Composite membrane, preparation method thereof, anode structure including the composite membrane, and lithium secondary battery including the anode structure

Patent metadata

Field	Value
Publication number	US-2016181585-A1
Application number	US-201514645544-A
Country	US
Kind code	A1
Filing date	Mar 12, 2015
Priority date	Dec 19, 2014
Publication date	Jun 23, 2016
Grant date	—

Abstract

A composite membrane includes: an organic layer having a plurality of through holes; and ion conductive inorganic particles disposed in the through holes, wherein a hydrophobic coating layer is disposed on a surface of the ion conductive inorganic particles.

First claim

What is claimed is:

1 . A composite membrane comprising:
an organic layer having a plurality of through holes; and ion conductive inorganic particles disposed in the through holes, wherein a hydrophobic coating layer is disposed on a surface of the ion conductive inorganic particles.

2 . The composite membrane of claim 1 , wherein the surface of the ion conductive inorganic particles on which the hydrophobic coating layer is disposed faces a surface of the organic layer.

3 . The composite membrane of claim 1 , wherein the composite membrane comprises a sea-island structure in which the ion conductive inorganic particles are discontinuously disposed in the organic layer.

4 . The composite membrane of claim 1 , wherein a cross section of the composite membrane comprises a structure in which the organic layer and the ion conductive inorganic particles are alternately aligned.

5 . The composite membrane of claim 1 , wherein the ion conductive inorganic particles disposed in the organic layer are disposed in the form of a monolayer.

6 . The composite membrane of claim 1 , wherein the organic layer comprises at least one selected from a homopolymer, a block copolymer, and a random copolymer.

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

wherein, in Formula 1, R 1 to R 3 each independently represent a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 20 arylalkyl group, a substituted or unsubstituted C 6 -C 20 aryloxy group, a substituted or unsubstituted C 2 -C 20 heteroaryl group, a substituted or unsubstituted C 2 -C 20 heteroaryloxy group, a substituted or unsubstituted C 3 -C 20 heteroarylalkyl group, a substituted or unsubstituted C 2 -C 20 heterocyclic group, or a halogen atom, and
R 4 represents hydrogen, a substituted or unsubstituted C 1 -C 20 alkyl group, or a substituted or unsubstituted C 6 -C 20 aryl group.

8 . The composite membrane of claim 7 , wherein the compound represented by Formula 1 comprises at least one selected from isobutyltrimethoxysilane, octyltrimethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, n-octadecyltriethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, and (3-mercaptopropyl)trimethoxysilane.

9 . The composite membrane of claim 7 , wherein an amount of the at least one condensation reaction product selected from compounds represented by Formula 1 is in a range of about 0.1 part by weight to about 30 parts by weight, based on 100 parts by weight of the ion conductive inorganic particles.

10 . The composite membrane of claim 1 , wherein the ion conductive inorganic particles are single-body particles without grain boundaries.

11 . The composite membrane of claim 1 , wherein an amount of the ion conductive inorganic particles is in a range of about 10 parts by weight to about 90 parts by weight, based on 100 parts by weight of a total weight of the composite membrane.

12 . The composite membrane of claim 1 , wherein the ion conductive inorganic particles comprise at least one selected from a glassy active metal ion conductor, an amorphous active metal ion conductor, a ceramic active metal ion conductor, and a glass-ceramic active metal ion conductor.

13 . The composite membrane of claim 1 , wherein the ion conductive inorganic particles comprise 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, 0≦y<3, BaTiO 3 , Pb(Zr x Ti 1-x )O 3 wherein 0≦x≦2, Pb 1-x La x Zr 1-y Ti y O 3 wherein in 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, 0<y<1, and 0<z<3, Li 1+x+y (Al q Ga 1-q ) x (Ti r Ge 1-r ) 2-x Si y P 3-y O 12 wherein 0≦x≦1, 0≦y≦1, 0≦q≦1, and 0≦r≦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, 0<y<1, 0<z<1, and 0<w<5, Li x N y wherein 0<x<4 and 0<y<2, SiS 2 (Li x Si y S z ) wherein 0<x<3, 0<y<2, and 0<z<4, a P 2 S 5 (Li x P y S z ) glass wherein 0<x<3, 0<y<3, 0<z<7, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 ceramic, a garnet ceramic, and Li 3+x La 3 M 2 O 12 where M is at least one selected from Te, Nb, and Zr.

14 . The composite membrane of claim 1 , wherein the ion conductive inorganic particles comprise Li 1.4 Ti 1.6 Al 0.4 P 3 O 12 or a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 ceramic.

15 . The composite membrane of claim 1 , wherein the organic layer comprises a polymer having a gas permeability of about 10 −3 cm 3 /m 2 day to about 1,000 cm 3 /m 2 day, based on a permeability of at least one selected from oxygen, carbon dioxide, and water vapor.

16 . The composite membrane of claim 1 , wherein the organic layer comprises a polymerization product of a polymerizable non-aqueous floating compound, or a polymerization product of a polymerizable non-aqueous floating compound and a polythiol having 3 or 4 thiol groups.

17 . The composite membrane of claim 1 , wherein the organic layer comprises:
(i) a polymerization product of at least one multifunctional monomer selected from a multifunctional acryl monomers and a multifunctional vinyl monomers, or (ii) a polymerization product of a polythiol having 3 or 4 thiol groups and at least one multifunctional monomer selected from a multifunctional acryl monomer and a multifunctional vinyl monomer.

18 . The composite membrane of claim 17 , wherein the multifunctional monomer comprises at least one selected from diurethane dimethacrylate, trimethylolpropane triacrylate, diurethane diacrylate, trimethylolpropane trimethacrylate, neopentyl glycol diacrylate, 3′-acryloxy-2′,2′-dimethylpropyl 3-acryloxy-2,2-dimethylpropionate, bisphenol A diacrylate, and 1,3,5,-triallyl-1,3,5-triazine-2,4,6-trione.

19 . The composite membrane of claim 17 , wherein the polythiol comprises at least one selected from pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, pentaerythritol tetrakis(2-mercaptoacetate), and trimethylolpropane tris(2-mercaptoacetate).

20 . The composite membrane of claim 1 , wherein an average particle diameter of the ion conductive inorganic particles is in a range of about 1 micrometer to about 300 micrometers.

21 . The composite membrane of claim 1 , wherein a gas permeability of the composite membrane is in a range of about 10 −3 cm 3 /m 2 day to about 1,000 cm 3 /m 2 day.

22 . The composite membrane of claim 1 , wherein an exposed area of the ion conductive inorganic particles is in a range of about 30 percent to about 80 percent, based on a total area of the composite membrane.

23 . The composite membrane of claim 1 , wherein a thickness of the hydrophobic coating layer is in a range of about 1 n

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Im Dongmin
• Kwon Soonchul
• Kim Sungcheol
• Kim Taeyoung

Classifications

• H01M2220/20

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

• H01M10/052 Primary

  Li-accumulators · CPC title

• H01M8/0247

  characterised by the form (characterised by a channel configuration H01M8/0258) · 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

• H01M50/497

  Ionic conductivity · CPC title