Sulfide-based solid electrolyte for lithium secondary battery
Provided is a sulfide-based solid electrolyte which is capable of suppressing the generation of hydrogen sulfide caused by reaction with moisture even when in contact with dry air in a dry room or the like, and capable of maintaining lithium ion conductivity. Proposed is a sulfide-based solid electrolyte for a lithium secondary battery, wherein the surface of a compound containing lithium, phosphorus, sulfur, and halogen, and having a cubic argyrodite-type crystal structure is coated with a compound containing lithium, phosphorus, and sulfur, and having a non-argyrodite-type crystal structure.
1. A sulfide-based solid electrolyte for a lithium secondary battery, wherein the surface of a core compound containing lithium, phosphorus, sulfur, and halogen, and having a cubic argyrodite-type crystal structure is coated with a coating compound containing lithium, phosphorus, and sulfur, and having a non-argyrodite-type crystal structure, and wherein the core compound having a cubic argyrodite-type crystal structure is represented by a compositional formula: Li 7-x-2y PS 6-x-y Ha x , where Ha represents a halogen and is at least one kind of element of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), and 0.4≤x≤1.7 and −0.9≤y≤−x+2 in the compositional formula.
2. The sulfide-based solid electrolyte for a lithium secondary battery according to claim 1 , wherein the coating compound having a non-argyrodite-type crystal structure constitutes a PS 4-R O R (0≤R<4) unit structure in the structure.
3. The sulfide-based solid electrolyte for a lithium secondary battery according to claim 1 , wherein the coating compound having a non-argyrodite-type crystal structure comprises a compound represented by a compositional formula: Li 3 PS 4-R O R (0≤R<4) as a main phase.
4. The sulfide-based solid electrolyte for a lithium secondary battery according to claim 1 , wherein the halogen is one of chlorine (Cl) or bromine (Br).
5. A lithium secondary battery comprising the sulfide-based solid electrolyte for a lithium secondary battery according to claim 1 .
6. A method of producing a sulfide-based solid electrolyte for a lithium secondary battery according to claim 1 , wherein a core compound containing lithium, phosphorus, sulfur, and halogen, and having a cubic argyrodite-type crystal structure, and a phosphorus sulfide or a phosphorus oxide, or both of these having a ratio of 0.1 to 42 mol in total relative to 100 mol of the core compound are mixed, and heated at a temperature of 100 to 300° C. in an inert atmosphere.
7. The sulfide-based solid electrolyte for a lithium secondary battery according to claim 2 , wherein the coating compound having a non-argyrodite-type crystal structure comprises a compound represented by a compositional formula: Li 3 PS 4-R O R (0≤R<4) as a main phase.
8. A lithium secondary battery comprising the sulfide-based solid electrolyte for a lithium secondary battery according to claim 2 .
9. A lithium secondary battery comprising the sulfide-based solid electrolyte for a lithium secondary battery according to claim 3 .
10. A lithium secondary battery comprising the sulfide-based solid electrolyte for a lithium secondary battery according to claim 4 .