Cation-disordered rocksalt lithium manganese oxides or oxyfluorides

Patent metadata

Field	Value
Publication number	US-11769876-B2
Application number	US-202016990157-A
Country	US
Kind code	B2
Filing date	Aug 11, 2020
Priority date	Aug 13, 2019
Publication date	Sep 26, 2023
Grant date	Sep 26, 2023

Abstract

A class of compositions in the Li—Mn—O—F chemical space for Li-ion cathode materials. The compositions are cobalt-free, high-capacity Li-ion battery cathode materials synthesized with cation-disordered rocksalt (DRX) oxide or oxyfluorides, with the general formula LixMn2-xO2-yFy (1.1≤x≤1.3333; 0≤y≤0.6667). The compositions are characterized by: (i) high capacities (e.g., >240 mAh/g); (ii) high energy densities (e.g., >750 Wh/kg between 1.5-4.8V); (iii) favorable cyclability; and (iv) low cost.

First claim

What is claimed is:

1. A lithium metal oxide or oxyfluoride compound having a general formula:
Li x Mn 2-x O 2-y F y , wherein 1.1≤x≤1.3333, 0>y≤0.6667, and wherein Mn is present in a single oxidation state of Mn(III).

2. The compound of claim 1 , wherein the compound is Li 1.3333 Mn(III) 0.6667 O 1.3333 F 0.6667 .

3. The compound of claim 1 , wherein the compound has a cation-disordered rocksalt (DRX) structure.

4. The compound of claim 3 , wherein the DRX structure is adapted for low-energy Li migration through 0-TM channels.

5. The compound of claim 3 , wherein the DRX structure has a lattice constant between 4.1477 Å and 4.1635 Å.

6. The compound of claim 1 , wherein the compound is adapted to utilize O 2 and/or Mn redox during charge and discharge phases.

7. The compound of claim 1 , wherein the compound exhibits, over 30 cycles in a range of 1.5-4.8 V, an average capacity from 242 to 336 mAh g −1 .

8. The compound of claim 1 , wherein the compound exhibits, over 30 cycles in a range of 1.5-4.8 V, a specific energy from 771 to 1059 Wh kg −1 .

9. The compound of claim 1 , wherein the compound exhibits, over 30 cycles in a range of 1.5-5.0 V, an average capacity from 256 to 349 mAh g −1 .

10. The compound of claim 1 , wherein the compound exhibits, over 30 cycles in a range of 1.5-5.0 V, a specific energy from 822 to 1068 Wh kg −1 .

11. An electrode material, comprising:
a compound according to claim 1 .

12. A lithium-ion battery, comprising:
an electrolyte; and
the electrode material of claim 11 .

13. The lithium-ion battery of claim 12 , wherein the electrode material forms a cathode.

14. The lithium-ion battery of claim 13 , wherein the cathode is a cathode film comprising the electrode material, a conductive additive, and polytetrafluoroethylene (PTFE) at a weight ratio of 70:20:10, respectively.

15. A portable electronic device, an automobile, or an energy storage system, comprising:
the lithium-ion battery of claim 12 .

16. A lithium-ion battery, comprising:
an electrolyte; an anode; and a cathode, wherein at least one of the electrolyte, the anode, and the cathode is composed, at least in part, of a compound according to claim 1 .

17. A method of making a compound according to claim 1 , comprising
combining a collection of stoichiometric compounds composed of Li, Mn, O, and F to yield a precursor powder; and
mechanically mixing the precursor powder to obtain the phase pure powder through mechanochemical alloying.

18. The method according to claim 17 , wherein the collection of stoichiometric compounds composed of Li, Mn, O, and F comprises one or more of: Li 2 O, MnO, Mn 2 O 3 , MnO 2 , and LiF.

19. The compound of claim 1 , wherein 1.25≤x≤1.3333.

20. A lithium metal oxide or oxyfluoride compound having a general formula:
Li x Mn 2-x O 2-y F y , wherein 1.1≤x≤1.3333, 0≤y≤0.6667, and wherein Mn is present in a combination of multiple oxidation states.

21. The compound of claim 20 , wherein the compound is Li 1.3333 Mn(III) 0.5 Mn(IV) 0.1667 O 1.5 F 0.5 .

22. The compound of claim 20 , wherein the compound is Li 1.3333 Mn(III) 0.3333 Mn(IV) 0.3333 O 1.6667 F 0.3333 .

23. The compound of claim 20 , wherein the compound is Li 1.25 MN(II) 0.1667 MN(III) 0.5833 O 1.3333 F 0.6667 .

24. The compound of claim 20 , wherein the compound is Li 1.1667 Mn(II) 0.3333 Mn(III) 0.5 O 1.3333 F 0.6667 .

25. The compound of claim 20 , wherein Mn comprises a redox couple of Mn in multiple oxidation states.

26. The compound of claim 25 , wherein the redox couple comprises Mn(III).

27. The compound of claim 20 , wherein the compound has a cation-disordered rocksalt (DRX) structure.

28. The compound of claim 27 , wherein the DRX structure is adapted for low-energy Li migration through 0-TM channels.

29. The compound of claim 27 , wherein the DRX structure has a lattice constant between 4.1477 Å and 4.1635 Å.

30. The compound of claim 20 , wherein the compound is adapted to utilize O 2 and/or Mn redox during charge and discharge phases.

31. The compound of claim 20 , wherein the compound exhibits, over 30 cycles in a range of 1.5-4.8 V, an average capacity from 242 to 336 mAh g −1 .

32. The compound of claim 20 , wherein the compound exhibits, over 30 cycles in a range of 1.5-4.8 V, a specific energy from 771 to 1059 Wh kg −1 .

33. The compound of claim 20 , wherein the compound exhibits, over 30 cycles in a range of 1.5-5.0 V, an average capacity from 256 to 349 mAh g −1 .

34. The compound of claim 20 , wherein the compound exhibits, over 30 cycles in a range of 1.5-5.0 V, a specific energy from 822 to 1068 Wh kg −1 .

35. An electrode material, comprising:
a compound according to claim 20 .

36. A lithium-ion battery, comprising:
an electrolyte; and
the electrode material of claim 35 .

37. The lithium-ion battery of claim 36 , wherein the electrode material forms a cathode.

38. The lithium-ion battery of claim 37 , wherein the cathode is a cathode film comprising the electrode material, a conductive additive, and polytetrafluoroethylene (PTFE) at a weight ratio of 70:20:10, respectively.

39. A lithium-ion battery, comprising:
an electrolyte; an anode; and a cathode, wherein
at least one of the electrolyte, the anode, and the cathode is composed, at least in part, of a compound according to claim 20 .

40. A portable electronic device, an automobile, or an energy storage system, comprising:
the lithium-ion battery of claim 36 .

41. A method of making a compound according to claim 20 , comprising
combining a collection of stoichiometric compounds composed of Li, Mn, O, and F to yield a precursor powder; and
mechanically mixing the precursor powder to obtain the phase pure powder through mechanochemical alloying.

42. The method according to claim 41 , wherein the collection of stoichiometric compounds composed of Li, Mn, O, and F comprises one or more of: Li 2 O, MnO, Mn 2 O 3 , MnO 2 , and LiF.

43. The compound of claim 20 , wherein 1.25≤x≤1.3333.

Assignees

• Univ California

Inventors

• Ceder Gerbrand
• Lun Zhengyan
• Ouyang Bin

Classifications

• C01G45/22

  Compounds containing manganese, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M4/505 Primary

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

• C01G45/006

  Chemistry & Metallurgy · mapped topic

• H01B1/08

  oxides · CPC title

• H01M4/1315

  containing halogen atoms, e.g. LiCoOxFy · CPC title