# US 10,501,335 B1 · Polycrystalline metal oxides with enriched grain boundaries

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

- Number: US 10,501,335 B1
- Document ID: US10501335B1
- Status: Granted
- Kind: B1
- Application number: 16/250,615
- Filed: 2019-01-17
- Granted: 2019-12-10
- Earliest claimed: 2019-01-17
- Assignees: CAMX Power LLC
- Applicants: CAMX Power LLC
- Inventors: Adrian W. Pullen; David Ofer; Suresh Sriramulu; Kenan Sahin; Jane Rempel
- Web page: https://patentgrep.com/patent/US10501335B1

## CPC

- C01G 53/506: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
- C01G 53/42: containing alkali metals, e.g. LiNiO2
- C01G 53/66: containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
- H01M 4/366: {as layered products}
- 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 2002/20: Two-dimensional structures
- C01P 2002/30: Three-dimensional structures
- C01P 2002/32: spinel-type (AB2O4)
- C01P 2002/52: containing elements as dopants
- C01P 2002/54: one element only
- C01P 2002/70: defined by measured X-ray, neutron or electron diffraction data
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/50: Agglomerated particles
- C01P 2006/40: Electric properties
- H01M 10/052: Li-accumulators
- H01M 2004/028: {Positive electrodes}
- 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

Provided are electrochemically active secondary particles that provide excellent capacity and improved cycle life. The particles are characterized by selectively enriched grain boundaries where the grain boundaries are enriched Al. The enrichment with Al reduces impedance generation during cycling thereby improving capacity and cycle life. Also provided are methods of forming electrochemically active materials, as well as electrodes and electrochemical cells employing the secondary particles.

## Claims

### Claim 1

A particle, comprising:
a plurality of crystallites comprising a first composition comprising lithium, nickel, and oxygen;
a grain boundary between adjacent crystallites of the plurality of crystallites and comprising a second composition having a layered α-NaFeO2-type structure, a cubic structure, a spinel structure, or a combination thereof;
wherein a concentration of aluminum in the grain boundary is greater than a concentration of aluminum in the crystallites.

### Claim 2 (depends on 1)

The particle of claim 1 wherein the aluminum is substantially uniformly distributed through said grain boundary.

### Claim 3 (depends on 1)

The particle of claim 1 wherein the amount of aluminum averaged in the grain boundary is 0.01 at % to 10 at % relative to the total transition metal averaged in the crystallites.

### Claim 4 (depends on 1)

The particle of claim 1 wherein the plurality of crystallites has an α-NaFeO2-type layered structure, a cubic structure, a spinel structure, or a combination thereof.

### Claim 5 (depends on 1)

The particle of claim 1 wherein the crystallites each comprise a first composition defined by Li1+xMO2+y, wherein
−0.1≤x≤0.3,
−0.3≤y≤0.3, and
wherein M comprises nickel at greater than or equal to 10 atomic percent.

### Claim 6 (depends on 5)

The particle of claim 5 wherein M comprises an atomic percent of nickel greater than or equal to 75 at %.

### Claim 7 (depends on 5)

The particle of claim 5, wherein
M further comprises an additional metal, wherein the additional metal is present in an amount of about 1 at % to about 90 at %;
the additional metal is selected from the group consisting of Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti, Nb, Ta, Cr, Fe, Mo, W, Hf, B, and any combination thereof.

### Claim 8 (depends on 5)

The particle of claim 5, wherein the crystallites comprise cobalt, with the cobalt concentration in the range of 1 at % to about 50 at % of M in the first composition.

### Claim 9 (depends on 5)

The particle of claim 5, wherein the crystallites comprise cobalt, with the cobalt concentration in the range of 1 at % to about 15 at % of M in the first composition.

### Claim 10 (depends on 1)

The particle of claim 1, wherein the grain boundary comprises aluminum in an amount of about 2 at % to about 99 at % relative to total transition metal in the second composition.

### Claim 11 (depends on 1)

The particle of claim 1, wherein
the crystallites comprise Mn present in an amount of about 1 at % to about 60 at %, and
the grain boundary comprises Mn present in an amount of about 1 at % to about 60 at %,
wherein the at % are relative to total transition metal in the crystallites or the grain boundary, respectively.

### Claim 12 (depends on 1)

The particle of claim 1 wherein the grain boundary comprises Ni and Al.

### Claim 13 (depends on 1)

The particle of claim 1, further comprising an outer coating on a surface of the particle, the outer coating comprising:
an oxide of one or more elements selected from Al, Y, Co, Ni, Zr, Mg, and Li;
a fluoride comprising one or more elements selected from Al, Zr and Li;
a sulfate comprising one or more elements selected from Al, Co, Ni, Mn, Zr and Li;
a carbonate comprising one or more elements selected from Al, Co, Ni, Mn, Zr and Li; or
a phosphate comprising one or more elements selected from Al and Li.

### Claim 14 (depends on 1)

An electrochemical cell comprising a cathode active material, said cathode active material comprising the particle of claim 1.

### Claim 15 (depends on 14)

The electrochemical cell of claim 14 characterized by an impedance growth at 4.2V less than 100% for greater than 100 cycles at 45° C.

### Claim 16 (depends on 14)

The electrochemical cell of claim 14 characterized by an impedance growth at 4.2V less than 100% for greater than 200 cycles at 45° C.

### Claim 17

An electrochemically active polycrystalline secondary particle comprising:
a plurality of crystallites, the plurality of crystallites comprising a first composition defined by Li1+xMO2+y, wherein
−0.1≤x≤0.3,
−0.3≤y≤0.3, and
wherein M comprises nickel at greater than or equal to 80 atomic percent; and
a grain boundary between adjacent crystallites of said plurality of crystallites and comprising a second composition optionally having an α-NaFeO2-type layered structure, a cubic structure, spinel structure, or a combination thereof, wherein a concentration of aluminum in the grain boundary is greater than a concentration of aluminum in the crystallites.

### Claim 18 (depends on 17)

The particle of claim 17 wherein M further comprises one or more elements selected from the group consisting of Al, Mg, Co, Mn, Ca, Sr, Ba, Zn, Ti, Zr, Y, Cr, Mo, Fe, V, Si, Ga and B, said one or more elements residing in a Li layer, a M layer, or both, of the crystallites.

### Claim 19 (depends on 17)

The particle of claim 17, wherein M comprises an atomic percent of nickel greater than or equal to 90 percent.