Reactive sintering of ceramic lithium-ion solid electrolytes

Patent metadata

Field	Value
Publication number	US-11502330-B2
Application number	US-202117194775-A
Country	US
Kind code	B2
Filing date	Mar 8, 2021
Priority date	Nov 29, 2011
Publication date	Nov 15, 2022
Grant date	Nov 15, 2022

Abstract

A method of forming a solid, dense, hermetic lithium-ion electrolyte membrane comprises combing an amorphous, glassy, or low melting temperature solid reactant with a refractory oxide reactant to form a mixture, casting the mixture to form a green body, and sintering the green body to form a solid membrane. The resulting electrolyte membranes can be incorporated into lithium-ion batteries.

First claim

What is claimed is:

1. A method of forming a solid lithium-ion electrolyte membrane, comprising:
forming a powder mixture comprising a refractory oxide reactant and at least one of an amorphous, glassy solid reactant or a low melting temperature solid reactant, the amorphous, glassy solid reactant comprising a softening point less than 850° C., and the refractory, and the low melting temperature solid reactant comprising a melting temperature less than 850° C.;
tape-casting the powder mixture to form a green body; and
reacting the amorphous, glassy solid reactant or the low melting temperature solid reactant to form the solid lithium-ion electrolyte membrane,
wherein:
the green body comprises at least one of a binder and a plasticizer, and
an average particle size of the amorphous, glassy solid reactant or the low melting temperature solid reactant is less than 0.5 μm, and an average particle size of the refractory oxide reactant is less than 0.5 μm.

2. The method of claim 1 , wherein the amorphous, glassy solid reactant or the low melting temperature solid reactant further comprises an oxide modifier.

3. The method of claim 1 , wherein the binder comprises polyvinylbutyral.

4. The method of claim 1 , wherein the reacting comprises sintering the green body at a temperature of less than 1100° C.

5. The method of claim 4 , wherein the reacting comprises sintering the green body at a temperature of less than 850° C.

6. The method of claim 1 , wherein a maximum processing temperature of the method is less than 1300° C.

7. The method of claim 6 , wherein the maximum processing temperature is less than 850° C.

8. The method of claim 1 , wherein the average particle size of the amorphous, glassy solid reactant or the low melting temperature solid reactant is less than 0.1 μm, and the average particle size of the refractory oxide reactant is less than 0.1 μM.

9. The method of claim 1 , wherein the solid lithium-ion electrolyte membrane comprises an average thickness of less than 200 μm and is free-standing.

10. The method of claim 9 , wherein the average thickness is at least 30 μm.

11. The method of claim 1 , wherein the solid lithium-ion electrolyte membrane comprises an average grain size of less than 10 μm.

12. The method of claim 11 , wherein the average grain size of the constituent electrolyte material is less than 1 μm.

13. The method of claim 1 , wherein a conductivity of the solid lithium-ion electrolyte membrane is greater than 10 −4 S/cm.

14. The method of claim 1 , wherein a density of the solid lithium-ion electrolyte membrane is at least 95% of its theoretical density.

15. The method of claim 1 , wherein the solid lithium-ion electrolyte membrane is hermetic such that the membrane is configured to provide a barrier between an anode and a cathode of a battery.

16. The method of claim 1 , wherein the solid lithium-ion electrolyte membrane comprises a composition represented by the formula Li i+x−y MxM′ 2−x−y M″ y (PO 4 ) 3 , wherein M is a 3 + ion, M′ is a 4 + ion, and M″ is a 5 + ion, 0≤x≤2, and 0≤y≤2.

17. The method of claim 16 , wherein M is Al or Fe, M′ is selected from the group consisting of Ti, Sn, Nb and Ge, and M″ is Nb.

18. The method of claim 1 , wherein the solid lithium-ion electrolyte membrane comprises Li 1.4 Al 0.4 Sn 1.6 (PO 4 ) 3 .

19. The method of claim 1 , wherein the solid lithium-ion electrolyte membrane comprises a NaZr 2 (PO 4 ) 3 crystal structure.

Assignees

• Corning Inc

Inventors

• Aitken Bruce Gardiner
• Badding Michael Edward
• Beall George Halsey
• Fekety Curtis Robert
• Kester Lanrik Wayne
• Morena Robert Michael
• Song Zhen

Classifications

• C03C3/16

  containing phosphorus · CPC title

• C03C8/20

  containing titanium compounds; containing zirconium compounds · CPC title

• C04B2235/77

  Density · CPC title

• C04B2235/36

  Glass starting materials for making ceramics, e.g. silica glass · CPC title

• C04B2235/5454

  nanometer sized, i.e. below 100 nm · CPC title