Polymer composite separator for a lithium secondary battery and manufacturing method

Patent metadata

Field	Value
Publication number	US-12519181-B2
Application number	US-202117324747-A
Country	US
Kind code	B2
Filing date	May 19, 2021
Priority date	May 19, 2021
Publication date	Jan 6, 2026
Grant date	Jan 6, 2026

Abstract

A flame-resistant polymer composite separator for use in a lithium battery, wherein the polymer composite separator comprises (a) a binder or matrix polymer; (b) 0.1% to 50% by weight of a lithium salt dispersed in the polymer; and (c) from 30% to 99% by weight of particles or fibers of an inorganic material or polymer fibers that are dispersed in or bonded by the polymer, wherein the polymer is a polymerization or crosslinking product of a reactive additive comprising (i) a first liquid solvent that is polymerizable, (ii) an initiator or crosslinking agent, and (iii) the lithium salt and wherein the polymer composite separator has a thickness from 50 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

I claim:

1 . A flame-resistant polymer composite separator for use in a lithium battery, wherein the polymer composite separator comprises (a) a binder or matrix polymer; (b) 0.1% to 50% by weight of a lithium salt dispersed in the polymer; and (c) from 30% to 99% by weight of particles or fibers of an inorganic material or polymer fibers that are dispersed in or bonded by the polymer, wherein the polymer is a polymerization or crosslinking product of a reactive additive comprising (i) a first liquid solvent that is polymerizable, (ii) an initiator or crosslinking agent, and (iii) the lithium salt and wherein the polymer composite separator has a thickness from 50 nm to 100 μm and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature;
wherein said inorganic material particles are non-uniformly distributed in the polymer matrix in such a manner that a concentration of the inorganic material particles in one region of the polymer matrix is greater than a concentration of the inorganic material particles in another region.

2 . The polymer composite separator of claim 1 , wherein the first liquid solvent is 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 ethylene sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), fluorinated ethers, fluorinated esters, sulfides, dinitriles, acrylonitrile (AN), sulfates, siloxanes, silanes, N-methylacetamide, acrylates, ethylene glycols, tetrahydrofuran, combinations thereof, and combinations thereof with phosphates, phosphonates, phosphinates, phosphines, phosphine oxides, phosphonic acids, phosphorous acid, phosphites, phosphoric acids, phosphazene compounds, ionic liquids, derivatives thereof, and mixtures thereof.

3 . The polymer composite separator of claim 1 , wherein said inorganic material comprises particles of an inorganic solid electrolyte material selected from an oxide, sulfide, hydride, halide, borate, phosphate, lithium phosphorus oxynitride (LiPON), Garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof.

4 . The polymer composite separator of claim 1 , wherein said 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.

5 . The polymer composite separator of claim 1 , wherein said 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 ), LiN(CF 3 SO 2 ) 2 , lithium bis(oxalato)borate (LiBOB), 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(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, x=0-1, y=1-4).

6 . The polymer composite separator of claim 1 , further comprising a second liquid solvent that permeates into the separator wherein the second liquid solvent has a higher flash point or lower vapor pressure as compared to the first liquid solvent.

7 . The polymer composite separator of claim 6 , wherein the second liquid solvent is selected from the group consisting of fluoroethylene carbonate, vinyl sulfite, vinyl ethylene sulfite, 1,3-propyl sultone, 1,3,5-trioxane (TXE), 1,3-acrylic-sultones, methyl ethylene sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), fluorinated ethers, fluorinated esters, fluorinated vinyl esters, fluorinated vinyl ethers, 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, derivatives thereof, and mixtures thereof.

8 . The polymer composite separator of claim 6 , wherein the first or the second liquid solvent comprises a sulfone or sulfide selected from vinyl sulfone, allyl sulfone, alkyl vinyl sulfone, aryl vinyl sulfone, vinyl sulfide, TrMS, MTrMS, TMS, EMS, MMES, EMES, EMEES, or a combination thereof:

9 . The polymer composite separator of claim 8 , wherein the vinyl sulfone or sulfide is selected from ethyl vinyl sulfide, allyl methyl sulfide, phenyl vinyl sulfide, phenyl vinyl sulfoxide, allyl phenyl sulfone, allyl methyl sulfone, divinyl sulfone, or a combination thereof.

10 . The polymer composite separator of claim 6 , wherein the first or the second liquid solvent comprises a nitrile, a dinitrile selected from AND, GLN, or SEN, or a combination thereof:

11 . The polymer composite separator of claim 6 , wherein the first or the second liquid solvent comprises a phosphate selected from allyl-type, vinyl-type, styrenic-type and (meth)acrylic-type monomers bearing a phosphonate moiety.

12 . The polymer composite separator of claim 6 , wherein the first liquid solvent or the second liquid solvent is selected from the group consisting of 2-alkoxy (or phenoxy)-2-oxo-1,3,2-dioxaphospholane (I) and 2-alkoxy (or phenoxy)-2-oxo-1,3,2-dioxaphosphorinane (II), derivatives thereof, and combinations thereof:

13 . The polymer composite separator of claim 6 , wherein the first liquid solvent or the second liquid solvent comprises phosphate, phosphonate, phosphonic acid, or phosphite selected from TMP, TEP, TFP, TDP, DPOF, DMMP, DMMEMP, tris(trimethylsilyl)phosphite (TTSPi), alkyl phosphate, triallyl phosphate (TAP), a combination thereof, wherein TMP, TEP, TFP, TDP, DPOF, DMMP, and DMMEMP have the following chemical formulae:

wherein an end group thereof or a functional group attached thereof comprises unsaturation for polymerization.

14 . The polymer composite separator of claim 6 , wherein the first liquid solvent or the second liquid solvent comprises phosphonate vinyl monomer selected from the group consisting of phosphonate bearing allyl monomers, phosphonate bearing vinyl monomers, phosphonate bearing styrenic monomers, phosphonate bearing (meth)acrylic monomers, vinylphosphonic acids, and combinations thereof.

15 . The polymer composite separator of claim 14 , wherein the phosphonate bearing allyl monomer is selected from a Dialkyl allylphosphonate monomer or Dioxaphosphorinane allyl monomer; the phosphonate bearing vinyl monomers is selected from a Dialkyl vinyl phosphonate monomer or Dialkyl vinyl ether phosphonate mono

Assignees

• Global Graphene Group Inc
• Honeycomb Battery Company

Inventors

• Jang Bor Z

Classifications

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0525

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

• H01M4/622

  being polymers · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title