Passivation of sulfide, oxide, and oxysulfide glass electrolyte films for lithium metal batteries
US-2018309166-A1 · Oct 25, 2018 · US
US10734673B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-10734673-B2 |
| Application number | US-201715631261-A |
| Country | US |
| Kind code | B2 |
| Filing date | Jun 23, 2017 |
| Priority date | Jun 23, 2017 |
| Publication date | Aug 4, 2020 |
| Grant date | Aug 4, 2020 |
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Fiber-reinforced separators/solid electrolytes suitable for use in a cell employing an anode comprising an alkali metal are disclosed. Such fiber-reinforced separators/solid electrolytes may be at least partially amorphous and prepared by compacting, at elevated temperatures, powders of an ion-conducting composition appropriate to the anode alkali metal. The separators/solid electrolytes may employ discrete high aspect ratio fibers and fiber mats or plate-like mineral particles to reinforce the separator solid electrolyte. The reinforcing fibers may be inorganic, such as silica-based glass, or organic, such as a thermoplastic. In the case of thermoplastic fiber-reinforced separators/solid electrolytes, any of a wide range of thermoplastic compositions may be selected provided the glass transition temperature of the polymer reinforcement composition is selected to be higher than the glass transition temperature of the amorphous portion of the separator/solid electrolyte.
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The invention claimed is: 1. A separator/solid electrolyte for an electrochemical cell comprising an anode comprising an alkali metal, a cathode, and the separator/solid electrolyte in the form of a thin sheet, the separator/solid electrolyte sheet comprising electrically and ionically non-conducting, fiber reinforcements, distributed and embedded in a continuous ion-conducting matrix for conduction of cations of the alkali metal, at least a portion of the ion-conducting matrix being amorphous, the amorphous portion having a glass transition temperature, the separator/solid electrolyte sheet having a thickness and two opposing sheet faces, one of the sheet faces being adapted for face-to-face contact with the alkali metal anode and the opposing sheet face for face-to-face contact with the cathode of the electrochemical cell. 2. The separator/solid electrolyte of claim 1 in which the separator/solid electrolyte has a thickness of up to 200 micrometers. 3. The separator/solid electrolyte of claim 1 in which the ion-conducting matrix incorporates mobile alkali metal cations and is one of the group consisting of a sulfide glass, and an oxy-sulfide glass. 4. The separator/solid electrolyte of claim 1 in which the distributed fiber reinforcements are one of, a plurality of individual chopped fibers, a non-woven fiber mat, a woven fiber mat, or a plurality of generally uniformly-distributed particles with a plate-like geometry. 5. The separator/solid electrolyte of claim 3 in which the distributed fiber reinforcements are present in an amount ranging from 2 to 40 percent by weight, the percentage of distributed fiber reinforcements being selected to increase the fracture toughness of the separator/solid electrolyte while maintaining the ionic conductivity of the reinforced separator/solid electrolyte at more than 10% of the ionic conductivity of a reinforcement-free separator/solid electrolyte of like, ion-conducting composition. 6. The separator/solid electrolyte of claim 1 in which the alkali metal is lithium or sodium. 7. The separator/solid electrolyte of claim 4 in which the reinforcing fibers are silica-based glass fibers, alumina fibers, boron nitride fibers or thermoplastic polymer fibers. 8. The separator/solid electrolyte of claim 7 in which the thermoplastic polymer fibers have a glass transition temperature and the thermoplastic polymer fiber glass transition temperature is greater than the glass transition temperature of the amorphous portion of the ion-conducting matrix. 9. The separator/solid electrolyte of claim 1 in which the separator/solid electrolyte has a density of at least 90% of the theoretical density. 10. The separator/solid electrolyte of claim 1 in which the separator/solid electrolyte is less than 200 micrometers thick and the ion-conducting matrix has the composition 70Li 2 S.30P 2 S 5 or 60Li 2 S.28SiS 2 12P 2 S 5 and the ion-conducting matrix is reinforced with 10 wt. % of aramid fiber. 11. An electrochemical cell comprising an anode comprising an alkali metal, a cathode, and a separator/solid electrolyte in the form of a thin sheet, the separator/solid electrolyte sheet comprising electrically and ionically non-conducting, fiber reinforcements, distributed and imbedded in a continuous ion-conducting matrix for conduction of cations of the alkali metal, at least a portion of the ion-conducting matrix being amorphous, the separator/solid electrolyte sheet having a thickness and two opposing sheet faces, one of the sheet faces being in face-to-face contact with the alkali metal anode and the opposing sheet face being in face-to-face contact with the cathode of the electrochemical cell. 12. The electrochemical cell of claim 11 in which the alkali metal is lithium. 13. The electrochemical cell of claim 11 in which the ion-conducting matrix incorporates mobile alkali metal cations and is one of the group consisting of a sulfide glass, and an oxy-sulfide glass. 14. The electrochemical cell of claim 11 in which the distributed fiber reinforcements are one of, a plurality of individual chopped fibers, a non-woven fiber mat, a woven fiber mat, or a plurality of generally uniformly-distributed particles with a plate-like geometry. 15. The electrochemical cell of claim 11 in which the fiber reinforcements are present in an amount ranging from 2 to 40 percent by weight, the percentage of distributed reinforcements being selected to increase the fracture toughness of the separator/solid electrolyte while maintaining the ionic conductivity of the reinforced separator/solid electrolyte at more than 10% of the ionic conductivity of a reinforcement-free separator/solid electrolyte of like ion-conducting composition.
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