Composite membrane, method of preparing the composite membrane, and lithium air battery including the composite membrane

Patent metadata

Field	Value
Publication number	US-2018040904-A1
Application number	US-201715646239-A
Country	US
Kind code	A1
Filing date	Jul 11, 2017
Priority date	Aug 2, 2016
Publication date	Feb 8, 2018
Grant date	—

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

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

3 . The composite membrane of claim 1 , wherein the plurality of gas blocking inorganic particles are arranged as a monolayer on the ion-conductive polymer layer.

4 . The composite membrane of claim 1 , wherein each gas blocking inorganic particle of the plurality of gas blocking inorganic particles includes a hydrophobic coating layer on a surface thereof.

5 . The composite membrane of claim 3 , wherein the hydrophobic coating layer comprises a condensation reaction product of at least one selected from compounds represented by Formula 1:

wherein, in Formula 1,
R 1 to R 3 are each independently selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroaryl group, a substituted or unsubstituted C2-C20 heteroaryloxy group, a substituted or unsubstituted C3-C20 heteroarylalkyl group, a substituted or unsubstituted C2-C20 heterocyclic group, and a halogen atom; and
R 4 is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, and a substituted or unsubstituted C6-C20 aryl group.

6 . The composite membrane of claim 5 , wherein the at least one selected from compounds represented by Formula 1 comprises at least one compound selected from isobutyltrimethoxysilane, octyltrimethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, n-octadecyltriethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, and (3-mercaptopropyl)trimethoxysilane.

7 . The composite membrane of claim 5 , wherein an amount of the condensation reaction product of the at least one selected from compounds represented by Formula 1 is from about 0.1 parts to about 30 parts by weight, based on 100 parts by weight of the plurality of gas blocking inorganic particles.

8 . The composite membrane of claim 1 , wherein an amount of the plurality of gas blocking inorganic particles 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 gas blocking inorganic particles in the composite membrane occupy about 70% or greater of a total area of the composite membrane.

9 . The composite membrane of claim 1 , wherein the plurality of gas blocking inorganic particles comprises at least one selected from a glassy active metal ionic conductor, an amorphous active metal ionic conductor, a ceramic active metal ionic conductor, and a glass-ceramic active metal ionic conductor.

10 . The composite membrane of claim 1 , wherein the plurality of gas blocking inorganic particles comprises at least one selected from 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 , 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 23 1and 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 , and 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.

11 . The composite membrane of claim 1 , wherein the ion-conductive polymer layer comprises at least one selected from 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, and ethoxylated (C1-C20 alkyl)phenol acrylate.

12 . The composite membrane of claim 1 , wherein the composite membrane further comprises at least one selected from an ionic liquid, a lithium salt, and a polymeric ionic liquid.

13 . The composite membrane of claim 11 , wherein the lithium salt comprises at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, Li(FSO 2 ) 2 N, LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) wherein x and y are natural numbers, LiF, LiBr, LiCl, LiOH, LiI, and LiB(C 2 O 4 ) 2 ,
wherein the ionic liquid comprises at least one selected from N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(3-trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and wherein the polymeric ionic liquid comprises at least one selected from poly(diallyldimethylammonium) trifluoromethanesulfonylimide, poly(1-methacryloyloxy propyl-3-methylimidazolium) bis(trifluoromethanesulfonesulfonyl imide), and poly(1-vinyl-3-ethylimidazolium) bis(trifluoromethanesulfonesulfonyl imide).

14 . The composite membrane of claim 1 , wherein the composite membrane is
a membrane comprisin

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Kim Hyunjin

Classifications

• C08J5/2231

  based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds · CPC title

• C08J2327/16

  Homopolymers or copolymers of vinylidene fluoride · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M8/0221

  Organic resins; Organic polymers · CPC title

• H01M8/0228 Primary

  in the form of layered or coated products · CPC title