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

Abstract

A solid state electrolyte including an oxy-sulfide glass or glass ceramic, solid state electrolyte layer having a thickness in the range of ten micrometers to two hundred micrometers is provide. The composition of the electrolyte layer is the reaction product of a mixture initially including either a glass former including sulfur or a glass co-former including sulfur, and a glass modifier including Li 2 O or Na 2 O. The solid-state electrolyte layer is further characterized as having a wholly amorphous microstructure or as having small recrystallized regions separated from each other in an amorphous matrix, the recrystallized regions having a size of up to five micrometers. The solid-state electrolyte layer includes mobile lithium ions or mobile sodium ions associated with sulfur anions chemically anchored in the microstructure.

What is claimed is: 
     
         1 . A solid state electrolyte comprising a sulfide or an oxy-sulfide glass or glass ceramic, solid state electrolyte layer having a thickness in the range of 10 μm to 200 μm, the composition of the electrolyte layer being the reaction product of a mixture initially comprising:
 a glass former comprising a glass-forming sulfide or oxide; and 
 a glass modifier comprising an alkali metal-containing sulfide or oxide, 
 wherein at least one of the glass former and glass modifier comprise a sulfide, and 
 wherein the solid-state electrolyte layer is further characterized as having a wholly amorphous microstructure or as having small recrystallized regions separated from each other in an amorphous matrix, the recrystallized regions having a size of up to five micrometers, the solid-state electrolyte layer comprising mobile lithium ions or mobile sodium ions associated with sulfur anions chemically anchored in the microstructure. 
 
     
     
         2 . The solid state electrolyte according to  claim 1 , wherein the glass modifier comprises Li 2 O. 
     
     
         3 . The solid state electrolyte according to  claim 1 , comprising the glass former comprising sulfur, the glass former being selected from the group consisting of P 2 S 5 , SiS 2 , GeS 2 , SnS 2 , As 2 S 3 , and combinations thereof. 
     
     
         4 . The solid state electrolyte according to  claim 3 , wherein the glass modifier further comprises Li 2 S. 
     
     
         5 . The solid state electrolyte according to  claim 3 , 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.   
     
     
         6 . The solid state electrolyte according to  claim 1 , comprising a glass co-former comprising sulfur, the glass co-former being selected from the group consisting of P 2 S 5 , SiS 2 , GeS 2 , SnS 2 , As 2 S 3 , and combinations thereof, the mixture further comprising a glass 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 solid state electrolyte according to  claim 1 , wherein the glass modifier comprises Na 2 O. 
     
     
         8 . A battery cell comprising the solid state electrolyte according to  claim 1 . 
     
     
         9 . A solid state electrolyte comprising the reaction product of a mixture comprising:
 a glass former comprising sulfur; and   a glass modifier comprising Li 2 O or Na 2 O,   wherein the solid state electrolyte has a non-crystalline microstructure having a glass transition temperature.   
     
     
         10 . The solid state electrolyte according to  claim 9 , wherein the solid state electrolyte is in a layer having a thickness of 10 μm to 200 μm. 
     
     
         11 . The solid state electrolyte according to  claim 9 , wherein the glass former comprises P 2 S 5 , SiS 2 , GeS 2 , SnS 2 , As 2 S 3 , or a combination thereof. 
     
     
         12 . The solid state electrolyte according to  claim 11 , 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. 
     
     
         13 . The solid state electrolyte according to  claim 9 , wherein the mixture further comprises:
 a glass dopant.   
     
     
         14 . The solid state electrolyte according to  claim 9 , wherein the solid state electrolyte has a porosity of up to 15%. 
     
     
         15 . The solid state electrolyte according to  claim 9 , wherein the solid state electrolyte is positioned between a cathode and an anode. 
     
     
         16 . A solid state electrolyte comprising the reaction product of a mixture comprising:
 a glass former comprising oxygen;   a glass co-former comprising sulfur; and   a glass modifier comprising Li 2 O or Na 2 O,   wherein the solid state electrolyte has a non-crystalline microstructure having a glass transition temperature.   
     
     
         17 . The solid state electrolyte according to  claim 16 , wherein the glass former comprises P 2 O 5 , B 2 O 3 , SiO 2 , Al 2 O 3 , or a combination thereof. 
     
     
         18 . The solid state electrolyte according to  claim 17 , wherein the mixture further comprises a glass co-former selected from the group consisting of P 2 S 5 , SiS 2 , GeS 2 , SnS 2 , As 2 S 3 , and combinations thereof. 
     
     
         19 . The solid state electrolyte according to  claim 16 , further comprising a glass dopant. 
     
     
         20 . The solid state electrolyte according to  claim 16 , wherein the solid state electrolyte is a layer that is interposed between an anode and a cathode.