Cobalt-Based Lithium Metal Oxide Cathode Material

Patent metadata

Field	Value
Publication number	US-2018190976-A1
Application number	US-201615738219-A
Country	US
Kind code	A1
Filing date	Jun 30, 2016
Priority date	Jul 2, 2015
Publication date	Jul 5, 2018
Grant date	—

Abstract

A layered lithium metal oxide powder for a cathode material used in a rechargeable battery, with the general formula (1−x)[Li a-b A b ] 3a [CO 1-c M c ] 3b [O 2-d-e N′ e ] 6c .xLi 3 PO 4 , with 0.0001≤x≤0.05, 0.90≤a≤1.10, 0<b+c≤0.1, −0.1≤d≤0.1 and e≤0.05, wherein A and M are one or more elements including at least one of the group consisting of Mg, Ti and Al; wherein N′ is either one or more dopants of the group consisting of F, S, N and P; the powder consisting of a core and an ion-conductive electron-insulating surface layer, the core having a layered crystal structure and the surface layer comprising a mixture of elements of the core material, oxides comprising either one or more elements of the group consisting of Mg, Ti and Al; and Li 3 PO 4 .

First claim

1 - 20 . (canceled)

21 . A layered lithium metal oxide powder for a cathode material used in a rechargeable battery, with the general formula (1−x)[Li a-b A b ] 3a [Co 1-c M c ] 3b [O 2-d-e N′ e ] 6c .xLi 3 PO 4 , with 0.0001≤x≤0.05, 0.90≤a≤1.10, 0<b+c≤0.1, −0.1≤d≤0.1 and e≤0.05, wherein the Li to Co+A+M+3P molar ratio is between 0.970 and 1.005, wherein A and M comprise one or more elements including at least one element selected from the group consisting of Mg, Ti and Al;
wherein N′ comprises one or more dopants selected from the group consisting of F, S, N and P;
wherein the powder comprises
a core having a layered crystal structure comprising the elements Li, Co and oxygen and having a molar ratio P to Co between 0 and less than 0.05,
and a surface layer comprising a mixture of the elements Li, Co and oxygen, oxides comprising one or more elements selected from the group consisting of Mg, Ti and Al, and Li 3 PO 4 , wherein the oxides optionally further comprise one or both of Li and Co.

22 . The lithium metal oxide powder of claim 21 , wherein
0.970≤[((1− x )·( a−b ))+3 x ]/[((1− x )·(1+ b ))+3 x]≤ 1.000.

23 . The lithium metal oxide powder of claim 21 , wherein
0.970≤[((1− x )·( a−b ))+3 x ]/[((1− x )·(1+ b ))+3 x]≤ 0.990.

24 . The lithium metal oxide powder of claim 21 , wherein Li 3 PO 4 is attached to a surface of the core in a combination of a film layer and discrete particles, thereby creating an ion-conductive electron-insulating surface layer on the core.

25 . The lithium metal oxide powder of claim 21 , wherein discrete particles of the Li 3 PO 4 have a size below 5 μm.

26 . The lithium metal oxide powder of claim 24 , wherein the Li 3 PO 4 present as a film layer covers at least 50% of the surface of the core.

27 . The lithium metal oxide powder of claim 24 , wherein a thickness of the film layer is less than 10 nm.

28 . The lithium metal oxide powder of claim 21 , wherein the Li 3 PO 4 is a crystalline compound.

29 . The lithium metal oxide powder of claim 21 , wherein the Li 3 PO 4 has up to 25 at % nitrogen doping on oxygen site.

30 . The lithium metal oxide powder of claim 24 , wherein a thickness of the ion-conductive electron-insulating surface layer, defined as the depth where the molar ratio of (A+M)/Co>(2·(b+c))/(1−c) mol/mol, as determined by XPS, is 1 μm or less.

31 . The lithium metal oxide powder of claim 30 , wherein the thickness of the ion-conductive electron-insulating surface layer is 0.5 μm or less.

32 . The lithium metal oxide powder of claim 21 , wherein A further comprises at least one element selected from the group consisting of Na, Si, S, K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Nb, Zr, W, F and rare earth metals.

33 . The lithium metal oxide powder of claim 21 , wherein M further comprises at least one element selected from the group consisting of Li, Na, Si, S, K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Nb, Zr, W, F and rare earth metals.

34 . The lithium metal oxide powder of claim 21 , wherein electronic conductivity of the powder at room temperature is below 10 −3 S/cm.

35 . The lithium metal oxide powder of claim 21 , wherein the P/Co molar ratio is between 0.01 and 5 mol %.

36 . The lithium metal oxide powder of claim 21 , wherein the Li/(Co+3P) molar ratio is between 0.980 and 1.020.

37 . The lithium metal oxide powder of claim 21 , having a soluble base content <20 μmol/g.

38 . A method for manufacturing the lithium metal oxide powder of claim 21 , comprising:
providing a first mixture of a first Co— or Co, A and M-comprising precursor powder and a first Li-comprising precursor powder, the first mixture having a Li:Co molar ratio >1.02, sintering the first mixture in an oxygen comprising atmosphere at a temperature Ti of at least 350° C., thereby obtaining a Li-enriched lithium metal oxide compound, providing a second Co— or Co, A and M-comprising precursor powder and a phosphate containing reagent, mixing the Li-enriched lithium metal oxide compound, the second Co— or Co, A and M-comprising precursor powder, and the phosphate containing reagent, thereby obtaining a second mixture wherein the Li to Co+A+M+3P molar ratio is between 0.970 and 1.005, and sintering the second mixture in an oxygen comprising atmosphere at a temperature T2 of at least 600° C.

39 . A method for manufacturing the lithium metal oxide powder of claim 21 , comprising:
providing a first mixture of a first Co— or Co, A and M-comprising precursor powder, and a first Li-comprising precursor powder, the first mixture having a Li:Co molar ratio >1.02, sintering the first mixture in an oxygen comprising atmosphere at a temperature Ti of at least 350° C., thereby obtaining a Li-enriched lithium metal oxide compound, mixing the Li-enriched lithium metal oxide compound with phosphate and lithium containing reagents, precipitating Li 3 PO 4 particles on the surface of the Li-enriched lithium metal oxide compound, thereby obtaining a second mixture, providing a second Co— or Co, A and M-comprising precursor powder, and mixing the second mixture and the second Co— or Co, A and M-comprising precursor powder, thereby obtaining a third mixture, whereby the third mixture has a Li to Co+A+M+3P molar ratio between 0.970 and 1.005, and sintering the third mixture in an oxygen comprising atmosphere at a temperature T2 of at least 600° C.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Blangero Maxime
• Choi Da-In
• Kumakura Shinichi

Classifications

• C01P2006/40

  Electric properties · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2004/80

  Particles consisting of a mixture of two or more inorganic phases · CPC title

• C01P2002/85

  by XPS, EDX or EDAX data · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title