# US 11,444,279 B2 · High tap density lithium positive electrode active material, intermediate and process of preparation

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,444,279 B2
- Document ID: US11444279B2
- Status: Granted
- Kind: B2
- Application number: 16/839,564
- Filed: 2020-04-03
- Published: 2020-07-30
- Granted: 2022-09-13
- Earliest claimed: 2015-08-27
- Assignees: Haldor TopsøE A/S
- Applicants: Haldor TopsøE A/S
- Inventors: Jon Fold Von Bülow; Søren Dahl; Jonathan Højberg; Jakob Weiland Høj
- Web page: https://patentgrep.com/patent/US11444279B2

## CPC

- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/54: of the type (Mn2O4)-, e.g. Li(NixMn2-x)O4 or Li(MyNixMn2-x-y)O4
- 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
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2002/32: spinel-type (AB2O4)
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/11: Powder tap density
- C01P 2006/40: Electric properties
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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)
- 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

A lithium positive electrode active material intermediate including less than 80 wt % spinel phase and a net chemical composition of LixNiyMn2-yO4-δ wherein 0.9≤x≤1.1; 0.4≤y≤0.5; and 0.1≤δ. Further, a process for the preparation of a lithium positive electrode active material with high tap density for a high voltage secondary battery where the cathode is fully or partially operated above 4.4 V vs. Li/Li+, comprising the steps of a)heating a precursor in a reducing atmosphere at a temperature of from 300° C. to 1200° C. to obtain a lithium positive electrode active material intermediate; b)heating the product of step a. in a non-reducing atmosphere at a temperature of from 300° C. to 1200° C.; wherein the mass of the product of step b. increases by at least 0.25% compared to the mass of the product of step a.

## Claims

### Claim 1

A process for the preparation of a lithium positive electrode active material for a high voltage secondary battery, where the cathode is fully or partially operated above 4.4 V vs. Li/Li+, said process comprising the steps of:
a. heat treating a precursor comprising lithium in a reducing atmosphere at a temperature of between 300° C. and 750° C. to obtain the lithium positive electrode active material intermediate;
b. heat treating the product of step a. in a non-reducing atmosphere at a temperature of between 700° C. and 1200° C.;
wherein the mass of the product of step b. increases by at least 0.25% compared to the mass of the product of step a,
wherein the reducing atmosphere is selected from the group consisting of a gas containing less than 15 vol % oxygen and a gas containing an added substance, which is capable of removing all or part of oxidizing species present in the gas.

### Claim 2 (depends on 1)

A process according to claim 1, wherein the mass of the product of step b. increases by at least 0.75% compared to the mass of the product of step a.

### Claim 3 (depends on 1)

A process according to claim 1, wherein the temperature of step a. is between 400° C. and 750° C.

### Claim 4 (depends on 1)

A process according to claim 1, wherein the temperature of step b. is between 800° C. and 1200° C.

### Claim 5 (depends on 1)

A process according to claim 1, wherein the reducing atmosphere is a gaseous composition containing less than 15 vol % oxygen.

### Claim 6 (depends on 1)

A process according to claim 1, wherein the reducing atmosphere is created by adding a substance to the precursor composition, by decomposition of the precursor or by adding a gaseous composition to the atmosphere in order to remove all or part of any oxidising species present in the atmosphere.

### Claim 7 (depends on 1)

A process according to claim 1, wherein the non-reducing atmosphere is a gaseous composition selected from the group consisting of air, and a composition comprising at least 5 vol % oxygen in an inert gas.

### Claim 8 (depends on 1)

A process according to claim 1, wherein the lithium positive electrode active material has a capacity of greater than 110 mAhg−1.

### Claim 9 (depends on 1)

A process according to claim 1, wherein the capacity of the lithium positive electrode active material decreases by no more than 7% over 100 cycles between from 3.5 to 5.0 V at 55° C.

### Claim 10 (depends on 1)

A process according to claim 1, wherein the product of step b. has a tap density equal to or greater than 1.8 g cm−3.

### Claim 11 (depends on 1)

A process according to claim 1, wherein the secondary particle size of the product of steps a. and b. has a D10 of greater than 100 μm, D50 of greater than 250 μm and D90 of greater than 800 μm.

### Claim 12 (depends on 1)

A process according to claim 1, wherein the precursor is prepared by one or more processes selected from the group consisting of mechanically mixing starting materials to obtain a homogenous mixture, mixing a lithium starting material with a composition prepared by either mechanically mixing or co-precipitating starting materials to obtain a homogenous mixture.

### Claim 13 (depends on 1)

A process according to claim 1, wherein the positive electrode active material comprises at least 95 wt % of spinel phase LixNiyMn2-yO4; wherein 0.9≤x≤1.1, and 0.4≤y≤0.5.