Cation-disordered rocksalt type high entropy cathode with reduced short-range order for li-ion batteries

Patent metadata

Field	Value
Publication number	US-2023047457-A1
Application number	US-202117758840-A
Country	US
Kind code	A1
Filing date	Feb 3, 2021
Priority date	Feb 7, 2020
Publication date	Feb 16, 2023
Grant date	—

Abstract

A class of compositions that are inclusive of a lithium metal oxide or oxyfluoride compound having a general formula: LiTM[n]OF where TM[n] represents a number of transition metal species inclusive of transitional metal species differentiated by charge or d0 electron shell conformation, with [n] being at least 4 of said transitional metal species, and wherein said lithium metal oxide or oxyfluoride has a cation-disordered rocksalt (DRX) structure and a mitigated SRO via a high entropy DRX design strategy. Also featured is a method of synthesizing the high entropy DRX lithium metal oxide or oxyfluoride compounds, as well as usage of the same in Li-ion batteries, with particular utility in cathodes of such Li-ion batteries.

First claim

1 . A lithium metal oxide or oxyfluoride compound having a general formula: Li 1+x TM[n] 1−x O 2−y F y , where TM[n] represents a number of transition metal species, inclusive of those differentiated by redox-active species or d° redox-inactive charge compensators, with [n] being at least four of said transitional metal species, and wherein said lithium metal oxide or oxyfluoride has a cation-disordered rocksalt (DRX) structure.

2 . The compound of claim 1 where TM[n] includes at least Mn 3+ and Ti 4+ .

3 . The compound of claim 1 , wherein [n] is at least 6.

4 . The compound of claim 3 , wherein [n] is from 6 to 10.

5 . The compound of claim 1 , wherein TM[n] represents four or more TM species selected from the group of Mn 3+ , Ti 4+ , Mn 2+ , Nb 5+ , Co 2+ , and Cr + .

6 . The compound of claim 1 , wherein the compound is Li 1.3 Mn 2+ 0.2 Mn 3+ 0.2 Ti 0.1 Nb 0.2 O 1.7 F 0.3 .

7 . The compound of claim 1 , wherein the compound is Li 1.3 Mn 2+ 0.1 Co 2+ 0.1 Cr 3+ 0.1 Mn 3+ 0.1 Ti 0.1 Nb 0.2 O 1.7 F 0.3 .

8 . The compound of claim 1 , which delivers a capacity of at least 307 mAH/g (955 Wh/kg) when cycled between 1.5 and 4.7 Vat a rate of 20 mA/g when provided in a cathode.

9 . The compound of claim 8 , which retains a capacity of at least 170 mA/g at a cycling rate of 2 A/g when provided in a cathode.

10 . The compound of claim 1 wherein the cation ion order reflects a mitigated short range order (SRO) characterized by the fact that, in TEM electron diffraction patterns, the SRO diffuse scattering pattern intensity is equal to or less than around 0.31 a.u. larger than the background intensity, and preferably equal to or less than around 0.19 a.u. larger than the background intensity.

11 . The compound of claim 1 having the formula: Li 1+x TM[1] a TM[2] b TM[3] c TM[4] d=(1−x−a−b−c) O 2−y F y , wherein 0.05≤x≤0.35, 0.1≤a≤0.3, 0.1≤b≤0.3, 0.1≤c≤0.3, 0.1≤d≤0.3, and 0≤y≤0.5.

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

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

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

15 . A portable electronic device, an automobile, or an energy storage system, comprising:
the lithium-ion battery of claim 14 .

16 . A method of making a lithium metal oxide or oxyfluoride compound having a general formula: LiTM[n]OF where TM[n] represents a number of transition metal species inclusive of transitional metal species differentiated by charge or d 0 electron shell conformation, comprising:
combining a collection of compounds composed of Li, TM[n], O, and optionally F, with Li present in excess, where TM[n] includes said transitional metal species, and [n] is at least four, to yield a precursor powder; and mixing the precursor powder to obtain a phase pure powder through mechanochemical alloying.

17 . The method according to claim 16 , wherein the four or more transition metal species are selected from Mn 3+ , Ti 4+ , Mn 2+ , Nb 5+ , Co 2+ , and Cr 3+ .

18 . The method according to claim 16 , wherein
the precursor powder is subjected to mechanical mixing by dispensing the precursor powder into a planetary ball mill.

19 . The method of claim 16 , wherein TM[n] is inclusive of Mn 3+ and Ti 4+ .

20 . The method of claim 16 , wherein the compound is Li 1.3 Mn 3+ a Ti b TM[3] c TM[4] d O 1.7 F 0.3 .

21 . The method of claim 16 , wherein the compound is Li 1.3 Mn 2+ 0.2 Mn 3+ 0.2 Ti 0.1 Nb 0.2 O 1.7 F 0.3 .

22 . The method of claim 16 , wherein, wherein the compound is Li 1.3 Mn 2+ 0.1 Co 2+ 0.1 Cr 3+ 0.1 Mn 3+ 0.1 Ti 0.1 Nb 0.2 O 1.7 F 0.3 .

23 . The method of claim 16 , wherein the compound has the formula:
Li 1+x TM[1] a TM[2] b TM[3] c TM[4] d=(1−x−a−b−c )O 2−y F y , wherein 0.05≤x≤0.35, 0.1≤a≤0.3, 0.1≤b≤0.3, 0.1≤c≤0.3, 0.1≤d≤0.3, and 0≤y≤0.5.

24 . A lithium metal oxide or oxyfluoride compound having a general formula LiTMOF, wherein the compound has a cation-disordered rocksalt (DRX) structure, and TM includes multiple transitional metal species comprising at least Mn 3+ and Ti 4+ .

25 . The compound according to claim 24 , further comprising at least two additional transitional metal species differentiated by charge or d 0 electron shell conformation and, selected from the group consisting of Mn 2+ , Co 2+ , Cr + , and Nb.

26 . The compound of claim 25 , wherein the compound is Li 1.3 Mn 2+ 0.2 Mn 3+ 0.2 Ti 0.1 Nb 0.2 O 1.7 F 0.3 .

27 . The compound of claim 25 , wherein the compound is Li 1.3 Mn 2+ 0.1 Co 2+ 0.1 Cr 3+ 0.1 Mn 3+ 0.1 Ti 0.1 Nb 0.2 O 1.7 F 0.3 .

28 . The compound of claim 24 wherein the cation ion order reflects a mitigated short range order (SRO) characterized by the fact that, in TEM electron diffraction patterns, the SRO diffuse scattering pattern intensity is equal to or less than around 1.07 a.u. larger than the background intensity, preferably equal to or less than around 0.31 a.u. larger than the background intensity, and more preferably equal to or less than around 0.19 a.u. larger than the background intensity.

29 . The compound according to claim 1 , wherein the compound exhibits an enhanced charging capacity based on an overall entropy corresponding to the number of transitional metal species TM[n] included therein, independent of any specific transitional metal specie included therein.

Assignees

• Univ California

Inventors

• Ceder Gerbrand
• Lun Zhengyan

Classifications

• C01G51/82

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

• C01G45/22 Primary

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

• H01M4/505

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

• C01G37/006

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

• C01P2006/40

  Electric properties · CPC title