Oxidative Delithiation of Alkali Nickel Oxide

Patent metadata

Field	Value
Publication number	US-2024282957-A1
Application number	US-202418625736-A
Country	US
Kind code	A1
Filing date	Apr 3, 2024
Priority date	Jan 23, 2020
Publication date	Aug 22, 2024
Grant date	—

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

1 .- 37 . (canceled)

38 . A method of preparing an electrochemically active cathode material, comprising:
reacting an alkali metal-containing nickel oxide having a formula A 1-a N 1+a−z M z O 2 , wherein A comprises an alkali metal, 0<a≤0.2, M comprises a transition metal or main group metal, and 0≤z≤0.2, with a chemical oxidant comprising a peroxydisulfate salt, a monopersulfate salt, or a combination thereof, in a fluid composition at a temperature of 50° C. or greater 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

;

0
≤
z
≤
0.2

;
and

0
<
n
<

2
.

39 . The method of claim 38 , wherein the temperature is in a range of about 55° C. to about 85° C.

40 . The method of claim 38 , wherein the oxidant comprises a peroxydisulfate salt.

41 . The method of claim 38 , wherein A comprises Li.

42 . The method of claim 38 , wherein the time sufficient to form the alkali metal-deficient nickel oxide electrochemically active cathode material is about 1 hour to about 24 hours.

43 . The method of claim 38 , wherein the time sufficient to form the alkali metal-deficient nickel oxide electrochemically active cathode material is about 1 hour to about 6 hours.

44 . The method of claim 38 , wherein the method does not include addition of mineral acid to the mixture.

45 . The method of claim 38 , wherein the fluid composition further comprises an alkali metal hydroxide, an ammonium hydroxide, or a combination thereof.

46 . The method of claim 38 , wherein the fluid composition has a pH in a range of about 8 to about 12.

47 . The method of claim 38 , wherein the fluid composition is substantially free of a hydroxide salt.

48 . The method of claim 38 , wherein the alkali metal-containing nickel oxide and the chemical oxidant are provided in a molar ratio of about 1:0.75 to about 1:2.

49 . The method of claim 45 , wherein the alkali metal-containing nickel oxide, the oxidant, and the hydroxide salt are provided in a molar ratio of about 1:0.75:1 to about 1:2:6.

50 . The method of claim 38 , wherein the oxidant comprises a counter cation selected from the group consisting of ammonium, sodium, potassium, lithium, and a combination thereof.

51 . The method of claim 45 , wherein a counter cation of the oxidant and a counter cation of the hydroxide salt are each ammonium.

52 . The method of claim 45 , wherein one of an oxidant counter cation or hydroxide counter cation comprises ammonium and the other comprises potassium.

53 . The method of claim 45 , wherein a counter cation of the oxidant comprises ammonium and a counter cation of the hydroxide salt comprises sodium.

54 . The method of claim 50 , wherein a counter cation of the oxidant comprises ammonium or sodium and the fluid composition is substantially free of a hydroxide.

55 . The method of claim 38 , wherein the oxidant comprises two different counter cations selected from the group consisting of ammonium, sodium, and potassium.

56 . The method of claim 38 , wherein the oxidant is a combination of a sodium peroxydisulfate and a potassium peroxydisulfate.

57 . The method of claim 38 , wherein y has a value of 0 to 0.29.

58 . The method of claim 38 , 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 A′ w H y Ni 1+α−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

;
and

0
<
n
<

2
.

59 . The method of claim 58 , wherein A comprises Li and A′ comprises K.

Assignees

• Duracell Us Operations Inc

Inventors

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

Classifications

• H01M4/366

  as layered products · CPC title

• H01M4/0471

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

• Y02E60/10

  Energy storage using batteries · CPC title

• C01P2006/40

  Electric properties · CPC title

• 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