Oxidative delithiation of alkali nickel oxide

Patent metadata

Field	Value
Publication number	US-11984594-B2
Application number	US-202117248404-A
Country	US
Kind code	B2
Filing date	Jan 22, 2021
Priority date	Jan 23, 2020
Publication date	May 14, 2024
Grant date	May 14, 2024

Abstract

Provided are methods of preparing an electrochemically active cathode material including the steps of combining an alkali metal-containing nickel oxide having a formula A 1−a Ni 1+a O 2 , wherein A comprises an alkali metal and 0<a≤0.2, with a fluid composition including an oxidant comprising a peroxydisulfate salt, a monopersulfate salt, or a combination thereof to form a mixture, heating the mixture to a temperature of 50° C. or greater; and maintaining the mixture at the temperature for at least a period of time sufficient to form an alkali metal-deficient nickel oxide electrochemically active cathode material having a general formula A x H y Ni 1+a O 2 ·nH 2 O, wherein A comprises an alkali metal; 0.08≤x<0.2; 0≤y<0.3; 0.02≤a≤0.2; and 0<n<2.

First claim

What is claimed:

1. A method of preparing an electrochemically active cathode material, comprising:
combining an alkali metal-containing nickel oxide having a formula A 1−a Ni 1+a O 2 , wherein A comprises an alkali metal and 0≤a≤0.2, with a fluid composition including a oxidant comprising a peroxydisulfate salt, a monopersulfate salt, or a combination thereof to form a mixture;
heating the mixture to a temperature of 50° C. or greater; and
maintaining the mixture at the temperature for at least a period of time sufficient to form, an alkali metal-deficient nickel oxide electrochemically active cathode material having a general formula A x H y Ni 1+a O 2 ·nH 2 O, wherein
A comprises an alkali metal;
0.08≤x<0.2;
0≤y<0.3;
0.02<a≤0.2; and
0<n<2.

2. The method of claim 1 , wherein the mixture is heated to a temperature of about 55° C. to about 85° C.

3. The method of claim 1 , wherein the oxidant comprises a peroxydisulfate salt.

4. The method of claim 1 , wherein A comprises Li.

5. The method of claim 1 , wherein the time sufficient to form the alkali metal-deficient nickel oxide electrochemically active cathode material is about 1 hour to about 24 hours.

6. The method of claim 1 , wherein the time sufficient to form the alkali metal-deficient nickel oxide electrochemically active cathode material is about 1 hour to about 6 hours.

7. The method of claim 1 , wherein the method does not include addition of mineral acid to the mixture.

8. The method of claim 1 , wherein the fluid composition further comprises an alkali metal hydroxide, an ammonium hydroxide, or a combination thereof.

9. The method of claim 1 , wherein the fluid composition has a pH in a range of about 8 to about 12.

10. The method of claim 8 , wherein the counter cation of the oxidant and counter cation of the hydroxide are each ammonium.

11. The method of claim 8 , wherein one of the oxidant counter cation or hydroxide counter cation comprises ammonium and the other comprises potassium.

12. The method of claim 8 , wherein the counter cation of the oxidant comprises ammonium and the counter cation of the hydroxide comprises sodium.

13. The method of claim 1 , wherein the fluid composition is substantially free of a hydroxide salt.

14. The method of claim 1 , wherein the alkali metal-containing nickel oxide and the oxidant are provided in a molar ratio of about 1:0.75 to about 1:2.

15. The method of claim 8 , wherein the alkali metal-containing nickel oxide, the oxidant, and the hydroxide are provided in a molar ratio of about 1:0.75:1 to about 1:2:6.

16. The method of claim 1 , wherein the oxidant comprises a counter cation selected from the group consisting of ammonium, sodium, potassium, lithium, and a combination thereof.

17. The method of claim 16 , wherein the counter cation of the oxidant comprises ammonium or sodium and the fluid composition is substantially free of a hydroxide.

18. The method of claim 1 , wherein the oxidant comprises two different counter cations selected from the group consisting of ammonium, sodium, and potassium.

19. The method of claim 1 , wherein the oxidant is a combination of a sodium peroxydisulfate and a potassium peroxydisulfate.

20. The method of claim 1 , wherein y has a value of 0 to 0.29.

21. The method of claim 1 , further comprising treating the alkali metal-deficient nickel oxide with an aqueous solution of an alkali hydroxide to form a compound according to the formula: A x Å′ w H y Ni 1+a O 2 ·nH 2 O,
wherein A comprises Li or Na;
A′ comprises K, Cs, or Rb;
0.08≤x<0.2;
0.03<w<0.20;
0≤y<0.3;
0.02≤a≤0.2; and
0<n<2.

22. The method of claim 21 , wherein A comprises Li and A′ comprises K.

23. The method of claim 1 , wherein the oxidant comprises the monopersulfate salt.

24. The method of claim 1 , wherein the oxidant is provided in an amount in a range of about 0.75 moles to about 1.0 moles.

25. A method of preparing an electrochemically active cathode material, comprising:
combining an alkali metal-containing nickel oxide having a formula A 1−a Ni 1+a−z M z O 2 , wherein A comprises an alkali metal and 0<a≤0.2, M comprises a transition metal or main group metal, and 0≤z≤0.2, with a fluid composition including a oxidant comprising a peroxydisulfate salt, a monopersulfate salt, or a combination thereof to form a mixture;
heating the mixture to a temperature of 50° C. or greater; and
maintaining the mixture at the temperature for at least a period of time sufficient to form, an alkali metal-deficient nickel oxide electrochemically active cathode material having a general formula A x H y Ni 1+a−z M z O 2 ·nH 2 O, wherein
A comprises an alkali metal;
0.08≤x<0.2;
0≤y<0.3;
0.02<a≤0.2;
0≤z≤0.2; and
0<n<2.

26. The method of claim 25 , further comprising treating the alkali metal-deficient nickel oxide with an aqueous solution of an alkali hydroxide to form a compound according to the formula: A x Å′ w H y Ni 1+a−z M z O 2 ·nH 2 O,
wherein A comprises Li or Na;
A′ comprises K, Cs, or Rb;
0.08≤x<0.2;
0.03<w<0.20;
0≤y<0.3;
0.02≤a≤0.2;
0≤z≤0.2;
M comprises a transition metal or main group metal; and
0<n<2.

Assignees

• Duracell Us Operations Inc

Inventors

• Zhang Fan
• Christian Paul A
• Nelson Jennifer A
• Anglin David L
• Wildgust Paul
• Baccaro Thomas

Classifications

• H01M4/525 Primary

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/0471

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

• H01M4/366

  as layered products · CPC title

• C01G53/42 Primary

  containing alkali metals, e.g. LiNiO2 · CPC title

• C01P2006/40

  Electric properties · CPC title