WO2023096069A1 - 분리막 및 그 제조방법 - Google Patents
분리막 및 그 제조방법 Download PDFInfo
- Publication number
- WO2023096069A1 WO2023096069A1 PCT/KR2022/010884 KR2022010884W WO2023096069A1 WO 2023096069 A1 WO2023096069 A1 WO 2023096069A1 KR 2022010884 W KR2022010884 W KR 2022010884W WO 2023096069 A1 WO2023096069 A1 WO 2023096069A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separator
- polyolefin
- weight
- molecular weight
- hydrophilic
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 36
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 28
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims description 34
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 27
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 27
- 230000008859 change Effects 0.000 claims description 24
- -1 polyethylene Polymers 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 230000007547 defect Effects 0.000 claims description 11
- 238000009998 heat setting Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical group C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
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- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 3
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000306 polymethylpentene Polymers 0.000 claims description 3
- 239000011116 polymethylpentene Substances 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 16
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 229920001903 high density polyethylene Polymers 0.000 description 9
- 239000004700 high-density polyethylene Substances 0.000 description 9
- 239000005662 Paraffin oil Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
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- 238000005266 casting Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 239000003240 coconut oil Substances 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 235000010446 mineral oil Nutrition 0.000 description 1
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- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- 239000003549 soybean oil Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
- C08J2201/0462—Elimination of a polymeric phase using organic solvents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- 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 and a method for manufacturing the same, and more particularly, to a separator for a lithium secondary battery with improved impregnability to an electrolyte solution and a method for manufacturing the same.
- Lithium secondary batteries are widely used as a power source for various electric products that require miniaturization and light weight, such as smartphones, laptops, and tablet PCs. Development of a lithium secondary battery having a large, long lifespan and high stability is required.
- a separator having micropores that separates the positive electrode and the negative electrode to prevent internal short circuits and facilitates the movement of lithium ions during charging and discharging especially thermally induced phase separation
- a separator having micropores that separates the positive electrode and the negative electrode to prevent internal short circuits and facilitates the movement of lithium ions during charging and discharging especially thermally induced phase separation
- polyolefins such as polyethylene
- the ion movement path between the positive electrode and the negative electrode is greatly reduced, and as a result, there is a problem in that the charging and discharging performance of the secondary battery is greatly deteriorated.
- the ceramic particles may be partially and continuously detached from the porous substrate, and in this case, the heat resistance of the separator may gradually decrease.
- the lithium secondary battery has a structure in which a non-aqueous electrolyte containing a lithium salt is impregnated in an electrode assembly in which a porous separator is interposed between a positive electrode and a negative electrode on which an active material is applied on an electrode current collector.
- a lithium secondary battery is a battery case made of a can or pouch of a certain size and shape after manufacturing an electrode assembly having a structure in which positive and negative electrodes are alternately laminated and a separator is interposed between the positive and negative electrodes. It is manufactured by inserting the electrode assembly into and finally injecting the electrolyte. At this time, the electrolyte solution permeates between the anode, the cathode and the separator by capillary force.
- the anode, cathode, and separator are hydrophobic, while the electrolyte is hydrophilic, so considerable time and difficult process conditions are required to improve the impregnation or wettability of the electrolyte to the electrode and separator. Accordingly, the electrolyte There is a limit to implementing and improving the impregnation and productivity of the process in a balanced way.
- the present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a separator and a manufacturing method that can realize mechanical properties, appearance properties, impregnation into electrolyte and productivity of the process in a balanced way will be.
- One aspect of the present invention is made of a porous film having a hydrophobic region containing polyolefin and a hydrophilic region containing a hydrophilic polymer dispersed in the hydrophobic region, wherein the content of the hydrophilic region in the porous film is 0.1 to 7.5% by weight.
- a phosphorus separation membrane is provided.
- the weight average molecular weight of the polyolefin may be 200,000 to 800,000.
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the polyolefin may be 0.1*10 -5 to 1.1*10 -5 .
- the weight average molecular weight of the polyolefin may be 900,000 to 2,000,000.
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the polyolefin may be 0.1*10 -5 to 0.75*10 -5 .
- the polyolefin may include one selected from the group consisting of polyethylene, polypropylene, polybutylene, polymethylpentene, and a combination of two or more thereof.
- the hydrophilic polymer is ethylene vinyl acetate, ethylene vinyl alcohol, polyvinyl alcohol, polyacrylic acid, polyoxyethylene-polyoxypropylene block copolymer, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl It may be one selected from the group consisting of acetal, polyvinyl butyral, cellulose derivatives, glycerol, and a combination of two or more of them.
- the longitudinal direction (MD) length change rate is 15 to 50%
- the transverse direction (TD) length change rate is 15 to 40 may be %.
- the number of surface defects present on the surface of the separator, having a brightness different from that of the surroundings, and having a size of 2 mm or more may be 10/m 2 or less.
- Another aspect of the present invention in the manufacturing method of the separator, (a) injecting a composition containing a polyolefin, a hydrophilic polymer and a pore former into an extruder and molding a base sheet; (b) preparing a base film by stretching the base sheet and then extracting the pore forming agent; and (c) heat-setting the base film.
- a separator according to an aspect of the present invention is composed of a porous film having a hydrophobic region including polyolefin and a hydrophilic region including a hydrophilic polymer dispersed in the hydrophobic region, and the content of the hydrophilic region in the porous film is 0.1 to 0.1%.
- a separator according to an aspect of the present invention is composed of a porous film having a hydrophobic region including polyolefin and a hydrophilic region including a hydrophilic polymer dispersed in the hydrophobic region, and the content of the hydrophilic region in the porous film is 0.1 to 0.1 7.5% by weight.
- the hydrophobic region and the hydrophilic region may constitute a continuous phase and a discontinuous phase, respectively.
- the hydrophilic region may be uniformly dispersed in a matrix composed of the hydrophobic region to impart substantially uniform hydrophilicity to the entire area and/or thickness direction of the separator. The impregnability of the separator to the electrolyte may be improved.
- matrix refers to a component constituting a continuous phase in a separation membrane including two or more components. That is, in the separation membrane, the hydrophobic region including the polyolefin may exist in a continuous phase, and the hydrophobic region including the hydrophilic polymer may be dispersed and present in a discontinuous phase.
- the content of the hydrophilic region in the porous film may be 0.1 to 7.5% by weight, preferably 1 to 6% by weight, more preferably 3 to 6% by weight. If the content of the hydrophilic region is 0.1% by weight, the required level of electrolyte impregnation cannot be realized, and if it exceeds 7.5% by weight, the electrolyte impregnability can be further improved, while the mechanical properties of the separator that can be realized through the polyolefin, Heat resistance may decrease.
- the content of the hydrophilic region exceeds 7.5% by weight, the dispersibility of the hydrophilic polymer is lowered, and the number of surface defects having a size of 2 mm or more and having a brightness different from that of the surroundings increases on the surface of the membrane, resulting in deterioration in appearance quality.
- a sudden change in resistance at a site and/or region where the hydrophilic polymer is arbitrarily aggregated on the surface and/or inside of the separator may adversely affect the electrochemical characteristics of the battery.
- the polyolefin may include one selected from the group consisting of polyethylene, polypropylene, polybutylene, polymethylpentene, and a combination of two or more thereof, and preferably may include at least one of polyethylene and polypropylene, More preferably, it may include polyethylene, but is not limited thereto.
- the weight average molecular weight of the polyethylene may be 200,000 to 800,000, preferably, 250,000 to 600,000, more preferably, 300,000 to 500,000, and the weight average of the high density polyethylene
- the ratio of the content of the hydrophilic region to the molecular weight is 0.1*10 -5 to 1.1*10 -5 , preferably 0.2*10 -5 to 1*10 -5 , more preferably 0.5*10 -5 to It can be 1*10 -5 .
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the high-density polyethylene is less than 0.1*10 -5 , the required level of electrolyte impregnability cannot be realized, and if it exceeds 1.1*10 -5 , the electrolyte impregnability is rather deteriorated. , mechanical properties and heat resistance of the separator, which can be realized through the high-density polyethylene, may be deteriorated.
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the high-density polyethylene exceeds 1.1 * 10 -5 , the dispersibility of the hydrophilic polymer is lowered, and the surface of the separator has a different brightness from the surroundings and has a size of 2 mm or more
- the number of surface defects may increase and the quality of appearance may deteriorate, and the resistance may change rapidly at the site and/or region where the hydrophilic polymer is arbitrarily aggregated on the surface and/or inside of the separator, which may adversely affect the electrochemical characteristics of the battery. there is.
- the weight average molecular weight of the polyethylene may be 900,000 to 2,000,000, preferably, 1,000,000 to 1,500,000, and the hydrophilic region for the weight average molecular weight of the ultra high molecular weight polyethylene
- the content ratio may be 0.1*10 -5 to 0.75*10 -5 , preferably 0.15*10 -5 to 0.6*10 -5 , more preferably 0.3*10 -5 to 0.6*10 -5 there is.
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the ultra-high molecular weight polyethylene is less than 0.1*10 -5 , the necessary level of electrolyte impregnability cannot be achieved, and if it exceeds 0.75*10 -5 , the electrolyte impregnability is rather deteriorated.
- the mechanical properties and heat resistance of the separator which can be realized through the ultra-high molecular weight polyethylene, may be deteriorated.
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the ultra-high molecular weight polyethylene exceeds 0.75*10 -5 , the dispersibility of the hydrophilic polymer is lowered, and the surface of the separator has a brightness different from that of the surroundings and has a size of 2 mm or more.
- the number of surface defects may increase and the quality of the appearance may deteriorate, and the resistance may change rapidly at the site and/or region where the hydrophilic polymer is arbitrarily aggregated on the surface and/or inside of the separator, which may adversely affect the electrochemical characteristics of the battery.
- the hydrophilic polymer is ethylene vinyl acetate, ethylene vinyl alcohol, polyvinyl alcohol, polyacrylic acid, polyoxyethylene-polyoxypropylene block copolymer, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl acetal, polyvinyl butyral , It may be one selected from the group consisting of a cellulose derivative, glycerol, and a combination of two or more thereof, preferably, may be ethylene vinyl acetate, more preferably, ethylene vinyl having a vinyl acetate content of 15 to 30% by weight It may be acetate, but is not limited thereto.
- the mechanical properties and hydrophilic properties of the separator may be deteriorated, and if it is greater than 30% by weight, processability and thus dispersibility of the hydrophilic polymer may be reduced.
- the hydrophilic polymer in addition to the above, various types of polymers having hydrophilic functional groups such as amine groups, amide groups, hydroxyl groups, carboxylic acid groups, etc. in the main chain and / or side chain may be applied.
- the rate of change in length in the longitudinal direction (MD) from immediately after the droplet of the electrolyte droplet added to the surface of the separator until 5 minutes have elapsed may be 15 to 50%, preferably, 20 to 45%, and the length in the transverse direction (TD)
- the change rate may be 15 to 40%, preferably 20 to 30%.
- MD1 and TD1 represent the longest lengths in the longitudinal direction (MD) and transverse direction (TD) immediately after the droplet of the electrolyte droplet added to the surface of the separator, and the longitudinal direction (MD) and transverse direction (TD) at the time of 5 minutes have elapsed therefrom.
- MD2 and TD2 are the longest lengths, the rate of change in length can be calculated by Equations 1 and 2 below.
- Transverse direction (TD) length change rate (%) (TD2-TD1)/(TD1)*100
- the electrolyte solution may be one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and a combination of two or more thereof, ,
- ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) may be mixed in a predetermined ratio, but is not limited thereto.
- the electrolyte for example, the electrolyte has a LiPF 6 concentration of 1.5M and a vinylene carbonate (VC) content of 1.5% by weight of ethylene carbonate (EC), diethyl carbonate (DEC), and
- EC ethylene carbonate
- DEC diethyl carbonate
- DMC dimethyl carbonate
- the transverse direction (TD) length of the electrolyte droplet The ratio of the longitudinal (MD) length change rate to the change rate may be 0.9 to 1.06, preferably 1 to 1.04.
- the polyolefin is ultra-high molecular weight polyethylene (UHMWPE)
- UHMWPE ultra-high molecular weight polyethylene
- the ratio of the content of the hydrophilic region to the weight average molecular weight of the ultra-high molecular weight polyethylene is 0.1*10 -5 to 0.75*10 -5
- the transverse direction of the electrolyte droplet The ratio of the longitudinal (MD) length change rate to the (TD) length change rate may be 0.9 to 1.8, preferably 1 to 1.7.
- the electrochemical characteristics of the battery may be deteriorated because the impregnation of the electrolyte into the separator is non-uniform along the direction. .
- the number of surface defects (white dots and / or black dots) present on the surface of the separator, having a brightness different from the surroundings and having a size of 2 mm or more is 10 / m 2 or less, preferably, 8 pieces/m 2 or less, more preferably, 6 pieces/m 2 or less. If the number of surface defects exceeds 10/m 2 , the appearance quality may be degraded, and the resistance rapidly changes in the region and/or region where the polyolefin and/or the hydrophilic polymer are arbitrarily aggregated on the surface of the separator, resulting in a sudden change in electrical power of the battery. Chemical properties may be adversely affected.
- the separation membrane is formed by: (a) introducing a composition including polyolefin, a hydrophilic polymer, and a pore-forming agent into an extruder and forming a base sheet; (b) preparing a base film by stretching the base sheet and then extracting the pore forming agent; and (c) heat-setting the base film.
- a composition containing 20 to 40% by weight of the polyolefin, 0.1 to 5% by weight of the hydrophilic polymer, and the remaining amount of the pore forming agent may be introduced into an extruder and a base sheet may be formed.
- the polyolefin and the hydrophilic polymer are the same as those described above for the types, physical properties, functional effects, and the like.
- the input amount of the polyolefin and the hydrophilic polymer may be adjusted so that the content of the hydrophilic region including the hydrophilic polymer in the separator is 0.1 to 7.5% by weight.
- the pore former is paraffin oil, paraffin wax, mineral oil, solid paraffin, soybean oil, rapeseed oil, palm oil, coconut oil, di-2-ethylhexyl phthalate, dibutyl phthalate, diisononyl phthalate, diisodecyl phthalate, bis(2- It may be one selected from the group consisting of propylheptyl) phthalate, naphthenoyl, and a combination of two or more thereof, preferably, it may be paraffin oil, more preferably, it may be paraffin oil having a kinematic viscosity of 50 to 100 cSt at 40 ° C. However, it is not limited thereto.
- a base film may be prepared by stretching the base sheet and then extracting the pore-forming agent.
- the stretching may be performed by a known method such as uniaxial stretching or biaxial stretching (sequential or simultaneous biaxial stretching).
- the stretching magnification may be 4 to 20 times in the transverse direction (MD) and the longitudinal direction (TD), respectively, and the plane magnification accordingly may be 16 to 400 times.
- the base film may be heat-set.
- Heat setting is to remove residual stress by fixing the film and applying heat to forcibly hold the film to be shrunk.
- a high heat setting temperature is advantageous for lowering the shrinkage rate, but if the temperature is excessively high, the pores formed by partially melting the film may be closed and transmittance may decrease.
- the heat setting temperature is preferably selected from a range in which 10 to 30% by weight of the crystalline portion of the base film melts. When the heat setting temperature is selected from the above range, the problem of no residual stress relieving effect of the film due to insufficient rearrangement of polyolefin molecules in the base film and the problem of lowering the permeability due to the closure of pores due to partial melting can be prevented.
- the heat setting temperature may be 120 to 150° C., preferably, 130 to 145° C.
- the heat setting time may be 5 seconds to 10 minutes, preferably 10 seconds to 1 minute.
- PE1, V600, HTC polyethylene having a weight average molecular weight (Mw) of 600,000, 0.5 parts by weight of ethylene vinyl acetate (EVA, HTC) having a vinyl acetate content of 28% by weight, and at 40 ° C.
- EVA, HTC ethylene vinyl acetate
- the twin-screw extruder discharges a T-Die having a width of 300 mm and passes through a casting roll at a temperature of 40 ° C to obtain a thickness of 800 ⁇ m.
- a base sheet was prepared.
- the base sheet was stretched 8 times in the longitudinal direction (MD) at 110° C. in a roll stretching machine, and stretched 9 times in the transverse direction (TD) at 125° C. in a tenter stretching machine to prepare a film.
- the film was impregnated in a dichloromethane leaching tank at 25°C to extract and remove paraffin oil for 1 minute, and then dried at 50°C for 5 minutes.
- a porous separator was prepared by heat-setting the film at 140° C. in a state in which it was relaxed by 25% in the transverse direction (TD).
- a porous separator was prepared in the same manner as in Example 1-1, except that the input amounts of PE1 and EVA were changed to 31 parts by weight and 1 part by weight, respectively.
- a porous separator was prepared in the same manner as in Example 1-1, except that the input amounts of PE1 and EVA were changed to 30.4 parts by weight and 1.6 parts by weight, respectively.
- a porous separator was prepared in the same manner as in Example 1-1, except that the amounts of PE1 and EVA were changed to 30 parts by weight and 2 parts by weight, respectively.
- a porous separator was prepared in the same manner as in Example 1-1, except that the amount of PE1 was changed to 32 parts by weight and EVA was not added.
- a porous separator was prepared in the same manner as in Example 1-1, except that the input amounts of PE1 and EVA were changed to 29.8 parts by weight and 2.2 parts by weight, respectively.
- Table 1 shows the weight average molecular weight of polyethylene constituting the separators according to Examples and Comparative Examples and the contents of ethylene vinyl acetate (EVA among PE1 and EVA) in the separators.
- Electrolyte impregnability of the separators prepared in Examples and Comparative Examples was measured in the following manner.
- EC ethylene carbonate
- DEC diethyl carbonate
- DMC dimethyl carbonate
- Example 1-1 3.28 1.86 4.02 2.31 22.6 24.2 2
- Comparative Example 1-1 3.28 1.86 3.48 1.96 6.1 5.4
- PE2 polyethylene
- VH100U polyethylene
- KPIC polyethylene
- EVA ethylene vinyl acetate
- VVA ethylene vinyl acetate
- the twin-screw extruder discharges a T-Die having a width of 300 mm and passes through a casting roll at a temperature of 40 ° C to obtain a thickness of 800 ⁇ m.
- a base sheet was prepared.
- the base sheet was stretched 8 times in the longitudinal direction (MD) at 110° C. in a roll stretching machine, and stretched 9 times in the transverse direction (TD) at 125° C. in a tenter stretching machine to prepare a film.
- the film was impregnated in a dichloromethane leaching tank at 25°C to extract and remove paraffin oil for 1 minute, and then dried at 50°C for 5 minutes.
- a porous separator was prepared by heat-setting the film at 135° C. in a state in which it was relaxed by 15% in the transverse direction (TD).
- a porous separator was manufactured in the same manner as in Example 2-1, except that the input amounts of PE2 and EVA were changed to 27 parts by weight and 1 part by weight, respectively.
- a porous separator was manufactured in the same manner as in Example 2-1, except that the input amounts of PE2 and EVA were changed to 26.4 parts by weight and 1.6 parts by weight, respectively.
- a porous separator was manufactured in the same manner as in Example 2-1, except that the input amounts of PE2 and EVA were changed to 26 parts by weight and 2 parts by weight, respectively.
- a porous separator was manufactured in the same manner as in Example 2-1, except that the amount of PE2 was changed to 28 parts by weight and EVA was not added.
- a porous separator was manufactured in the same manner as in Example 2-1, except that the input amounts of PE2 and EVA were changed to 25.8 parts by weight and 2.2 parts by weight, respectively.
- Example 2-1 1,000,000 1.8 0.18
- Example 2-2 1,000,000 3.6 0.36
- Example 2-3 1,000,000 5.7 0.57
- Example 2-4 1,000,000 7.1 0.71 Comparative Example 2-1 1,000,000 0 0.00 Comparative Example 2-2 1,000,000 7.9 0.79
- Example 2-1 3.28 1.86 3.97 2.24 21.0 20.4 3
- Example 2-2 3.28 1.86 4.04 2.27 23.2 22.0 6
- Example 2-3 3.28 1.86 4.72 2.34 43.9 25.8 9
- Example 2-4 3.28 1.86 3.9 2.15 18.9 15.6 10 Comparative Example 2-1 3.28 1.86 3.68 2.13 12.2 14.5 2 Comparative Example 2-2 3.28 1.86 3.73 1.98 13.7 15.1 19
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Abstract
Description
구분 | PE1 중량평균분자량 (Mw, A) |
EVA 함량 (중량%, B) |
B/A (*10-5) |
실시예 1-1 | 600,000 | 1.6 | 0.26 |
실시예 1-2 | 600,000 | 3.1 | 0.52 |
실시예 1-3 | 600,000 | 5.0 | 0.83 |
실시예 1-4 | 600,000 | 6.3 | 1.04 |
비교예 1-1 | 600,000 | 0 | 0.00 |
비교예 1-2 | 600,000 | 6.9 | 1.15 |
구분 | MD1 (mm) |
TD1 (mm) |
MD2 (mm) |
TD2 (mm) |
MD 변화율 (%) |
TD 변화율 (%) |
표면결점 (개) |
실시예 1-1 | 3.28 | 1.86 | 4.02 | 2.31 | 22.6 | 24.2 | 2 |
실시예 1-2 | 3.28 | 1.86 | 4.16 | 2.35 | 26.8 | 26.3 | 5 |
실시예 1-3 | 3.28 | 1.86 | 4.2 | 2.38 | 28.0 | 28.0 | 7 |
실시예 1-4 | 3.28 | 1.86 | 3.92 | 2.21 | 19.5 | 18.8 | 8 |
비교예 1-1 | 3.28 | 1.86 | 3.48 | 1.96 | 6.1 | 5.4 | 1 |
비교예 1-2 | 3.28 | 1.86 | 3.77 | 2.12 | 14.9 | 14.0 | 15 |
구분 | PE2 중량평균분자량 (Mw, A) |
EVA 함량 (중량%, B) |
B/A (*10-5) |
실시예 2-1 | 1,000,000 | 1.8 | 0.18 |
실시예 2-2 | 1,000,000 | 3.6 | 0.36 |
실시예 2-3 | 1,000,000 | 5.7 | 0.57 |
실시예 2-4 | 1,000,000 | 7.1 | 0.71 |
비교예 2-1 | 1,000,000 | 0 | 0.00 |
비교예 2-2 | 1,000,000 | 7.9 | 0.79 |
구분 | MD1 (mm) |
TD1 (mm) |
MD2 (mm) |
TD2 (mm) |
MD 변화율 (%) |
TD 변화율 (%) |
표면결점 (개) |
실시예 2-1 | 3.28 | 1.86 | 3.97 | 2.24 | 21.0 | 20.4 | 3 |
실시예 2-2 | 3.28 | 1.86 | 4.04 | 2.27 | 23.2 | 22.0 | 6 |
실시예 2-3 | 3.28 | 1.86 | 4.72 | 2.34 | 43.9 | 25.8 | 9 |
실시예 2-4 | 3.28 | 1.86 | 3.9 | 2.15 | 18.9 | 15.6 | 10 |
비교예 2-1 | 3.28 | 1.86 | 3.68 | 2.13 | 12.2 | 14.5 | 2 |
비교예 2-2 | 3.28 | 1.86 | 3.73 | 1.98 | 13.7 | 15.1 | 19 |
Claims (10)
- 폴리올레핀을 포함하는 소수성 영역 및 상기 소수성 영역 중에 분산된 친수성 고분자를 포함하는 친수성 영역을 가지는 다공성 필름으로 이루어지고,상기 다공성 필름 중 상기 친수성 영역의 함량은 0.1~7.5중량%인, 분리막.
- 제1항에 있어서,상기 폴리올레핀의 중량평균분자량은 200,000~800,000인, 분리막.
- 제2항에 있어서,상기 폴리올레핀의 중량평균분자량에 대한 상기 친수성 영역의 함량의 비는 0.1*10-5~1.1*10-5인, 분리막.
- 제1항에 있어서,상기 폴리올레핀의 중량평균분자량은 900,000~2,000,000인, 분리막.
- 제4항에 있어서,상기 폴리올레핀의 중량평균분자량에 대한 상기 친수성 영역의 함량의 비는 0.1*10-5~0.75*10-5인, 분리막.
- 제1항에 있어서,상기 폴리올레핀은 폴리에틸렌, 폴리프로필렌, 폴리부틸렌, 폴리메틸펜텐 및 이들 중 2 이상의 조합으로 이루어진 군에서 선택된 하나를 포함하는, 분리막.
- 제1항에 있어서,상기 친수성 고분자는 에틸렌비닐아세테이트, 에틸렌비닐알코올, 폴리비닐알코올, 폴리아크릴산, 폴리옥시에틸렌-폴리옥시프로필렌 블록 공중합체, 폴리에틸렌글리콜, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 폴리비닐아세탈, 폴리비닐부티랄, 셀룰로오스 유도체, 글리세롤 및 이들 중 2 이상의 조합으로 이루어진 군에서 선택된 하나인, 분리막.
- 제1항에 있어서,상기 분리막의 표면에 적가된 전해액 액적의 적가 직후부터 5분이 경과한 시점까지 세로방향(MD) 길이 변화율은 15~50%이고, 가로방향(TD) 길이 변화율은 15~40%인, 분리막.
- 제1항에 있어서,상기 분리막의 표면에 존재하고, 주변과 상이한 명도를 가지며 2mm 이상의 크기를 가지는 표면결점의 수는 10개/m2 이하인, 분리막.
- 제1항 내지 제9항 중 어느 한 항에 따른 분리막의 제조방법에 있어서,(a) 폴리올레핀, 친수성 고분자 및 기공형성제를 포함하는 조성물을 압출기에 투입하고 베이스 시트를 성형하는 단계;(b) 상기 베이스 시트를 연신한 후, 상기 기공형성제를 추출하여 베이스 필름을 제조하는 단계; 및(c) 상기 베이스 필름을 열고정하는 단계;를 포함하는, 분리막의 제조방법.
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KR101094267B1 (ko) * | 2009-09-07 | 2011-12-20 | 한국생산기술연구원 | 친수성 폴리올레핀계 분리막, 및 이의 제조방법 |
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KR20200085406A (ko) * | 2019-01-04 | 2020-07-15 | 주식회사 엘지화학 | 가교 폴리머 분리막 및 이의 제조방법 |
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JP2003132870A (ja) * | 2001-10-26 | 2003-05-09 | Toyobo Co Ltd | 親水性官能基を有するポリオレフィンを主体とする樹脂組成物からなる二次電池用セパレータ |
KR101094267B1 (ko) * | 2009-09-07 | 2011-12-20 | 한국생산기술연구원 | 친수성 폴리올레핀계 분리막, 및 이의 제조방법 |
KR102121293B1 (ko) * | 2017-11-28 | 2020-06-10 | 아사히 가세이 가부시키가이샤 | 축전 디바이스용 세퍼레이터 및 그의 제조 방법, 그리고 축전 디바이스 및 그의 제조 방법 |
KR20200039060A (ko) * | 2018-10-04 | 2020-04-16 | 더블유스코프코리아 주식회사 | 분리막 및 그 제조방법 |
KR20200085406A (ko) * | 2019-01-04 | 2020-07-15 | 주식회사 엘지화학 | 가교 폴리머 분리막 및 이의 제조방법 |
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