# US 11,999,630 B2 · Method of tuning the conversion temperature of cubic phase of aluminum-doped lithium lanthanum zirconium oxide

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- Number: US 11,999,630 B2
- Document ID: US11999630B2
- Status: Granted
- Kind: B2
- Application number: 16/901,998
- Filed: 2020-06-15
- Published: 2020-12-17
- Granted: 2024-06-04
- Earliest claimed: 2019-06-14
- Assignees: Uchicago Argonne, LLC
- Applicants: Uchicago Argonne, LLC
- Inventors: Joseph A. Libera; Yujia Liang; Trevor L. Dzwiniel; Krzysztof Pupek; Gregory K. Krumdick; Stephen Cotty
- Web page: https://patentgrep.com/patent/US11999630B2

## CPC

- C01G 25/006: {Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements}
- B01J 2/06: in a liquid medium
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/76: by a space-group or by other symmetry indications
- C01P 2004/02: obtained by optical microscopy
- C01P 2004/03: obtained by SEM
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2006/12: Surface area
- 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)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 process for forming cubic LLZO through the use of atomic mixing of metal salts used in an aerosol process. The cubic LLZO is formed at temperatures below 1000° C.

## Claims

### Claim 1

A method, comprising:
mixing metal nitrate salts comprising lanthanum nitrate, lithium nitrate, aluminum nitrate, and zirconium nitrate;
forming a feed solution comprising a dopant with the metal nitrate salts in a solvent;
generating a droplet from the feed solution;
converting the droplet to an atomically mixed powder; and
calcining the atomically mixed powder at a temperature less than 1000° C., forming cubic LLZO.

### Claim 2 (depends on 1)

The method of claim 1, wherein the solvent is flammable and converting the droplet to a powder comprises flame spray pyrolysis.

### Claim 3 (depends on 1)

The method of claim 1, wherein the dopant comprises aluminum, the dopant being different a different composition than the aluminum nitrate.

### Claim 4 (depends on 1)

The method of claim 1, wherein the calcining is at a calcination temperature is below 800° C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the calcining is at a calcination temperature is 650° C. to 900° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein converting the droplet to a powder comprises converting at least a portion of the droplets to particles without combusting the portion of the droplets.

### Claim 7 (depends on 1)

The method of claim 1, converting the droplet to a powder comprises combusting a second portion of the droplets a flame forming a gas and further converting the gas into particles.

### Claim 8 (depends on 1)

The method of claim 1, where converting the droplet comprises drying the droplets via a spray drying process.

### Claim 9 (depends on 1)

The method of claim 1, wherein converting the droplet comprises pyrolysis via a spray pyrolysis process.

### Claim 10

A method, comprising:
forming a feed solution comprising an aluminum dopant, lanthanum precursor, lithium precursor, and zirconium precursor dissolved in a solvent comprising xylene and ethylhexanoic acid;
generating a plurality of droplets 2-10 microns in diameter;
exposing the plurality of droplets to a flame;
converting at least a portion of the plurality of droplets to particles, forming a powder comprising atomically mixed aluminum, lanthanum, lithium, and zirconium; and
calcinating powder at a calcine temperature of 650° C. to 1000° C. to form a cubic LLZO.

### Claim 11 (depends on 10)

The method of claim 10, wherein the aluminum dopant is alumatrane.

### Claim 12 (depends on 10)

The method of claim 10, wherein the feed solution comprises 3-9% ceramic loading.

### Claim 13 (depends on 10)

The method of claim 10, wherein exposing the plurality of droplets to the flame comprise directing the flame with a flame guide.

### Claim 14 (depends on 10)

The method of claim 10, wherein the cubic LLZO has a formula of Li(7-3x)La2Zr3O7Alx where x is 0.19 to 0.389.

### Claim 15 (depends on 10)

The method of claim 10, wherein the cubic LLZO has a formula of Li(7-3x)La2Zr3O7Alx where x is 0.25.