Reactive sintering of ceramic lithium ion electrolyte membranes

Patent metadata

Field	Value
Publication number	US-9673483-B2
Application number	US-201514599692-A
Country	US
Kind code	B2
Filing date	Jan 19, 2015
Priority date	Jan 19, 2015
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

Disclosed herein are methods for making a solid lithium ion electrolyte membrane, the methods comprising combining a first reactant chosen from amorphous, glassy, or low melting temperature solid reactants with a second reactant chosen from refractory oxides to form a mixture; heating the mixture to a first temperature to form a homogenized composite, wherein the first temperature is between a glass transition temperature of the first reactant and a crystallization onset temperature of the mixture; milling the homogenized composite to form homogenized particles; casting the homogenized particles to form a green body; and sintering the green body at a second temperature to form a solid membrane. Solid lithium ion electrolyte membranes manufactured according to these methods are also disclosed herein.

First claim

What is claimed is:

1. A method for making a solid lithium ion electrolyte membrane, comprising:
combining a first reactant chosen from lithium phosphate glasses, germanium phosphate glasses, lithium aluminum phosphate glasses, and crystallized lithium aluminum phosphate ceramics with a second reactant chosen from refractory oxides to form a mixture;
heating the mixture to a first temperature to form a homogenized composite comprising unreacted first and second reactants, wherein the first temperature is between a glass transition temperature of the first reactant and a crystallization onset temperature of the mixture;
milling the homogenized composite to form homogenized particles;
casting the homogenized particles to form a green body; and
reactively sintering the green body at a second temperature to form a solid membrane.

2. The method of claim 1 , wherein the first reactant further comprises an oxide modifier.

3. The method of claim 2 , wherein the oxide modifier is chosen from TiO 2 , GeO 2 , SiO 2 , B 2 O 3 , Fe 2 O 3 , Nb 2 O 5 , V 2 O 5 , Sb 2 O 3 , CoO, WO 3 , SnO 2 , and combinations thereof.

4. The method of claim 1 , wherein the first reactant is lithium aluminum phosphate.

5. The method of claim 1 , wherein the second reactant is chosen from TiO 2 , SnO 2 , GeO 2 , and combinations thereof.

6. The method of claim 1 , wherein the first reactant has an average particle size of less than about 10 microns, and the second reactant has an average particle size of less than about 1 micron.

7. The method of claim 1 , wherein the first temperature is at least about 350° C.

8. The method of claim 1 , wherein the first temperature ranges from about 350° C. to about 550° C.

9. The method of claim 1 , wherein the homogenized particles have an average diameter ranging from about 1 micron to about 2 microns.

10. The method of claim 1 , wherein the second temperature is less than about 1100° C.

11. The method of claim 1 , wherein casting comprises tape casting the homogenized particles to form a green tape.

12. The method of claim 1 , wherein the solid membrane has a thickness of less than about 200 microns, a density of at least about 95% of a theoretical density of the solid membrane, and a conductivity of at least about 1×10 −4 S/cm.

13. The method of claim 1 , wherein the solid membrane is substantially flat.

14. The method of claim 13 , wherein the method does not comprise a flattening step after the sintering step.

Assignees

• Corning Inc

Inventors

• Badding Michael Edward
• Dutta Indrajit
• Iyer Sriram Rangarajan
• Kent Brian Alan
• Lonnroth Nadja Teresia

Classifications

• C03B19/06

  by sintering, {e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction} · CPC title

• H01M10/052 Primary

  Li-accumulators · CPC title

• H01M2300/0068

  inorganic · CPC title

• C01B25/45

  containing plural metal, or metal and ammonium · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title