WO2022250507A1 - 전기화학소자용 세퍼레이터 및 이를 구비한 전기화학소자 - Google Patents
전기화학소자용 세퍼레이터 및 이를 구비한 전기화학소자 Download PDFInfo
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- WO2022250507A1 WO2022250507A1 PCT/KR2022/007613 KR2022007613W WO2022250507A1 WO 2022250507 A1 WO2022250507 A1 WO 2022250507A1 KR 2022007613 W KR2022007613 W KR 2022007613W WO 2022250507 A1 WO2022250507 A1 WO 2022250507A1
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- Prior art keywords
- poly
- separator
- inorganic particles
- electrochemical device
- inorganic
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- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
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- 238000002847 impedance measurement Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical group [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a separator for an electrochemical device and an electrochemical device having the same.
- a lithium secondary battery is a battery that can best satisfy these demands, and research on this is being actively conducted.
- These lithium secondary batteries are composed of a positive electrode, a negative electrode, an electrolyte solution, and a separator.
- the separator has high ionic conductivity to increase the permeability of lithium ions based on insulation and high porosity to electrically insulate the positive electrode and the negative electrode. is required
- a polyolefin separator to which a polyolefin-based porous substrate is applied is widely used.
- polyolefin separators have safety problems such as internal short circuits by exhibiting extreme thermal contraction behavior at high temperatures due to material characteristics and manufacturing process characteristics.
- the problem to be solved by the present invention is to provide a separator for an electrochemical device capable of improving safety at high temperatures and ensuring assembly fairness, and an electrochemical device having the same.
- a separator for an electrochemical device of the following embodiments is provided.
- a first organic-inorganic composite porous layer located on one surface of the porous polymer substrate and containing a first inorganic particle and a first binder polymer;
- porous polymer substrate It is located on the other surface of the porous polymer substrate and includes a second organic-inorganic composite porous layer including the first inorganic particles, the second inorganic particles, and the second binder polymer,
- the average particle diameter of the first inorganic particles is 1 nm to 100 nm
- a separator for an electrochemical device characterized in that the average particle diameter of the second inorganic particles is larger than the average particle diameter of the first inorganic particles is provided.
- the average particle diameter of the second inorganic particles may be 1.01 to 50 times greater than the average particle diameter of the first inorganic particles.
- the second inorganic particles may have an average particle diameter of 150 nm to 800 nm.
- the weight ratio of the first inorganic particles to the second inorganic particles in the second organic-inorganic composite porous layer may be 40:60 to 92:8.
- the first inorganic particles may include inorganic particles of a fumed type.
- the first inorganic particle may include fumed alumina, fumed silica, fumed titanium dioxide, or two or more of them.
- the second inorganic particles are BaTiO 3 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) , Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), Hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, Mg(OH) 2 , NiO, CaO , ZnO, ZrO 2 , SiO 2 , Y 2 O 3 , Al 2 O 3 , AlOOH, Al(OH) 3 , SiC, TiO 2 , lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y ( PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), lithium aluminum titanium phosphate (Li x Al y Ti z (
- An arithmetic average roughness of the surface of the second organic-inorganic composite porous layer of the separator for an electrochemical device may be 400 nm to 1000 nm.
- a heat shrinkage rate may be 10% or less in a machine direction (MD) and a transverse direction (TD), respectively.
- the first binder polymer is poly(vinylidene fluoride-hexafluoropropylene) (poly(vinylidene fluoride-co-hexafluoropropylene)), poly(vinylidene fluoride-chlorotrifluoroethylene) (poly(vinylidene fluoride-co -chlorotrifluoroethylene)), poly(vinylidene fluoride-co-tetrafluoroethylene)), poly(vinylidene fluoride-co-trichloroethylene) ), acrylic copolymer, styrene-butadiene copolymer, poly(acrylic acid), poly(methylmethacrylate), poly(butylacrylate) (poly(butylacrylate)) , poly(acrylonitrile), poly(vinylpyrrolidone), poly(vinylalcohol), poly(vinylacetate) ), ethylene vinyl acetate copolymer (poly(ethylene-co-
- the second binder polymer is poly(vinylidene fluoride-hexafluoropropylene) (poly(vinylidene fluoride-co-hexafluoropropylene)), poly(vinylidene fluoride-chlorotrifluoroethylene) (poly(vinylidene fluoride-co -chlorotrifluoroethylene)), poly(vinylidene fluoride-co-tetrafluoroethylene)), poly(vinylidene fluoride-co-trichloroethylene) ), acrylic copolymer, styrene-butadiene copolymer, poly(acrylic acid), poly(methylmethacrylate), poly(butylacrylate) (poly(butylacrylate)) , poly(acrylonitrile), poly(vinylpyrrolidone), poly(vinylalcohol), poly(vinylacetate) ), ethylene vinyl acetate copolymer (poly(ethylene-co-
- an electrochemical device of the following embodiments is provided.
- An electrochemical device characterized in that the separator is the separator for an electrochemical device according to any one of the first to eleventh embodiments is provided.
- the electrochemical device may be a cylindrical lithium secondary battery.
- a separator for an electrochemical device includes first inorganic particles having an average particle diameter of 1 nm to 100 nm on one side of a porous polymer substrate, thereby improving high-temperature safety, and on the other side of the porous polymer substrate. Assembling fairness may be secured by including the organic-inorganic composite porous layer including the second inorganic particles having an average particle diameter greater than the average particle diameter of the first inorganic particles together with the first inorganic particles.
- the heat shrinkage rate of the separator after being left at 180 ° C. for 1 hour is 10% or less in the machine direction (MD, Machine Direction) and the transverse direction (TD, Transverse Direction), respectively.
- the arithmetic mean roughness of the surface of the second organic-inorganic composite porous layer of the separator for an electrochemical device according to an embodiment of the present invention may be 400 nm to 1000 nm.
- FIG. 1 is a diagram schematically showing a separator for an electrochemical device according to an embodiment of the present invention.
- FIG. 2 is a roughness curve recorded by enlarging a cut surface of a surface of a second organic-inorganic composite porous layer of a separator according to an embodiment of the present invention.
- Example 3 is a diagram showing the surface roughness of the second organic-inorganic composite porous layer of the separator for an electrochemical device manufactured in Example 1;
- Example 4 is a diagram showing the surface roughness of the second organic-inorganic composite porous layer of the separator for an electrochemical device manufactured in Example 2;
- Example 5 is a diagram showing the surface roughness of the second organic-inorganic composite porous layer of the separator for an electrochemical device manufactured in Example 3;
- Example 6 is a diagram showing the surface roughness of the second organic-inorganic composite porous layer of the separator for an electrochemical device manufactured in Example 4;
- a separator for an electrochemical device according to an aspect of the present invention
- a first organic-inorganic composite porous layer located on one surface of the porous polymer substrate and containing a first inorganic particle and a first binder polymer;
- porous polymer substrate It is located on the other surface of the porous polymer substrate and includes a second organic-inorganic composite porous layer including the first inorganic particles, the second inorganic particles, and the second binder polymer,
- the average particle diameter of the first inorganic particles is 1 nm to 100 nm
- the average particle diameter of the second inorganic particles is larger than the average particle diameter of the first inorganic particles.
- FIG. 1 is a diagram schematically showing a separator for an electrochemical device according to an embodiment of the present invention.
- a separator 1 for an electrochemical device includes a porous polymer substrate 10 .
- the porous polymer substrate 10 any material that can be commonly used as a material for a separator for a secondary battery may be used without particular limitation.
- the porous polymer substrate 10 is a thin film containing a polymer material, and non-limiting examples of the polymer material include polyolefin resin, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polycarbonate, and polyimide. , polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, and polymer resins such as polyethylene naphthalene.
- the porous polymer substrate 10 may be a non-woven fabric or a porous polymer film formed of the above-described polymer material, or a laminate of two or more of them.
- the porous polymer substrate 10 may be any one of the following a) to e).
- a non-woven fabric web manufactured by integrating filaments obtained by melting/spinning a polymer resin
- a multi-layer porous membrane comprising at least two of a) to d).
- the thickness of the porous polymer substrate 10 is not particularly limited, but may be 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 30 ⁇ m.
- the thickness of the porous polymer substrate 10 is within the aforementioned range, it is possible to secure energy density while preventing a problem in which the separator may be easily damaged during use of the battery.
- the average pore size and porosity of the porous polymer substrate 10 are not particularly limited as long as they are suitable for use in electrochemical devices, and the average pore size may be 0.01 ⁇ m to 50 ⁇ m, or 0.1 ⁇ m to 20 ⁇ m, and the pores The degree may be 5% to 95%.
- the pore size and porosity are within the aforementioned ranges, it may be easy to prevent the porous polymer substrate 10 from acting as resistance, and it may be easy to maintain mechanical properties of the porous polymer substrate 10 .
- the "average pore size” means the arithmetic average value of pore sizes.
- the porosity and pore size of the porous polymer substrate 10 can be measured using a scanning electron microscope (SEM) image, a mercury porosimeter, a capillary flow porosimeter, or a pore distribution analyzer (Porosimetry analyzer; It can be measured by the BET 6-point method by the nitrogen gas adsorption flow method using Bell Japan Inc., Belsorp-II mini).
- the separator 1 for an electrochemical device includes a first organic/inorganic composite porous layer 20 on one surface of the porous polymer substrate 10 .
- the first organic-inorganic composite porous layer 20 includes first inorganic particles 40 and a first binder polymer.
- the first organic-inorganic composite porous layer 20 attaches the first inorganic particles 40 and the first inorganic particles 40 to each other so as to maintain a state in which they are bound to each other (ie, the first binder polymer is the first binder polymer). It includes a first binder polymer that connects and fixes between the inorganic particles 40, and the first inorganic particles 40 and the porous polymer substrate 10 can be maintained in a bound state by the first binder polymer. .
- the first inorganic particles 40 have an average particle diameter of 1 nm to 100 nm. When the first inorganic particles 40 have an average particle diameter within the above-described range, inorganic particles per unit area of the separator may be more densely provided, thereby improving thermal safety of the separator.
- the first organic-inorganic composite porous layer 20 includes first inorganic particles 40 having an average particle diameter of 1 nm to 100 nm to prevent the porous polymer substrate 10 from exhibiting extreme heat shrinkage behavior at high temperatures, thereby forming a separator. safety can be improved.
- the average particle diameter of the first inorganic particles 40 may be 20 nm to 100 nm, 20 nm to 50 nm, or 20 nm to 30 nm.
- the thermal shrinkage rate of the separator at a high temperature may be further improved. For example, after being left at 180 ° C. for 1 hour, the heat shrinkage rate of the separator is 10% or less, or 5% or less, or 0% to 5% in the machine direction (MD, Machine Direction) and the transverse direction (TD, Transverse Direction), respectively. , or 0% to 2%.
- the 'Machine Direction' refers to the direction in which the separator is continuously produced or the direction in which the manufactured separator is wound, and refers to the long length direction of the separator
- the 'Transverse Direction' denotes a transverse direction of the machine direction, that is, a direction perpendicular to the traveling direction when the separator is continuously produced, or a direction perpendicular to the long length direction of the separator, which is a direction in which the manufactured separator is wound.
- the average particle diameter of inorganic particles means the D 50 particle diameter
- D 50 particle diameter means the particle diameter at the 50% point of the cumulative distribution of the number of particles according to the particle diameter.
- the particle size can be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in a dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac S3500) to measure the difference in diffraction pattern according to the particle size when the particles pass through the laser beam to distribute the particle size. yields The D50 particle size can be measured by calculating the particle size at the point where it becomes 50% of the cumulative distribution of the number of particles according to the particle size in the measuring device.
- a laser diffraction particle size measuring device e.g., Microtrac S3500
- the first inorganic particles 40 may include inorganic particles of a fumed type.
- the fumed type inorganic particles are primary particles formed by hydrolysis in a flame of 1,000 °C or higher connected to each other due to collision to form secondary particles, and these secondary particles are three-dimensional aggregates (aggregates, agglomerates) It refers to the inorganic particles formed by
- the average particle diameter of the first inorganic particles 40 is 1 nm to 100 nm, or 20 nm to 50 nm, or 1 nm to 15 nm, Or 15 nm to 100 nm, or 15 nm to 50 nm, or 15 nm to 20 nm may be more convenient.
- the first inorganic particles 40 may include fumed alumina, fumed silica, fumed titanium dioxide, or two or more of them.
- the thermal contraction rate of the separator measured after being left at 180 ° C. for 1 hour is in the machine direction (MD, Machine Direction) and the right angle direction (TD, Transverse Direction ) to 5% or less, or 0% to 5% or less, or 0% to 2% or less.
- the first binder polymer may be a binder polymer commonly used in forming the organic-inorganic composite porous layer.
- the first binder polymer may have a glass transition temperature (Tg) of -200 to 200 °C. When the glass transition temperature of the first binder polymer satisfies the aforementioned range, mechanical properties such as flexibility and elasticity of the finally formed first organic-inorganic composite porous layer 20 may be improved.
- the first binder polymer may have ion conduction ability. When the first binder polymer has ion conductivity, battery performance can be further improved.
- the first binder polymer is poly (vinylidene fluoride-hexafluoropropylene) (poly (vinylidene fluoride-co-hexafluoropropylene)), poly (vinylidene fluoride-chlorotrifluoroethylene) ) (poly(vinylidene fluoride-co-chlorotrifluoroethylene)), poly(vinylidene fluoride-co-tetrafluoroethylene) (poly(vinylidene fluoride-co-tetrafluoroethylene)), poly(vinylidene fluoride-trichloroethylene) (poly (vinylidene fluoride-co-trichloroethylene)), acrylic copolymer, styrene-butadiene copolymer, poly(acrylic acid), poly(methylmethacrylate), poly(butyl acrylate) (poly(butylacrylate)), poly(acrylonitrile
- the acrylic copolymer is ethyl acrylate-acrylic acid-N,N-dimethylacrylamide copolymer, ethyl acrylate-acrylic acid-2-(dimethylamino)ethyl acrylate copolymer, ethyl acrylate-acrylic acid-N,N-di ethyl acrylamide copolymer, ethyl acrylate-acrylic acid-2-(diethylamino)ethyl acrylate copolymer, or two or more thereof, but is not limited thereto.
- the weight ratio of the first inorganic particles 40 and the first binder polymer is determined in consideration of the thickness, pore size, and porosity of the first organic-inorganic composite porous layer 20, but 50 :50 to 99.9:0.1, or 95:5 to 99.9:0.1.
- the weight ratio of the first inorganic particles 40 and the first binder polymer is in the above-described range, an empty space formed between the first inorganic particles 40 is sufficiently secured to form the first organic-inorganic composite porous layer 20 It may be easy to secure the pore size and porosity of In addition, it may be easy to secure adhesion between the first inorganic particles 40 and between the first inorganic particles 40 and the porous polymer substrate 10 .
- the first organic-inorganic composite porous layer 20 may further include an additive such as a dispersing agent and/or a thickening agent.
- the additive is citric acid, hydroxy ethyl cellulose (HEC), hydroxy propyl cellulose (HPC), ethylhydroxy ethyl cellulose (ethylhydroxy ethyl cellulose, EHEC), methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxyalkyl methyl cellulose, cyanoethylene polyvinyl alcohol , or two or more of these may be included.
- the first organic-inorganic composite porous layer 20 is bound to each other by the first binder polymer in a state in which the first inorganic particles 40 are charged and in contact with each other, thereby causing the first Interstitial volumes may be formed between 1 inorganic particles 40, and the interstitial volumes between the first inorganic particles 40 may be empty spaces to form pores. have.
- the average pore size of the first organic-inorganic composite porous layer 20 may be 0.001 ⁇ m to 10 ⁇ m.
- the average pore size of the first organic-inorganic composite porous layer 20 may be measured by capillary flow porometry.
- the capillary flow pore diameter measurement method is a method in which the diameter of the smallest pore in the thickness direction is measured.
- the first organic-inorganic composite porous layer 20 is separated from the porous polymer substrate 10 It should be measured in a state where the separated first organic-inorganic composite porous layer 20 is wrapped in a non-woven fabric capable of supporting it, and at this time, the pore size of the non-woven fabric should be much larger than the pore size of the first organic-inorganic composite porous layer 20. do.
- the porosity of the first organic-inorganic composite porous layer 20 is 5% to 95%, or 10% to 95%, or 20% to 90%, or 30% may be 80%.
- the porosity is calculated as the weight and density of each component of the first organic-inorganic composite porous layer 20 in the volume calculated in terms of the thickness, width, and length of the first organic-inorganic composite porous layer 20. It corresponds to the value obtained by subtracting the volume.
- the porosity of the first organic-inorganic composite porous layer 20 can be measured using a scanning electron microscope (SEM) image, a mercury porosimeter, a capillary flow porometer, or a porosimetry analyzer. ; Bell Japan Inc, Belsorp-II mini) can be measured by the BET 6-point method by the nitrogen gas adsorption flow method.
- the thickness of the first organic-inorganic composite porous layer 20 may be 1.5 ⁇ m to 5.0 ⁇ m on one side of the porous polymer substrate 10 .
- the cell strength of the battery may be easily increased while having excellent adhesion to the electrode.
- the separator 1 for an electrochemical device includes a second organic/inorganic composite porous layer 30 on the other surface of the porous polymer substrate 10 .
- the second organic-inorganic composite porous layer 30 includes the first inorganic particles 40, the second inorganic particles 50, and a second binder polymer.
- the second organic-inorganic composite porous layer 30 includes the first inorganic particles 40, the second inorganic particles 50, and the first inorganic particles 40 and the second inorganic particles 50. Attach them to each other so that they can remain bound to each other (that is, the second binder polymer is between the first inorganic particles 40, between the second inorganic particles 50, and between the first inorganic particles 40). 2 It includes a second binder polymer that connects and fixes between the inorganic particles 50, and the first inorganic particles 40 and the second inorganic particles 50 and the porous polymer substrate 10 are formed by the second binder polymer. ) can remain bound.
- the organic-inorganic composite porous layer containing only inorganic particles having an average particle diameter of 1 nm to 100 nm is included on both sides of the porous polymer substrate, the safety of the separator at high temperatures is improved, but the roughness and / or frictional force with the winding core during assembly is improved. There was a problem that fairness was not secured due to differences in For example, creases in the separator during battery assembly. There was a problem with meandering and the like.
- the inventors of the present invention have an organic-inorganic composite porous layer containing first inorganic particles having an average particle diameter of 1 nm to 100 nm on one side of a porous polymer substrate, and on the other side, together with the first inorganic particles, an average of more than the first inorganic particles.
- the present invention was completed by finding that, when the organic-inorganic composite porous layer containing the second inorganic particles having a large particle diameter is located, the slip phenomenon during assembly or the tail loss problem during winding core discharge is minimized.
- the second inorganic particle 50 has a larger average particle diameter than the first inorganic particle 40 .
- the second organic-inorganic composite porous layer 30 includes the first inorganic particles 40 and the second inorganic particles 50 together, compared to the case of using the first inorganic particles 40 alone. , assembly fairness can be secured.
- the second organic-inorganic composite porous layer 30 includes the first inorganic particles 40, so that the thermal safety of the separator including the first inorganic particles 40 alone can be secured.
- the average particle diameter of the second inorganic particles 50 is 1.01 times to 50 times, or 1.15 times to 25 times, or 1.5 times to 13.3 times the average particle diameter of the first inorganic particles 40 times, or 13.3 times to 50 times, or 13.3 times to 25 times.
- the average particle diameter of the second inorganic particles 50 satisfies the aforementioned range, it may be easier to secure assembly fairness.
- the average particle diameter of the second inorganic particles 50 is 150 nm to 800 nm, or 200 nm to 600 nm, or 300 nm to 500 nm, or 200 nm to 500 nm, or 200 nm to 300 nm, or 200 nm to 800 nm.
- the average particle diameter of the second inorganic particles 50 satisfies the aforementioned range, it may be easier to secure assembly fairness.
- the second inorganic particle 50 is not particularly limited as long as it is electrochemically stable. That is, the second inorganic particles 50 that can be used in the present invention are those in which oxidation and/or reduction reactions do not occur in the operating voltage range (eg, 0 to 5V based on Li/Li + ) of the applied electrochemical device. Not limited. In particular, when inorganic particles having a high permittivity are used as the second inorganic particles 50, the dissociation degree of an electrolyte salt, for example, a lithium salt, in the liquid electrolyte may be increased, thereby improving ionic conductivity of the electrolyte solution.
- an electrolyte salt for example, a lithium salt
- the second inorganic particles 50 may include high dielectric constant inorganic particles having a dielectric constant of 5 or more, preferably 10 or more.
- inorganic particles having a dielectric constant of 5 or more include BaTiO 3 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, 0 ⁇ x ⁇ 1 , 0 ⁇ y ⁇ 1), Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, Mg( OH) 2 , NiO, CaO, ZnO, ZrO 2 , SiO 2 , Y 2 O 3 , Al 2 O 3 , AlOOH, Al(OH) 3 , SiC, TiO 2 , or mixtures thereof.
- an inorganic particle having a lithium ion transport ability that is, an inorganic particle containing a lithium element but not storing lithium and having a function of moving lithium ion
- Non-limiting examples of inorganic particles having lithium ion transport ability include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), (LiAlTiP) x O y series glass (0 ⁇ x ⁇ 4 , 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), lithium germanium thiophosphat
- the weight ratio of the first inorganic particles 40 and the second inorganic particles 50 in the second organic-inorganic composite porous layer is 40:60 to 92:8, or 60:40 to 92 :8, or 60:40 to 84:16, or 60:40 to 76:24, or 76:24 to 92:8, or 84:16 to 92:8, or 76:24 to 84:16. .
- the thermal stability at high temperatures can be improved and the separator's manufacturing process is sufficient to secure assembly fairness. 2 It may be easier to secure the arithmetic average roughness value of the surface of the organic-inorganic composite porous layer.
- the arithmetic average roughness of the surface of the second organic-inorganic composite porous layer of the separator for an electrochemical device is 400 nm to 1000 nm, or 500 nm to 1000 nm, or 400 nm to 970 nm, or 600 nm to 970 nm.
- the arithmetic mean roughness of the surface of the second organic-inorganic composite porous layer of the separator cuts the surface of the second organic-inorganic composite porous layer of the separator in a plane perpendicular to the surface of the second organic-inorganic composite porous layer of the separator.
- the roughness curve recorded by enlarging the cut surface as much as the reference length L is extracted as shown in FIG. It refers to a value expressed by the roughness curve in Equation 1 below.
- the arithmetic mean roughness may be measured using, for example, an optical profiler (NV-2700) of Nano Systems.
- the arithmetic average roughness value of the surface of the second organic-inorganic composite porous layer is 600 nm to 970 nm.
- the arithmetic average roughness value of the surface of the second organic-inorganic composite porous layer of the separator may be advantageous to secure assembly fairness.
- the second binder polymer may be a binder polymer commonly used in forming the organic-inorganic composite porous layer.
- the second binder polymer may be the same as or different from the first binder polymer.
- the second binder polymer may have a glass transition temperature (glass transition temperature, Tg) of -200 to 200 °C. When the glass transition temperature of the second binder polymer satisfies the aforementioned range, mechanical properties such as flexibility and elasticity of the finally formed second organic-inorganic composite porous layer 30 may be improved.
- the second binder polymer may have ion conduction ability. When the second binder polymer has ion conductivity, battery performance can be further improved.
- the dielectric constant of the second binder polymer satisfies the aforementioned range, the degree of salt dissociation in the electrolyte may be improved.
- the second binder polymer is poly (vinylidene fluoride-hexafluoropropylene) (poly (vinylidene fluoride-co-hexafluoropropylene)), poly (vinylidene fluoride-chlorotrifluoroethylene) ) (poly(vinylidene fluoride-co-chlorotrifluoroethylene)), poly(vinylidene fluoride-co-tetrafluoroethylene) (poly(vinylidene fluoride-co-tetrafluoroethylene)), poly(vinylidene fluoride-trichloroethylene) (poly (vinylidene fluoride-co-trichloroethylene)), acrylic copolymer, styrene-butadiene copolymer, poly(acrylic acid), poly(methylmethacrylate), poly(butyl acrylate) (poly(butylacrylate)), poly(acrylonitrile
- the acrylic copolymer is ethyl acrylate-acrylic acid-N,N-dimethylacrylamide copolymer, ethyl acrylate-acrylic acid-2-(dimethylamino)ethyl acrylate copolymer, ethyl acrylate-acrylic acid-N,N-di ethyl acrylamide copolymer, ethyl acrylate-acrylic acid-2-(diethylamino)ethyl acrylate copolymer, or two or more thereof, but is not limited thereto.
- the weight ratio of the total inorganic particles obtained by combining the first inorganic particles 40 and the second inorganic particles 50 to the second binder polymer is the finally prepared second organic-inorganic composite porous layer (30 ), but determined in consideration of the thickness, pore size, and porosity, it may be 50:50 to 99.9:0.1, or 95:5 to 99.9:0.1.
- the weight ratio of all of the inorganic particles to the second binder polymer is within the aforementioned range, between the first inorganic particles 40, between the second inorganic particles 50, and between the first inorganic particles 40 and the second inorganic material.
- the pore size and porosity of the second organic-inorganic composite porous layer 30 may be easy to secure by sufficiently securing an empty space formed between the particles 50 .
- between the first inorganic particles 40, between the second inorganic particles 50, between the first inorganic particles 40 and the second inorganic particles 50, and between the entire inorganic particle and the porous polymer substrate 10 It may also be easy to secure the adhesion between the liver.
- the above description of the first organic-inorganic composite porous layer 20 is referred to.
- the separator for an electrochemical device includes an organic-inorganic composite porous layer on both sides of a porous polymer substrate, so that impregnation into an electrolyte solution can be improved. Accordingly, the capacity of the electrochemical device having the separator for the electrochemical device may increase.
- organic-inorganic composite porous layer is included on both sides of the porous polymer substrate, safety when the separator is stored at high temperature, for example, about 80° C., can be improved, and internal short circuit safety can also be improved.
- a separator for an electrochemical device includes first inorganic particles having an average particle diameter of 1 nm to 100 nm on one side of a porous polymer substrate, and the first inorganic particle and the second inorganic particle on the other side of the porous polymer substrate.
- first inorganic particles having an average particle diameter of 1 nm to 100 nm on one side of a porous polymer substrate
- second inorganic particles having a larger average particle diameter than the average particle diameter of the first inorganic particles, safety at high temperatures may be improved and assembly fairness may be improved.
- the heat shrinkage after leaving the separator for an electrochemical device at 180 ° C. for 1 hour is 10% or less in the machine direction (MD, Machine Direction) and the transverse direction (TD, Transverse Direction), respectively, or 5% or less, or 0% to 5%, or 0% to 2%.
- the arithmetic average roughness of the surface of the second organic-inorganic composite porous layer of the separator for an electrochemical device is 400 nm to 1000 nm, or 500 nm to 1000 nm, or 400 nm to 970 nm, or 600 nm to 970 nm.
- the arithmetic mean roughness of the surface of the second organic-inorganic composite porous layer of the separator satisfies the above-mentioned range, it may be easy to secure assembly fairness without breaking or cracking the separator.
- the arithmetic average roughness of the surface of the second organic-inorganic composite porous layer of the separator is 600 nm to 970 nm, it may be advantageous to secure assembly fairness without cutting or cracking the separator.
- the arithmetic average roughness value of the surface of the second organic-inorganic composite porous layer of the separator for an electrochemical device is the content ratio of the first inorganic particles to the second inorganic particles, the average particle diameter of the first inorganic particles, and the average particle diameter of the second inorganic particles. , It may be determined by the surface state of the first inorganic particle and / or the second inorganic particle.
- the separator for an electrochemical device according to the present invention may be manufactured by the following method, but is not limited thereto.
- the average particle diameter of the first inorganic particles is 1 nm to 100 nm
- An average particle diameter of the second inorganic particles may be greater than an average particle diameter of the first inorganic particles.
- porous polymer substrate is prepared.
- porous polymer substrate refer to the above description.
- the porous polymer substrate is formed by a conventional method known in the art, such as a wet method using a solvent, a diluent or a pore forming agent, or a dry method using a stretching method to secure excellent air permeability and porosity from the above-described material. It can be made by forming
- a slurry for forming a first organic-inorganic composite porous layer including a first inorganic particle, a first binder polymer, and a first dispersion medium is coated on one surface of the porous polymer substrate and dried.
- first inorganic particles and the first binder polymer refer to the above description.
- the first dispersion medium may serve as a solvent for dissolving the first binder polymer or may serve as a dispersion medium for dispersing the first binder polymer without dissolving it, depending on the type of the first binder polymer.
- the first dispersion medium is N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, dimethylformamide ( diemthylformaide), dimethyl acetamide, methanol, ethanol, isopropyl alcohol, or two or more of these organic solvents, or water.
- the slurry for forming the first organic-inorganic composite porous layer may be prepared by dissolving or dispersing the first binder polymer in the first dispersion medium, then adding and dispersing the first inorganic particles, but the method for preparing the slurry It is not limited to this.
- Non-limiting examples of the method of coating the slurry for forming the first organic-inorganic composite porous layer on one surface of the porous polymer substrate include a die coating method, a roll coating method, a comma coating method, There are a microgravure coating method, a doctor blade coating method, a reverse roll coating method, and a direct roll coating method.
- a non-solvent for the first binder polymer is used according to a conventional method known in the art
- a step of phase separation may be further included.
- the phase separation step may be performed to form a pore structure in the first organic-inorganic composite porous layer.
- the phase separation step may be a humidified phase separation.
- the humidified phase separation may be carried out under conditions of a temperature in the range of 15 ° C to 70 ° C or a temperature in the range of 20 ° C to 50 ° C and a relative humidity in the range of 15% to 80% or 30% to 50%. While the slurry for forming the first organic-inorganic composite porous layer undergoes a drying process, it may have phase change characteristics due to a vapor-induced phase separation phenomenon known in the art.
- a non-solvent for the first binder polymer may be introduced in a gaseous state.
- the non-solvent for the first binder polymer is not particularly limited as long as it does not dissolve the first binder polymer and has partial compatibility with the dispersion medium.
- the solubility of the first binder polymer at 25 ° C is 5% by weight. Less than that can be used.
- the nonsolvent for the first binder polymer may be water, methanol, ethanol, isopropanol, butanol, butanediol, ethylene glycol, propylene glycol, tripropylene glycol, or two or more of these.
- a slurry for forming a second organic-inorganic composite porous layer containing the first inorganic particles, the second inorganic particles, the second binder polymer, and the second dispersion medium is coated on the other surface of the porous polymer substrate and dried.
- the first inorganic particle the second inorganic particle, and the second binder polymer, refer to the above description.
- the second dispersion medium may serve as a solvent for dissolving the second binder polymer or may serve as a dispersion medium for dispersing the second binder polymer without dissolving it, depending on the type of the second binder polymer.
- the second dispersion medium is N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, dimethylformamide ( diemthylformaide), dimethyl acetamide, methanol, ethanol, isopropyl alcohol, or two or more of these organic solvents, or water.
- the slurry for forming the second organic-inorganic composite porous layer may be prepared by dissolving or dispersing the second binder polymer in the second dispersion medium, adding the first inorganic particles and the second inorganic particles, and dispersing them.
- the manufacturing method of the slurry is not limited thereto.
- Non-limiting examples of the method of coating the second organic-inorganic composite porous layer-forming slurry on the other surface of the porous polymer substrate include a die coating method, a roll coating method, a comma coating method, There are a microgravure coating method, a doctor blade coating method, a reverse roll coating method, and a direct roll coating method.
- phase separation may be further included.
- the phase separation step may be performed to form a pore structure in the second organic-inorganic composite porous layer.
- the phase separation step may be a humidified phase separation.
- the humidified phase separation may be carried out under conditions of a temperature in the range of 15 ° C to 70 ° C or a temperature in the range of 20 ° C to 50 ° C and a relative humidity in the range of 15% to 80% or 30% to 50%. While the slurry for forming the second organic-inorganic composite porous layer undergoes a drying process, it may have phase change characteristics due to a vapor-induced phase separation phenomenon known in the art.
- a non-solvent for the second binder polymer may be introduced in a gaseous state.
- the non-solvent for the second binder polymer is not particularly limited as long as it does not dissolve the second binder polymer and has partial compatibility with the dispersion medium.
- the solubility of the second binder polymer at 25 ° C is 5% by weight. Less than that can be used.
- the nonsolvent for the second binder polymer may be water, methanol, ethanol, isopropanol, butanol, butanediol, ethylene glycol, propylene glycol, tripropylene glycol, or two or more of these.
- the phase separation after the slurry for forming the first organic-inorganic composite porous layer is coated may occur simultaneously with the phase separation after the slurry for forming the second organic-inorganic composite porous layer is coated.
- phase separation of the slurry for forming the first organic-inorganic composite porous layer may occur.
- An electrochemical device may be manufactured by interposing the separator for an electrochemical device between an anode and a cathode.
- the electrochemical device of the present invention includes all devices that undergo an electrochemical reaction, and specific examples include all types of primary and secondary cells, fuel cells, solar cells, or capacitors such as supercapacitor devices. .
- the electrochemical device may be a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
- the electrochemical device may be a cylindrical lithium secondary battery. Assembly fairness of the separator for an electrochemical device according to an embodiment of the present invention can be secured, and when the separator for an electrochemical device according to an embodiment of the present invention is provided as a separator for a cylindrical lithium secondary battery, assembly of the battery This may be easier.
- the electrode to be applied together with the separator for an electrochemical device of the present invention is not particularly limited, and an electrode active material layer including an electrode active material, a conductive material, and a binder is bound to a current collector according to a conventional method known in the art. can be manufactured with
- Non-limiting examples of the negative electrode active material include conventional negative electrode active materials that can be used for negative electrodes of conventional electrochemical devices, and in particular, lithium metal or lithium alloy, carbon, petroleum coke, activated carbon, A lithium adsorption material such as graphite or other carbons may be used.
- Non-limiting examples of the anode current collector include a foil made of aluminum, nickel or a combination thereof, and non-limiting examples of the cathode current collector include copper, gold, nickel or a copper alloy or a combination thereof. There are manufactured foils and the like.
- the conductive material used in the negative electrode and the positive electrode may be each independently added in an amount of 1% to 30% by weight based on the total weight of the active material layer.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and server black; conductive fibers such as carbon fibers and metal fibers; fluorinated carbon; metal powders such as aluminum and nickel powder; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.
- the binder used in the negative electrode and the positive electrode is a component that independently assists in the bonding of the active material and the conductive material and the bonding to the current collector, typically 1% by weight based on the total weight of the active material layer. to 30% by weight.
- binders examples include polyvinylidene fluoride (PVdF), polyacrylic acid (PAA), polyvinyl alcohol, carboxyl methyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluorocarbons, roethylene, polyethylene, polypropylene, ethylene-propylene-dienter polymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluororubber, various copolymers, and the like.
- PVdF polyvinylidene fluoride
- PAA polyacrylic acid
- CMC carboxyl methyl cellulose
- EPDM ethylene-propylene-dienter polymer
- EPDM ethylene-propylene-dienter polymer
- EPDM ethylene-propylene-dienter polymer
- EPDM ethylene-propylene-dienter polymer
- EPDM ethylene-propy
- the electrochemical device includes an electrolyte solution, and the electrolyte solution may include an organic solvent and a lithium salt.
- the electrolyte solution may include an organic solvent and a lithium salt.
- an organic solid electrolyte or an inorganic solid electrolyte may be used as the electrolyte solution.
- organic solvent examples include N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimethoxyethane , tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid Triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-ibidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, ethyl propionate
- An aprotic organic solvent such as may be used.
- the lithium salt is a material that is easily soluble in the organic solvent, and is, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, lithium chloroborane, lithium lower aliphatic carbonate, lithium 4-phenyl borate, imide, and the like can be used. have.
- pyridine triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide
- Nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N,N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxy ethanol, aluminum trichloride, etc. may be added.
- halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included to impart incombustibility
- carbon dioxide gas may be further included to improve high-temperature storage properties.
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, polyagitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, A polymer containing an ionic dissociation group or the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitride, halide, sulfate, and the like of Li such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , etc. may be used.
- the injection of the electrolyte may be performed at an appropriate stage in the battery manufacturing process according to the manufacturing process and required physical properties of the final product. That is, it may be applied before battery assembly or at the final stage of battery assembly.
- the separator for an electrochemical device in addition to winding, which is a general process, lamination, stack, and folding processes of separators and electrodes are possible.
- the separator for the electrochemical device may be interposed between the positive electrode and the negative electrode of the electrochemical device, and when configuring an electrode assembly by collecting a plurality of cells or electrodes, between adjacent cells or electrodes may be intervened.
- the electrode assembly may have various structures such as a simple stack type, a jelly-roll type, a stack-folding type, and a lamination-stack type.
- a polyethylene porous film having a thickness of 11 ⁇ m was prepared as a porous polymer substrate.
- a slurry for forming a first organic-inorganic composite porous layer was prepared by crushing and dispersing the first inorganic particles using a ball mill method for a total of 12 hours. At this time, the average particle diameter of the crushed first inorganic particles was 15 nm.
- the slurry for forming the first organic-inorganic composite porous layer is coated on one surface of the porous polymer substrate by a roll coating method, and then dried for 1 minute under a moisture atmosphere at 23 ° C. and a relative humidity of 42% to form the first organic-inorganic composite porous layer layer was formed.
- Fumed alumina (average particle diameter: 20 nm) as the first inorganic particle and alumina (average particle diameter: 500 nm) as the second inorganic particle were mixed with acetone at a weight ratio of 92:8.
- the first and second binder polymers were added by ball mill method for a total of 12 hours.
- a slurry for forming a second organic-inorganic composite porous layer was prepared by crushing and dispersing the second inorganic particles. At this time, the average particle diameter of the crushed first inorganic particles was 15 nm, and the average particle diameter of the crushed second inorganic particles was 200 nm.
- a separator for an electrochemical device was prepared in the same manner as in Example 1, except that fumed alumina as the first inorganic particle and alumina as the second inorganic particle were mixed in a weight ratio of 84:16.
- a separator for an electrochemical device was prepared in the same manner as in Example 1, except that fumed alumina as the first inorganic particle and alumina as the second inorganic particle were mixed in a weight ratio of 76:24.
- a separator for an electrochemical device was manufactured in the same manner as in Example 1, except that fumed alumina as the first inorganic particle and alumina as the second inorganic particle were mixed in a weight ratio of 60:40.
- a polyethylene porous film having a thickness of 11 ⁇ m was used as a separator for an electrochemical device without any treatment.
- a polyethylene porous film having a thickness of 11 ⁇ m was prepared as a porous polymer substrate.
- the slurry for forming the organic-inorganic composite porous layer was coated on both sides of the porous polymer substrate by dip coating, and then dried for 1 minute at 23° C. and 42% relative humidity under a moisture atmosphere to prepare a separator for an electrochemical device.
- a polyethylene porous film having a thickness of 11 ⁇ m was prepared as a porous polymer substrate.
- a slurry for forming an organic-inorganic composite porous layer was prepared by crushing and dispersing inorganic particles using a ball mill method. At this time, the average particle diameter of the crushed inorganic particles was 15 nm.
- the slurry for forming the organic-inorganic composite porous layer was coated on both sides of the porous polymer substrate by dip coating, and then dried at 23° C. and 42% relative humidity for 1 minute to prepare a separator for an electrochemical device.
- laser diffraction particle size It was introduced into a measuring device (Microtrac S3500) to calculate the particle size distribution by measuring the difference in diffraction pattern according to the particle size when the particles passed through the laser beam.
- the average particle diameter (D50) was measured by calculating the particle diameter at the point where it becomes 50% of the cumulative distribution of the number of particles according to the particle diameter in the measuring device.
- the heat shrinkage rate after standing for a period of time is shown in Table 1 below.
- Air permeability was measured by the ASTM D726-94 method. Gurley, as used herein, is the resistance to the flow of air, measured by a Gurley densometer. The air permeability value described here is expressed as the time (seconds) required for 100 cc of air to pass through the cross section of the separator 1 in 2 under a pressure of 12.2 in H 2 O, that is, the air permeability time.
- Basis weight (g/m 2 ) was evaluated by preparing a sample so that each of the width and length of the separator was 1 m, and measuring its weight.
- a coin cell was prepared using the separators of Examples 1 to 4 and Comparative Examples 1 to 3, and the coin cell was left at room temperature for 1 day, and then the resistance of the separator was measured by an impedance measurement method.
- the coin cell was manufactured as follows.
- a negative electrode was prepared by coating and drying the negative electrode slurry on a copper current collector with a loading of 3.8 mAh/cm 2 .
- LiCoO 2 as a cathode active material, Denka black as a conductive material, and polyvinylidene fluoride (PVdF) as a binder were added to N-methylpyrrolidone (NMP) as a solvent in a weight ratio of 85:5:10 to form a slurry of the cathode active material prepared.
- NMP N-methylpyrrolidone
- the cathode active material slurry was coated on a sheet-shaped aluminum current collector and dried to form a cathode active material layer such that the final cathode loading amount was 3.3 mAh/cm 2 .
- a separator of each of the Examples and Comparative Examples was interposed between the negative electrode and the positive electrode prepared as described above, and a non-aqueous electrolyte (1M LiPF 6 , ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC)) ( Volume ratio: 3:3:4) was injected to manufacture a coin cell.
- a non-aqueous electrolyte (1M LiPF 6 , ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC)
- a specimen having a size of 50 mm X 50 mm was prepared.
- the arithmetic average roughness (Ra) of the surfaces of the separators prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was measured using an optical profiler (NV-2700) from Nano System.
- a test piece was prepared by cutting the separators prepared in Examples 1 to 4 and Comparative Examples 1 to 3 into a size of 50 mm (length) x 50 mm (width), and kept in an oven heated to 180 ° C. for 1 hour, , then the specimen was retrieved and calculated by measuring the changed length for each of the machine and orthogonal directions:
- Heat shrinkage rate (%) after being left at 180 ° C for 1 hour ⁇ (Dimension before shrinkage - Dimension after shrinkage)/Dimension before shrinkage ⁇ X 100
- the arithmetic average roughness of the surface of the second organic-inorganic composite porous layer of the separator is the arithmetic average roughness of the surface of the organic-inorganic composite porous layer of the separator prepared in Comparative Example 3. It was confirmed that it was greater than the average roughness.
- the separators prepared in Examples 1 to 4 have very low heat shrinkage rates in the machine direction (MD, Machine Direction) and the transverse direction (TD, Transverse Direction) after being left at 180 ° C. for 1 hour. there was.
- the separator prepared in Comparative Example 2 uses only inorganic particles having a relatively large average particle diameter and is allowed to stand at 180 ° C for 1 hour. It was confirmed that the shrinkage rate was significantly inferior to the heat shrinkage rate of the separators prepared in Examples 1 to 4 after being allowed to stand at 180° C. for 1 hour.
- the separator prepared in Comparative Example 3 is a separator in the machine direction (MD, Machine Direction) and the right angle direction (TD, Transverse Direction) after leaving it at 180 ° C. for 1 hour using only inorganic particles having an average particle diameter of 1 to 100 nm Although the thermal shrinkage rate of was excellent, it was confirmed that it was difficult to secure assembly fairness because the arithmetic average roughness value of the surface of the organic-inorganic composite porous layer of the separator was very low.
- Evaluation Example 3 Evaluation of the arithmetic average roughness of the separator surface
- the arithmetic mean roughness of the surface of the second organic-inorganic composite porous layer was measured using an optical profiler (NV-2700) of Nano System, and is shown in FIGS. 3 to 6, respectively.
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Abstract
Description
Claims (13)
- 다공성 고분자 기재;상기 다공성 고분자 기재의 일면에 위치하며, 제1 무기물 입자 및 제1 바인더 고분자를 포함하는 제1 유무기 복합 다공성층; 및상기 다공성 고분자 기재의 타면에 위치하며, 상기 제1 무기물 입자, 제2 무기물 입자, 및 제2 바인더 고분자를 포함하는 제2 유무기 복합 다공성층을 포함하고,상기 제1 무기물 입자의 평균 입경이 1 nm 내지 100 nm이고,상기 제2 무기물 입자의 평균 입경이 상기 제1 무기물 입자의 평균 입경보다 큰 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제2 무기물 입자의 평균 입경이 상기 제1 무기물 입자의 평균 입경 대비 1.01배 내지 50배인 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제2 무기물 입자는 평균 입경이 150 nm 내지 800 nm인 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제2 유무기 복합 다공성층에서 상기 제1 무기물 입자와 제2 무기물 입자의 중량비는 40:60 내지 92:8인 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제1 무기물 입자는 흄드(fumed) 타입의 무기물 입자를 포함하는 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제5항에 있어서,상기 제1 무기물 입자는 흄드(fumed) 알루미나, 흄드 실리카, 흄드 이산화티탄, 또는 이들 중 2 이상을 포함하는 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제2 무기물 입자는 BaTiO3, Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3(PLZT, 0<x<1, 0<y<1), Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT), 하프니아(HfO2), SrTiO3, SnO2, CeO2, MgO, Mg(OH)2, NiO, CaO, ZnO, ZrO2, SiO2, Y2O3, Al2O3, AlOOH, Al(OH)3, SiC, TiO2, 리튬포스페이트(Li3PO4), 리튬티타늄포스페이트(LixTiy(PO4)3, 0<x<2, 0<y<3), 리튬알루미늄티타늄포스페이트(LixAlyTiz(PO4)3, 0 < x < 2, 0 < y < 1, 0 < z < 3), (LiAlTiP)xOy 계열 glass (0<x<4, 0<y<13), 리튬란탄티타네이트(LixLayTiO3, 0<x<2, 0<y<3), 리튬게르마니움티오포스페이트(LixGeyPzSw, 0<x<4, 0<y<1, 0<z<1, 0<w< 5), 리튬나이트라이드(LixNy, 0<x<4, 0<y<2), SiS2 계열 glass(LixSiySz, 0<x<3, 0<y<2, 0<z<4), P2S5 계열 glass(LixPySz, 0<x< 3, 0<y<3, 0<z<7), 또는 이들 중 2 이상을 포함하는 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 전기화학소자용 세퍼레이터의 제2 유무기 복합 다공성층의 표면의 산술 평균 거칠기가 400 nm 내지 1000 nm인 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 전기화학소자용 세퍼레이터를 180℃에서 1시간 동안 방치한 후의 열수축율이 기계방향(MD, Machine Direction) 및 직각 방향(TD, Transverse Direction)으로 각각 10% 이하인 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제1 바인더 고분자가 폴리(비닐리덴 플루오라이드-헥사플루오로프로필렌) (poly(vinylidene fluoride-co-hexafluoropropylene)), 폴리(비닐리덴 플루오라이드-클로로트리플루오로에틸렌) (poly(vinylidene fluoride-co-chlorotrifluoroethylene)), 폴리(비닐리덴 플루오라이드-테트라플루오로에틸렌) (poly(vinylidene fluoride-co-tetrafluoroethylene)), 폴리(비닐리덴 플루오라이드-트리클로로에틸렌) (poly(vinylidene fluoride-co-trichloroethylene)), 아크릴계 공중합체, 스티렌-부타디엔 공중합체, 폴리(아크릴산)(poly(acrylic acid)), 폴리(메틸메타크릴레이트) (poly(methylmethacrylate)), 폴리(부틸아크릴레이트) (poly(butylacrylate)), 폴리(아크릴로니트릴) (poly(acrylonitrile)), 폴리(비닐피롤리돈) (poly(vinylpyrrolidone)), 폴리(비닐알콜) (poly(vinylalcohol)), 폴리(비닐아세테이트) (poly(vinylacetate)), 에틸렌 비닐 아세테이트 공중합체 (poly(ethylene-co-vinyl acetate)), 폴리(에틸렌옥사이드) (poly(ethylene oxide)), 폴리(아릴레이트) (poly(arylate)), 셀룰로오스 아세테이트 (cellulose acetate), 셀룰로오스 아세테이트 부티레이트 (cellulose acetate butyrate), 셀룰로오스 아세테이트 프로피오네이트 (cellulose acetate propionate), 시아노에틸풀루란 (cyanoethylpullulan), 시아노에틸폴리비닐알콜(cyanoethylpolyvinylalcohol), 시아노에틸셀룰로오스 (cyanoethylcellulose), 시아노에틸수크로오스(cyanoethylsucrose), 풀루란 (pullulan), 또는 이들 중 2 이상을 포함하는 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 제1항에 있어서,상기 제2 바인더 고분자가 폴리(비닐리덴 플루오라이드-헥사플루오로프로필렌) (poly(vinylidene fluoride-co-hexafluoropropylene)), 폴리(비닐리덴 플루오라이드-클로로트리플루오로에틸렌) (poly(vinylidene fluoride-co-chlorotrifluoroethylene)), 폴리(비닐리덴 플루오라이드-테트라플루오로에틸렌) (poly(vinylidene fluoride-co-tetrafluoroethylene)), 폴리(비닐리덴 플루오라이드-트리클로로에틸렌) (poly(vinylidene fluoride-co-trichloroethylene)), 아크릴계 공중합체, 스티렌-부타디엔 공중합체, 폴리(아크릴산)(poly(acrylic acid)), 폴리(메틸메타크릴레이트) (poly(methylmethacrylate)), 폴리(부틸아크릴레이트) (poly(butylacrylate)), 폴리(아크릴로니트릴) (poly(acrylonitrile)), 폴리(비닐피롤리돈) (poly(vinylpyrrolidone)), 폴리(비닐알콜) (poly(vinylalcohol)), 폴리(비닐아세테이트) (poly(vinylacetate)), 에틸렌 비닐 아세테이트 공중합체 (poly(ethylene-co-vinyl acetate)), 폴리(에틸렌옥사이드) (poly(ethylene oxide)), 폴리(아릴레이트) (poly(arylate)), 셀룰로오스 아세테이트 (cellulose acetate), 셀룰로오스 아세테이트 부티레이트 (cellulose acetate butyrate), 셀룰로오스 아세테이트 프로피오네이트 (cellulose acetate propionate), 시아노에틸풀루란 (cyanoethylpullulan), 시아노에틸폴리비닐알콜(cyanoethylpolyvinylalcohol), 시아노에틸셀룰로오스 (cyanoethylcellulose), 시아노에틸수크로오스(cyanoethylsucrose), 풀루란 (pullulan), 또는 이들 중 2 이상을 포함하는 것을 특징으로 하는 전기화학소자용 세퍼레이터.
- 양극, 음극, 및 상기 양극과 음극 사이에 개재된 세퍼레이터를 포함하고,상기 세퍼레이터가 제1항 내지 제11항 중 어느 한 항에 따른 전기화학소자용 세퍼레이터인 것을 특징으로 하는 전기화학소자.
- 제12항에 있어서,상기 전기화학소자는 원통형 리튬 이차전지인 것을 특징으로 하는 전기화학소자.
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EP22811698.4A EP4343949A1 (en) | 2021-05-28 | 2022-05-27 | Separator for electrochemical device, and electrochemical device comprising same |
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KR20100058579A (ko) * | 2007-08-21 | 2010-06-03 | 에이일이삼 시스템즈 인코포레이티드 | 전기화학전지용 분리막 및 이의 제조방법 |
KR20130123568A (ko) * | 2012-05-03 | 2013-11-13 | 주식회사 엘지화학 | 전기화학소자용 분리막, 이의 제조방법 및 이를 포함하는 전기화학소자 |
KR20150050498A (ko) * | 2013-10-30 | 2015-05-08 | 주식회사 엘지화학 | 무기물 입자가 혼입되어 있는 다공성 분리막, 이를 포함하는 전기화학 소자 및 상기 분리막의 제조방법 |
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KR20200078011A (ko) * | 2018-12-21 | 2020-07-01 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 분리막 및 이를 포함하는 리튬 이차 전지 |
KR20210069553A (ko) | 2019-12-03 | 2021-06-11 | 니혼 고꾸 덴시 고교 가부시끼가이샤 | 커넥터 조립체 |
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- 2022-05-27 KR KR1020220065680A patent/KR20220161218A/ko unknown
- 2022-05-27 CN CN202280038655.0A patent/CN117397111A/zh active Pending
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KR20100058579A (ko) * | 2007-08-21 | 2010-06-03 | 에이일이삼 시스템즈 인코포레이티드 | 전기화학전지용 분리막 및 이의 제조방법 |
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KR20210069553A (ko) | 2019-12-03 | 2021-06-11 | 니혼 고꾸 덴시 고교 가부시끼가이샤 | 커넥터 조립체 |
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