Composite membrane including ion-conductive polymer layer and gas blocking inorganic particles, method of preparing the composite membrane, and lithium air battery including the composite membrane

Patent metadata

Field	Value
Publication number	US-11600828-B2
Application number	US-202016906151-A
Country	US
Kind code	B2
Filing date	Jun 19, 2020
Priority date	Aug 2, 2016
Publication date	Mar 7, 2023
Grant date	Mar 7, 2023

Abstract

A composite membrane includes an ion-conductive polymer layer; and a plurality of gas blocking inorganic particles non-continuously aligned on the ion-conductive polymer layer, wherein the composite membrane has a radius of curvature of about 10 millimeters or less.

First claim

What is claimed is:

1. A composite membrane comprising:
an ion-conductive polymer layer having a first surface and an opposite second surface;
a plurality of gas blocking inorganic particles non-continuously aligned as a single monolayer in a substantially horizontal direction and disposed on the first or the second surface of the ion-conductive polymer layer, or a plurality of gas blocking inorganic particles as a single monolayer within the ion-conductive polymer, wherein the plurality of the non-continuously aligned particles disposed on the first or the second surface, and the plurality of particles within the ion-conductive polymer, do not extend from the first surface to the opposite second surface of the ion-conductive polymer layer; and
wherein the composite membrane has a radius of curvature of about 10 millimeters or less.

2. The composite membrane of claim 1 , wherein the radius of curvature is about 2 millimeters to about 5 millimeters.

3. The composite membrane of claim 1 , wherein the composite membrane further comprises a porous layer.

4. The composite membrane of claim 1 , wherein the particles within the ion-conductive polymer layer do not contact the first and the opposite second surface of the ion-conductive polymer layer.

5. The composite membrane of claim 1 , wherein the plurality of aligned particles, or the plurality of particles within the ion-conductive polymer, have an average particle diameter of about 1 micrometer to about 300 micrometers, and the plurality of aligned particles disposed on the composite membrane occupy about 70% or greater of a total area of the composite membrane.

6. The composite membrane of claim 1 , wherein the plurality of aligned particles disposed on the first or the second surface of the ion-conductive polymer layer, or the plurality of particles within the ion-conductive polymer layer, comprise at least one of a glassy active metal ionic conductor, an amorphous active metal ionic conductor, a ceramic active metal ionic conductor, or a glass-ceramic active metal ionic conductor.

7. The composite membrane of claim 1 , wherein the total amount of the plurality of aligned particles, or the plurality of particles within the ion-conductive polymer, is from about 10 parts to about 90 parts by weight, based on 100 parts by weight of a total weight of the composite membrane, and
wherein the plurality of aligned particles disposed on the surface of the composite membrane occupy about 70% or greater of a total area of the surface of the composite membrane.

8. The composite membrane of claim 1 , wherein the plurality of aligned particles, or the plurality of particles within the ion-conductive polymer, comprise at least one of Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2 and 0≤y<3, BaTiO 3 , Pb(Zr r Ti 1−r )O 3 wherein 0≤r≤1, Pb 1−x La x Zr 1−y Ti y O 3 wherein 0≤x<1 and 0≤y<1, Pb(Mg 3 Nb 2/3 )O 3 —PbTiO 3 (PMN-PT), HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , SiC, Li 3 PO 4 , Li x Ti y (PO 4 ) 3 , wherein 0<x<2 and 0<y<3, Li x Al y Ti z (PO 4 ) 3 , wherein 0<x<2 and 0<y<1 and 0<z<3, Li 1+x+y (Al q Ga 1−q ) x (Ti h Ge 1−h ) 2−x Si y P 3−y O 12 wherein 0≤q≤1 and 0≤h≤1 and 0≤x≤1 and 0≤y≤1, Li x La y TiO 3 wherein 0<x<2 and 0<y<3, Li x Ge y P z S w wherein 0<x<4 and 0<y<1 and 0<z<1 and 0<w<5, Li x N y wherein 0<x<4 and 0<y<2, Li x Si y S z wherein 0≤x<3 and 0<y<2 and 0<z<4, Li x P y S z wherein 0≤x<3 and 0<y<3 and 0<z<7, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , or Li 3+x La 3 M 2 O 12 wherein M is Te, Nb, or Zr, and x is an integer from 1 to 10.

9. The composite membrane of claim 1 , wherein the ion-conductive polymer layer comprises at least one of polyethylene oxide, polyvinylidene fluoride, polyvinylpyrrolidone, polyvinyl alcohol, poly 2-vinylpyridine, polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, a perfluoroalkoxy copolymer, a fluorinated cyclic ether, polyethylene oxide diacrylate, polyethylene oxide dimethacrylate, polypropylene oxide diacrylate, polypropylene oxide dimethacrylate, polymethyleneoxide diacrylate, polymethyleneoxide dimethacrylate, poly(C1-C4 alkyl)diol diacrylate, poly(C1-C4 alkyl)diol dimethacrylate, polydivinylbenzene, polyether, polycarbonate, polyamide, polyester, polyvinyl chloride, polyimide, polycarboxylic acid, polysulfonic acid, polysulfone, polystyrene, polyethylene, polypropylene, poly(p-phenylene), polyacetylene, poly(p-phenylene vinylene), polyaniline, polypyrrole, polythiophene, polyacene, poly(naphthalene-2,6-diyl), polypropylene oxide, a vinylidene fluoride-hexafluoropropylene copolymer, poly(vinyl acetate), poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate), poly(methyl methacrylate-co-ethyl acrylate), polyacrylonitrile, poly(vinyl chloride-co-vinyl acetate), poly(1-vinyl pyrrolidone-co-vinyl acetate), polyacrylate, polymethacrylate, polyurethane, polyvinyl ether, an acrylonitrile-butadiene rubber, a styrene-butadiene rubber, an acrylonitrile-butadiene-styrene rubber, a sulfonated styrene/ethylene-butylene triblock copolymer, epoxide resin, and a polymer obtained from at least one acrylate monomer selected from ethoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, a C10-C30 alkyl acrylate, ethoxylated aliphatic urethane acrylate, or ethoxylated (C1-C20 alkyl)phenol acrylate.

10. The composite membrane of claim 1 , wherein the ion-conductive polymer comprises polyvinylidene fluoride, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, and lithium bis(trifluoromethylsulfonyl)imide, and the plurality of aligned particles, or the plurality of particles within the ion-conductive polymer, comprises SiO 2 , and Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2 and 0≤y<3; or
the composite membrane further comprises a porous layer, the ion conductive layer comprises poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide, N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and plurality of aligned particles, or the plurality of particles within the ion-conductive polymer, comprises SiO 2 , and Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2 and 0≤y<3, wherein the ion-conductive polymer and the plurality of aligned particles are disposed on the porous layer; or
the ion-conducting polymer comprises polyvinylidene fluoride, N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, and lithium bis(trifluoromethylsulfonyl)imide, and the plurality of aligned particles, or the plurality of particles within the ion-conductive polymer, comprises SiO 2 , and Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 , wherein 0<x<2, 0≤y<3, and at least a portion of the aligned particles, and the plurality of particles within the ion-conductive polymer, include a hydrophobic coating layer on a surface; or
the composite membrane further comprises a porous layer; the ion-conductive layer comprises poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide, N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, and lithium bis(trifluoromethanesulfonyl)imide, and the plurality of aligned particles, and the plurality of particles within the ion-conductive polymer, comprise SiO 2 , and Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 , wherein 0<x<2 and 0≤y<3, and at least a portion of the aligned particles, or the plurality of particles within the ion-conductive polymer, include a hydrophobic coating layer on a surface on the porous layer.

11. The composite membrane of claim 1 , further comprisi

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Kim Hyunjin

Classifications

• H01M50/457

  comprising three or more layers · CPC title

• H01M8/0221

  Organic resins; Organic polymers · CPC title

• H01M50/434

  Ceramics · CPC title

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• H01M12/08 Primary

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title