Precursor and Method for Preparing Li Transition Metal Oxide Cathodes for Rechargeable Batteries

• US 20190074511A1
• Filed: 08/25/2016
• Published: 03/07/2019
• Est. Priority Date: 09/08/2015
• Status: Active Grant

• Current Assignee: Umicore Korea Ltd. (Umicore S.A.), Umicore S.A.
• Original Assignee: Umicore Korea Ltd. (Umicore S.A.), Umicore S.A.
• Inventors: BLANGERO, Maxime, PARK, DongGun, PAULSEN, Jens, ZHANG, Jing
• Granted Patent: US 10,644,312 B2
• Time in Patent Office: Days
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/50 Solid solutions
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/60 Compounds characterised by their crystallite size
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/74 by peak-intensities or a ratio thereof only
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/52 highly monodisperse size distribution
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A crystalline precursor compound is described for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor having a general formula Li_1−a((Ni_z(Ni_1/4 Mn_1/4)_y M′_x)_1−kA_k)_1+a0₂, wherein x+y+z=1, 0<x≤0.2, 0.55<z≤0.90, M′ is either one or both of Co and Al, A is a dopant, 0≤k≤0.1, and 0.05≤a≤0.40, wherein the precursor an integrated intensity ratio I003/I104<1, wherein I003 and I104 are the peak intensities of the Bragg peaks (003) and (104) of the XRD pattern of the crystalline precursor compound. Also a method is described for manufacturing a positive electrode material having a general formula Li_1−aM_1−a′O₂, with M=(Ni_z(Ni_1/2 Mn_1/2)_y M′_x)_1−k A_k), wherein x+y+z=1, 0<x≤0.2, 0.55<z≤0.90, M′ is either one or both of Co and Al, A is a dopant, 0≤k≤0.1 and 0.01<a′<0.10 by sintering the crystalline precursor compound in an oxidizing CO₂-free atmosphere at a temperature T between 750 and 950° C., for a time t between 6 and 36 hrs.

Claims

1-17. -17. (canceled)

18. A crystalline precursor compound for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor having a general formula Li₁₋

a((Ni_z(Ni_1/2Mn_1/2)_yM′

_x)<sub>1−

k</sub>A_k)_1+aO₂, wherein x+y+z=1, 0<

x≤

0.2, 0.55<

z≤

0.90, M′

is either one or both of Co and Al, A is a dopant, 0≤

k≤

0.1, and 0.05≤

a≤

0.40, wherein the precursor has an integrated intensity ratio I003/I104<

1, wherein I003 and I104 are the peak intensities of the Bragg peaks (003) and (104) of the XRD pattern of the crystalline precursor compound.

19. The crystalline precursor compound of claim 18, wherein the precursor has a ratio R of the intensities of the combined Bragg peak (102,006) and the Bragg peak (101) with R=((I102+I006)/I101) and 0.5<

R<

1.16.

20. The crystalline precursor compound of claim 18, having a Li₂CO₃ content <

0.4 wt %

21. The crystalline precursor compound of claim 18, wherein 0.55<

z≤

0.75 and 0.12≤

a≤

0.25, the precursor having a crystalline size L expressed in nm, with 20≤

L≤

80.

22. The crystalline precursor compound of claim 18, wherein M′

is Co and k=0, 0<

x<

0.2, 0.60<

z<

0.75.

23. The crystalline precursor compound of claim 18, wherein M′

=Co_cAl_d with 0.75≤

c≤

0.95, c+d=1.00, and y=0, k=0, 0<

x<

0.2 and 0.75<

z<

0.90.

24. The crystalline precursor compound of claim 18, wherein the amount of Ni atoms on the Li 3a octahedral sites is at least 4%.

29. The method according to claim 24, wherein the second mixture is sintered at a temperature between 775 and 850°

C., for a time between 8 and 12 hrs.

25. A method for preparing a positive electrode material having a general formula Li_1+a′

M<sub>1−

a′</sub>

O₂, with M=(Ni_z(Ni_1/2Mn_1/2)_yM′

_x)<sub>1−

k</sub>A_k, wherein x+y+z=1, 0<

x≤

0.2, 0.55<

z≤

0.90, M′

is either one or both of Co and Al, A is a dopant, 0≤

k≤

0.1 and 0.01≤

a′

≤

0.10, comprising;

providing a M-based precursor prepared from the co-precipitation of metal sulphates with a base;

mixing the M-based precursor with either one of LiOH and LiOH.H₂O, thereby obtaining a first mixture, whereby the Li to transition metal ratio in the first mixture is between 0.60 and 0.90,

sintering the first mixture in an oxidizing atmosphere at a temperature between 750 and 850°

C., for a time between 8 and 36 hrs, thereby obtaining a lithium deficient precursor powder,

mixing the lithium deficient precursor powder with either one of LiOH and LiOH.H₂O, thereby obtaining a second mixture,

sintering the second mixture in an oxidizing and CO2-free atmosphere at a temperature between 750 and 950°

C., for a time between 6 and 36 hrs.

26. The method according to claim 25, wherein the Li to transition metal ratio in the first mixture is between 0.75 and 0.90.

28. The method according to claim 25, wherein the first mixture is sintered in dry air, and the second mixture is sintered in oxygen.

32. A positive electrode material having a general formula Li_1+a′

;

M<sub>1−

a′</sub>

;

O₂, with M=(Ni_z(Ni_1/2Mn_1/2)_yM′

_x)<sub>1−

k</sub>A_k, wherein x+y+z=1, 0<

x≤

0.2, 0.55<

z≤

0.90, M′

is either one or both of Co and Al, A is a dopant, 0≤

k≤

0.1 and 0.01≤

a′

≤

0.10, prepared by two successive lithiation reactions, wherein the first lithiation reaction yields an intermediate compound that is lithium deficient versus the positive electrode material, and the second lithiation reaction is performed in a CO₂-free atmosphere.