Claims
- 1. A molecular composite electrolyte material comprising:
a silicate condensate framework, an electrolytic polymeric material contained within said silicate condensate framework, and a charge-carrying species contained within said polymeric material; wherein the electrolytic polymeric material has an outer surface, an interior bulk portion, and a skin portion at or near said outer surface, said skin portion substantially being comprised of crosslinked polymers to improve dimensional stability of said electrolyte material and to reduce adhesiveness of the electrolytic polymeric material outer surface, and the bulk portion substantially being comprised of un-crosslinked polymers so that conductivity of the electrolytic polymeric material is retained by maintaining polymer segmental motion and charge-carrying species mobility within said bulk portion.
- 2. A molecular composite electrolyte material as in claim 1, wherein the crosslinked polymers in said skin portion are crosslinked by exposure to UV radiation.
- 3. A molecular composite electrolyte material as in claim 2, wherein the crosslinked polymers in said skin portion comprise one or more components that have high molar extinction coefficients in an ultraviolet range of radiation, so that substantially no ultraviolet radiation penetrates into the bulk portion.
- 4. A molecular composite electrolyte material as in claim 3, wherein said crosslinked polymers in said skin portion comprise a component selected from the group consisting of an aromatic component and a phenolic component.
- 5. A molecular composite electrolyte material as in claim 1, wherein the crosslinked polymers in said skin portion comprise crosslinking of alkyl or allyl groups.
- 6. A molecular composite electrolyte material as in claim 3, wherein the polymeric material comprises polymers selected from the group consisting of polyphosphazenes, polysiloxanes and mixtures thereof.
- 7. A molecular composite electrolyte material as in claim 3, wherein the electrolytic polymeric material is selected from the group consisting of: polyether containing phosphazenes, polythioether containing phosphazenes, polyethers containing polysiloxanes, polythioether containing polysiloxanes, polyetherthiol containing containing phosphazenes, polyetherthiol containing phosphazenes, polyetherthiol containing polysiloxanes, and polyetherthiol containing polysiloxanes, and mixtures thereof.
- 8. A molecular composite electrolyte material as in claim 1, wherein the electrolytic polymeric material has a thickness and the skin portion has a thickness equal to about 2-10% of the electrolytic polymeric material thickness.
- 9. A molecular composite electrolyte material as in claim 1, wherein the electrolytic polymeric material has a thickness and the skin portion has a thickness equal to about 2-3% of the electrolytic polymeric material thickness.
- 10. A molecular composite electrolyte material as in claim 1, wherein said electrolytic polymer material comprises polymers comprising a backbone and ligands bonded to the backbone, said ligands comprising an ion carrying group and a hydrophobic, UV-light absorbing group, wherein said hydrophobic, UV-absorbing group comprises at least one moiety selected from the group consisting of aromatic moieties and phenolic moieties.
- 11. A molecular composite electrolyte material as in claim 1, wherein said skin portion substantially being comprised of crosslinked polymers exhibits adhesion to aluminum at 35° C. of less than 1 KN/M2, while said bulk portion exhibits adhesion to aluminum at 35° C. of greater than 2 KN/M2.
- 12. A method of manufacturing molecular composite electrolyte material, the method comprising:
providing a composite electrolyte material comprising an ion-conductive polymer within a ceramic condensate framework, the composite electrolyte material having an outer surface and an interior bulk portion; irradiating an outer surface of said composite electrolyte material with ultraviolet radiation to form a crosslinked polymer skin portion only at or near said outer surface; and not irradiating said interior bulk portion; so that adhesiveness of said crosslinked polymer skin portion is reduced compared to adhesiveness of said bulk portion, and so that mobility of ions is maintained within said interior bulk portion.
- 13. A method as in claim 12, wherein said bulk portion is substantially comprised of uncrosslinked polymers.
- 14. A method as in claim 12, wherein said irradiating is done with 200-400 nm ultraviolet radiation at a power of 5-50 Watts.
- 15. A method as in claim 14, wherein said irradiating is done for a duration of less than 3 hours.
- 16. A method as in claim 14, wherein said irradiation reduces adhesiveness of said skin portion compared to adhesiveness of said bulk portion by at least 50%.
- 17. A method as in claim 12, wherein said irradiation is conducted to an extent that forms a skin portion of substantially crosslinked polymers having a thickness that is 2-10% of the molecular composite electrolyte material thickness.
- 18. A method as in claim 12, wherein said irradiation is conducted to an extent that forms a skin portion of substantially crosslinked polymers having a thickness that is 2-3% of the molecular composite electrolyte material thickness.
- 19. A battery comprising one or more electric-current-producing electrochemical cells, said cells comprising an anode, a cathode, and an electrolyte that is a coating on the anode, said electrolyte comprised of a polymer-ceramic material formed by the catalyzed condensation of a ceramic precursor in the presence of a solvated polymer material, wherein:
the polymer-ceramic material has an outer surface, a skin portion at or near the outer surface, and an interior bulk portion, wherein the skin portion substantially comprises crosslinked polymers and the bulk portion comprises polymers that are substantially un-crosslinked.
- 20. A battery as in claim 19, wherein the crosslinked polymers in said skin portion are crosslinked by exposure to UV radiation.
- 21. A battery as in claim 20, wherein the crosslinked polymers in said skin portion comprise one or more components that have high molar extinction coefficients in an ultraviolet range of radiation, so that substantially no ultraviolet radiation penetrates into the bulk portion.
- 22. A battery as in claim 21, wherein said crosslinked polymers in said skin portion comprise a component selected from the group consisting of an aromatic component and a phenolic component.
- 23. A battery as in claim 21, wherein the crosslinked polymers in said skin portion comprise crosslinking of alkyl or allyl groups.
- 24. A battery as in claim 21, wherein the polymeric material comprises polymers selected from the group consisting of polyphosphazenes, polysiloxanes and mixtures thereof.
- 25. A battery as in claim 21, wherein the electrolytic polymeric material is selected from the group consisting of: polyether containing phosphazenes, polythioether containing phosphazenes, polyethers containing polysiloxanes, polythioether containing polysiloxanes, polyetherthiol containing containing phosphazenes, polyetherthiol containing phosphazenes, polyetherthiol containing polysiloxanes, and polyetherthiol containing polysiloxanes, and mixtures thereof.
- 26. A battery as in claim 21, wherein the electrolytic polymeric material has a thickness and the skin portion has a thickness equal to about 2-10% of the electrolytic polymeric material thickness.
- 27. A battery as in claim 21, wherein the electrolytic polymeric material has a thickness and the skin portion has a thickness equal to about 2-3% of the electrolytic polymeric material thickness.
- 28. A battery as in claim 21, wherein said electrolytic polymer material comprises polymers comprising a backbone and ligands bonded to the backbone, said ligands comprising an ion carrying group and a hydrophobic, UV-light absorbing group, wherein said hydrophobic, UV-absorbing group comprises at least one moiety selected from the group consisting of aromatic moieties and phenolic moieties.
- 29. A battery as in claim 28, wherein said ion carrying group is selected from the group consisting of an ethylene oxy group, an ethylene thiol group, and an ethylene oxy-thiol group.
- 30. The battery of claim 21 wherein the ceramic precursor is a metal alkoxide.
- 31. The battery of claim 30 wherein the metal alkoxide is selected from the group consisting of silicon alkoxides, titanium alkoxides, zirconium alkoxides, aluminum alkoxides, and mixtures thereof.
- 32. The battery of claim 30 wherein the metal alkoxide is selected from the group consisting of tetraethylorthosilicate, tetraisopropoxyorthotitanate, zirconium n-butoxide butanol complex, aluminum tri-sec butoxide, and mixtures thereof.
- 33. The battery of claim 21 wherein the electrolyte comprises a charge-carrying species selected from the group consisting of lithium cations, sodium cations, and magnesium cations.
- 34. The battery of claim 21 which is a reactive metal-water battery, wherein:
said anode is a metal selected from the group consisting of periodic table Group 1A, periodic table Group 2A, and mixtures thereof; and said cathode comprises water.
- 35. The battery of claim 21 which is a reactive metal-water battery, wherein:
said anode is a metal selected from the group consisting of lithium and magnesium; and said cathode comprises water.
- 36. A composite solid polymer-ceramic electrolyte having improved conductivity, dimensional stability, and surface adherency, the electrolyte comprising:
a molecular composite material comprising a polymer material incorporated within a ceramic network, wherein the polymer material is crosslinked only at or near its outer surface, and wherein:
said electrolyte exhibits a conductivity of at least 10−4 S/cm at about 20-25° C.; and said electrolyte does not flow while subjected to pressures in the range of 475 g/cm2—525 g/cm2in the range of 20-25° C.
- 37. A composite solid polymer-ceramic electrolyte as in claim 36, wherein the polymer is crosslinked only at or near its outer surface by exposure to UV radiation.
- 38. A composite solid polymer-ceramic electrolyte as in claim 36 having a thickness, and wherein said polymer is crosslinked only in a surface skin portion having a thickness equal to about 2-10% of the electrolyte thickness.
- 39. A composite solid polymer-ceramic electrolyte as in claim 36 having a thickness, and wherein said polymer is crosslinked only in a surface skin portion having a thickness equal to about 2-3% of the electrolyte thickness.
CONTRACTUAL ORIGIN OF THE INVENTION
[0001] The United States Government has rights in the following invention pursuant to Contract No. DE-AC07-99ID13727 between the United States Department of Energy and Bechtel BWXT Idaho, LLC.