Lithium, phosphorus, sulfur, and iodine including electrolyte and catholyte compositions, electrolyte membranes for electrochemical devices, and annealing methods of making these electrolytes and catholytes
The present disclosure sets forth battery components for secondary and/or traction batteries. Described herein are new solid-state lithium (Li) conducting electrolytes including monolithic, single layer, and bi-layer solid-state sulfide-based lithium ion (Li + ) conducting catholytes or electrolytes. These solid-state ion conductors have particular chemical compositions which are arranged and/or bonded through both crystalline and amorphous bonds. Also provided herein are methods of making these solid-state sulfide-based lithium ion conductors including new annealing methods. These ion conductors are useful, for example, as membrane separators in rechargeable batteries.
1. A method of making an electrolyte characterized by Li x P y S z I t , wherein 5≤x≤12; 1≤y≤3; 5≤z≤9, and 0.1≤t≤2; and
said electrolyte is characterized by an x-ray powder diffraction (XRD) pattern comprising primary peaks at 20°±1° and at 29°±1° (2Θ),
wherein the peak at 20°±1° (2Θ) has a full-width at half-maximum (FWHM) of 2°±1°,
wherein the peak at 29°±1° (2Θ) has a full-width at half-maximum (FWHM) of 2°±1°;
wherein the method comprises the following steps:
providing a lithium sulfide compound,
providing a phosphorous sulfide compound,
providing a lithium iodide compound,
mixing the lithium sulfide compound, phosphorus sulfide compound, and lithium iodide compound to form a mixture,
milling the mixture to formed a milled mixture; and
heating the mixture from about 100 to about 300° C.
2. The method of claim 1 , wherein the electrolyte is characterized by an XRD pattern having the following reflections: 20, 25, 27, 29, and 45±1° (2Θ).
3. The method of claim 1 , wherein the electrolyte is semiamorphous.
4. The method of claim 1 , wherein the electrolyte is Li a P b S c I d , wherein 7.2≤a≤7.6, 1.4≤b≤1.8, 7.0≤c≤7.4, and 0.8≤d≤1.2.
5. The method of claim 1 , wherein the electrolyte is Li 7.4 P 1.6 S 7.2 I.
6. The method of claim 1 , further comprising providing a polymer and mixing the polymer with the electrolyte.
7. The method of claim 6 , wherein the weight loading of Li x P y S z I t is at least 50% (w/w) but less than 95% (w/w).
8. The method of claim 6 , wherein the weight loading of the polymer is about at least 0.01 (w/w) but less than 50% (w/w).
9. The method of claim 6 , wherein the weight loading the polymer is selected from the group consisting of epoxies, epoxides, polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), polybutadiene (PBD), polybutadiene rubber (PB), cross-linked polybutadiene (cPBD), polystyrene (PS), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylene cyclopentane) (PE-co-PMCP), poly methyl-methacrylate, acrylics, acrylonitrile-butadiene rubber (NBR), polyvinyl acetacetal resin, polyvinylbutylal resin, PVB stereoblock polypropylenes, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymers, nitriles, nitrile butadiene rubber, carboxymethyl cellulose (CMC), polyisoprene rubber (PI), polychloroprene rubber (CR), polyethyl acrylate (PEA), polyvinylidene fluoride (PVDF), aqueous-compatible polymers, silicone, PMX-200 (polydimethylsiloxane, PDMS), methyl methacrylate, ethyl methacrylate, polyvinylbutyral (PVB), poly ethyl methacrylate (PEMA), polyvinyl pyrrolidone (PVP), stereo block polypropylenes, polypropylene polymethylpentene copolymer, polypropylene carbonate, polyethylene, and combinations thereof.
10. The method of claim 1 , comprising forming the electrolyte into a thin film having a film thickness from about 10 nm to about 100 μm.
11. The method of claim 10 , wherein the thin film has a surface roughness from 0.5 μm Rt to 30 μm Rt, wherein Rt is the maximum surface roughness peak height of sampled surface, or a surface roughness from 0.5 μm Ra to 30 μm Ra, wherein Ra is the average peak height of sampled surface roughness.
12. A bi-layer solid-state electrolyte, having a top layer and a bottom layer, wherein the top layer comprises an electrolyte made by the method of claim 1 and wherein the bottom layer comprises a compound characterized by the empirical formula (1−x)(60:40 Li 2 S:SiS 2 )(x)(Li 3 PO 4 ) wherein x is from 0.01 to 0.99.
13. An electrochemical device comprising the electrolyte of claim 12 .