Lithium nickel-based composite oxide as a positive electrode active material for rechargeable solid-state batteries

Patent metadata

Field	Value
Publication number	US-2025054967-A1
Application number	US-202218719283-A
Country	US
Kind code	A1
Filing date	Dec 16, 2022
Priority date	Dec 17, 2021
Publication date	Feb 13, 2025
Grant date	—

Abstract

A positive electrode active material comprises Li, M′, and oxygen. M′ comprises Ni in a content x, Mn in a content y, Co in a content z, D in a content a, Zr in a content b, wherein 55.0 mol %≤x≤95.0 mol %, 0.0 mol %≤y≤40.0 mol %, 0.0 mol %≤z≤40.0 mol %, 0.0 mol %≤a≤2.0 mol %, and 0.01 mol %≤b≤5.0 mol %. D is at least one element other than Li, Ni, Mn, Co, and O. The positive electrode active material has a Zr content Zr X and a carbon content C. Zr X is expressed as a molar fraction compared to the sum of molar fractions of Co, Mn, Ni, and Zr. C is expressed in wt. % by total weight of the positive electrode active material. The ratio of Zr X to C is between 52−0.413·x and 42−0.413·x.

First claim

1 - 18 . (canceled)

19 . A positive electrode active material for solid-state batteries, wherein the positive electrode active material comprises Li, M′, and oxygen, wherein M′ comprises:
Ni in a content x, wherein 55.0 mol %≤x≤95.0 mol %,
Mn in a content y, wherein 0.0 mol %≤y≤40.0 mol %,
Co in a content z, wherein 0.0 mol %≤z≤40.0 mol %,
D in a content a, wherein 0.0 mol %≤a≤2.0 mol %, wherein D is at least one element other than Li, Ni, Mn, Co, and O,
Zr in a content b, wherein 0.01 mol %≤b≤5.0 mol %,
wherein x, y, z, a, and b are measured by ICP-OES,
wherein x+y+z+a+b is 100.0 mol %,
wherein the positive electrode active material has a Zr content Zr X , wherein Zr X is determined by XPS analysis, wherein Zr X is expressed as a molar fraction compared to the sum of molar fractions of Co, Mn, Ni, and Zr as measured by XPS analysis,
wherein the positive electrode active material comprises carbon in a content C, wherein C is in wt. % by total weight of the positive electrode active material, as measured by carbon analyzer,
wherein the ratio of Zr X to C is between 52−0.413·x and 42−0.413·x (wt. %) −1 .

20 . The positive electrode active material according to claim 19 , wherein D is at least one element other than Li, Ni, Mn, Co, Zr and O.

21 . The positive electrode active material according to claim 19 , wherein D comprises at least one element selected from the group consisting of: Al, B, Ba, Ca, Cr, Fe, Mg, Mo, Nb, S, Si, Sr, Ti, Y, V, W, and Zn.

22 . The positive electrode active material according to claim 19 , wherein the ratio Zr X to C is between 50−0.413·x and 43−0.413·x (wt. %) −1 .

23 . The positive electrode active material according to claim 19 , wherein C≤0.15 wt. % by total weight of the positive electrode active material.

24 . The positive electrode active material according to claim 19 , having a surface area SA, as determined by BET measurement, wherein the ratio of C to SA is at most 0.25 wt. % (g/m 2 ).

25 . The positive electrode active material according to claim 19 , wherein 60.0 mol %≤x≤90.0 mol %.

26 . The positive electrode active material according to claim 19 , wherein 0.05 mol %≤b≤2.5 mol %.

27 . The positive electrode active material according to claim 19 , wherein the positive electrode active material is a poly-crystalline powder.

28 . The positive electrode active material according to claim 26 , wherein the secondary particle median size D50 is at least 2.0 μm and at most 15.0 μm, as determined by laser diffraction particle size analysis.

29 . A method for manufacturing a positive electrode active material, wherein said method comprises:
preparing a slurry of lithium transition metal-based oxide compound, Li, water, and an alcohol, mixing said slurry with a source of Zr, and heating the mixture under an oxidizing atmosphere in a furnace at a temperature between 250° C. and less than 500° C. for a time between 1 hour and 20 hours to obtain the positive electrode active material.

30 . The method according to claim 29 , wherein the method further comprises a step, before heating said mixture, of filtering and drying said mixture.

31 . The method according to claim 29 , wherein the source of Zr is Zr-propoxide.

32 . The method according to claim 29 , wherein the amount of water in the slurry is between 0.5 mol % to 25.0 mol %, with respect to metal content in the lithium transition metal oxide compound.

33 . The method according to claim 29 , wherein the positive electrode active material comprises Li, M′, and oxygen, wherein M′ comprises:
Ni in a content x, wherein 55.0 mol %≤x≤95.0 mol %,
Mn in a content y, wherein 0.0 mol %≤y≤40.0 mol %,
Co in a content z, wherein 0.0 mol %≤z≤40.0 mol %,
D in a content a, wherein 0.0 mol %≤a≤2.0 mol %, wherein D is at least one element other than Li, Ni, Mn, Co, and O,
Zr in a content b, wherein 0.01 mol %≤b≤5.0 mol %,
wherein x, y, z, a, and b are measured by ICP-OES,
wherein x+y+z+a+b is 100.0 mol %,

wherein the positive electrode active material has a Zr content Zr X , wherein Zr X is determined by XPS analysis, wherein Zr X is expressed as a molar fraction compared to the sum of molar fractions of Co, Mn, Ni, and Zr as measured by XPS analysis,
wherein the positive electrode active material comprises carbon in a content C, wherein C is in wt. % by total weight of the positive electrode active material, as measured by carbon analyzer, wherein the ratio of Zr X to C is between 52−0.413·x and 42−0.413·x (wt. %) −1 .

34 . A solid-state battery comprising the positive electrode active material according to claim 19 .

35 . The solid-state battery according to claim 34 , wherein said solid-state battery comprises a sulfide based solid electrolyte comprising Li, P, and S.

36 . A portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle or a hybrid electric vehicle comprising the solid-state battery according to claim 34 .

Assignees

• Umicore Nv

Inventors

• Kumakura Shinichi
• Goossens Veerle
• Yang Taehyeon

Classifications

• H01M2300/0068

  inorganic · CPC title

• H01M10/0562

  Solid materials · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01P2006/12

  Surface area · CPC title

• C01P2002/85

  by XPS, EDX or EDAX data · CPC title