Multi-layer solid electrolyte separator for a lithium secondary battery and manufacturing method

Patent metadata

Field	Value
Publication number	US-12592453-B2
Application number	US-202117338492-A
Country	US
Kind code	B2
Filing date	Jun 3, 2021
Priority date	Jun 3, 2021
Publication date	Mar 31, 2026
Grant date	Mar 31, 2026

Abstract

A flame-resistant composite separator for use in a lithium battery, wherein the composite separator comprises at least a first layer and a second layer laminated together, wherein: (A) the first layer comprises a layer of inorganic solid electrolyte (e.g., a sintered solid structure) or a layer of polymer composite comprising 60%-99% by volume of inorganic material particles, inorganic material fibers, and/or polymer fibers dispersed in or bonded by a first polymer; and (B) the second layer comprises a second polymer and from 0.1% to 50% by weight of a lithium salt dispersed in the second polymer; wherein the first layer and the second layer each has a thickness from 20 nm to 100 μm and a lithium-ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature.

First claim

The invention claimed is:

1 . A flame-resistant composite separator for use in a lithium battery, wherein the composite separator comprises at least a first layer and a second layer laminated together, wherein:
a) the first layer comprises a layer of sintered or consolidated inorganic solid electrolyte or a layer of polymer composite comprising 60%-99% by volume of inorganic material particles, inorganic material fibers, and/or polymer fibers dispersed in or bonded by a first polymer; and b) the second layer comprises a second polymer and from 0.1% to 50% by weight of a lithium salt dispersed in the second polymer wherein the first polymer is the same as or different than the second polymer; wherein the first layer and the second layer each has a thickness from 20 nm to 100 μm and a lithium-ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature; wherein the inorganic solid electrolyte or the inorganic material particles in the first layer comprise an inorganic solid electrolyte material selected from a sulfide, hydride, halide, borate, phosphate, lithium phosphorus oxynitride (LiPON), or Garnet.

2 . A flame-resistant composite separator for use in a lithium battery, wherein the composite separator comprises at least a first layer and a second layer laminated together, wherein:
a) the first layer comprises a layer of polymer composite comprising 60%-99% by volume of inorganic material particles, inorganic material fibers, and/or polymer fibers dispersed in or bonded by a first polymer; and b) the second layer comprises a layer of sintered or consolidated inorganic solid electrolyte, wherein the inorganic solid electrolyte or the inorganic material particles in the first layer comprise an inorganic solid electrolyte material selected from a sulfide, hydride, halide, borate, phosphate, lithium phosphorus oxynitride (LiPON), or Garnet.

3 . The flame-resistant composite separator of claim 1 , wherein the inorganic material particles comprise a material selected from a transition metal oxide, aluminum oxide, silicon dioxide, transition metal sulfide, transition metal selenide, alkylated ceramic particles, metal phosphate, metal carbonate, or a combination thereof, or the inorganic material fibers are selected from ceramic fibers, glass fibers, or a combination thereof.

4 . The flame-resistant composite separator of claim 1 , wherein the first polymer or the second polymer is produced by polymerizing or curing a first liquid solvent selected from the group consisting of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinyl sulfite, vinyl ethylene sulfite, vinyl ethylene carbonate, 1,3-propyl sultone, 1,3,5-trioxane (TXE), 1,3-acrylic-sultones, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), fluorinated ethers, fluorinated esters, sulfones, sulfides, dinitriles, acrylonitrile (AN), sulfates, siloxanes, silanes, N-methylacetamide, acrylates, ethylene glycols, tetrahydrofuran, phosphates, phosphonates, phosphinates, phosphines, phosphine oxides, phosphonic acids, phosphorous acid, phosphites, phosphoric acids, phosphazene compounds, ionic liquids, thermosetting resins, derivatives thereof, and mixtures thereof.

5 . The flame-resistant composite separator of claim 4 , wherein the thermosetting resin is selected from the group consisting of epoxy, epoxy novolac, polyurethane, phenolic resin or phenol formaldehyde, polyimide, polyether imide, polyester, vinyl ester, polyamide, polyamide-imide, melamine resin, bismaleimide, cyanate ester, silicone, polyurea-urethane, Diallyl-phthalate, benzoxazines, ladder polymers, copolymers thereof, interpenetrating networks thereof, and combinations thereof.

6 . The flame-resistant composite separator of claim 1 , wherein the second polymer comprises a lithium ion-conducting polymer selected from polypropylene oxide, polyoxymethylene, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, poly(vinylidene fluoride)-hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate, a single Li-ion conducting solid polymer with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, poly(ethylene glycol) diacrylate, poly(ethylene glycol) methyl ether acrylate, polyurethane, polyurethan-urea, polyacrylamide, a polyionic liquid, polymerized 1,3-dioxolane, polyepoxide ether, polysiloxane, poly(acrylonitrile-butadiene), polynorbornene, poly(hydroxyl styrene), poly(ether ether ketone), polypeptoid, poly(ethylene-maleic anhydride), polycaprolactone, a copolymer thereof, a sulfonated derivative thereof, or a combination thereof.

7 . The flame-resistant composite separator of claim 1 , wherein the lithium salt is selected from lithium perchlorate, LiClO 4 , lithium hexafluorophosphate, LiPF 6 , lithium borofluoride, LiBF 4 , lithium hexafluoroarsenide, LiAsF 6 , lithium trifluoro-methanesulfonate, LiCF 3 SO 3 , lithium bis(oxalato) borate, LiBOB, lithium oxalyldifluoroborate, LiBF 2 C 2 O 4 , lithium oxalyldifluoroborate, LiBF 2 C 2 O 4 , lithium nitrate, LiNO 3 , Li-Fluoroalkyl-Phosphates, LiPF 3 (CF 2 CF 3 ) 3 , lithium bisperfluoro-ethylsulfonylimide, LiBETI, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, an ionic liquid-based lithium salt, Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , or a combination thereof, wherein X═F, Cl, I, or Br, R═ a hydrocarbon group, 0<x≤1, 1≤y≤4.

8 . The flame-resistant composite separator of claim 1 , wherein the second polymer further comprises a flame retardant additive dispersed therein.

9 . The flame-resistant composite separator of claim 8 , wherein the flame retardant additive is selected from a halogenated flame retardant, phosphorus-based flame retardant, melamine flame retardant, metal hydroxide flame retardant, silicon-based flame retardant, biomolecular flame retardant, or a combination thereof.

10 . The flame-resistant composite separator of claim 1 , further comprising a third layer wherein the second layer is sandwiched between the first layer and the third layer, and the third layer comprises a layer of inorganic solid electrolyte or a layer of polymer composite comprising 60%-99% by volume of inorganic material particles or fibers dispersed in or bonded by a third polymer and the third layer is the same as or different than the first layer in composition or structure.

11 . The flame-resistant composite separator of claim 1 , wherein the second polymer further comprises inorganic particles, glass fibers, ceramic fibers, and/or polymer fibers dispersed in or bonded by the second polymer and the polymer fibers are selected from the fiber group consisting essentially of polyacrylonitriles, polyolefins, polyamides, polyimides, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polymethyl pentene, polyphenylene sulfide, polyacetal, polyurethane, polypropylene terephthalate, polymethyl methacrylate, polystyrene, synthetic cellulosic polymers, rigid-rod polymers, ladder polymers, and blends, mixtures and copolymers including said polymeric materials.

12 . The flame-resistant composite separator of claim 1 , wherein the second layer further comprises a second liquid solvent that permeates into the second polymer.

13 . The flame-resistant composite separator of claim 12 , wherein the second liquid solvent is selected from the group con

Assignees

• Global Graphene Group Inc
• Honeycomb Battery Company

Inventors

• Jang Bor Z

Classifications

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• H01M10/0525

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

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title