# US 10,833,321 B2 · Cathode materials for lithium ion batteries

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

- Number: US 10,833,321 B2
- Document ID: US10833321B2
- Status: Granted
- Kind: B2
- Application number: 14/641,003
- Filed: 2015-03-06
- Published: 2016-09-08
- Granted: 2020-11-10
- Earliest claimed: 2015-03-06
- Assignees: Uchicago Argonne, LLC
- Applicants: UChicago Argonne, LLC
- Inventors: Huiming Wu; Khalil Amine; Jun Lu
- Web page: https://patentgrep.com/patent/US10833321B2

## CPC

- H01M 4/366: {as layered products}
- C01G 45/024: Manganese dioxide
- C01G 51/05: Hydroxides; Oxyhydroxides
- C01G 53/04: Oxides
- C01G 53/05: Hydroxides; Oxyhydroxides
- H01M 4/0419: {involving spraying}
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/139: Processes of manufacture
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- C01G 49/00: Compounds of iron
- C01G 49/02: Oxides; Hydroxides {(C01G49/0018 takes precedence)}
- C01G 51/42: containing alkali metals, e.g. LiCoO2
- C01G 53/42: containing alkali metals, e.g. LiNiO2
- H01M 4/04: Processes of manufacture in general
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- 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
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- 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)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A process of forming a coated cathode active material include preparing a cathode material precursor by co-precipitation; coating the cathode material precursor with an electrochemically inert coating material precursor by precipitation to form a coated cathode material precursor; lithiating the coated cathode material precursor with a lithium source material to form a lithiated coated cathode material precursor; and sintering the lithiated coated cathode material precursor to form a cathode active material coated with an electrochemically inert material.

## Claims

### Claim 1

A process of forming a coated cathode active material particle, the process comprising:
preparing a cathode active material precursor particle in aqueous solution, the preparing comprising:
providing an aqueous acidic solution of a metal ion and an aqueous basic solution; and
combining the aqueous basic solution and the aqueous acidic solution to effect co-precipitation of the cathode active material precursor as a particle;
wherein a concentration of the metal ion is continuously increased or reduced during formation of the cathode active material precursor particle such that the cathode active material precursor contains an increasing or decreasing metal concentration along a radius of the particle;
coating the cathode active material precursor particle in aqueous solution with a coating material precursor to form a coated cathode active material precursor particle wherein the coating material precursor comprises Al(OH)3, Al2(CO3)3, Al2(C2O4)3, AlF3, AlPO4, Zr(OH)4, Ti(OH)4, Mg(OH)2, Zn(OH)2, ZnCO3, or Zr(CO3)2;
lithiating or sodiating the coated cathode active material precursor particle in aqueous solution with a lithium or sodium source material to form a lithiated or sodiated coated cathode active material precursor particle;
collecting the lithiated or sodiated coated cathode active material precursor particle; and
sintering the lithiated or sodiated coated cathode active material precursor particle to form the coated cathode active material particle.

### Claim 2 (depends on 1)

The process of claim 1, wherein the coating of the cathode active material precursor with the coating material comprises:
providing an aqueous acidic solution of a first coating material precursor and an_aqueous basic solution; and
combining the aqueous basic solution and the aqueous acidic solution to effect precipitation of a second coating material precursor;
wherein the second coating material precursor precipitates as a layer coating on individual particles of the cathode active material precursor to form the coated cathode active material precursor.

### Claim 3 (depends on 2)

The process of claim 2, wherein a concentration of the first coating material precursor in the aqueous acidic solution increased or reduced during precipitation of the second electrochemically inert material precursor such that the layer of the second coating material precursor has an increasing or decreasing concentration along a radius of the layer.

### Claim 4 (depends on 1)

The process of claim 1, wherein the coating material precursor is a precursor for an electrochemically active coating, and the cathode is coated with the electrochemically active coating.

### Claim 5 (depends on 1)

The process of claim 1, wherein the coating material precursor is a precursor for an electrochemically inert coating, and the cathode is coated with the electrochemically inert coating.

### Claim 6 (depends on 1)

The process of claim 1, wherein the cathode active material precursor comprises Co(OH)2, Ni(OH)2, CoCO3, MnCO3, NiC2O4, FePO4, CoxNiyMn1−x−y(OH)2, CoxNiyMn1−x−yCO3, or CoxNiyMn1−x−yC2O4.

### Claim 7 (depends on 1)

The process of claim 1, wherein the coating material precursor comprises a metal hydroxide, a metal carbonate, a metal oxalate, a metal fluoride, a metal phosphate, or a metal oxyfluoride.

### Claim 8 (depends on 1)

The process of claim 1, wherein a coating material comprises a metal oxide, a metal fluoride, a metal phosphate, or a metal oxyfluoride.

### Claim 9 (depends on 1)

The process of claim 1, wherein the coating material comprises Al2O3, ZrO2, MgO, ZnO, NiO, MnO2, TiO2, MgF2, CaF2, AlF3, AlPO4, CoPO4, Li2MnO3, LiAlO2, LiV3O8, or Li5FeO4.

### Claim 10 (depends on 1)

The process of claim 1, wherein the coating material comprises Al2O3.

### Claim 11 (depends on 1)

The process of claim 1 comprising the lithiating, wherein a lithium source material comprises lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium oxalate, lithium benzoate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium oxide, lithium peroxide, lithium sulfate, lithium alloys, lithium silicate, lithium aluminate, or lithium phosphate.

### Claim 12 (depends on 1)

The process of claim 1 comprising the sodiating, wherein a sodium source material comprises sodium carbonate, sodium hydroxide, sodium nitrate, sodium acetate, sodium oxalate, sodium benzoate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium oxide, sodium peroxide, sodium sulfate, sodium alloys, sodium silicate, sodium aluminate, or sodium phosphate.

### Claim 13 (depends on 1)

The process of claim 1, wherein the cathode active material precursor particle comprises nickel and cobalt as the metal, and the coating material precursor comprises aluminum.

### Claim 14 (depends on 1)

The process of claim 1, wherein preparing the cathode active material precursor particle comprises:
providing the aqueous acidic solution comprises MxXy;
during co-precipitation of the cathode active material precursor particle, adding Ax′By′ to effect co-precipitation of the coating material precursor;
wherein:
M is Ni, Co, Mn, Al, Mg, Fe, Cu, Zn, V, Mo, Nb, Cr, Si, Ti, Zr, or a mixture of any two or more thereof;
X is NO3−, SO42−, CO32−, PO43−, F−, Cl−, Br−, I−, or a mixture of any two more thereof;
A is Li, Al, Mg, Fe, Cu, Zn, Cr, Mn, Ni, Co, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, or a mixture of any two or more thereof;
B is O2−, F−, O−, Br−, I−, S2−, N3−, −OH, CO32−, C2O42−, (P2O7)4−, PO43−, SO42− or a mixture of any two or more thereof;
x, x′, y, and y′ are individually 1, 2, or 3; and
wherein M and A are different.

### Claim 15 (depends on 14)

The process of claim 14, wherein A is Al.

### Claim 16 (depends on 14)

The process of claim 14, wherein a concentration of MxXy is reduced during formation of the cathode active material precursor particle such that the cathode active material precursor particle contains a decreasing concentration along a radius of the particle, and a concentration of the Ax′By′ is increased during formation of the cathode active material precursor particle such that the coating material precursor contains an increasing concentration along a radius of the particle.

### Claim 17 (depends on 1)

The process of claim 1, wherein the coated cathode active material precursor particle comprises Mn having a constant concentration along a radius of the particle, Ni having an increasing concentration along the radius of the particle, and Co having a decreasing concentration along the radius of the particle and the coating comprising aluminum.

### Claim 18 (depends on 1)

The coated cathode active material particle produced by the process of claim 1.

### Claim 19 (depends on 18)

The coated cathode active material particle of claim 18 comprising Mn having a constant concentration along a radius of the particle, Ni having an increasing concentration along the radius of the particle, and Co having a decreasing concentration along the radius of the particle and the coating comprising aluminum.

### Claim 20 (depends on 18)

A cathode comprising the coated cathode active material particle of claim 18 and a binder.

### Claim 21 (depends on 20)

An electrochemical device comprising the cathode of claim 20 and an anode.