wherein said brownmillerite-type transition metal oxide is represented by General Formula (1) below:
A 2 B 1 B 2 O 5   (1)

where A represents Ca, Sr, Ba, or a rare earth element (RE),
B 1 is a metal atom that forms a tetrahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Ni, and Zn,
B 2 is a metal atom that forms an octahedral structure together with oxygen atoms, and is at least one metal atom selected from the group consisting of Fe, Co, Cr, Ni, Ti, and Cu, and
said B 1 and B 2 represent different elements.

17. The electrolytic method according to claim 16 ,
wherein said brownmillerite-type transition metal oxide is Ca 2 FeCoO 5 .

Assignees

• Univ Hokkaido Nat Univ Corp
• Hitachi Shipbuilding Eng Co
• National Univ Corporation Hokkaid Univ

Inventors

• TSUJI Etsushi
• Motohashi Teruki
• Habazaki Hiroki
• Noda Hiroyuki
• Takeguchi Tatsuya

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M12/04

  composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type · CPC title

• H01M4/9016 Primary

  Oxides, hydroxides or oxygenated metallic salts · CPC title

• H01M4/42

  Alloys based on zinc · CPC title

• H01M2004/027

  Negative electrodes · CPC title