Solid-state hybrid electrolytes, methods of making same, and uses thereof

Patent metadata

Field	Value
Publication number	US-2020112050-A1
Application number	US-201816499203-A
Country	US
Kind code	A1
Filing date	Mar 29, 2018
Priority date	Mar 29, 2017
Publication date	Apr 9, 2020
Grant date	—

Abstract

Provided are solid-state hybrid electrolytes. The hybrid electrolytes have a polymeric material layer, which may be a polymer/copolymer layer or a gel polymer/copolymer layer, disposed on at least a portion of an exterior surface or all of the exterior surfaces of a solid-state electrolyte. A hybrid electrolyte can form an interface with an electrode of an ion-conducting battery that exhibits desirable properties. The solid-state electrolyte can comprise a monolithic SSE body, a mesoporous SSE body, or an inorganic SSE having fibers or strands, which may be aligned. In the case of solid-state electrolytes that have strands, the strands can be formed using a sacrificial template. The hybrid solid-state electrolytes can be used in ion-conducting batteries, which may be flexible, ion-conducting batteries.

First claim

1 . A solid-state hybrid electrolyte comprising:
an inorganic solid-state electrolyte (SSE); and a polymeric material disposed on at least a portion an exterior surface of or all of the exterior surfaces of the solid-state electrolyte material.

2 . The hybrid electrolyte of claim 1 , wherein the SSE material is a monolithic SSE body or a mesoporous SSE body.

3 . The hybrid electrolyte material of claim 1 , wherein the SSE material is a disc, a sheet, or a polyhedron.

4 . The hybrid electrolyte of claim 1 , wherein the polymeric material has at one or more points a thickness of 10 nm-10 microns.

5 . The hybrid electrolyte of claim 1 , wherein the SSE comprises a plurality of fibers or strands.

6 . The hybrid electrolyte material of claim 5 , wherein the fibers are present as a woven substrate.

7 . The hybrid electrolyte material of claim 5 , wherein the fibers are randomly arranged or aligned.

8 . The hybrid electrolyte of claim 5 , wherein the fibers or strands of the inorganic SSE material form an interconnected 3-D network.

9 . The hybrid electrolyte of claim 1 , wherein the SSE material comprises a lithium-ion conducting SSE material, a sodium-ion conducting SSE material, or a magnesium-ion conducting SSE material.

10 . The hybrid electrolyte of claim 9 , wherein the lithium-ion conducting SSE material is selected from the group consisting of lithium perovskite materials, Li 3 N, Li-β-alumina, Lithium Super-ionic Conductors (LISICON), Li 2.88 PO 3.86 N 0.14 (LiPON), Li 9 AlSiO 8 , Li 10 GeP 2 S 12 , lithium garnet materials, doped lithium garnet materials, lithium garnet composite materials, and combinations thereof.

11 . The hybrid electrolyte of claim 10 , wherein the lithium garnet material is cation-doped Li 5 La 3 M 1 2 O 12 , wherein M 1 is Nb, Zr, Ta, or combinations thereof, cation-doped Li 6 La 2 BaTa 2 O 12 , cation-doped Li 7 La 3 Zr 2 O 12 , and cation-doped Li 6 BaY 2 M 1 2 O 12 , wherein M 1 is Nb, Zr, Ta, or combinations thereof wherein cation dopants are barium, yttrium, zinc, or combinations thereof.

12 . The hybrid electrolyte of claim 10 , wherein the lithium garnet material is Li 5 La 3 Nb 2 O 12 , Li 5 La 3 Ta 2 O 12 , Li 7 La 3 Zr 2 O 12 , Li 6 La 2 SrNb 2 O 12 , Li 6 La 2 BaNb 2 O 12 , Li 6 La 2 SrTa 2 O 12 , Li 6 La 2 BaTa 2 O 12 , Li 7 Y 3 Zr 2 O 12 , Li 6.4 Y 3 Zr 1.4 Ta 0.6 O 12 , Li 6.5 La 2.5 Ba 0.5 TaZrO 12 , Li 6 BaY 2 M 1 2 O 12 , Li 7 Y 3 Zr 2 O 12 , Li 6.75 BaLa 2 Nb 1.75 Zn 0.25 O 12 , Li 6.75 BaLa 2 Ta 1.75 Zn 0.25 O 12 , and combinations thereof.

13 . The hybrid electrolyte of claim 9 , wherein the sodium-ion conducting SSE material is selected from the group consisting of β″-Al 2 O 3 , Na 4 Zr 2 Si 2 PO 12 (NASICON), cation-doped NASICON, and combinations thereof.

14 . The hybrid electrolyte of claim 9 , wherein the magnesium-ion conducting SSE material is selected from the group consisting of Mg 1+x (Al,Ti) 2 (PO 4 ) 6 , wherein x is 4 to 5, NASICON-type magnesium-ion conducting materials, and combinations thereof.

15 . The hybrid electrolyte of claim 1 , wherein the inorganic SSE has pores exposed to an exterior surface of the inorganic SSE and the hybrid electrolyte further comprises at least one cathode material and/or at least one anode material disposed in at least a portion of the pores, and
wherein in the case where at least one cathode material and at least one anode material is disposed in at least a portion of the pores the at least one cathode material and at least one anode material are disposed in discrete and electrically separated regions of the inorganic SSE.

16 . The hybrid electrolyte of claim 1 , wherein the polymeric material comprises (e.g., the polymeric material is) a polymer selected from the group consisting of poly(ethylene) (PE), poly(ethylene oxide) (PEO), poly(propylene) (PP), poly(propylene oxide), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), poly[bis(methoxy ethoxyethoxide}-phosphazene], poly(dimethylsiloxane) (PDMS), cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, polyvinylidene difluoride (PVdF), polyvinylpyrrolidone (PVP), polystyrene, sulfonate (PSS), polyvinylchloride (PVC) group, poly(vinylidene chloride) polypropylene oxide, polyvinylacetate, polytetrafluoroethylene, poly(ethylene terephthalate) (PET), polyimide, polyhydroxyalkanoate (PHA), PEO containing co-polymers (e.g., polystyrene (PS)—PEO copolymers and poly(methyl methacrylate) (PMMA)—PEO copolymers), polyacrylonitrile (PAN), poly(acrylonitrile-co-methylacrylate), PVdF containing co-polymers, PMMA co-polymers, derivatives thereof, and combinations thereof.

17 . The hybrid electrolyte of claim 1 , wherein the polymeric material is a gel.

18 . The hybrid electrolyte of claim 17 , wherein the gel comprises a liquid selected from the group consisting of ethylene carbonate (EC), diethyl carbonate (DEC), dimethoxyethane (DME), dioxolane (DOL), N-Propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR 13 TFSI), and combinations thereof and/or a salt selected from the group consisting of LiPF 6 , LiTFSI, LiTFSI, and combinations thereof.

19 . The hybrid electrolyte of claim 17 , wherein the polymeric material of the gel comprises (e.g., the polymeric material is) a polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylpyrrolidone (PVP), PEO, PMMA, PAN, polystyrene (PS), polyethylene (PE), and combinations thereof.

20 . The hybrid electrolyte of claim 1 , wherein the polymeric material comprises a metal salt.

21 . The hybrid electrolyte of claim 1 , wherein the polymeric material comprises a ceramic filler.

22 . The hybrid electrolyte of claim 21 , wherein the ceramic filler is selected from the group consisting of conductive particles, non-conductive particles, ceramic nanomaterials.

23 . A device comprising a hybrid electrolyte of claim 1 .

24 . The device of claim 23 , wherein the device is a battery comprising:
the hybrid electrolyte; an anode; and a cathode,
wherein the hybrid electrolyte is disposed between the cathode and anode.

25 . The device of claim 24 , wherein the battery further comprises a current collector disposed on at least a portion of the cathode and/or the anode.

26 . The device of claim 25 , wherein the current collector is a conducting metal or metal alloy.

27 . The device of claim 24 , wherein the battery is a lithium-ion conducting solid-state battery and the hybrid electrolyte is a lithium ion-conducting SSE material.

28 . The device of claim 24 , wherein the battery is a sodium-ion conducting solid-state battery and the hybrid electrolyte is a sodium ion-conducting SSE material.

29 . The device of claim 24 , wherein the battery is a magnesium-ion conducting solid-state battery and the hybrid electrolyte is a magnesium ion-conducting SSE material.

30 . The device of claim 24 , wherein the cathode and/or anode comprises a conducting carbon material, and the cathode material, optionally, further comprises an organic or gel ion-conducting electrolyte.

31 . The device of claim 24 , wherein the cathode comprises a material selected from sulfur, sulfur composite materials, and polysulfide materials, or the cathode is air.

Assignees

• Univ Maryland

Inventors

• Hu Liangbing
• Wachsman Eric D
• Liu Boyang
• Gong Yunhui
• Fu Kun

Classifications

• H01M10/0525

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

• H01M2300/0068

  inorganic · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M10/056 Primary

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

• H01M2300/0094

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