Stabilized lithium, manganese AB2O4 spinel for rechargeable lithium electrochemical systems through A and B site doping, method of preparing the same, and Li electrochemical cell containing the same

Patent metadata

Field	Value
Publication number	US-11623875-B2
Application number	US-201715724255-A
Country	US
Kind code	B2
Filing date	Oct 3, 2017
Priority date	Oct 3, 2017
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

A process for preparing a stable Li x K y Mn 2-z Me z O 4 is provided. The general formula of the potassium “A” site and Group VIII Period 4 (Fe, Co and Ni) “B” site modified lithium manganese-based AB 2 O 4 spinel is Li x K y Mn 2-z Me z O 4 where Me is Fe, Co, or Ni. In addition, a Li x K y Mn 2-z Me z O 4 cathode material for electrochemical systems is provided. Furthermore, a lithium or lithium-ion rechargeable electrochemical cell is provided, incorporating the Li x K y Mn 2-z Me z O 4 cathode material in a positive electrode.

First claim

What is claimed is:

1. A method of preparing a homogeneously dispersed potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material, the method comprising:
mixing a manganese source and a Group VIII Period 4 source to form a first mixture;
calcining the first mixture to produce a manganese mixed metal-based metal oxide;
mixing the manganese mixed metal-based metal oxide, a lithium source, and a potassium source to produce a second mixture; and
calcining the second mixture to produce the homogeneously dispersed potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material,

wherein Me is iron.

2. The method according to claim 1 , wherein the lithium source is selected from a group consisting of lithium carbonate, lithium hydroxide, lithium oxide, and lithium peroxide, wherein the potassium source is selected from a group consisting of potassium carbonate, potassium hydroxide, potassium oxide, and potassium peroxide, and wherein the manganese source is selected from a group consisting of manganese acetate and manganese nitrate.

3. The method according to claim 1 , wherein x ranges from 0.05 to 1.95, wherein y ranges from 0.05 to 0.2, and wherein z ranges from 0.005 to 0.6.

4. The method according to claim 1 , further comprising: mixing ammonium hydroxide with the first mixture to form an intermediate gel; and drying the intermediate gel,
wherein the manganese source is manganese acetate, and wherein the Group VIII Period 4 source is iron acetate.

5. The method according to claim 4 , wherein the first mixture is calcined at a time ranging from 0.5 hours to 2 hours and at a temperature ranging from 300° C. to 450° C., and wherein the second mixture is calcined at a time ranging from 12 hours to 72 hours and at a temperature ranging from 600° C. to 1200° C.

6. The method according to claim 1 , further comprising: mixing the first mixture with a chelating agent to form an intermediate mixture; and calcining the intermediate mixture to produce an ash, wherein the manganese source is manganese nitrate, and wherein the Group VIII Period 4 source is iron nitrate.

7. The method according to claim 6 , wherein the intermediate mixture is calcined for a time ranging from 1 hour to 4 hours and at a temperature ranging from 350° C. to 800° C., and wherein the second mixture is calcined for a time ranging from 12 hours to 72 hours and at a temperature ranging from 600° C. to 1200° C.

8. A homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material, prepared by a process comprising:
mixing a manganese source and a Group VIII Period 4 source to form a first mixture;
calcining the first mixture to produce a manganese mixed metal-based metal oxide;
mixing the manganese mixed metal-based metal oxide, a lithium source, and a potassium source to produce a second mixture; and
calcining the second mixture to produce the homogeneously dispersed potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 , AB 2 O 4 spinel cathode material, wherein Me is iron.

9. The homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material according to claim 8 , wherein the lithium source is selected from a group consisting of lithium carbonate, lithium hydroxide, lithium oxide, and lithium peroxide, wherein the potassium source is selected from a group consisting of potassium carbonate, potassium hydroxide, potassium oxide, and potassium peroxide, and wherein the manganese source is selected from a group consisting of manganese acetate and manganese nitrate.

10. The homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material according to claim 8 , wherein x ranges from 0.05 to 1.95, wherein y ranges from 0.05 to 0.2, and wherein z ranges from 0.005 to 0.6.

11. The homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material according to claim 8 , wherein the process further comprises: mixing ammonium hydroxide with the first mixture to form an intermediate gel; and drying the intermediate gel, wherein the manganese source is manganese acetate, and wherein the Group VIII Period 4 source is iron acetate.

12. The homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material according to claim 11 , wherein the process further comprises: calcining the first mixture for a time ranging from 0.5 hours to 2 hours and at a temperature ranging from 300° C. to 450° C.; and calcining the second mixture for a time ranging from 12 to 72 hours and at a temperature ranging from 600° C. to 1200° C.

13. The homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material according to claim 8 , wherein the process further comprises: mixing the first mixture with a chelating agent to form an intermediate mixture; and heating the intermediate mixture to produce an ash, wherein the manganese source is manganese nitrate, and wherein the Group VIII Period 4 source is iron nitrate.

14. The homogeneously dispersed, potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material according to claim 13 , wherein the process further comprises: calcining the intermediate mixture at a time ranging from 0.5 hours to 2 hours and at a temperature ranging from 300° C. to 450° C., and calcining the second mixture at a time ranging from 12 hours to 72 hours and at a temperature ranging from 600° C. to 1200° C.

15. A lithium electrochemical cell comprising: an anode; and
a cathode comprising a homogeneously dispersed potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material prepared by a process comprising:
mixing a manganese source and a Group VIII Period 4 source to form a first mixture;
calcining the first mixture to produce a manganese mixed metal-based metal oxide;
mixing the manganese mixed metal-based metal oxide, a lithium source, and a potassium source to produce a second mixture; and
calcining the second mixture to produce the homogeneously dispersed potassium-modified lithium manganese-based Li x K y Mn 2-z Me z O 4 spinel cathode material,
wherein Me is iron.

16. The lithium electrochemical cell according to claim 15 , wherein the lithium source is selected from a group consisting of lithium carbonate, lithium hydroxide, lithium oxide, and lithium peroxide, wherein the potassium source is selected from a group consisting of potassium carbonate, potassium hydroxide, potassium oxide, and potassium peroxide, and wherein the manganese source is selected from a group consisting of manganese acetate and manganese nitrate.

17. The lithium electrochemical cell according to claim 15 , wherein x ranges from 0.05 to 1.95, wherein y ranges from 0.05 to 0.2, and wherein z ranges from 0.005 to 0.6.

18. The lithium electrochemical cell according to claim 15 , wherein the process further comprises: mixing ammonium hydroxide with the first mixture to form an intermediate gel; drying the intermediate gel; calcining the first mixture at a time ranging from 0.5 hours to 2 hours and at a temperature ranging from 300° C. to 450° C.; and calcining the second mixture at a time ranging from 12 to 72 hours and at a temperature ranging from 600° C. to 1200° C., wherein the manganese source is manganese acetate, and wherein the Group VIII Period 4 source is iron acetate.

Assignees

• Us Gov As Represented By The Secretary Of The Army
• Us Gov Sec Army

Inventors

• Atwater Terrill B
• Howarth Yakira J

Classifications

• C01G51/52

  of the type (Mn2O4)2-, e.g. Li2(CoxMn2-x)O4 or Li2(MyCoxMn2-x-y)O4 · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/623

  fluorinated polymers · CPC title

• C01P2006/40

  Electric properties · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title