Lithium, phosphorus, sulfur, and iodine including electrolyte and catholyte compositions, electrolyte membranes for electrochemical devices, and annealing methods of making these electrolytes and catholytes

Patent metadata

Field	Value
Publication number	US-2017162901-A1
Application number	US-201615367103-A
Country	US
Kind code	A1
Filing date	Dec 1, 2016
Priority date	Dec 4, 2015
Publication date	Jun 8, 2017
Grant date	—

Abstract

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.

First claim

1 . An electrolyte comprising a compound 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
characterized by an x-ray powder diffraction (XRD) pattern having at least one of the following reflections at: 20, 25, 27, 29, or 45±1° (2Θ);
wherein subscripts x, y, z, and t are rational numbers;
wherein the compound is neutrally charged.

2 . The electrolyte of claim 1 , consisting essentially of Li x P y S z I t , wherein 5≦x≦12; 1≦y≦3; 5≦z≦9, and 0.1≦t≦2; and
characterized by an XRD pattern having at least one of the following reflections at: 20, 25, 27, 29, or 45±1° (2Θ);
wherein subscripts x, y, z, and t are rational numbers;

wherein the compound is neutrally charged.

3 . The electrolyte of claim 1 , wherein the composition is characterized by an XRD pattern having the following reflections at 20, 25, 27, 29, and 45±1° (2Θ).

4 . The electrolyte of claim 1 , wherein the composition is characterized by an XRD pattern having the following primary peaks at 20, 25, 27, 29, and 45±1° (2Θ).

5 . The electrolyte of claim 1 , wherein the composition is semiamorphous.

6 . The electrolyte of claim 1 , wherein the composition is not:
a member selected from the group consisting of (Li 3 PS 4 )3(LiI), (Li 3 PS 4 )2(LiI), (Li 3 PS 4 )(LiI), 2(Li 3 PS 4 )(LiI), 3(Li 3 PS 4 )(LiI), and combinations thereof; a member selected from the group consisting of Li 7 P 2 S 8 I, Li 6 PS 5 F, Li 6 PS 5 Cl, Li 6 PS 5 Br, Li 6 PS 5 I, and combinations thereof; a member selected from the group consisting of 80(70L 2 S.30P 2 S 5 )20(LiI), 70(70L 2 S.30P 2 S 5 )30(LiI), and combinations thereof; a member selected from the group consisting of a solid solution of L 3 PS 4 , LiI, Li 2 S, P 2 S 5 , and combinations thereof; (100-X)(80L 2 S.20P 2 S 5 )X(LiI), wherein X is 0, 2, 5, 10, 15, 20 or 30; or a mixture of Li 2 S, P 2 S 5 , LiF, LiCl, LiBr, LiI or combinations thereof.

7 . The electrolyte of claim 1 , wherein the composition is not Li 7 P 2 S 8 I or Li 6 PS 5 I.

8 . The electrolyte of claim 1 , wherein the composition does not have an argyrodite crystal structure.

9 . The electrolyte of claim 1 , wherein the composition does not comprise germanium (Ge) or any germanium species.

10 . The electrolyte of claim 1 , wherein the composition does not comprise arsenic (As) or any arsenic species.

11 . The electrolyte of claim 1 , wherein the composition is Li 7.4 P 1.6 S 7.2 I.

12 . The electrolyte of claim 1 , wherein the composition is Li a P b S c I d , wherein a is from 7.2 to 7.6, b is from 1.4 to 1.8, c is from 7.0 to 7.4, and d is from 0.8 to 1.2, and wherein the electrolyte is charge neutral.

13 . The electrolyte of claim 1 , wherein the composition is Li 7.4 P 1.6 S 7.2 I±5% of the value of the recited subscripts.

14 . The electrolyte of claim 1 , wherein the composition is Li 7 P 2 S 8 I wherein the subscript values may vary by ±5%.

15 . The electrolyte of claim 1 , wherein the composition is Li 7 P 2 S 8 I wherein the subscript values may vary by ±5%.

16 . The electrolyte of claim 1 further comprising a polymer.

17 . The electrolyte of claim 16 , wherein the weight loading of Li x P y S z I t in the composition further comprising a polymer is at least 50% (w/w) but less than 95% (w/w).

18 . The electrolyte of claim 17 , wherein the volume loading of Li x P y S z I t in the composition further comprising a polymer is at least 50% (v/v).

19 . The electrolyte of claim 17 , wherein the volume loading of Li x P y S z I t in the composition further comprising a polymer is at least 70% (v/v).

20 . The electrolyte of claim 17 , wherein the volume loading of Li x P y S z I t in the composition further comprising a polymer is at between 70%-85% (v/v).

21 . The electrolyte of claim 17 , wherein the volume loading of Li x P y S z I t in the composition further comprising a polymer is at between 75%-85% (v/v).

22 . The electrolyte of claim 16 , wherein the polymer is selected from the group consisting of epoxies, epoxides, polypropylene (PP), atactic polypropylene (aPP), isotactive polypropylene (iPP), polybutyl diene, 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), PE-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.

23 . The electrolyte of claim 16 , wherein the polymer is attached, bonded, adhered, or adsorbed to the LPSI.

24 . The electrolyte of claim 16 , wherein the polymer is bonded to the surface of the LPSI.

25 . The electrolyte of claim 16 , wherein the polymer is present at about 0.01-50% w/w.

26 . The electrolyte of claim 1 formed as a thin film having a film thickness from about 10 nm to about 100 μm.

27 . The electrolyte of claim 1 formed as a monolith having an average monolith thickness from about 10 nm to about 100 microns.

28 . The electrolyte of claim 26 , wherein the film thickness is from about 20 μm to about 60 μm.

29 . The electrolyte of claim 26 , wherein the film thickness is about 10 μm, 20 μm, 30 μm, 40 μm, 50 μm or 60 μm.

30 . The electrolyte of claim 1 , comprising LiI.

31 . The electrolyte of claim 1 , comprising Li 2 S.

32 . The electrolyte of claim 1 , having an ionic conductivity of about 1×10 −3 S/cm or greater.

33 . The electrolyte of claim 1 , wherein the compound 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 has a porosity of less than 20, 15, 10, 5 or 1% as determined by SEM and geometric measurements.

34 . The electrolyte of claim 1 , wherein the compound 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 has a density of at least 80, 85, 90, 95, or 99% as determined by SEM and geometric measurements.

35 . The electrolyte of claim 1 , wherein the first major XRD peak at 29° (2Θ) has a full-width at half-maximum (FWHM) of 3°±1°.

36 . The electrolyte of claim 1 , wherein the composition is semiamorphous.

37 . The electrolyte of claim 1 , having a chemical composition selected from Li 7.4 P 1.6 S 7.2 I or Li 11 P 2 S 6 I.

38 . An electrolyte comprising a compound 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 characterized by an XRD pattern not having at least one of the f

Assignees

• Quantumscape Corp

Inventors

• Chen Zhebo
• Holme Tim
• Hudson William
• Kerman Kian
• Mair Sunil
• Mehrotra Amal
• Van Berkel Kim

Classifications

• H01M10/056 Primary

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M2300/0094

  in the form of layered products, e.g. coatings · CPC title

• C01B25/14

  Sulfur, selenium, or tellurium compounds of phosphorus · CPC title