JP2007165150A - イオン伝導体 - Google Patents
イオン伝導体 Download PDFInfo
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- JP2007165150A JP2007165150A JP2005360766A JP2005360766A JP2007165150A JP 2007165150 A JP2007165150 A JP 2007165150A JP 2005360766 A JP2005360766 A JP 2005360766A JP 2005360766 A JP2005360766 A JP 2005360766A JP 2007165150 A JP2007165150 A JP 2007165150A
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 9
- 125000001033 ether group Chemical group 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 60
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 35
- 239000011737 fluorine Substances 0.000 claims description 35
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000005587 carbonate group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 101100335429 Caenorhabditis elegans cfz-2 gene Proteins 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- JVSZDADEHKJNLY-UHFFFAOYSA-N C(O)(O)=O.[F] Chemical group C(O)(O)=O.[F] JVSZDADEHKJNLY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 5
- 150000005676 cyclic carbonates Chemical group 0.000 abstract description 4
- 229920001774 Perfluoroether Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 18
- -1 alkali metal salt Chemical class 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
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- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- 0 CCC1C(CC)C(C2)C2*1 Chemical compound CCC1C(CC)C(C2)C2*1 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- METIGIXCFPEQNM-UHFFFAOYSA-M amino-(2-bromoethyl)-dimethylazanium;bromide Chemical compound [Br-].C[N+](C)(N)CCBr METIGIXCFPEQNM-UHFFFAOYSA-M 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- FFZANLXOAFSSGC-UHFFFAOYSA-N phosphide(1-) Chemical compound [P-] FFZANLXOAFSSGC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
-
- 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
-
- 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
- H01M10/056—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
【解決手段】環状カーボネート基とエーテル基を側鎖に有するイオン伝導性化合物(I)と電解質塩(II)とを含み、該イオン伝導性化合物(I)が、側鎖にフルオロエーテル基を有する非晶性含フッ素ポリエーテル化合物またはその架橋物であるイオン伝導体。
【選択図】なし
Description
一方、カーボネート単位をポリマー主鎖に導入したり、アクリレートのエステル部分をカーボネートとし側鎖に導入するとともに、EO含有非フッ素系アクリレートと共重合させることも提案されている(特許文献5)。さらにビニルカーボネートとEO含有非フッ素系アクリレートと共重合させることも提案されている(特許文献6、特許文献7)。
しかし、これらは耐熱性、耐酸化性、イオン伝導性の点で、不充分である。
該イオン伝導性化合物(I)が、式(I):
−(M1)−(M2)−(M3)− (I)
[式中、構造単位M1は、式(1):
構造単位M3は、式(3):
−(M1)−(M2)−(M3)− (I)
[式中、構造単位M1は、式(1):
構造単位M3は、式(3):
であり、
構造単位M1を0.1〜90モル%、構造単位M2を0〜99.9モル%および構造単位M3を0〜99.9モル%含み、かつ構造単位M2と構造単位M3の合計が10〜99.9モル%である]で示される非晶性含フッ素ポリエーテル化合物(IA)である。
−Ra−Rf3−X (2a)
(式中、−Rf3−は−(OCF2CF2CF2)n1−、−(CF2CF2CF2O)n1−、−(OCFZ1CF2)n1−、−(CFZ1CF2O)n1−、−(OCF2CFZ1)n1−、−(CF2CFZ1O)n1−、−(OCFZ2)n1−、−(CFZ2O)n1−、−(OCH2CF2CF2)n1−、−(CH2CF2CF2O)n1−、−(OCF2CF2CH2)n1−、−(CF2CF2CH2O)n1−、−(OCH2CH2CF2)n1−、−(CH2CH2CF2O)n1−、−(OCF2CH2CH2)n1−、−(CF2CH2CH2O)n1−、−(OCF2CF2CF2CF2)n1−、−(CF2CF2CF2CF2O)n1−、−(OCFZ2CH2)n1−、−(CH2CFZ2O)n1−、−(OCH(CH3)CF2CF2)n1−、−(CH(CH3)CF2CF2O)n1−、−(OCF2CF2CH(CH3))n1−、−(CF2CF2CH(CH3)O)n1−、−(OCZ3 2)n1−および−(CZ3 2O)n1−(式中、Z1、Z2は同じかまたは異なり、いずれもH、FまたはCF3;Z3はCF3;n1は1〜3の整数)よりなる群から選ばれる少なくとも1種を含む含フッ素エーテル単位;Xは水素原子、ハロゲン原子または炭素数1〜20の架橋性官能基を含んでいてもよい含フッ素アルキル基;Raは結合手またはフッ素原子を含んでいてもよいアルキレン基;ただし、−Ra−Rf3−X中に−O−O−結合を含まない)で示される基があげられる。
などがあげられる。これらのうち誘電率の向上性に優れる点でH、−CH3、F、−CF3などの架橋性基を有さない基;さらに架橋性に優れていることから−CH2OH、−COOCH3、−COOH、−CONH2、−CON(CH3)2、−C≡N、
−(CF2CF2O)n1−CH3 (n1=1〜40の整数)、
−CH2−O−CF2CF2−H、
−CH2−O−CF2CF2−F、
−CH2−O−CF2CF2−CF3、
−CH2−O−CF2CF2CF2−H、
−CH2−O−CF2CF2CF2−F、
−CH2−O−CF2CF2CF2−CF3、
−CH2−O−CF2−H、
−CH2−O−CF2−F、
−CH2−O−CF2−CF3、
−CH2−O−CH2CF2CF2−H、
−CH2−O−CH2CF2CF2−F、
−CH2−O−CH2CF2CF2−CF3、
−CH2−O−CF(CF3)CF2−H、
−CH2−O−CF(CF3)CF2−F、
−CH2−O−CF(CF3)CF2−CF3、
−CH2−O−CF(CF3)−H、
−CH2−O−CF(CF3)−CF3、
−CH2CF2CF2O−H、
−CH2CF2CF2O−CH3、
−CH2CF2CF2O−CF3、
−CH2CF2CF2CF2O−H、
−CH2CF2CF2CF2O−CH3、
−CH2CF2CF2CF2O−CF3、
−CH2CF2O−H、
−CH2CF2O−CH3、
−CH2CF2O−CF3、
−CH2CH2CF2CF2O−H、
−CH2CH2CF2CF2O−CH3、
−CH2CH2CF2CF2O−CF3、
−CH2CF(CF3)CF2O−H、
−CH2CF(CF3)CF2O−CH3、
−CH2CF(CF3)CF2O−CF3、
−CH2CF(CF3)O−H、
−CH2CF(CF3)O−CH3、
−CH2CF(CF3)O−CF3
などのほか、式(2−1):
測定条件:282MHz(トリクロロフルオロメタン=0ppm)
1H−NMR:
測定条件:300MHz(テトラメチルシラン=0ppm)
Perkin Elmer社製フーリエ変換赤外分光光度計1760Xで室温にて測定する。
熱分解温度(Td0.1およびTd1.0)は、セイコーインストルメンツ(株)製のTG/DTA−6200を用いて室温から20℃/minで昇温したときのデータより算出する。
交流4端子法にて、室温にてイオン伝導率の測定を行う。インピーダンス測定装置としては東陽テクニカ(株)製のSI1280Bを用い、周波数は104Hz〜101Hzの範囲で測定を行う。
3電極式電圧測定セル(作用極、対極:白金、参照極:Li。宝泉(株)製のHSセル)に入れ、ポテンシオスタットで50mV/secで電位走引し、分解電流が0.1mA以上流れなかった範囲を耐電圧(V)とする。
攪拌装置を備えた100mlのガラス製四つ口フラスコに、側鎖に環状カーボネート基を有する単量体(m1−1):
合成例1で得た共重合体2gとプロピレンカーボネート0.2gの混合物に電解質としてLiN(SO2C2F5)2を過飽和量溶解させ、6mlサンプル瓶中で一晩静置した。一晩後、上層に透明な重合体相、下層に固体が析出した。上層を取り出し、長方形の膜を作製したのち、イオン伝導率の測定を行ったところ、3.8×10-5S/cmであった。
合成例1で得た共重合体2gとアセトニトリル0.5gの混合物に電解質としてトリエチルメチルアンモニウムテトラフルオロボレート(TEMABF4)を過飽和量溶解させ、6mlのサンプル瓶中で一晩放置した。一晩後、上層に透明な重合体混合物相、下層に固体が析出した。上層を取り出し、耐電圧を測定したところ4.5Vを示した。
攪拌装置を備えた100mlのガラス製四つ口フラスコに、側鎖に環状カーボネート基を有する単量体(m1−1):
合成例2で得た共重合体2gとプロピレンカーボネート0.2gの混合物に電解質としてLiN(SO2C2F5)2を過飽和量溶解させ、6mlサンプル瓶中で一晩静置した。一晩後、上層に透明な重合体相、下層に固体が析出した。上層を取り出し、長方形の膜を作製したのち、イオン伝導率の測定を行ったところ、2.4×10-5S/cmであった。
合成例2で得た共重合体2gとアセトニトリル0.5gの混合物に電解質としてTEMABF4を過飽和量溶解させ、6mlのサンプル瓶中で一晩放置した。一晩後、上層に透明な重合体混合物相、下層に固体が析出した。上層を取り出し、耐電圧を測定したところ4.5Vを示した。
Claims (6)
- イオン伝導性化合物(I)と電解質塩(II)とを含み、
該イオン伝導性化合物(I)が、式(I):
−(M1)−(M2)−(M3)− (I)
[式中、構造単位M1は、式(1):
構造単位M2は、式(2):
構造単位M3は、式(3):
であり、
構造単位M1を0.1〜90モル%、構造単位M2を0〜99.9モル%および構造単位M3を0〜99.9モル%含み、かつ構造単位M2と構造単位M3の合計が10〜99.9モル%である]で示される非晶性含フッ素ポリエーテル化合物またはその架橋物であるイオン伝導体。 - 前記構造単位M1が、式(1)において、X1およびX2がHでX3がHまたはCH3である非フッ素系カーボネート基含有構造単位である請求項1記載のイオン伝導体。
- 前記構造単位M1が、式(1)において、X1およびX2がHでX3がFまたはCF3である含フッ素系カーボネート基含有構造単位である請求項1記載のイオン伝導体。
- 前記構造単位M2が、式(2)において、−Rf1が、式(2a):
−Ra−Rf3−X (2a)
(式中、−Rf3−は−(OCF2CF2CF2)n1−、−(CF2CF2CF2O)n1−、−(OCFZ1CF2)n1−、−(CFZ1CF2O)n1−、−(OCF2CFZ1)n1−、−(CF2CFZ1O)n1−、−(OCFZ2)n1−、−(CFZ2O)n1−、−(OCH2CF2CF2)n1−、−(CH2CF2CF2O)n1−、−(OCF2CF2CH2)n1−、−(CF2CF2CH2O)n1−、−(OCH2CH2CF2)n1−、−(CH2CH2CF2O)n1−、−(OCF2CH2CH2)n1−、−(CF2CH2CH2O)n1−、−(OCF2CF2CF2CF2)n1−、−(CF2CF2CF2CF2O)n1−、−(OCFZ2CH2)n1−、−(CH2CFZ2O)n1−、−(OCH(CH3)CF2CF2)n1−、−(CH(CH3)CF2CF2O)n1−、−(OCF2CF2CH(CH3))n1−、−(CF2CF2CH(CH3)O)n1−、−(OCZ3 2)n1−および−(CZ3 2O)n1−(式中、Z1、Z2は同じかまたは異なり、いずれもH、FまたはCF3;Z3はCF3;n1は1〜3の整数)よりなる群から選ばれる少なくとも1種を含む含フッ素エーテル単位;Xは水素原子、ハロゲン原子または炭素数1〜20の架橋性官能基を含んでいてもよい含フッ素アルキル基;Raは結合手またはフッ素原子を含んでいてもよいアルキレン基;ただし、−Ra−Rf3−X中に−O−O−結合を含まない)で示される構造単位である請求項1〜3のいずれかに記載のイオン伝導体。 - さらに有機溶媒(III)を含む請求項1〜4のいずれかに記載のイオン伝導体。
- 請求項1〜5のいずれかに記載のイオン伝導体からなる高分子電解質。
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JP2008293974A (ja) * | 2007-05-25 | 2008-12-04 | Commissariat A L'energie Atomique | 電解有機ガラス、その製造方法およびそれを含むデバイス |
WO2009110292A1 (ja) * | 2008-03-05 | 2009-09-11 | コニカミノルタホールディングス株式会社 | 電気化学表示素子 |
WO2011125436A1 (ja) * | 2010-03-31 | 2011-10-13 | Jsr株式会社 | 電解質組成物及び色素増感型太陽電池 |
WO2012043136A1 (ja) * | 2010-09-30 | 2012-04-05 | Jsr株式会社 | 電極用バインダー組成物、電極用スラリー、電極、及び電気化学デバイス |
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JP2014506275A (ja) * | 2010-12-17 | 2014-03-13 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | フッ素化コポリマー |
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JP2008293974A (ja) * | 2007-05-25 | 2008-12-04 | Commissariat A L'energie Atomique | 電解有機ガラス、その製造方法およびそれを含むデバイス |
WO2009110292A1 (ja) * | 2008-03-05 | 2009-09-11 | コニカミノルタホールディングス株式会社 | 電気化学表示素子 |
JP5585441B2 (ja) * | 2008-03-05 | 2014-09-10 | コニカミノルタ株式会社 | 電気化学表示素子 |
WO2011125436A1 (ja) * | 2010-03-31 | 2011-10-13 | Jsr株式会社 | 電解質組成物及び色素増感型太陽電池 |
US20120228026A1 (en) * | 2010-07-21 | 2012-09-13 | Sony Chemical & Information Device Corporation | Anisotropic conductive film, connection structure and method of producing the same |
US9515042B2 (en) * | 2010-07-21 | 2016-12-06 | Dexerials Corporation | Anisotropic conductive film, connection structure and method of producing the same |
WO2012043136A1 (ja) * | 2010-09-30 | 2012-04-05 | Jsr株式会社 | 電極用バインダー組成物、電極用スラリー、電極、及び電気化学デバイス |
JP5057125B2 (ja) * | 2010-09-30 | 2012-10-24 | Jsr株式会社 | 電極用バインダー組成物、電極用スラリー、電極、及び電気化学デバイス |
JP2014506275A (ja) * | 2010-12-17 | 2014-03-13 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | フッ素化コポリマー |
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