Sulfide and oxy-sulfide glass and glass-ceramic films for batteries incorporating metallic anodes

Patent metadata

Field	Value
Publication number	US-10680281-B2
Application number	US-201715480505-A
Country	US
Kind code	B2
Filing date	Apr 6, 2017
Priority date	Apr 6, 2017
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

Thin amorphous or partially crystalline lithium-containing and conducting sulfide or oxysulfide glass electrode/separator members are prepared from a layer of molten glass or of glass powder. The resulting glass films are formed to lie face-to face against a lithium metal anode or a sodium metal anode and a cathode and to provide for good transport of lithium ions between the electrodes during repeated cycling of the cell and to prevent shorting of the cell by dendrites growing from the lithium metal or sodium metal anode.

First claim

What is claimed is:

1. A method of forming a solid-state electrolyte layer for face-to-face engagement with an alkali metal anode in an electrochemical cell, the alkali metal being one of lithium or sodium, the method comprising:
applying a layer of a glassy powder precursor on a flat surface of a substrate material layer that is not chemically reactive with the glassy powder precursor, the glassy powder precursor having been made by melting a mixture comprising: (i) a glass former comprising a glass-forming sulfide or oxide and (ii) a glass modifier comprising an alkali metal-containing sulfide or oxide, at least one of the glass former and glass modifier comprising a sulfide or oxy-sulfide, cooling the melted mixture to form a glassy precursor, and pulverizing the glassy precursor to form the glassy powder precursor;
heating the layer of the glassy powder precursor to form a solid amorphous layer of a glassy composition comprising an alkali metal, and a sulfide or oxy-sulfide, the solid amorphous layer being of substantially uniform thickness, having a predetermined planar shape and dimensions, and having a porosity of up to 15% by volume, the heating being performed at a temperature of at least about 100° C. below the temperature at which the solid amorphous layer will crystallize;
heating the solid amorphous layer on the substrate at a temperature greater than the glass transition temperature and less than the temperature at which the solid amorphous layer will crystallize and for a time sufficient to remove residual stress in the layer and to form an annealed, flexible, uniformly amorphous microstructure, or heating the solid amorphous layer on the substrate at a temperature greater than the temperature at which the solid amorphous layer will crystallize and for a time sufficient to remove residual stress in the layer and to form a microstructure characterized by recrystallized regions isolated in an amorphous matrix, the annealed layer having a smooth surface engaging the substrate and a smooth surface opposite the substrate;
cooling the annealed layer to an ambient room temperature on the substrate; and
removing the cooled annealed layer from the surface of the substrate to provide the solid-state electrolyte layer, the thickness of the solid amorphous layer enabling the thickness of the solid-state electrolyte layer to be in the range of ten micrometers to two hundred micrometers,
wherein the solid-state electrolyte layer comprises a glass or a glass ceramic that conducts alkali metal ions and, when in face-to-face engagement with an alkali metal anode, is resistant to penetration of dendrites formed on the surface of the alkali metal anode.

2. The method according to claim 1 , wherein the alkali metal is lithium and the glass modifier is dilithium sulfide.

3. The method according to claim 1 , further comprising:
cutting the solid-state electrolyte layer to a size suitable for application in a battery or cell.

4. The method according to claim 1 , further comprising:
placing the solid-state electrolyte layer against an alkali metal anode in a battery or cell.

5. The method according to claim 1 , wherein the glass former is selected from the group consisting of P 2 S 5 , SiS 2 , GeS 2 , SnS 2 , As 2 S 3 , and combinations thereof.

6. The method according to claim 5 , wherein the mixture further comprises a glass co-former selected from the group consisting of P 2 O 5 , B 2 O 3 , SiO 2 , Al 2 O 3 , and combinations thereof.

7. The method according to claim 6 , wherein the glass modifier comprises Li 2 S, Na 2 S, Li 2 O, Na 2 O, or combinations thereof.

8. The method according to claim 7 , wherein the glass modifier comprises Li 2 O or Na 2 O.

9. The method according to claim 1 , wherein the glass modifier comprises Li 2 O or Na 2 O.

10. A method of forming a solid-state electrolyte for face-to-face engagement with an alkali metal anode in an electrochemical cell, the alkali metal being one of lithium or sodium, the method comprising:
applying to a suitable substrate a generally uniform layer of particles comprising an amorphous, glassy solid composition formed by melting a mixture comprising a glass former comprising a glass-forming sulfide, or oxide and a glass modifier comprising an alkali metal-containing sulfide or oxide, at least one of the glass former and glass modifier containing a sulfide or oxy-sulfide, cooling the melted mixture to form a glassy precursor, and pulverizing the glassy precursor to form the particles;
heating the layer of particles to a predetermined temperature less than the temperature at which the amorphous, glassy solid composition recrystallizes;
applying a pressure to the heated layer of particles for a predetermined time, the predetermined time and pressure being sufficient to consolidate and compact the particles into a solid layer on the substrate, the solid layer having a porosity of up to 15% by volume;
annealing the solid layer at a second predetermined temperature greater than the glass transition temperature and less than the temperature at which the amorphous solid recrystallizes but sufficient to relieve any stresses introduced into the layer by the consolidation operation stresses while retaining the solid in an amorphous state, or, optionally, at a second predetermined temperature sufficient to partially crystallize the solid layer; and
cooling the annealed solid layer to room temperature to form the solid-state electrolyte.

11. The method according to claim 10 , wherein the alkali metal is lithium and the alkali metal-containing sulfide is dilithium sulfide.

12. The method according to claim 10 wherein the particles range in size up to twenty micrometers.

13. The method according to claim 10 , wherein the applying the pressure comprises compacting the heated layer of particles through one or more sets of opposed rollers or of opposed heated rollers.

14. The method according to claim 10 , wherein the substrate is a layer of quartz.

15. The method according to claim 10 , wherein less than forty percent by volume of the amorphous, glassy solid composition is crystallized.

16. The method according to claim 10 , wherein the annealed solid layer contains a plurality of dispersed crystallized regions distributed in an amorphous matrix.

17. The method according to claim 16 , wherein the crystallized regions have a characteristic dimension of five micrometers or less.

18. The method according to claim 10 , wherein the glass former comprises P 2 S 5 , SiS 2 , GeS 2 , SnS 2 , P 2 O 5 , B 2 O 3 , SiO 2 , Al 2 O 3 , or combinations thereof.

19. The method according to claim 18 , wherein the glass modifier comprises Li 2 S, Na 2 S, Li 2 O, Na 2 O, or combinations thereof.

20. The method according to claim 10 , wherein the glass modifier comprises Li 2 O or Na 2 O.

Assignees

• Gm Global Tech Operations Llc

Inventors

• Yersak Thomas A
• Salvador James R
• Nguyen Han

Classifications

• C03B17/062

  combined with flowing onto a solid or gaseous support from which the sheet is drawn · CPC title

• H01M2300/0068

  inorganic · CPC title

• C03C10/00

  Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C03B2201/86

  Chalcogenide glasses, i.e. S, Se or Te glasses · CPC title