Precursor and method for preparing Li transition metal oxide cathodes for rechargeable batteries

• US 10,644,312 B2
• Filed: 08/25/2016
• Issued: 05/05/2020
• Est. Priority Date: 09/08/2015
• Status: Active Grant

• Current Assignee: Umicore Korea Ltd. (Umicore S.A.), Umicore S.A.
• Original Assignee: Umicore S.A.
• Inventors: Blangero, Maxime, Park, DongGun, Paulsen, Jens, Zhang, Jing
• Primary Examiner(s): Oyer, Andrew J.
• Application Number:
  US15/757,035
• Publication Number:
  US 20190074511A1
• Time in Patent Office: 1,349 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+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 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. 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≤

0.75, M′

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

k≤

0.1, and 0.12≤

a≤

0.25, 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, and wherein the precursor has a crystalline size L expressed in nm, with 20≤

L≤

80.

2. The crystalline precursor compound of claim 1, 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.

3. The crystalline precursor compound of claim 1, having a Li₂CO₃ content <

0.4 wt %.

4. The crystalline precursor compound of claim 1, wherein M′

is Co and k=0, 0<

x<

0.2, 0.60<

z<

0.75.

5. The crystalline precursor compound of claim 1, wherein M′

=Co_cAl_d with 0.75≤

c≤

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

x<

0.2.

6. The crystalline precursor compound of claim 1, wherein the amount of Ni atoms on the Li 3a octahedral sites is at least 4%.

7. 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.

8. The method according to claim 7, wherein the Li to transition metal ratio in the first mixture is between 0.75 and 0.90.

9. The method according to claim 7, wherein the lithium deficient precursor powder has a general formula L_1-a((Ni_z(Ni_1/2Mn_1/2)_yM′

_x)A_k)_1+aO₂, wherein x+y+z=1, 0<

x<

0.2, 0.55<

z≤

0.75, M′

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

k≤

0.1, and 0.12≤

a≤

0.25, 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, and wherein the precursor has a crystalline size L expressed in nm, with 20≤

L≤

80.

10. The method according to claim 7, wherein the first mixture is sintered in dry air, and the second mixture is sintered in oxygen.

11. The method according to claim 7, wherein the second mixture is sintered at a temperature between 775 and 850°

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