Silanated silica-ceramic materials, and methods of making and using the same
The invention provides a novel ceramic-metal oxide-polymer composite material. A functionalized metal oxide nanolayer coating can be bonded between LICGCs and polymers/oligomers, which protects the LICGC from corrosion, has a low interfacial resistance to Li + migration, and can be a SIC. Hybrid ceramic-polymer electrolytes were formed by engineering the interface between a LICGC and a polymer, polyethylene oxide (PEO), by sputter coating a 200 nm thick SiO 2 layer onto a lithium ion conducting glass ceramic (LICGC) and silanating the SiO 2 with a functionalized PEG in the presence of LiTFSI. A low interfacial resistance (R interfacial ) was measured, the same as that obtained for a SiO 2 interface soaked with liquid tetraglyme/LiTFSI. The pegylated SiO 2 interface (unlike the tetraglyme/LiTFSI interface) protected the LICGC from corrosion by Li 0 metal. The (PEG-LiTFSI)—SiO 2 -LICGC could be bonded with polyethylene oxide/LiTFSI. This procedure provides a general method to bond other LICGCs to PEO-based polymers, and to incorporate other functionalities such as single ion conductivity into the interface via the incorporation of coupling agents with pendant anions.
1. A composite material comprising a ceramic portion, a metal oxide portion, and a coupling agent portion, wherein the coupling agent is covalently bonded to the metal oxide and the metal oxide portion has a different composition than the ceramic portion.
2. The composite material of claim 1 , wherein the ceramic comprises one or more of Li 2 O, Al 2 O 3 , SiO 2 , P 2 O 5 , TiO 2 , or GeO 2 .
3. The composite material of claim 1 , wherein the metal oxide is selected from the group consisting of silica or alumina.
4. The composite material of claim 1 , wherein the coupling agent is selected from the group consisting of a silane, a carboxylic acid, a carboxylate, or an organic coupling agent.
5. The composite material of claim 1 , wherein the coupling agent is derived from one of a functionalized PEG, a reactive coupling agent, or a coupling agent containing a pendant anion.
6. The composite material of claim 1 , wherein the coupling agent is derived from one of 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane, CH 3 O—(CH 2 CH 2 O) x —(CH 2 ) 3 Si(OCH 3 ) 3 , silyl sulfonylazide, trimethoxysilyl modified polyethylene, C 16 H 38 O 6 Si 2 pendant dipodal silane, 1,2-bis(trimethyoxysilyl)decane, 1,2-bis(trimethyoxysilyl)octane, (C 2 H 5 O) 3 Si(CH 2 ) 8 Si(OC 2 H 5 ) 3 , 6-azidosulfonylhexyl-triethoxy silane, an anion silane, wherein x=9-12, a 2-[methoxy(polyethyleneoxy)propyl]carboxylate, a 2-[methoxy(polyethyleneoxy)propyl] carboxylic acid, a modified polyethylene carboxylic acid, a PEG functionalized carboxylic acid, a PEO functionalized carboxylic acid, an organic carboxylic acid, and an organic coupling agent.
7. The composite material of claim 1 , further comprising a polymer.
8. The composite material of claim 7 , wherein the polymer is selected from the group consisting of polyethylene oxide, polyethylene, and polypropylene.
9. The composite material of claim 1 , wherein the ceramic is in the form of particles.
10. The composite material of claim 1 , wherein the composite material has a conductivity of about 1.5×10 −4 S/cm at 30° C.; or
wherein the material forms an SIC interface.
11. A membrane comprising the composite material of claim 1 .
12. A battery separator comprising the membrane of claim 11 .
13. A method for making a composite material comprising a ceramic, the method comprising:
depositing a metal oxide layer on a ceramic material, and
treating the metal oxide surface with a coupling agent in the presence of a lithium salt, wherein the metal oxide layer has a different composition than the ceramic material.
14. The method of claim 13 , wherein the metal oxide is selected from the group consisting of silica or alumina.
15. The method of claim 13 , wherein the ceramic is in the form of particles.
16. The method of claim 13 , wherein the coupling agent is selected from the group consisting of a silanating agent, functionalized PEG, a reactive coupling agent, or a coupling agent containing a pendant anion.
17. The method of claim 13 , wherein the coupling agent is selected from the group consisting of 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane, CH 3 O—(CH 2 CH 2 O) x —(CH 2 ) 3 Si(OCH 3 ) 3 , silyl sulfonylazide, trimethoxysilyl modified polyethylene, C 16 H 38 O 6 Si 2 pendant dipodal silane, 1,2-bis(trimethyoxysilyl)decane, 1,2-bis(trimethyoxysilyl)octane, (C 2 H 5 O) 3 Si(CH 2 ) 8 Si(OC 2 H 5 ) 3 , 6-azidosulfonylhexyl-triethoxy silane, an anion silane, wherein x=9-12, a 2-[methoxy(polyethyleneoxy)propyl]carboxylate, a 2-[methoxy(polyethyleneoxy)propyl]carboxylic acid, a modified polyethylene carboxylic acid, a PEG functionalized carboxylic acid, a PEO functionalized carboxylic acid, an organic carboxylic acid, and an organic coupling agent.
18. The method of claim 13 , wherein the lithium salt is LiTFSI.
19. The method of claim 13 , further comprising heating, casting, or melting.
20. The method of claim 13 , further comprising applying a polymer layer.
21. The method of claim 20 , wherein the polymer is selected from the group consisting of polyethylene oxide, polyethylene, and polypropylene.