Disordered rock salt electrodes for lithium batteries

Patent metadata

Field	Value
Publication number	US-12206101-B2
Application number	US-202117203999-A
Country	US
Kind code	B2
Filing date	Mar 17, 2021
Priority date	Jun 2, 2017
Publication date	Jan 21, 2025
Grant date	Jan 21, 2025

Abstract

Cation-stabilized materials and compositions are described herein, which suppress the structural and electrochemical instability of lithium-metal-oxide spinel and lithiated lithium-metal-oxide spinel electrodes for lithium batteries, notably lithium-ion batteries. The lithium metal oxide electrode material comprises a disordered rock salt structure with partial lithiated-spinel character, wherein, for example, the disordered rock salt structure comprises a formula Li 2 (M″ 2-a M′″ a )O 4 , which has the crystallographic formula: [Li 2-b M′″ b ] 16c [M″ 2-a M′″ a-b Li b ] 16d O 4 wherein 16c and 16d refer to the octahedral sites of the prototypic space group symmetry Fd 3 m; M″ and M′″ are metal ions; 0<a≤0.5; and 0<b<0.5. These stabilized materials are useful as positive electrodes for lithium batteries in their own right or when used as a structural component to stabilize layered metal oxide electrode systems, such as a two-component layered-layered system or a multi-component layered-layered-spinel system.

First claim

The embodiments in which an exclusive property or privilege is claimed are defined as follows:

1. A lithium metal oxide electrode material comprising a disordered rock salt structure with partial lithiated-spinel character, wherein the material has a formula Li 2 (M″ 2-a M′ a )O 4 ; wherein M″ comprises Co; M′″ comprises one or more metals selected from the group consisting of Al, Mg and Ti; 0<a≤0.5; and the material of formula Li 2 (M″ 2-a M′″ a )O 4 has the crystallographic formula: [Li 2-b M′″ b ] 16c [M″ 2-a M′ a-b Li b ] 16d O 4 , wherein 16c and 16d refer to the octahedral sites of the prototypic space group symmetry Fd3m, and 0<b<0.5.

2. The electrode material of claim 1 , wherein M″ further comprises one or more metal selected from the group consisting of Ni, Mn, V, and Fe.

3. The electrode material of claim 1 , wherein 0<a-b<0.2.

4. The electrode material of claim 1 , wherein 0<a<0.3 and 0<a-b<0.1.

5. The electrode material of claim 1 , wherein 0<a-b<0.05.

6. The electrode material of claim 1 , wherein M″ comprises one or more metals selected from the group consisting of Co, Ni, and Mn; and M′″ is Al.

7. The electrode material of claim 6 , wherein M″ is Co.

8. The electrode material of claim 6 , wherein 0<a<0.3 and 0<a-b<0.1.

9. The electrode material of claim 6 , wherein 0<a-b<0.05.

10. The electrode material of claim 6 , wherein the material has a structure that is either cation or anion deficient, or both.

11. The electrode material of claim 1 , wherein the material has a structure that is either cation or anion deficient, or both.

12. The electrode material of claim 1 , wherein the Li, M″ and M′″ cations are partially disordered over the 16c and 16d octahedral sites.

13. The electrode material of claim 1 , wherein the lithium metal oxide electrode material is structurally integrated with a two-component layered-layered material of formula: wLi 2 MnO 3 ·(1−w)LiMO 2 , wherein M comprises one or more metal cations; and 0<w<1.

14. The electrode material of claim 13 , wherein M comprises one or more cations selected from the group consisting of Ni, Mn, and Co.

15. The electrode material of claim 13 , wherein the Li, Co, Ni, Mn, M″ and M′″ cations are partially disordered over octahedral sites of layered and lithiated spinel component structures.

16. The electrode material of claim 6 , wherein the lithium metal oxide electrode material is structurally integrated with a two-component layered-layered material of formula: wLi 2 MnO 3 ·(1−w)LiMO 2 , wherein M comprises one or more metal cations; and 0<w<1.

17. The electrode material of claim 16 , wherein M comprises one or more cations selected from the group consisting of Ni, Mn, and Co.

18. The electrode material of claim 16 , wherein the Li, Co, Ni, Mn, M″ and M′″ cations are partially disordered over octahedral sites of layered and lithiated spinel component structures.

19. An electrode comprising the electrode material of claim 1 supported on a metallic current collector.

20. An electrochemical cell comprising an anode, a cathode, and a lithium-containing electrolyte contacting the anode and cathode, wherein one or more of the anode and the cathode is the electrode of claim 19 .

21. A battery comprising a plurality of electrochemical cells of claim 20 electrically connected in series, in parallel, or in both series and parallel.

22. A lithium metal oxide electrode material comprising a disordered rock salt structure with partial lithiated-spinel character, wherein the material has a formula Li 2 (M″ 2-a M′″ a )O 4 ; wherein M″ comprises Co; M′″ comprises one or more metals selected from the group consisting of Al, Mg and Ti; 0<a≤0.5; and less than 25 percent of the Li in the material resides in octahedral crystallographic sites that also contain both M″ and M′″.

Assignees

• Uchicago Argonne Llc

Inventors

• Thackeray Michael M
• Lee Eungje
• Croy Jason R

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/525

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

• H01M4/131 Primary

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

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title