Passivated LLZO particles and tape casting of LLZO films

Patent metadata

Field	Value
Publication number	US-12002924-B2
Application number	US-202117333339-A
Country	US
Kind code	B2
Filing date	May 28, 2021
Priority date	May 28, 2021
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

Abstract

Passivated Li7La3Zr2O12 (LLZO) particles, tape casting powders and slip compositions including the particles, methods of forming the particles, methods of tape casting using the particles, green tapes including the particles, cast LLZO films formed from the particles, and lithium batteries including the cast LLZO film. A passivated LLZO particle includes an LLZO core, wherein the LLZO is optionally doped with one or more elements. The passivated LLZO particle also includes a shell including H-LLZO, H3O+-LLZO, and/or Li2CO3.

First claim

What is claimed is:

1. A passivated Li 7 La 3 Zr 2 O 12 (LLZO) particle comprising:
an LLZO core, wherein the LLZO is optionally doped with one or more elements;
a shell comprising Li 2 CO 3 ; and
an H 3 O + -LLZO and/or H-LLZO layer between the core and the shell.

2. The passivated particle of claim 1 , wherein the particle has a diameter of 0.1 micron to 5 microns.

3. The passivated particle of claim 1 , wherein the LLZO is doped with Al, Ga, Ta, Nb, W, Ca, or a combination thereof.

4. The passivated particle of claim 1 , wherein the LLZO has the formula Li 6.7-6.3 La 3 Zr 1.7-1.3 Ta 0.3-0.7 O 12 or Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 .

5. The passivated particle of claim 1 , wherein the LLZO core is 20 wt % to 99.99 wt % of the particle, wherein the shell is 0.01 wt % to 80 wt % of the particle.

6. A tape casting powder comprising a plurality of the passivated LLZO particles of claim 1 , further comprising sufficient excess lithium source such that the tape casting powder has an amount of Li that is 1% to 40% in excess of a stoichiometric amount of Li in the LLZO, wherein the excess lithium source comprises Li 2 CO 3 , LiOH, Li 2 O, LiCl, LiNO 3 , Li-citrate, Li-acetate, Li-oleate, LiF, Li 2 SO 4 , or combinations thereof.

7. A tape casting slip composition comprising a plurality of the passivated LLZO particles of claim 1 .

8. The tape casting slip composition of claim 7 , wherein the tape casting slip composition comprises an excess lithium source, wherein a sufficient amount of the excess lithium source is present such that the tape casting slip composition comprises an amount of Li that is 1% to 40% in excess based on a stoichiometric amount of Li in the LLZO, wherein the excess lithium source comprises Li 2 CO 3 , LiOH, Li 2 O, LiCl, LiNO 3 , Li-citrate, Li-acetate, Li-oleate, LiF, Li 2 SO 4 , or combinations thereof.

9. A method of forming the passivated particle of claim 1 , the method comprising:
heating LLZO in air or CO 2 at room temperature to 650° C. for a suitable duration to form the passivated particle, wherein the LLZO is optionally doped with one or more elements.

10. The method of claim 9 , wherein the heating comprises heating in air at room temperature to 300° C. for 24 hours to 30 days.

11. A method of tape casting, the method comprising
tape casting a tape casting slip composition to form a green tape, the tape casting slip composition comprising a plurality of passivated Li 7 La 3 Zr 2 O 12 (LLZO) particles each comprising:
an LLZO core, wherein the LLZO is optionally doped with one or more elements,
a shell comprising Li 2 CO 3 , and
an H 3 O + -LLZO and/or H-LLZO layer between the core and the shell,

wherein the tape casting slip composition comprises an excess lithium source in sufficient quantity such that the tape casting slip composition comprises an amount of Li that is 1% to 40% in excess based on a stoichiometric amount of Li in the LLZO core, wherein the excess lithium source comprises Li 2 CO 3 , LiOH, Li 2 O, LiCl, LiNO 3 , Li-citrate, Li-acetate, Li-oleate, LiF, Li 2 SO 4 , or combinations thereof;
drying the green tape; and
sintering the green tape in the absence of a mother powder.

12. A cast LLZO film formed by the method of claim 9 .

13. A lithium battery comprising the cast LLZO film of claim 12 .

14. The method of claim 11 , wherein the sintering comprises heating in air to 1000° C. to 1400° C. using a temperature ramp up of 100° C./min to 1000° C./min for 0.5 min to 30 min, wherein the sintering is performed in the absence of the mother powder.

15. The passivated particle of claim 1 , wherein the shell has a thickness of from 1 nm to 2.5 micrometers.

16. The passivated particle of claim 1 , wherein the shell has a thickness of from 10 nm to 40 nm.

17. The passivated particle of claim 1 , wherein a total amount of Li present in the passivated LLZO particle is equal to a stoichiometric amount of Li in the LLZO.

Assignees

• Corning Inc

Inventors

• Song Zhen
• Badding Michael Edward
• Brown Jacqueline Leslie
• Conway Brent Daniel
• Degeorge Aaron David
• Chen Yinghong
• Brown Jason Allen

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• B28B1/26

  by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor (B28B1/52 takes precedence){; specially for manufacturing articles starting from a ceramic slip; Moulds therefor (of tubular articles B28B21/08)} · CPC title

• C01G25/02

  Oxides · CPC title

• H01M10/052 Primary

  Li-accumulators · CPC title

• C01P2002/52

  containing elements as dopants · CPC title