# US 8,785,042 B2 · Island-covered lithium cobaltite oxides

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- Number: US 8,785,042 B2
- Document ID: US8785042B2
- Status: Granted
- Kind: B2
- Application number: 12/374,532
- Filed: 2008-01-17
- Published: 2009-12-17
- Granted: 2014-07-22
- Earliest claimed: 2007-01-29
- Assignees: Umicore AG & Co. KG
- Applicants: Jens Martin Paulsen; Thomas Lau
- Inventors: Jens Martin Paulsen; Thomas Lau
- Web page: https://patentgrep.com/patent/US8785042B2

## CPC

- C01G 51/42: containing alkali metals, e.g. LiCoO2
- C01G 45/1228: of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
- C01G 51/50: of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
- C01G 53/502: containing lithium and cobalt
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- 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
- C01P 2002/52: containing elements as dopants
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/03: obtained by SEM
- C01P 2004/50: Agglomerated particles
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/11: Powder tap density
- C01P 2006/12: Surface area
- C01P 2006/40: Electric properties
- Y02E 60/10: Energy storage using batteries
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Disclosed is a cathode active material and a method to produce the same at low cost. The cathode powder comprises modified LiCoO2, and possibly a second phase which is LiM′O2 where M′ is Mn, Ni, Co with a stoichiometric ratio Ni:Mn≧1. The modified LiCoO2 is Ni and Mn bearing and has regions of low and high manganese content, where regions with high manganese content are located in islands on the surface. The cathode material has high cycling stability, a very high rate performance and good high temperature storage properties.

## Claims

### Claim 1

A powderous lithium transition metal oxide comprising
a first phase consisting of Mn and Ni bearing LiCoO2 particles, said particles having a plurality of discrete and detached Mn and Ni enriched islands partially covering surfaces thereof, wherein said islands have a Mn and Ni concentration that is higher than in the bulk of said particles and said islands comprise at least 5 mol % of Mn; and
a second island-free phase having a generalized formula of Li1+aM′1−aO2±b, with −0.03<a<0.05 and b<0.02, M′=NimMnnCo1−m−n, with m≧n, and 0.1<m+n<0.9; wherein the first phase originates from a reaction of LiCoO2 particles and the second island-free phase.

### Claim 2 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein said Mn and Ni enriched islands have a thickness of at least 100 nm and cover less than 70% of the surfaces of said Mn and Ni bearing LiCoO2 particles.

### Claim 3 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein the Mn concentration in said islands is at least 4 mol % higher than the Mn concentration in the bulk of said Mn and Ni bearing LiCoO2 particles.

### Claim 4 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein the Ni concentration in said Mn and Ni enriched islands is at least 2 mol % higher than the Ni concentration in the bulk of said Mn and Ni bearing LiCoO2 particles.

### Claim 5 (depends on 1)

The powderous lithium transition metal oxide of claim 1, having Mn and Ni bearing LiCoO2 particles comprising at least 3 mol % of both Ni and Mn.

### Claim 6 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein crystallographic lattice constants a and c of said Mn and Ni bearing LiCoO2 particles are respectively 2.815+/−0.002 and 14.05+/−0.01.

### Claim 7 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein the Mn and Ni bearing LiCoO2 particles are monolithic and free of inner porosities.

### Claim 8 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein the size distribution of said Mn and Ni bearing LiCoO2 particles has a d50 larger than 10 μm.

### Claim 9 (depends on 1)

The powderous lithium transition metal oxide of claim 1, comprising between 30 wt. % and 95 wt. % of said Mn and Ni bearing LiCoO2 particles.

### Claim 10 (depends on 1)

The powderous lithium transition metal oxide of claim 1, having a composition of LixMyO2±δ with:
0.97<x<1.03, 0.97<y<1.03, x+y=2;
δ<0.05;
and M=Co1−f−gNifMng, with 0.05<f+g<0.5 and f>g.

### Claim 11 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein crystallographic lattice constants a′ and c′ of said island-free phase have the following relationship with lattice constants a″ and c″ of a corresponding island-free phase of a reference lithium transition metal (Mref) oxide, having the same composition LixMyO2±δ and consisting of pure LiCoO2 particles and said corresponding island-free phase:
0.980<a′/a″<0.998 and 0.9860<c′/c″<0.9985.

### Claim 12 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein said island-free phase has secondary particles having a size distribution with a d50 between 2 and 10 micrometer, said secondary particles consisting of sintered agglomerates of primary crystallites having a particle size distribution with a d50 between 0.5 and 2 μm.

### Claim 13 (depends on 1)

The powderous lithium transition metal oxide of claim 1, wherein both said Mn and Ni enriched islands and said island-free phase further comprise Ti, wherein the Ti content is less than 10 mol % of M in the oxide LixMyO2±δ.

### Claim 14 (depends on 10)

The powderous lithium transition metal oxide of claim 10, further comprising less than 5 mol % of M of one or more dopants selected from the group consisting of Al and Mg, and less than 1 mol % of M of one or more dopants selected from the group consisting of Be, B, Ca, Zr, S, F, and P.

### Claim 15 (depends on 1)

An electrochemical cell comprising a cathode comprising as an active material the powderous lithium transition metal oxide of claim 1.

### Claim 16 (depends on 1)

A method for preparing the powderous lithium transition metal oxide of claim 1, comprising:
providing a mixture of LiCoO2 powder or a cobalt containing precursor compound having a cobalt content of at least 90 mol %, and a Li—Ni—Mn—Co-oxide or a Ni—Mn—Co precursor powder and a Li-precursor compound; and
sintering said mixture at a temperature T of at least 910° C. for a time t between 1 and 48 hrs;
to obtain Mn and Ni bearing LiCoO2 particles having Mn and Ni enriched islands partially covering surfaces thereof.

### Claim 17

The method of 16, wherein the Ni—Mn—Co precursor powder is a transition metal hydroxide, oxyhydroxide, carbonate, oxycarbonate, or lithium transition metal compound, wherein the transition metal composition M″ is M″=NioMnpCo1-o-p, with o+p>0.5 and o>p.

### Claim 18 (depends on 16)

The method of claim 16, wherein the Ni—Mn—Co precursor powder comprises between 5 and 70 mol % of the transition metal content of said powderous lithium transition metal oxide.

### Claim 19 (depends on 16)

The method of claim 16, wherein the LiCoO2 powder has a tap density of at least 2 g/cm3, and consists of monolithic particles with a d50 of at least 10 μm.

### Claim 20 (depends on 16)

The method of claim 16, wherein the cobalt containing precursor compound is selected from the group consisting of cobalt hydroxide, oxyhydroxide, carbonate, and mixtures thereof.

### Claim 21 (depends on 16)

The method of claim 16, wherein said LiCoO2 or cobalt containing precursor comprises at least 80% of the transition metal of said powderous lithium transition metal oxide, and the Ni—Mn—Co comprising precursor powder consists of particles having a particle size distribution with a d50 between 1 and 3 μm.

### Claim 22 (depends on 16)

The method of claim 16, wherein said LiCoO2 or cobalt containing precursor comprises less than 80% of the transition metal of said powderous lithium transition metal oxide, and the Ni—Mn—Co comprising precursor consists of particles of an agglomerated type having a particle size distribution with a d50 between 4 and 10 μm.

### Claim 23 (depends on 16)

The method of claim 16, wherein the Ni—Mn—Co comprising precursor further comprises Ti, preferably in the form of TiO2 particles with a d50 less than 100 nm.