Nickel hydroxide positive electrode for alkaline rechargeable battery

Patent metadata

Field	Value
Publication number	US-9935315-B2
Application number	US-201514614753-A
Country	US
Kind code	B2
Filing date	Feb 5, 2015
Priority date	Feb 5, 2015
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example ≥325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni 1+ , is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

First claim

The invention claimed is:

1. A nickel hydroxide cathode active material for use in an alkaline rechargeable electrochemical cell, which active material is capable of transferring >1.67 electrons per Ni atom, and where Ni reaches an oxidation state of less than + 2 during charge/discharge cycling of an alkaline rechargeable cell.

2. A cathode active material according to claim 1 , where the specific capacity of the material is ≥330 mAh/g.

3. A cathode active material according to claim 1 , which exhibits a discharge plateau near 0.8 V vs. a metal hydride anode during charge/discharge cycling of an alkaline rechargeable cell.

4. A cathode active material according to claim 3 , which also exhibits a discharge plateau near 1.2 V and a discharge plateau at >1.2 V and <1.3 V.

5. A cathode active material according to claim 1 comprising one or more modifiers selected from the group consisting of Al, Ba, Bi, Ca, Co, Cr, Cu, F, Fe, In, K, La, Li, Mg, Mn, Na, Nd, Pb, Pr, Ru, Sb, Sc, Se, Sn, Sr, Te, Ti, Y and Zn.

6. A cathode active material according to claim 1 comprising one or more modifiers selected from the group consisting of Co, Zn and Al.

7. A cathode active material according to claim 1 selected from the group consisting of (Ni,Co,Zn)(OH) 2 , (Ni,Co)(OH) 2 , (Ni,Co,Al)(OH) 2 and (Ni,Co,Zn,Al)(OH) 2 .

8. A cathode active material according to claim 7 selected from the group consisting of (Ni,Co)(OH) 2 nickel hydroxides where Ni is present from about 89 atomic percent (at %) to about 99 at % and Co is present from about 1 at % to about 11 at %, based on 100 at % total of Ni and Co combined.

9. A cathode active material according to claim 7 selected from the group consisting of (Ni,Co,Al)(OH) 2 nickel hydroxides where Ni is present from about 80 at % to about 90 at % and Co and Al together are from about 10 to about 20 at %, based on 100 at % total of Ni, Co and Al combined.

10. A cathode active material according to claim 9 where the atomic ratio of Co to Al is from about 1:1 to about 1:5.

11. A cathode active material according to claim 7 selected from the group consisting of (Ni,Co,Zn,Al)(OH) 2 nickel hydroxides where Ni is present from about 64 to about 74 at % and Co, Zn and Al together are present from about 26 to about 36 at %, based on 100 at % total of Ni, Co, Zn and Al combined.

12. A cathode active material according to claim 11 where the atomic ratio of Co to Al is from about 1:1 to about 1:5.

13. A cathode active material according to claim 11 where the atomic ratio of Co to Zn is from about 1:2 to about 2:1.

14. A cathode active material according to claim 11 where the atomic ratio of Zn to Al is from about 1:1 to about 1:5.

15. A cathode active material according to claim 7 selected from the group consisting of Ni 0.94 Co 0.06 (OH) 2 , Ni 0.85 Co 0.05 Al 0.10 (OH) 2 and Ni 0.69 Co 0.05 Zn 0.06 Al 0.2 (OH) 2 .

16. A positive electrode for use in an alkaline rechargeable electrochemical cell, the electrode comprising a cathode active material according to claim 1 , a conductive substrate and optionally one or more components selected from binders and additives.

17. A nickel hydroxide cathode active material for use in an alkaline rechargeable electrochemical cell, where the specific capacity of the material is ≥330 mAh/g, and where Ni reaches an oxidation state of less than +2 during charge/discharge cycling of an alkaline rechargeable cell.

18. A cathode active material according to claim 17 , which exhibits a discharge plateau near 0.8 V vs. a metal hydride anode during charge/discharge cycling of an alkaline rechargeable cell.

19. A cathode active material according to claim 18 , which also exhibits a discharge plateau near 1.2 V and a discharge plateau at >1.2 V and <1.3 V.

20. A cathode active material according to claim 17 comprising one or more modifiers selected from the group consisting of Al, Ba, Bi, Ca, Co, Cr, Cu, F, Fe, In, K, La, Li, Mg, Mn, Na, Nd, Pb, Pr, Ru, Sb, Sc, Se, Sn, Sr, Te, Ti, Y and Zn.

21. A cathode active material according to claim 17 comprising one or more modifiers selected from the group consisting of Co, Zn and Al.

22. A cathode active material according to claim 17 selected from the group consisting of (Ni,Co,Zn)(OH) 2 , (Ni,Co)(OH) 2 , (Ni,Co,Al)(OH) 2 and (Ni,Co,Zn,Al)(OH) 2 nickel hydroxides.

23. A cathode active material according to claim 22 selected from the group consisting of (Ni,Co)(OH) 2 nickel hydroxides where Ni is present from about 89 atomic percent (at %) to about 99 at % and Co is present from about 1 at % to about 11 at %, based on 100 at % total of Ni and Co combined.

24. A cathode active material according to claim 22 selected from the group consisting of (Ni,Co,Al)(OH) 2 nickel hydroxides where Ni is present from about 80 at % to about 90 at % and Co and Al together are from about 10 to about 20 at %, based on 100 at % total of Ni, Co and Al combined.

25. A cathode active material according to claim 24 where the atomic ratio of Co to Al is from about 1:1 to about 1:5.

26. A cathode active material according to claim 22 selected from the group consisting of (Ni,Co,Zn,Al)(OH) 2 nickel hydroxides where Ni is present from about 64 to about 74 at % and Co, Zn and Al together are present from about 26 to about 36 at %, based on 100 at % total of Ni, Co, Zn and Al combined.

27. A cathode active material according to claim 26 where the atomic ratio of Co to Al is from about 1:1 to about 1:5 or from about 1:2 to about 1:4.

28. A cathode active material according to claim 26 where the atomic ratio of Co to Zn is from about 1:2 to about 2:1.

29. A cathode active material according to claim 26 where the atomic ratio of Zn to Al is from about 1:1 to about 1:5.

30. A positive electrode for use in an alkaline rechargeable electrochemical cell, the electrode comprising a cathode active material according to claim 17 , a conductive substrate and optionally one or more components selected from binders and additives.

Assignees

• Basf Corp

Inventors

• Young Kwo
• Wang Lixin
• Mays William
• Reichman Benjamin
• Chao-Ian Hu
• Wong Diana
• Nei Jean

Classifications

• H01M4/52 Primary

  of nickel, cobalt or iron · CPC title

• H01M10/30

  Nickel accumulators (H01M10/34 takes precedence) · CPC title

• H01M4/32

  Nickel oxide or hydroxide electrodes · CPC title

• H01M10/345

  Gastight metal hydride accumulators · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title