KR100324713B1 - New blended gel polymer electrolyte(I)and a method for manufacturing thereof - Google Patents
New blended gel polymer electrolyte(I)and a method for manufacturing thereof Download PDFInfo
- Publication number
- KR100324713B1 KR100324713B1 KR1019990045646A KR19990045646A KR100324713B1 KR 100324713 B1 KR100324713 B1 KR 100324713B1 KR 1019990045646 A KR1019990045646 A KR 1019990045646A KR 19990045646 A KR19990045646 A KR 19990045646A KR 100324713 B1 KR100324713 B1 KR 100324713B1
- Authority
- KR
- South Korea
- Prior art keywords
- polymer electrolyte
- lithium
- electrolyte composition
- gel polymer
- vinylidene fluoride
- Prior art date
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 34
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 itaconic acid alkali salt Chemical class 0.000 claims abstract description 23
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 229920000554 ionomer Polymers 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims description 26
- RXNWFGQCYAZACC-UHFFFAOYSA-L dilithium;2-methylidenebutanedioate Chemical group [Li+].[Li+].[O-]C(=O)CC(=C)C([O-])=O RXNWFGQCYAZACC-UHFFFAOYSA-L 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000011147 inorganic material Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- 239000012046 mixed solvent Substances 0.000 claims 2
- RBYDCVNTVVKIQT-UHFFFAOYSA-L dipotassium;2-methylidenebutanedioate Chemical compound [K+].[K+].[O-]C(=O)CC(=C)C([O-])=O RBYDCVNTVVKIQT-UHFFFAOYSA-L 0.000 claims 1
- IZZSMHVWMGGQGU-UHFFFAOYSA-L disodium;2-methylidenebutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(=C)C([O-])=O IZZSMHVWMGGQGU-UHFFFAOYSA-L 0.000 claims 1
- 125000003010 ionic group Chemical group 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 신규한 젤 고분자 전해질 조성물 및 그의 제조방법에 관한 것으로, 좀더 상세하게는 비닐리덴플루오라이드 계열의 고분자와 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머와의 블랜드를 기초로 한 젤 고분자 전해질 조성물에 관한 것이다.The present invention relates to a novel gel polymer electrolyte composition and a method for preparing the same, and more particularly, a gel based on a blend of a vinylidene fluoride-based polymer and an ionomer copolymerized with methyl methacrylate and itaconic acid alkali salt. A polymer electrolyte composition is disclosed.
본 발명의 목적은 이온전도 특성, 전기화학적 안정성, 기계적 물성 및 계면특성이 우수한 새로운 젤 고분자 전해질 조성물 및 그의 제조방법을 제공함에 있다.An object of the present invention is to provide a novel gel polymer electrolyte composition excellent in ion conductivity, electrochemical stability, mechanical properties and interfacial properties and a method for producing the same.
본 발명에 의한 젤 고분자 전해질 조성물은 유기용매와의 상용성이 상용성이 향상되어 벌크에서의 이온전도 특성, 계면안정성 등이 향상되고, 전기화학적으로도 안정한 장점을 지닌다.Gel polymer electrolyte composition according to the present invention has the advantage that the compatibility with the organic solvent is improved to improve the ion conductivity characteristics, interfacial stability, etc. in the bulk, and is also electrochemically stable.
Description
본 발명은 신규한 젤 고분자 전해질 조성물 및 그의 제조방법에 관한 것으로, 좀더 상세하게는 비닐리덴플루오라이드 계열의 고분자와 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머와의 블랜드를 기초로 한 젤 고분자 전해질 조성물에 관한 것이다.The present invention relates to a novel gel polymer electrolyte composition and a method for preparing the same, and more particularly, a gel based on a blend of a vinylidene fluoride-based polymer and an ionomer copolymerized with methyl methacrylate and itaconic acid alkali salt. A polymer electrolyte composition is disclosed.
전기, 전자, 통신 및 컴퓨터 산업이 급속히 발전함에 따라 고성능, 고안전성의 이차 전지에 대한 수요는 점차 증가되어 왔고, 특히 전기, 전자 제품의 경박 단소화 및 휴대화 추세에 따라 이 분야의 핵심 부품인 이차전지도 경량화, 소형화가 요구되고 있다.With the rapid development of the electrical, electronics, telecommunications and computer industries, the demand for high performance and high safety secondary batteries has been gradually increasing. Secondary batteries are also required to be lighter and smaller.
또한, 자동차의 대량보급에 따른 대기오염과 소음 등의 환경공해 문제 및 석유 고갈에 따른 새로운 형태의 에너지 수급원의 필요성이 대두됨에 따라 이를 해결할 수 있는 전기 자동차 개발의 필요성이 증가되어 왔으며 이들의 동력원으로서 고출력, 고에너지 밀도를 갖는 전지의 개발이 요구되어 지고 있다.In addition, as the necessity of new forms of energy supply and demand due to air pollution and noise caused by mass distribution of automobiles and the depletion of oil has emerged, the necessity of developing electric vehicles to solve this problem has increased. As a result, development of batteries having high power and high energy density has been demanded.
이와 같은 요구에 부응하여 최근 가장 많은 각광을 받고 있는 고성능 차세대 첨단 신형 전지중의 하나가 리튬 고분자 이차전지(Lithium Polymer Battery, LPB)이다. LPB는 크게 부극(anode), 고분자 전해질(polymer electrolyte), 정극(cathode)으로 구성되는데, 부극 활물질로는 리튬, 탄소등이 사용되고, 고분자 전해질은 고분자와 염, 비수계 유기용매 및 기타첨가제 등으로 구성되며, 정극활물질로는 전이금속산화물, 금속칼코겐 화합물, 전도성 고분자 등이 사용된다.In order to meet such demands, one of the high-performance, next-generation advanced new batteries, which has been attracting the most attention recently, is a lithium polymer battery (LPB). LPB is largely composed of an anode, a polymer electrolyte, and a cathode, and lithium, carbon, etc. are used as the anode active material, and the polymer electrolyte is composed of polymers, salts, non-aqueous organic solvents, and other additives. The positive electrode active material is composed of a transition metal oxide, a metal chalcogen compound, a conductive polymer, and the like.
액체 전해질을 이용한 기존의 리튬 이온 전지(Lithium Ion Battery, LIB)는 안전성에 문제가 제기되고 있어, 이를 보완하는 전극물질과 안전 장치를 장착하는 방법등이 개발되고 있으나 제조단가가 비싸고 대형이차 전지로 적용하기 어려운 문제점이 있다.Lithium ion batteries (LIBs) using liquid electrolytes have raised safety issues, and methods for mounting electrode materials and safety devices have been developed. However, manufacturing costs are high and large secondary batteries There is a problem that is difficult to apply.
이에 반하여 고분자 전해질을 사용하는 LPB는 보다 값싸게 제조할 수 있고, 크기나 모양을 원하는 대로 조절할 수 있으며, 안전하고, 단위무게당 에너지 밀도가 크다는 장점을 가진다. 따라서 유연성을 갖는 박막의 LPB는 휴대용 코드리스 전자제품 이외에도 적층에 의한 고전압·대용량의 전지 개발이 용이하여 전기 자동차용 전원으로도 개발이 가능하다.On the contrary, LPB using a polymer electrolyte can be manufactured more inexpensively, can be adjusted in size or shape as desired, and is safe and has a high energy density per unit weight. Therefore, the flexible thin film LPB can be developed as a power source for electric vehicles because it is easy to develop high voltage and large capacity batteries by lamination as well as portable cordless electronic products.
이러한 우수한 장점을 가지는 LPB를 상업화하기 위하여, 우수한 이온 전도 특성, 전기화학적 안정성 및 우수한 전극과의 계면특성 등을 만족시키는 고분자 전해질을 개발하려는 많은 연구가 진행되어 왔다.In order to commercialize LPB having such excellent advantages, many studies have been conducted to develop polymer electrolytes that satisfy excellent ion conduction properties, electrochemical stability, and interfacial properties with electrodes.
초기에는 주로 폴리에틸렌옥사이드, 폴리프로필렌옥사이드 등을 근간으로 하는 무용매계 고분자 전해질에 관한 연구가 오랫동안 진행되어 왔으나(미합중국특허 제5,102,752호), 상온 전도도가 매우 낮은 문제점 때문에, 현재 폴리아크릴로니트릴, 폴리비닐클로라이드, 폴리비닐리덴플루오라이드, 폴리메틸메타크릴레이트 등의 고분자에 에틸렌카보네이드, 프로필렌카보네이트 등의 유기용매를 염과 함께 첨가하여 10-3S/cm 이상의 높은 이온전도도를 나타내는 젤 형태의 가소화된 고분자 전해질들에 관한 연구가 진행되고 있다(O. Bohnke et al., Solid State Ionics,66, 97(1993), 미합중국특허 제5,219,697호).Initially, studies on solvent-free polymer electrolytes mainly based on polyethylene oxide and polypropylene oxide have been conducted for a long time (US Pat. No. 5,102,752). Gelation plasticization showing high ionic conductivity of 10 -3 S / cm or more by adding organic solvents such as ethylene carbonate and propylene carbonate together with salts to polymers such as chloride, polyvinylidene fluoride and polymethyl methacrylate Studies on the polymer electrolytes have been conducted (O. Bohnke et al., Solid State Ionics, 66 , 97 (1993), US Pat. No. 5,219,697).
그러나, 폴리아크릴로니트릴, 폴리비닐클로라이드, 폴리비닐리덴플루오라이드를 기초로 한 젤 고분자 전해질은 필름의 기계적 물성은 우수하나 첨가된 유기용매와 고분자간의 상용성이 좋지않아서 유기용매의 새어나옴(leakage)현상에 따른 이온 전도 특성 및 전극과의 계면에서의 안정성 등에 있어서 문제가 되고 있다.However, the gel polymer electrolyte based on polyacrylonitrile, polyvinyl chloride, and polyvinylidene fluoride has excellent mechanical properties of the film, but the organic solvent leaks due to poor compatibility between the added organic solvent and the polymer. This is a problem in ion conduction characteristics due to the phenomenon and stability at the interface with the electrode.
반면에, 폴리메틸메타크릴레이트와 같은 아크릴레이트 계열의 고분자를 기초로 한 젤 고분자 전해질의 경우 가소제와의 상용성은 우수하나 기계적 물성이 취약하여 유기용매의 함량에 따라 필름이 열화되는 단점이 있다.On the other hand, gel polymer electrolytes based on acrylate-based polymers such as polymethyl methacrylate have excellent compatibility with plasticizers, but have a disadvantage in that the film deteriorates depending on the content of the organic solvent because of poor mechanical properties.
이에 본 발명자들은 상기의 문제점을 해결하기 위한 연구를 수행한 결과, 높은 유기용매의 함량에서도 기계적 물성이 유지되는 고분자 및 유기용매와의 상용성이 우수한 고분자들 각각의 특성을 이용하여 비닐리덴플루오라이드 계열의 고분자와 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머가 블랜드된 젤 고분자 전해질을 제조할 수 잇음을 알아내고 본 발명을 완성하였다.Accordingly, the present inventors have conducted research to solve the above problems, and as a result, vinylidene fluoride is used by using polymers having excellent mechanical compatibility with high organic solvents and polymers having excellent compatibility with organic solvents. The present invention was completed by finding out that a polymer polymer of a series and an ionomer copolymerized with methyl methacrylate and itaconic acid alkali salt can be prepared.
따라서, 본 발명의 목적은 이온전도 특성, 전기화학적 안정성, 기계적 물성 및 계면특성이 우수한 새로운 젤 고분자 전해질 조성물을 제공함에 있다.Accordingly, an object of the present invention is to provide a new gel polymer electrolyte composition having excellent ion conductivity, electrochemical stability, mechanical properties and interfacial properties.
본 발명의 또다른 목적은 이온전도 특성, 전기화학적 안정성, 기계적 물성 및 계면특성이 우수한 새로운 젤 고분자 전해질 조성물의 제조방법을 제공함에 있다.Still another object of the present invention is to provide a method for preparing a new gel polymer electrolyte composition having excellent ion conductivity, electrochemical stability, mechanical properties and interfacial properties.
도 1은 비닐리덴플루오라이드 계열의 고분자와 본 발명에 의한 젤 고분자 전해질의 온도에 따른 이온전도 특성비교,1 is a comparison of the ion conductivity characteristics according to the temperature of the vinylidene fluoride-based polymer and the gel polymer electrolyte according to the present invention,
도 2는 본 발명에 의한 젤 고분자 전해질의 리튬전극과의 계면저항을 나타낸 것이다.Figure 2 shows the interfacial resistance with the lithium electrode of the gel polymer electrolyte according to the present invention.
본 발명은 이차전지용 고분자 전해질 조성물에 있어서, 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머와 비닐리덴플루오라이드 계열의 고분자가 블랜드된 젤 고분자 매트릭스와, 상기 젤 고분자 매트릭스에 리튬염과 무기물이 첨가된 유기용매가 함유된 것을 특징으로 하는 젤 고분자 전해질 조성물 임을 특징으로 한다.The present invention relates to a polymer electrolyte composition for a secondary battery, wherein a gel polymer matrix in which an ionomer copolymerized with methyl methacrylate and an itaconic acid alkali salt and a vinylidene fluoride-based polymer are blended, and a lithium salt and an inorganic material in the gel polymer matrix Gel polymer electrolyte composition characterized in that the added organic solvent is contained.
또한, 본 발명은 이차전지용 고분자 전해질 조성물의 제조방법에 있어서, 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머와 비닐리덴플루오라이드 계열의 고분자를 공용매를 이용하여 블랜딩하는 단계와,상기 블랜딩된 용액에 유기용매와 리튬염을 첨가한 후, 전기 용액에 무기물을 첨가하여 제조한 균일한 용액을 유리판에 캐스팅하여 공용매를 증발시키는 단계로 구성되어지는 것을 특징으로 하는 젤 고분자 전해질 조성물의 제조방법 임을 특징으로 한다.In addition, the present invention is a method for producing a polymer electrolyte composition for a secondary battery, the step of blending a polymer of the ionomer and vinylidene fluoride-based polymer copolymerized with methyl methacrylate and itaconic acid alkali salt using the co-solvent, the blending After the addition of the organic solvent and the lithium salt to the prepared solution, and preparing a gel polymer electrolyte composition comprising the step of evaporating the co-solvent by casting a uniform solution prepared by adding the inorganic material to the electric solution on a glass plate Characterized by the method.
본 발명에 의한 젤 고분자 전해질 조성물은 폴리비닐리덴플루오라이드, 비닐리덴플루오라이드와 핵사플루오로프로필렌의 공중합체, 비닐리덴플루오라이드와 트리플루오로에틸렌의 공중합체, 비닐리덴플루오라이드와 테트라플루오로에틸렌의 공중합체 등과 같은 비닐리덴플루오라이드 계열의 고분자와 메틸메타크릴레이트와 이타콘산 알카리염의 공중합체 이오노머와의 블랜드를 통하여 제조된 고분자 매트릭스에 에틸렌카보네이트, 프로필렌카보네이트, 디메틸카보네이트 등과 같은 유기용매와 리튬퍼클로레이트, 리튬헥사플루오로포스페이트, 리튬테트라플루오로보레이트 등과 같은 리튬염을 첨가하고, 여기에 알루미늄옥사이드, 리튬알루미늄옥사이드, 실리카, 제올라이트 등의 무기물을 첨가하여 제조하는데, 본 발명에서 사용된 이타콘산 알카리염으로는 I족의 알카리금속염은 모두 가능하나, 리튬염, 나트륨염 또는 칼륨염이 바람직하다.Gel polymer electrolyte composition according to the present invention is a polyvinylidene fluoride, a copolymer of vinylidene fluoride and nucleus fluoropropylene, a copolymer of vinylidene fluoride and trifluoroethylene, vinylidene fluoride and tetrafluoroethylene Organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate and lithium perchlorate in a polymer matrix prepared through a blend of a vinylidene fluoride-based polymer such as a copolymer of It is prepared by adding a lithium salt such as lithium hexafluorophosphate, lithium tetrafluoroborate and the like, and adding inorganic materials such as aluminum oxide, lithium aluminum oxide, silica, zeolite, and the like. Alkali metal salts of Group I can be used as the alkali salt, but lithium salt, sodium salt or potassium salt is preferable.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
우선, 이오노머를 제조하기 위하여 메틸메타크릴레이트와 이타콘산 단량체를 일정한 비율로 첨가하여 일반식(Ⅰ)과 같은 화학구조를 갖는 여러 종류의 메틸메타크릴레이트와 이타콘산의 공중합체를 합성한다.First, to prepare ionomers, methylmethacrylate and itaconic acid monomers are added at a constant ratio to synthesize copolymers of various kinds of methyl methacrylate and itaconic acid having the chemical structure of general formula (I).
X = 이타콘산 몰%X = mol of itaconic acid
(Ⅰ)(Ⅰ)
위와 같은 고분자를 합성하기 위하여 테트라하이드로퓨란을 용매로 사용하여 일정량의 단량체인 메틸메타크릴레이트와 이타콘산을 함께 반응기에 넣고 질소 분위기하에서 교반한다.In order to synthesize the above polymer, tetrahydrofuran is used as a solvent, methyl methacrylate and itaconic acid, which are a certain amount of monomer, are put together in a reactor and stirred under a nitrogen atmosphere.
교반이 끝난 후 개시제를 일정량 주입하고 반응시키고, 반응이 끝난 후의 생성물을 메탄올 용매속에 침전시켜 공중합체를 여과하여 얻는다. 이렇게 얻어진 공중합체를 상온에서 건조시킨 후 진공오븐에서 다시 건조시켜 용매를 완전히 제거한다.After stirring, a certain amount of initiator is injected and reacted, and the product after the reaction is precipitated in methanol solvent to obtain a copolymer by filtration. The copolymer thus obtained is dried at room temperature and then dried in a vacuum oven to completely remove the solvent.
합성된 메틸메타크릴레이트와 이타콘산의 공중합체를 이오노머로 만들기 위해 0.1노르말농도의 알카리메탈 하이드록사이드의 메탄올 용액을 이용하여 메타크릴레이트와 이타콘산의 공중합체를 중화하여 일반식(Ⅱ)와 같은 화학구조를 갖는 원하는 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머를 얻는다.In order to make the synthesized copolymer of methyl methacrylate and itaconic acid into an ionomer, a copolymer of methacrylate and itaconic acid was neutralized using methanol solution of alkali metal hydroxide of 0.1 normal concentration to formula (II) and The ionomer obtained by copolymerizing the desired methyl methacrylate and the itaconic acid alkali salt having the same chemical structure is obtained.
이때 얻어진 메틸메타크릴레이트와 이타콘산 알카리염의 공중합체 이오노머는 10,000-200,000으로서, 이오노머 내의 이타콘산 알카리염의 함량이 0에서 50몰%, 바람직하게는 2에서 30몰%인 고분자이다.The copolymer ionomer of the methyl methacrylate and the itaconic acid alkali salt obtained at this time is 10,000-200,000, and the content of the itaconic acid alkali salt in the ionomer is 0 to 50 mol%, preferably 2 to 30 mol%.
M = Li+, Na+, K+ M = Li + , Na + , K +
X = 이타콘산의 알카리염 몰%X = mol of alkaline salt of itaconic acid
(Ⅱ)(Ⅱ)
합성한 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머와 분자량이 100,000에서 350,000까지의 폴리비닐리덴플루오라이드 고분자와 헥사플루오로프로필렌의 조성이 1 ∼ 30몰%인 비닐리덴플루오라이드와 헥사플루오로프로필렌의 공중합체, 트리플루오로에틸렌의 조성이 1 ∼ 30몰%인 비닐리덴플루오라이드와 트리플루오로에틸렌의 공중합체, 테트라플루오로에틸렌의 조성이 1 ∼ 30몰%인 비닐리덴플루오라이드와 테트라플루오로에틸렌에서 선택된 1종의 비닐리덴플루오라이드 계열의 고분자를 중량비로 1 : 1 내지 1 : 10, 바람직하게는 1 : 1 내지 1 : 9까지의 비율로 정량하여 공용매인 테트라하이드로퓨란에 녹여 균일한 용액을 만든다.Synthesized methyl methacrylate and itaconic acid alkali salt copolymerized ionomer, polyvinylidene fluoride polymer having a molecular weight of 100,000 to 350,000, vinylidene fluoride and hexafluorine having a composition of 1 to 30 mol% Copolymer of low propylene, vinylidene fluoride having a composition of trifluoroethylene of 1 to 30 mol%, copolymer of trifluoroethylene, vinylidene fluoride having a composition of tetrafluoroethylene of 1 to 30 mol%, One vinylidene fluoride-based polymer selected from tetrafluoroethylene is quantified in a ratio of 1: 1 to 1: 10, preferably 1: 1 to 1: 9 by weight, and dissolved in tetrahydrofuran, a cosolvent. Make a uniform solution.
여기에 고분자를 기준으로 50중량%에서 500중량%, 바람직하게는 100 ∼ 300중량%인 에틸렌 카보네이트, 프로필렌 카보네이트, 디메틸카보네이트, 디에틸카보네이트, 감마부틸로락톤, 에틸메틸카보네이트, 디메톡시에탄, 디에톡시에탄 또는 2-메틸테트라하이드로퓨란에서 선택된 1종 또는 2종 이상의 혼합물을 첨가하고, 고분자를 기준으로 1중량%에서 50중량%, 바람직하게는 5 ∼ 25중량%인 리튬퍼클로레이트, 리튬헥사플루오로포스페이트, 리튬트리플레이트, 리튬비스트리플루오로메틸설포닐이미드 또는 리튬테트라플루오로보레이트염에서 선택된 1종의 염을 첨가하며, 고분자를 기준으로 1에서 50중량%, 바람직하게는5 ∼ 25중량%인 알루미늄옥사이드, 리튬알루미늄옥사이드, 실리카 또는 제올라이트에서 선택된 1종의 무기물을 첨가하여 제조된 균일한 용액을 유리판에 캐스팅하여 공용매를 증발시킨 후 고분자 필름을 얻는다.50 to 500% by weight, preferably 100 to 300% by weight, based on the polymer of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, gamma butyrolactone, ethyl methyl carbonate, dimethoxyethane, die One or two or more mixtures selected from oxyethane or 2-methyltetrahydrofuran are added, and lithium perchlorate and lithium hexafluoro are 1 to 50% by weight, preferably 5 to 25% by weight, based on the polymer. One salt selected from phosphate, lithium triflate, lithium bistrifluoromethylsulfonylimide or lithium tetrafluoroborate salt is added and is 1 to 50% by weight, preferably 5 to 25% by weight, based on the polymer. Uniform solution prepared by adding one inorganic material selected from aluminum oxide, lithium aluminum oxide, silica or zeolite Cast on a glass plate to evaporate the cosolvent to obtain a polymer film.
비닐리덴플루오라이드 계열의 고분자 중 비닐리덴플루오라이드와 헥사플루오로프로필렌의 공중합체를 이타콘산 리튬염의 함량이 4몰%인 메틸메타크릴레이트와 이타콘산 리튬염 공중합체와의 7 : 3(중량비) 블랜드를 기초로 하여 제조한 젤 고분자 전해질의 온도에 따른 이온 전도 특성을 도 1에 나타내었으며, 상기방법에 의하여 제조된 고분자 전해질의 리튬 전극과의 계면 저항에 관한 결과를 도 2에 나타내었다.The copolymer of vinylidene fluoride and hexafluoropropylene in the vinylidene fluoride-based polymer is 7: 3 (weight ratio) of methyl methacrylate and lithium itaconate salt having a content of 4 mol% of lithium itaconic acid salt. The ion conduction characteristics of the gel polymer electrolyte prepared based on the blend according to the temperature are shown in FIG. 1, and the results regarding the interfacial resistance with the lithium electrode of the polymer electrolyte prepared by the above method are shown in FIG. 2.
상기한 방식으로 제조된 고분자 전해질은 상온 이온 전도도가 2.2×10-3S/cm로 기존의 젤 형태의 고분자 전해질보다 우수하거나 유사하며, 저온 이온 전도 특성도 10-4S/cm 수준을 유지하여 매우 우수함을 확인할 수 있다. 이와 동시에 리튬 전극과의 계면안정성도 이오노머를 도입함에 따라 개선되어짐을 계면저항의 감소를 통하여 확인할 수 있다. 이로 인하여 상기 방식으로 제조된 젤 고분자 전해질은 리튬 고분자 이차전지용 고분자 전해질의 재료로서 유용하게 사용될 수 있을 것으로 판단된다.The polymer electrolyte prepared in the above-described manner has room temperature ion conductivity of 2.2 × 10 -3 S / cm, which is superior to or similar to that of a conventional gel-type polymer electrolyte, and maintains low temperature ion conductivity of 10 -4 S / cm. It can be confirmed that it is very excellent. At the same time, it can be confirmed that the interface stability with the lithium electrode is also improved by introducing the ionomer through the reduction of the interface resistance. For this reason, the gel polymer electrolyte prepared in the above manner may be usefully used as a material of the polymer electrolyte for lithium polymer secondary batteries.
이하 실시예 및 시험예를 통하여 본 발명을 상세히 설명한다. 그러나 이들 실시예 및 시험예는 본 발명을 상세히 설명하기 위한 것으로 제공되는 것일 뿐, 본 발명의 권리범위가 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through Examples and Test Examples. However, these examples and test examples are provided only to explain the present invention in detail, and the scope of the present invention is not limited thereto.
<실시예 1><Example 1>
이타콘산 리튬염의 함량이 4몰%인 메틸메타크릴레이트와 이타콘산 리튬염의 공중합체를 비닐리덴플루오라이드 계열의 고분자 중 비닐리덴플루오라이드와 헥사플루오로프로필렌의 공중합체와 중량비로 3 : 7 이 되도록 정량한 후 에틸렌카보네이트와 프로필렌카보네이트의 1 : 1(몰비) 혼합물을 고분자의 전체무게를 기준으로 300중량%가 되도록 첨가하고, 리튬퍼클로레이트를 고분자의 전체무게를 기준으로 10중량%, 실리카를 고분자의 전체무게를 기준으로 10중량%가 되도록 첨가하여 테트라하이드로퓨란 용매에 녹인 후에 테프론판에 캐스팅하여 용매를 증발시켜 젤 고분자 전해질 필름을 얻었다.The copolymer of methyl methacrylate and lithium itaconic acid salt containing 4 mol% lithium itaconic acid salt in a vinylidene fluoride-based polymer with a copolymer of vinylidene fluoride and hexafluoropropylene in a weight ratio of 3: 7 After quantification, a 1: 1 (molar ratio) mixture of ethylene carbonate and propylene carbonate is added to 300% by weight based on the total weight of the polymer, lithium perchlorate is 10% by weight based on the total weight of the polymer, and silica is used 10 wt% of the total weight was added, dissolved in a tetrahydrofuran solvent, cast on teflon plate, and the solvent was evaporated to obtain a gel polymer electrolyte film.
<실시예 2><Example 2>
폴리비닐리덴플루오라이드를 이타콘산 리튬염의 함량이 4몰%인 메틸메타크릴레이트와 이타콘산 리튬염의 공중합체와 블랜드 한 것을 제외하고는 상기한 실시예 1에서와 같은 구성성분 및 조성을 갖는 혼합물을 사용하여 실시예 1과 동일한 방법으로 젤 고분자 전해질을 제조하였다.A mixture having the same constituents and compositions as in Example 1 was used except that polyvinylidene fluoride was blended with a copolymer of methyl methacrylate and lithium itaconate having a content of lithium itaconic acid salt of 4 mol%. To prepare a gel polymer electrolyte in the same manner as in Example 1.
<실시예 3><Example 3>
비닐리덴플루오라이드와 테트라플루오로에틸렌의 공중합체와 이타콘산 리튬염의 함량이 4몰%인 메틸메타크릴레이트와 이타콘산 리튬염의 공중합체를 블랜드한 것을 제외하고는 상기한 실시예 1에서와 같은 구성성분 및 조성을 갖는 혼합물을 사용하여 실시예 1과 동일한 방법으로 젤 고분자 전해질을 제조하였다.The same composition as in Example 1 except that a copolymer of vinylidene fluoride and tetrafluoroethylene and a copolymer of methyl methacrylate and lithium itaconate having a content of 4 mol% of lithium itaconate salt were blended. Gel polymer electrolyte was prepared in the same manner as in Example 1, using a mixture having components and compositions.
<실시예 4><Example 4>
폴리비닐리덴플루오라이드와 이타콘산 리튬염의 함량이 4몰%인 메틸메타크릴레이트와 이타콘산 리튬염의 공중합체를 중량비로 6 : 4 가 되도록 혼합한 것을 제외하고는 상기한 실시예 1에서와 같은 구성성분 및 조성을 갖는 혼합물을 사용하여 실시예 1과 동일한 방법으로 젤 고분자 전해질을 제조하였다.The same constitution as in Example 1 except that a copolymer of methyl methacrylate having a content of 4 mol% of polyvinylidene fluoride and lithium itaconate and lithium itaconate was mixed in a weight ratio of 6: 4 Gel polymer electrolyte was prepared in the same manner as in Example 1, using a mixture having components and compositions.
<실시예 5>Example 5
비닐리덴플루오라이드와 테트라플루오로에틸렌의 공중합체와 이타콘산 리튬염의 함량이 4몰%인 메틸메타크릴레이트와 이타콘산 리튬염의 공중합체를 중량비로 6 : 4 가 되도록 혼합한 것을 제외하고는 상기한 실시예 1에서와 같은 구성성분 및 조성을 갖는 혼합물을 사용하였고 동일한 방법으로 젤 고분자 전해질을 제조하였다.Except that the copolymer of vinylidene fluoride and tetrafluoroethylene and the copolymer of methyl methacrylate and lithium itaconate salt having a content of 4 mol% of lithium itaconate salt in a weight ratio of 6: 4 Mixtures having the same composition and composition as in Example 1 were used and gel polymer electrolytes were prepared in the same manner.
<시험예 1><Test Example 1>
실시예 1 내지 실시예 5에서 제조한 젤 고분자 전해질의 이온전도 특성을 알아보기 위하여 각각의 고분자 전해질 필름을 스테인레스 스틸 전극과 접착시킨 후, 폴리에틸렌이 코팅된 알루리늄 포장재로 밀봉한 다음 주파수응답 분석기(Frequency Response Analyzer, FRA)를 이용하여 1 MHz ~ 100 Hz 사이의 입력전압의 주파수에 따른 전류의 변화로부터 저항값을 계산하여 이온전도도를 측정하였다.In order to examine the ion conduction characteristics of the gel polymer electrolytes prepared in Examples 1 to 5, each polymer electrolyte film was bonded with a stainless steel electrode, and then sealed with a polyethylene-coated aluminium packaging material and then a frequency response analyzer. Using the (Frequency Response Analyzer, FRA) the ion conductivity was measured by calculating the resistance value from the change of current according to the frequency of the input voltage between 1 MHz ~ 100 Hz.
<시험예 2><Test Example 2>
실시예 1 내지 실시예 5에서 제조한 젤 고분자 전해질의 계면특성을 알아보기 위하여 리튬전극을 고분자 전해질 필름의 양쪽에 집전체와 같이 접착시킨다음 상기 주파수응답분석기를 이용하여 1 MHz ~ 50 mHz 사이의 입력전압의 주파수 변화에 따른 전류의 변화로부터 1 KHz 이하의 주파수 범위내에서 계면저항을 관찰하였다.In order to examine the interfacial properties of the gel polymer electrolytes prepared in Examples 1 to 5, a lithium electrode was attached to both sides of the polymer electrolyte film as a current collector, and then, between 1 MHz and 50 mHz using the frequency response analyzer. The interfacial resistance was observed within the frequency range of 1 KHz or less from the change of current according to the frequency change of the input voltage.
본 발명에 의한 젤 고분자 전해질 조성물은 유기용매와의 상용성이 상용성이 향상되어 벌크에서의 이온전도 특성, 계면안정성 등이 향상되고, 전기화학적으로도 안정한 장점을 지닌다.Gel polymer electrolyte composition according to the present invention has the advantage that the compatibility with the organic solvent is improved to improve the ion conductivity characteristics, interfacial stability, etc. in the bulk, and is also electrochemically stable.
즉, 이온전도특성이 우수한 비닐리덴플루오라이드 계열의 고분자에 유기용매와의 상용성이 우수한 메틸메타크릴레이트와 이타콘산 알카리염이 공중합된 이오노머를 블랜드를 통하여 도입함으로써 젤 고분자 전해질내의 유기용매가 비교적 긴 시간동안 고분자내에 안전하게 유지되게 하여 유기용매의 새어나옴(leakage)현상에 따른 고분자 전해질내의 내부저항의 증가와 그로 인한 이온 전도도의 감소를 억제하며 고분자 전해질과 전극간의 반응성을 억제하여 계면에서의 안정성을 증대시킬 수 있다.In other words, the organic solvent in the gel polymer electrolyte is relatively introduced by introducing a vinylidene fluoride-based polymer having excellent ion conduction properties into an ionomer copolymerized with methyl methacrylate and itaconic acid alkali salt having excellent compatibility with the organic solvent through a blend. It keeps safely in the polymer for a long time, thereby suppressing the increase of internal resistance in the polymer electrolyte and the decrease of ionic conductivity due to the leakage of organic solvent, and the stability at the interface by suppressing the reactivity between the polymer electrolyte and the electrode. Can be increased.
따라서, 본 발명에 의한 젤 고분자 전해질 조성물을 기존의 리튬 이차전지에 응용할 경우 충분한 경쟁력으로 기존의 이차전지 시장에서 우위를 확보할 수 있다.Therefore, when the gel polymer electrolyte composition according to the present invention is applied to a conventional lithium secondary battery, it is possible to secure an advantage in the existing secondary battery market with sufficient competitiveness.
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