JP2014192074A - Polymer electrolyte gel composition for secondary battery use, and method for manufacturing the same - Google Patents
Polymer electrolyte gel composition for secondary battery use, and method for manufacturing the same Download PDFInfo
- Publication number
- JP2014192074A JP2014192074A JP2013067928A JP2013067928A JP2014192074A JP 2014192074 A JP2014192074 A JP 2014192074A JP 2013067928 A JP2013067928 A JP 2013067928A JP 2013067928 A JP2013067928 A JP 2013067928A JP 2014192074 A JP2014192074 A JP 2014192074A
- Authority
- JP
- Japan
- Prior art keywords
- gel composition
- polymer electrolyte
- electrolyte gel
- secondary battery
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 103
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title abstract description 21
- 229920001400 block copolymer Polymers 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 26
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 22
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 claims abstract description 21
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 halogen anion Chemical group 0.000 claims abstract description 17
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 15
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001879 gelation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 21
- 229910001416 lithium ion Inorganic materials 0.000 description 21
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 description 9
- 229910003002 lithium salt Inorganic materials 0.000 description 9
- 159000000002 lithium salts Chemical class 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000011244 liquid electrolyte Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920006324 polyoxymethylene Polymers 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 4
- 229940080818 propionamide Drugs 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-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
- 241000238366 Cephalopoda Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
Description
本発明は、二次電池用高分子電解質ゲル組成物およびその製造方法に関する。 The present invention relates to a polymer electrolyte gel composition for a secondary battery and a method for producing the same.
近年、携帯電話、携帯用コンピューター等のポータブル電子機器が多く登場し、その小型軽量化が図られている。それに伴い、電子機器のポータブル電源として、電池、特に二次電池の開発が活発に進められている。中でも、リチウムイオン二次電池は、高いエネルギー密度を実現できるものとして注目されており、薄型で折り曲げ可能な形状の自由度が高いものについても多く研究されている。 In recent years, many portable electronic devices such as mobile phones and portable computers have appeared, and their size and weight have been reduced. Accordingly, the development of batteries, particularly secondary batteries, has been actively promoted as portable power sources for electronic devices. In particular, lithium ion secondary batteries are attracting attention as being capable of realizing a high energy density, and many studies have been made on thin and high-flexible shapes that can be bent.
リチウムイオン二次電池としては、正極、負極および正負極間に介在するセパレータを含んで構成され、当該セパレータに電解質と非水系溶媒を含む液体電解質組成物が含浸したものが知られている。このようなリチウムイオン二次電池は、液体電解質組成物が液状であるため、イオン伝導性すなわち電池性能が高いが、液漏れや短絡事故による火災防止のために、液体電解質組成物を封入したり衝撃による事故を防いだりするための強固なケーシングが必須となり、電池の形状が制限され、薄型化や軽量化が困難であった。 Known lithium ion secondary batteries include a positive electrode, a negative electrode, and a separator interposed between the positive and negative electrodes, and the separator is impregnated with a liquid electrolyte composition containing an electrolyte and a non-aqueous solvent. Such a lithium ion secondary battery has high ionic conductivity, that is, battery performance because the liquid electrolyte composition is in a liquid state, but in order to prevent a fire due to liquid leakage or a short circuit accident, the liquid electrolyte composition may be enclosed. A strong casing for preventing accidents due to impact is essential, and the shape of the battery is limited, making it difficult to reduce the thickness and weight.
これに対し、高分子に電解質塩を溶解させた全固体状の高分子電解質組成物（以後「全固体型高分子電解質組成物」と称すことがある）を用いるリチウムイオン二次電池が知られている。全固体型高分子電解質組成物を用いるリチウムイオン二次電池は、漏出防止のための特別な構造を必要としない。また、全固体型高分子電解質組成物と電極、セパレータ等とを接着することができるので、電池の強度や形状保持性を高めることができる。したがって、電池を薄型化し、電池の形状自由度を高める上で有効である。しかしながら、全固体型高分子電解質組成物のイオン伝導性は液体電解質組成物のイオン伝導性に比較してかなり小さいという問題を有している。 On the other hand, a lithium ion secondary battery using an all-solid polymer electrolyte composition in which an electrolyte salt is dissolved in a polymer (hereinafter sometimes referred to as “all-solid polymer electrolyte composition”) is known. ing. A lithium ion secondary battery using an all-solid-type polymer electrolyte composition does not require a special structure for preventing leakage. In addition, since the all solid-type polymer electrolyte composition can be bonded to the electrode, the separator and the like, the strength and shape retention of the battery can be improved. Therefore, it is effective in reducing the thickness of the battery and increasing the degree of freedom of shape of the battery. However, the ionic conductivity of the all solid-type polymer electrolyte composition has a problem that it is considerably smaller than the ionic conductivity of the liquid electrolyte composition.
上記の問題を解決するものとして、高分子に電解液を保持させたゲル状の高分子電解質組成物（以後「高分子電解質ゲル組成物」と称すことがある）を用いるリチウムイオン二次電池が知られている。高分子電解質ゲル組成物を用いるリチウムイオン二次電池は、高分子電解質ゲル組成物において高分子マトリックスが電解液を保持しているために全固体型高分子電解質組成物を用いるリチウムイオン二次電池に比べて活物質との接触性およびイオン伝導性に優れており、また、セパレータに液体電解質組成物が含浸されたタイプのリチウムイオン二次電池に比べても漏液が起こりにくいという特徴を有することから注目を浴びている。 As a solution to the above problem, a lithium ion secondary battery using a gel polymer electrolyte composition in which an electrolyte is held in a polymer (hereinafter sometimes referred to as “polymer electrolyte gel composition”) Are known. A lithium ion secondary battery using a polymer electrolyte gel composition is a lithium ion secondary battery using an all-solid-type polymer electrolyte composition because the polymer matrix holds an electrolyte in the polymer electrolyte gel composition. Compared with the active material, it has excellent contact properties and ionic conductivity, and also has a characteristic that liquid leakage is less likely to occur compared to a lithium ion secondary battery in which a separator is impregnated with a liquid electrolyte composition. It attracts attention.
高分子電解質ゲル組成物に用いられる高分子として、例えば、ポリエーテル系の高分子をはじめとして、メタクリル酸メチル系重合体、アクリロニトリル系重合体、ポリフッ化ビニリデンまたはフッ化ビニリデンとヘキサフルオロプロピレンとの共重合体等の様々な物質が研究されている。 Examples of the polymer used in the polymer electrolyte gel composition include a polyether polymer, a methyl methacrylate polymer, an acrylonitrile polymer, polyvinylidene fluoride, or vinylidene fluoride and hexafluoropropylene. Various materials such as copolymers have been studied.
高分子電解質ゲル組成物に用いられる高分子として、ポリビニルホルマール、ポリビニルブチラール等のビニルアセタール系重合体が知られている。例えば、特許文献１〜３には、ビニルアセタール系重合体と電解液とを含む高分子電解質ゲル組成物が記載されている。また、特許文献４では、ポリビニルアセタールに含まれる水酸基を化学修飾してその量を調整することにより、電解液の量を増やすことが検討されている。 As a polymer used in the polymer electrolyte gel composition, vinyl acetal polymers such as polyvinyl formal and polyvinyl butyral are known. For example, Patent Documents 1 to 3 describe polymer electrolyte gel compositions containing a vinyl acetal polymer and an electrolytic solution. In Patent Document 4, it is studied to increase the amount of the electrolytic solution by chemically modifying a hydroxyl group contained in polyvinyl acetal and adjusting the amount thereof.
また、特許文献５には、リチウム塩としてビス（トリフルオロメタンスルホニル）イミドリチウムを用いることで、含水ビニルアセタール系重合体をそのまま用いて高分子電解質ゲル組成物を製造する方法が報告されている。 Patent Document 5 reports a method for producing a polymer electrolyte gel composition by using bis (trifluoromethanesulfonyl) imide lithium as a lithium salt and using a hydrous vinyl acetal polymer as it is.
さらに、特許文献６には、ビニルアセタール系重合体にカチオン性官能基をランダムに導入した共重合体を用いた高分子電解質ゲル組成物が報告されている。 Further, Patent Document 6 reports a polymer electrolyte gel composition using a copolymer in which cationic functional groups are randomly introduced into a vinyl acetal polymer.
しかしながら、ビニルアセタール系重合体はその構造中に親水性の水酸基を有するとともに、その製造において水が使用されるため、通常、特許文献１〜４のビニルアセタール系重合体は多くの水分を含んでいる。そのため、ヘキサフルオロリン酸リチウムやテトラフルオロホウ酸リチウムなどの汎用のリチウム塩を電解質として用いると、リチウム塩が容易に加水分解してフッ化水素などの分解物を生じ、これが電池の正極、負極、電解液中の非水系溶媒などと反応して、電池の容量低下、内部抵抗の増大、サイクル特性の低下等、種々の問題を引き起こす虞がある。 However, since the vinyl acetal polymer has a hydrophilic hydroxyl group in its structure and water is used in its production, the vinyl acetal polymer of Patent Documents 1 to 4 usually contains a lot of water. Yes. Therefore, when a general-purpose lithium salt such as lithium hexafluorophosphate or lithium tetrafluoroborate is used as the electrolyte, the lithium salt easily hydrolyzes to produce decomposition products such as hydrogen fluoride, which are the positive and negative electrodes of the battery. Then, it may react with a non-aqueous solvent in the electrolytic solution to cause various problems such as a decrease in battery capacity, an increase in internal resistance, and a decrease in cycle characteristics.
また、特許文献５および６では、液体電解質と比べるとイオン伝導度が著しく低下しており、液体電解質に匹敵するほどのイオン伝導度を有する二次電池用高分子電解質ゲル組成物を得ることができない。 In Patent Documents 5 and 6, the ionic conductivity is remarkably reduced as compared with the liquid electrolyte, and a polymer electrolyte gel composition for a secondary battery having an ionic conductivity comparable to the liquid electrolyte can be obtained. Can not.
そこで本発明は、イオン伝導度が高く、イオンの移動性に優れた二次電池を与え得る二次電池用高分子電解質ゲル組成物とその製造方法を提供することを目的とする。 Accordingly, an object of the present invention is to provide a polymer electrolyte gel composition for a secondary battery that can provide a secondary battery having high ion conductivity and excellent ion mobility, and a method for producing the same.
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、ビニルブチラール重合体成分と特定のイオン性重合体成分とで構成されるブロック共重合体（Ｐ）と、特定のリチウム塩とを組み合わせると、リチウム塩の加水分解によるフッ化水素などの分解物を抑制することができるだけでなく、イオン伝導度が向上した二次電池用高分子電解質ゲル組成物を容易に製造することができることを見出し、当該知見に基づいてさらに検討を重ねて本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventors have determined that a block copolymer (P) composed of a vinyl butyral polymer component and a specific ionic polymer component, and a specific lithium salt In addition to suppressing decomposition products such as hydrogen fluoride due to hydrolysis of lithium salt, it is possible to easily produce a polymer electrolyte gel composition for secondary batteries with improved ionic conductivity. The present invention has been completed through further investigation based on the findings.
すなわち、本発明の第１の実施形態は、
ビス（トリフルオロメタンスルホニル）イミドリチウムおよび非水系溶媒を含む電解液と、
下記一般式（１）
That is, the first embodiment of the present invention
An electrolyte containing bis (trifluoromethanesulfonyl) imidolithium and a non-aqueous solvent;
The following general formula (1)
［式中、Ｘはハロゲンアニオンもしくはビス（トリフルオロメタンスルホニル）イミドアニオンを示す。］
で示されるビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）と、
で少なくとも構成された二次電池用高分子電解質ゲル組成物である。
[Wherein, X represents a halogen anion or a bis (trifluoromethanesulfonyl) imide anion. ]
A block copolymer (P) composed of a vinyl butyral polymer component and an ionic polymer component represented by:
A polymer electrolyte gel composition for a secondary battery at least constituted by
前記式（１）では、
８０≦（ａ＋ｃ）／（ａ＋ｂ＋ｃ）×１００≦９９．９９であってもよく、
５０≦ｃ／（ａ＋ｂ＋ｃ）×１００≦９５であってもよく
１≦ｄ／（ａ＋ｂ＋ｃ＋ｄ）×１００≦３０であってもよい。
In the formula (1),
80 ≦ (a + c) / (a + b + c) × 100 ≦ 99.99 may be satisfied,
50 ≦ c / (a + b + c) × 100 ≦ 95 may be satisfied, and 1 ≦ d / (a + b + c + d) × 100 ≦ 30 may be satisfied.
また、リチウム原子のモル数（ＭＬｉ）に対するビニルブチラール系重合体成分に含まれるビニルアルコール単位のモル数（ＭＯＨ）の割合（ＭＯＨ／ＭＬｉ）が０．１〜０．８程度であってもよい。 Further, in a proportion (M OH / M Li) of about 0.1 to 0.8 moles of lithium atoms (M Li) number of moles of vinyl alcohol units contained in the polyvinyl butyral component to (M OH) There may be.
二次電池用高分子電解質ゲル組成物中、ブロック共重合体（Ｐ）の含有率が０．５〜１５質量％程度であってもよく、ブロック共重合体（Ｐ）１００質量部に対する含水量は０．５〜５質量部の範囲内であってもよい。 In the polymer electrolyte gel composition for secondary batteries, the content of the block copolymer (P) may be about 0.5 to 15% by mass, and the water content relative to 100 parts by mass of the block copolymer (P). May be in the range of 0.5 to 5 parts by mass.
また、本発明の第２の実施形態は、ビス（トリフルオロメタンスルホニル）イミドリチウムおよび非水系溶媒を含む電解液と、ビニルブチラール重合体成分およびイオン性重合体成分から構成されるブロック共重合体（Ｐ）とを接触させる工程と、
前記ブロック共重合体（Ｐ）が電解液で膨潤し、ゲル化した二次電池用高分子電解質ゲル組成物を得るゲル化工程と、
を少なくとも備える、前記二次電池用高分子電解質ゲル組成物の製造方法である。
Moreover, the second embodiment of the present invention is a block copolymer comprising an electrolytic solution containing bis (trifluoromethanesulfonyl) imide lithium and a non-aqueous solvent, a vinyl butyral polymer component and an ionic polymer component ( P), and
A gelation step of obtaining a polymer electrolyte gel composition for a secondary battery in which the block copolymer (P) is swollen and gelled with an electrolyte;
Is a method for producing a polymer electrolyte gel composition for a secondary battery.
なお、本発明において、高分子電解質ゲル組成物とは、三次元網目構造を持つネットワーク構造を有した高分子マトリックスに対して、電解塩と非水系溶媒とで構成された電解液が捕液され、全体としてゲル状の膨潤体を示す状態を意味している。 In the present invention, the polymer electrolyte gel composition refers to a polymer matrix having a network structure having a three-dimensional network structure in which an electrolyte solution composed of an electrolytic salt and a non-aqueous solvent is collected. The state which shows the gel-like swelling body as a whole is meant.
本発明の二次電池用高分子電解質ゲル組成物は、ビニルブチラール重合体成分および特定のイオン性重合体成分からなるブロック共重合体（Ｐ）を用いることによって、イオン伝導度が高い二次電池用高分子電解質ゲル組成物を容易に製造することができ、このような二次電池用高分子電解質ゲル組成物は、二次電池の充放電特性を向上させることが可能である。 The polymer electrolyte gel composition for secondary batteries of the present invention is a secondary battery having high ionic conductivity by using a block copolymer (P) comprising a vinyl butyral polymer component and a specific ionic polymer component. The polymer electrolyte gel composition for a secondary battery can be easily produced, and such a polymer electrolyte gel composition for a secondary battery can improve the charge / discharge characteristics of the secondary battery.
以下、本発明について具体的に説明する。
本発明の二次電池用高分子電解質ゲル組成物は、ビス（トリフルオロメタンスルホニル）イミドリチウムおよび非水系溶媒を含む電解液と、ビニルブチラール重合体成分およびイオン性重合体成分から構成されたブロック共重合体（Ｐ）とで少なくとも構成される。
Hereinafter, the present invention will be specifically described.
The polymer electrolyte gel composition for a secondary battery of the present invention is a block copolymer composed of an electrolytic solution containing bis (trifluoromethanesulfonyl) imide lithium and a non-aqueous solvent, a vinyl butyral polymer component, and an ionic polymer component. And at least a polymer (P).
［ブロック共重合体（Ｐ）］
本発明において使用されるビニルブチラール重合体成分およびイオン性重合体成分から構成されたブロック共重合体（Ｐ）は、下記式（１）で示される。
[Block copolymer (P)]
The block copolymer (P) composed of the vinyl butyral polymer component and the ionic polymer component used in the present invention is represented by the following formula (1).
［式中、Ｘはハロゲンアニオンもしくはビス（トリフルオロメタンスルホニル）イミドアニオンを示す。なお、８０≦（ａ＋ｃ）／（ａ＋ｂ＋ｃ）×１００≦９９．９９であってもよく、５０≦ｃ／（ａ＋ｂ＋ｃ）×１００≦９５であってもよく、１≦ｄ／（ａ＋ｂ＋ｃ＋ｄ）×１００≦３０であってもよい。］ [Wherein, X represents a halogen anion or a bis (trifluoromethanesulfonyl) imide anion. 80 ≦ (a + c) / (a + b + c) × 100 ≦ 99.99 may be satisfied, 50 ≦ c / (a + b + c) × 100 ≦ 95 may be satisfied, and 1 ≦ d / (a + b + c + d) × 100 ≦ It may be 30. ]
本発明において使用されるビニルブチラール重合成分としては、ビニルアルコール単位（−ＣＨ２−ＣＨ（ＯＨ）−）と、ビニルエステル単位と、２つのビニルアルコール単位が有する２つの水酸基がブチラール化されたブチラール単位とを繰り返し単位から構成される。各繰り返し単位の配列順序は特に限定されず、ランダムに配列されていてもよいし、ブロック状に配列されていてもよい。 Examples of the vinyl butyral polymerization component used in the present invention include butyral in which two hydroxyl groups of a vinyl alcohol unit (—CH 2 —CH (OH) —), a vinyl ester unit, and two vinyl alcohol units are butyralized. The unit is composed of repeating units. The arrangement order of each repeating unit is not particularly limited, and may be arranged randomly or in a block shape.
上記のブチラール単位は、下記式（２）で示すことができる。 The above butyral unit can be represented by the following formula (2).
また、上記のビニルエステル単位は、下記式（３）で示すことができる。 Moreover, said vinyl ester unit can be shown by following formula (3).
本発明において使用されるイオン性重合体成分は、下記式（４）で示すことができる。 The ionic polymer component used in the present invention can be represented by the following formula (4).
［式中、Ｘはハロゲンアニオンもしくはビス（トリフルオロメタンスルホニル）イミドアニオンを示す。］ [Wherein, X represents a halogen anion or a bis (trifluoromethanesulfonyl) imide anion. ]
本発明において使用される、ビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）は、例えば、特許第４７７６６８３号明細書や、国際公開第２０１０／１１０３３３Ａ１号パンフレットに記載の方法で製造できるビニルアルコール重合体成分とイオン性重合体成分（例えば、塩化ビニルベンジルトリメチルアンモニウムなど）から構成されるブロック共重合体（Ｐ’）をブチラール化することにより製造することができる。 The block copolymer (P) composed of a vinyl butyral polymer component and an ionic polymer component used in the present invention is disclosed in, for example, Japanese Patent No. 4767683 and International Publication No. 2010 / 110333A1 pamphlet. It can be produced by butyralizing a block copolymer (P ′) composed of a vinyl alcohol polymer component and an ionic polymer component (for example, vinylbenzyltrimethylammonium chloride, etc.) that can be produced by the described method. .
上記のビニルアルコール系重合成分の重合度は、ビニルアルコール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ’）の原料であるメルカプト基含有ビニルアルコール系重合体の重合度に相当し、ＪＩＳＫ６７２６−１９９４に規定されるポリビニルアルコール試験方法に準じて測定される平均重合度として、好ましくは１００〜５０００の範囲内であり、より好ましくは１５０〜３５００の範囲内であり、さらに好ましくは２００〜２５００の範囲内である。 The degree of polymerization of the above-mentioned vinyl alcohol polymer component is the degree of polymerization of the mercapto group-containing vinyl alcohol polymer which is a raw material of the block copolymer (P ′) composed of the vinyl alcohol polymer component and the ionic polymer component. The average degree of polymerization measured according to the polyvinyl alcohol test method specified in JISK 6726-1994 is preferably in the range of 100 to 5000, more preferably in the range of 150 to 3500, Preferably it exists in the range of 200-2500.
ブチラール化する際の条件としては、例えば、ビニルアルコール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ’）の水溶液とブチラール化に用いられる化合物（ブチルアルデヒド等）とを、酸触媒の存在下にブチラール化反応させて重合体の粒子を析出させる水媒法；ビニルアルコール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ’）を有機溶媒中に分散させ、酸触媒の存在下にブチラール化に用いられる化合物（ブチルアルデヒド等）とブチラール化反応させ、この反応液から、得られるビニルアセタール系重合体に対する貧溶媒（水等）により重合体を析出させる溶媒法などが挙げられる。これらの方法のうちで水媒法が好ましい。また、酸触媒としては、塩酸、硝酸、硫酸、炭酸等の無機酸；酢酸、プロピオン酸等の有機酸などを用いることができる。このうち特に塩酸、硝酸が好ましく用いられる。 As conditions for butyralization, for example, an aqueous solution of a block copolymer (P ′) composed of a vinyl alcohol polymer component and an ionic polymer component and a compound (butyraldehyde, etc.) used for butyralization are used. An aqueous medium method in which polymer particles are precipitated by a butyralization reaction in the presence of an acid catalyst; a block copolymer (P ′) composed of a vinyl alcohol polymer component and an ionic polymer component in an organic solvent. In the presence of an acid catalyst and a butyralization reaction with a compound used for butyralization (butyraldehyde, etc.). Examples of the solvent method include precipitation. Of these methods, the aqueous medium method is preferable. As the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and carbonic acid; organic acids such as acetic acid and propionic acid can be used. Of these, hydrochloric acid and nitric acid are particularly preferred.
本発明においては、ビニルアルコール重合体成分とイオン性重合体成分から構成される同一のブロック共重合体（Ｐ’）を単独で使用してもよいし、ビニルアルコール重合体成分および／またはイオン性重合体成分の割合が異なっている、異種のブロック共重合体（Ｐ’）を２種以上併用してもよい。 In the present invention, the same block copolymer (P ′) composed of a vinyl alcohol polymer component and an ionic polymer component may be used alone, or a vinyl alcohol polymer component and / or an ionic property. Two or more different types of block copolymers (P ′) having different polymer component ratios may be used in combination.
本発明の二次電池用高分子電解質ゲル組成物に含まれるビニルブチラール系重合体成分のブチラール化度は、好ましくは５０〜９５モル％の範囲内であり、より好ましくは５５〜９０モル％の範囲内であり、さらに好ましくは６０〜８５モル％の範囲内である。ビニルブチラール系重合体成分のブチラール化度が上記範囲にあることにより非水系溶媒との親和性を向上させることができる。 The degree of butyralization of the vinyl butyral polymer component contained in the polymer electrolyte gel composition for secondary batteries of the present invention is preferably in the range of 50 to 95 mol%, more preferably 55 to 90 mol%. It is in the range, and more preferably in the range of 60 to 85 mol%. When the degree of butyralization of the vinyl butyral polymer component is in the above range, the affinity with a non-aqueous solvent can be improved.
なお本明細書において「ブチラール化度」とは、ブチラール単位を構成する構成単位、ビニルアルコール単位およびビニルエステル単位の合計モル数に対する、ブチラール単位を構成する構成単位のモル数の割合を意味する。 In the present specification, the “degree of butyralization” means the ratio of the number of moles of the structural unit constituting the butyral unit to the total number of moles of the structural unit, vinyl alcohol unit and vinyl ester unit constituting the butyral unit.
ビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）において、上記式（１）に示したビニルアルコール単位：ａ、ビニルエステル単位：ｂ、ブチラール単位：ｃからは、ブチラール化度（モル％）＝ｃ／（ａ＋ｂ＋ｃ）×１００で示すことができ、好ましくは５０〜９５モル％の範囲内であり、より好ましくは５５〜９０モル％の範囲内であり、さらに好ましくは６０〜８５モル％の範囲内である。 In the block copolymer (P) composed of a vinyl butyral polymer component and an ionic polymer component, the vinyl alcohol unit: a, the vinyl ester unit: b, and the butyral unit: c shown in the above formula (1) , Butyralization degree (mol%) = c / (a + b + c) × 100, preferably in the range of 50 to 95 mol%, more preferably in the range of 55 to 90 mol%, Preferably it exists in the range of 60-85 mol%.
本発明の二次電池用高分子電解質ゲル組成物、および、本発明の製造方法により製造される二次電池用高分子電解質ゲル組成物に含まれるビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）のけん化度は上記式（１）に示したビニルアルコール単位：ａ、ビニルエステル単位：ｂ、ブチラール単位：ｃからは、けん化度（モル％）＝（ａ＋ｃ）／（ａ＋ｂ＋ｃ）×１００で示すことができ、好ましくは８０〜９９．９９モル％の範囲内であり、より好ましくは８５〜９９．９５モル％の範囲内であり、さらに好ましくは９０〜９９．９モル％の範囲内である。 From the vinyl butyral polymer component and the ionic polymer component contained in the polymer electrolyte gel composition for secondary battery of the present invention and the polymer electrolyte gel composition for secondary battery produced by the production method of the present invention The saponification degree of the block copolymer (P) is determined from the vinyl alcohol unit: a, the vinyl ester unit: b, and the butyral unit: c shown in the above formula (1) from the saponification degree (mol%) = (a + c ) / (A + b + c) × 100, preferably in the range of 80 to 99.99 mol%, more preferably in the range of 85 to 99.95 mol%, still more preferably 90 to 99. Within the range of 9 mol%.
本発明の二次電池用高分子電解質ゲル組成物、および、本発明の製造方法により製造される二次電池用高分子電解質ゲル組成物に含まれるビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）に含まれるイオン性変性量は上記式（１）に示したビニルアルコール単位：ａ、ビニルエステル単位：ｂ、ブチラール単位：ｃ、イオン性モノマー単位：ｄからは、イオン性変性量（モル％）＝ｄ／（ａ＋ｂ＋ｃ＋ｄ）×１００で示すことができ、好ましくは１〜３０モル％の範囲内であり、より好ましくは３〜２０モル％の範囲内であり、さらに好ましくは５〜１５モル％の範囲内である。 From the vinyl butyral polymer component and the ionic polymer component contained in the polymer electrolyte gel composition for secondary battery of the present invention and the polymer electrolyte gel composition for secondary battery produced by the production method of the present invention The amount of ionic modification contained in the constituted block copolymer (P) is from the vinyl alcohol unit: a, vinyl ester unit: b, butyral unit: c, and ionic monomer unit: d shown in the above formula (1). Ionic modification amount (mol%) = d / (a + b + c + d) × 100, preferably in the range of 1-30 mol%, more preferably in the range of 3-20 mol% More preferably, it is in the range of 5 to 15 mol%.
本発明の二次電池用高分子電解質ゲル組成物が含む電解液は、ビス（トリフルオロメタンスルホニル）イミドリチウム（ＬｉＮ（ＳＯ２ＣＦ３）２）および非水系溶媒を含む。電解液、ひいては二次電池用高分子電解質ゲル組成物がビス（トリフルオロメタンスルホニル）イミドリチウムを含むことにより、当該ビス（トリフルオロメタンスルホニル）イミドリチウムは電解質として機能することができる。 The electrolyte solution included in the polymer electrolyte gel composition for a secondary battery of the present invention contains bis (trifluoromethanesulfonyl) imidolithium (LiN (SO 2 CF 3 ) 2 ) and a non-aqueous solvent. The bis (trifluoromethanesulfonyl) imide lithium can function as an electrolyte when the electrolytic solution, and hence the polymer electrolyte gel composition for a secondary battery, contains bis (trifluoromethanesulfonyl) imide lithium.
上記電解液はリチウム塩としてビス（トリフルオロメタンスルホニル）イミドリチウムのみを含むことが好ましいが、本発明の効果が奏される限り、ビス（トリフルオロメタンスルホニル）イミドリチウムと共に、トリフルオロメタンスルホン酸リチウム（ＣＦ３ＳＯ３Ｌｉ）、ビス（パーフルオロエタンスルホニル）イミドリチウム（ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２）、トリス（トリフルオロメタンスルホニル）メチルリチウム（ＬｉＣ（ＳＯ２ＣＦ３）３）、トリス（パーフルオロエタンスルホニル）メチルリチウム（ＬｉＣ（ＳＯ２Ｃ２Ｆ５）３）など、ビス（トリフルオロメタンスルホニル）イミドリチウム以外の他のリチウム塩を用いてもよい。 The electrolyte preferably contains only bis (trifluoromethanesulfonyl) imide lithium as a lithium salt. However, as long as the effect of the present invention is exhibited, lithium trifluoromethanesulfonate (CF) together with bis (trifluoromethanesulfonyl) imide lithium. 3 SO 3 Li), bis (perfluoroethanesulfonyl) imidolithium (LiN (SO 2 C 2 F 5 ) 2 ), tris (trifluoromethanesulfonyl) methyllithium (LiC (SO 2 CF 3 ) 3 ), tris (per Other lithium salts other than bis (trifluoromethanesulfonyl) imidolithium such as fluoroethanesulfonyl) methyllithium (LiC (SO 2 C 2 F 5 ) 3 ) may be used.
上記した他のリチウム塩は、例えば、ビス（トリフルオロメタンスルホニル）イミドリチウムに対して１０モル％以下の割合で含まれていてもよい。 Other lithium salt mentioned above may be contained in the ratio of 10 mol% or less with respect to bis (trifluoromethanesulfonyl) imide lithium, for example.
また、電解液には、必要に応じてビス（トリフルオロメタンスルホニル）イミドリチウム等のリチウム塩および非水系溶媒以外の他の各種添加剤をさらに含んでいてもよい。 Further, the electrolyte solution may further contain various additives other than lithium salts such as bis (trifluoromethanesulfonyl) imide lithium and non-aqueous solvents as required.
本発明において使用される非水系溶媒としては、例えば、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、ε−カプロラクトン等のラクトン；炭酸エチレン、炭酸プロピレン、炭酸ブチレン、炭酸ビニレン、炭酸ジメチル、炭酸エチルメチル、炭酸ジエチル等の炭酸エステル；１，２−ジメトキシエタン、１−エトキシ−２−メトキシエタン、１，２−ジエトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフラン等のエーテル；アセトニトリル等のニトリル；スルホラン系化合物；リン酸類；リン酸エステル；ピロリドン類などが挙げられる。これらの非水系溶媒は、１種を単独で用いても、２種以上を併用してもよい。 Examples of the non-aqueous solvent used in the present invention include lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone; ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, Carbonates such as ethyl methyl carbonate and diethyl carbonate; ethers such as 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran; nitriles such as acetonitrile; Examples include sulfolane compounds; phosphoric acids; phosphate esters; pyrrolidones. These non-aqueous solvents may be used alone or in combination of two or more.
これらの中でも、ラクトン、炭酸エステルが好ましく、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチルが特に好ましい。また、炭酸エステルを使用する場合には、ビス（トリフルオロメタンスルホニル）イミドリチウムの解離の促進とリチウムイオンの易動度の両立の観点から、環状の炭酸エステルと鎖状の炭酸エステルとを併用するのが好ましい。 Among these, lactones and carbonates are preferable, and γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are particularly preferable. Moreover, when using carbonate ester, from the viewpoint of coexistence of promotion of dissociation of bis (trifluoromethanesulfonyl) imide lithium and mobility of lithium ion, a cyclic carbonate ester and a chain carbonate ester are used in combination. Is preferred.
電解液におけるビス（トリフルオロメタンスルホニル）イミドリチウムの濃度は、好ましくは０．１〜１０ミリモル／ｇの範囲内であり、より好ましくは０．２〜５ミリモル／ｇの範囲内であり、さらに好ましくは０．５〜２ミリモル／ｇの範囲内である。 The concentration of bis (trifluoromethanesulfonyl) imide lithium in the electrolytic solution is preferably in the range of 0.1 to 10 mmol / g, more preferably in the range of 0.2 to 5 mmol / g, and still more preferably. Is in the range of 0.5 to 2 mmol / g.
本発明の二次電池用高分子電解質ゲル組成物においては、当該二次電池用高分子電解質ゲル組成物に含まれる全てのリチウム原子のモル数（ＭＬｉ）に対する、当該二次電池用高分子電解質ゲル組成物に含まれるビニルブチラール系重合体成分に含まれる全ビニルアルコール単位のモル数（ＭＯＨ）の割合（ＭＯＨ／ＭＬｉ）が０．１〜０．８の範囲内であることが好ましい。
当該割合が低すぎるとビス（トリフルオロメタンスルホニル）イミドリチウムの電離度が低下する。一方、当該割合が高すぎるとイオン伝導度やリチウムイオン輸率が低下する。これは、電気陰性度の高い水酸基の酸素原子がリチウムイオンと強く相互作用するためと考えられる。ビス（トリフルオロメタンスルホニル）イミドリチウムの電離度、イオン伝導度およびリチウムイオン輸率の観点から、上記割合は０．１〜０．７５の範囲内であることが好ましく、０．１〜０．７の範囲内であることがより好ましい。
リチウム塩の電離度が高く、リチウムイオン輸率が高い高分子電解質ゲル組成物を用いた場合、リチウムイオン二次電池としての性能が高いものとなる。
In the polymer electrolyte gel composition for secondary batteries of the present invention, the polymer for secondary batteries with respect to the number of moles (M Li ) of all lithium atoms contained in the polymer electrolyte gel composition for secondary batteries. The ratio (M OH / M Li ) of the number of moles (M OH ) of all vinyl alcohol units contained in the vinyl butyral polymer component contained in the electrolyte gel composition is in the range of 0.1 to 0.8. Is preferred.
When the ratio is too low, the ionization degree of bis (trifluoromethanesulfonyl) imide lithium is lowered. On the other hand, if the ratio is too high, the ionic conductivity and the lithium ion transport number decrease. This is considered because the oxygen atom of the hydroxyl group having high electronegativity strongly interacts with lithium ions. From the viewpoint of ionization degree, ionic conductivity and lithium ion transport number of bis (trifluoromethanesulfonyl) imide lithium, the above ratio is preferably in the range of 0.1 to 0.75, and 0.1 to 0.7. It is more preferable to be within the range.
When a polymer electrolyte gel composition having a high lithium ionization degree and a high lithium ion transport number is used, the performance as a lithium ion secondary battery is high.
また、本発明の二次電池用高分子電解質ゲル組成物におけるブロック共重合体（Ｐ）の含有率は、ゲルの安定性と電解液の保持の双方を満足させる観点から、０．５〜１５質量％の範囲内であることが好ましく、１〜１２質量％の範囲内であることがより好ましく、２〜１０質量％の範囲内であることがさらに好ましい。 The content of the block copolymer (P) in the polymer electrolyte gel composition for secondary batteries of the present invention is 0.5 to 15 from the viewpoint of satisfying both the stability of the gel and the retention of the electrolyte. It is preferably within the range of mass%, more preferably within the range of 1 to 12 mass%, and even more preferably within the range of 2 to 10 mass%.
このような高分子電解質ゲル組成物では、高分子のゲル安定性が高めることができるため、電解液ひいては電解質の含有割合を高くすることができる。その結果、より優れたイオン伝導性を示す高分子電解質ゲル組成物を得ることが可能となり、リチウムイオン二次電池としての性能を向上することができる。 In such a polymer electrolyte gel composition, since the gel stability of the polymer can be increased, the content of the electrolytic solution and thus the electrolyte can be increased. As a result, it is possible to obtain a polymer electrolyte gel composition exhibiting more excellent ion conductivity, and the performance as a lithium ion secondary battery can be improved.
本発明の二次電池用高分子電解質ゲル組成物は、上記した電解液およびブロック共重合体（Ｐ）に加えて、他の成分をさらに含んでいてもよい。このような他の成分としては、例えば、充填材、架橋促進剤やその反応生成物などが挙げられる。
二次電池用高分子電解質ゲル組成物に占める、電解液およびブロック共重合体（Ｐ）の合計の質量割合は、５０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。
The polymer electrolyte gel composition for a secondary battery of the present invention may further contain other components in addition to the above-described electrolytic solution and block copolymer (P). Examples of such other components include fillers, cross-linking accelerators and reaction products thereof.
The total mass ratio of the electrolytic solution and the block copolymer (P) in the polymer electrolyte gel composition for secondary batteries is preferably 50% by mass or more, and more preferably 80% by mass or more. And more preferably 95% by mass or more.
なお、本発明の二次電池用高分子電解質ゲル組成物には水が含まれていてもよく、例えば、ブロック共重合体（Ｐ）１００質量部に対する含水量は０．５〜５質量部の範囲内であってもよい。当該含水量が０．５質量部未満の二次電池用高分子電解質ゲル組成物を調製するためには、水の混入を防ぐための特別な装置や操作が必要になる。一方、当該含水量が高すぎると、得られるリチウムイオン二次電池が劣化しやすくなる。 In addition, the polymer electrolyte gel composition for secondary batteries of the present invention may contain water. For example, the water content with respect to 100 parts by mass of the block copolymer (P) is 0.5 to 5 parts by mass. It may be within the range. In order to prepare the polymer electrolyte gel composition for a secondary battery having a water content of less than 0.5 parts by mass, a special device and operation for preventing water from being mixed are required. On the other hand, when the water content is too high, the obtained lithium ion secondary battery tends to deteriorate.
上記含水量は、二次電池用高分子電解質ゲル組成物の製造時や使用時において水の混入を防止するための管理を厳密に行う必要性を解消することができるとともに得られる二次電池の劣化をより効果的に防止することができることから、０．６〜４質量部の範囲内であることが好ましく、０．７〜３質量部の範囲内であることがより好ましい。なお、二次電池用高分子電解質ゲル組成物における含水量はカールフィッシャー法により測定される水分率から容易に算出することができる。 The water content of the secondary battery obtained can eliminate the necessity of strictly performing management for preventing water contamination during the production and use of the polymer electrolyte gel composition for secondary batteries. Since deterioration can be prevented more effectively, it is preferably in the range of 0.6 to 4 parts by mass, and more preferably in the range of 0.7 to 3 parts by mass. The water content in the polymer electrolyte gel composition for secondary batteries can be easily calculated from the moisture content measured by the Karl Fischer method.
［二次電池用高分子電解質ゲル組成物の製造方法］
本発明の二次電池用高分子電解質ゲル組成物の製造方法は、ビス（トリフルオロメタンスルホニル）イミドリチウムおよび非水系溶媒を含む電解液と、ビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）とを接触させる工程を有する。
[Method for producing polymer electrolyte gel composition for secondary battery]
The method for producing a polymer electrolyte gel composition for a secondary battery of the present invention comprises an electrolytic solution containing bis (trifluoromethanesulfonyl) imide lithium and a non-aqueous solvent, a vinyl butyral polymer component and an ionic polymer component. A step of contacting the block copolymer (P).
前記接触させる工程では、ブロック共重合体（Ｐ）は、以下の形態などであってもよい。
（ｉ）粉粒体
（ｉｉ）粉粒体以外の固体形状（例えば、フィルム状など）
（ｉｉｉ）ブロック共重合体（Ｐ）を溶解可能な有機溶媒により溶解された液状。
In the contacting step, the block copolymer (P) may be in the following form.
(I) Granule (ii) Solid shape other than powder (eg, film)
(Iii) A liquid form dissolved in an organic solvent capable of dissolving the block copolymer (P).
なお、ブロック共重合体（Ｐ）は、乾燥処理により水分を低下させた状態で用いてもよいが、ブロック共重合体（Ｐ）は、煩雑な水分の除去操作を施さずに通常の製造工程において含有するであろう水分量を有する状態、または比較的弱い乾燥条件を経た後の水分量を有する状態であってもよい。そのような水分含量はすでに上述している。 さらに、ブロック共重合体（Ｐ）、必要に応じて、水以外に有機溶媒などの成分をさらに含んでいてもよい。 The block copolymer (P) may be used in a state where the water content is lowered by a drying treatment, but the block copolymer (P) is a normal production process without performing a complicated water removal operation. It may be in a state having a moisture content that would be contained in or in a state having a moisture content after undergoing relatively weak drying conditions. Such moisture content has already been mentioned above. Furthermore, you may further contain components, such as an organic solvent, other than water as needed with a block copolymer (P).
（ｉ）ブロック共重合体（Ｐ）が粉粒状である場合、電解液とブロック共重合体（Ｐ）とを接触させる方法としては、例えば、電解液と粉粒状のブロック共重合体（Ｐ）とを混合する工程が挙げられ、この混合工程により、ブロック共重合体（Ｐ）が電解液で膨潤し、ゲル化した二次電池用高分子電解質ゲル組成物を得ることができる。
この場合、混合物に対して所定の形状を付与することにより、得られる二次電池用高分子電解質ゲル組成物を成形加工してもよい。
(I) When block copolymer (P) is granular, as a method of making electrolyte solution and block copolymer (P) contact, electrolyte solution and granular block copolymer (P), for example In this mixing step, the polymer electrolyte gel composition for a secondary battery in which the block copolymer (P) is swollen with an electrolytic solution and gelled can be obtained.
In this case, the obtained polymer electrolyte gel composition for a secondary battery may be molded by giving a predetermined shape to the mixture.
（ｉｉ）ブロック共重合体（Ｐ）が粉粒状以外の固体形状である場合、粉粒状以外の固体形状のブロック共重合体（Ｐ）に対し、電解液を含浸させる工程が挙げられ、この含浸工程により、ブロック共重合体（Ｐ）が電解液で膨潤し、ゲル化した二次電池用高分子電解質ゲル組成物を得ることができる。
なお、このような固体形状としては、二次電池用高分子電解質ゲル組成物に対して求められる形状に応じて、適宜必要な形状であればよく、例えば、ブロック共重合体（Ｐ）をキャスト製膜、溶融押出製膜等により製膜して得られたフィルム形状などであってもよい。
(Ii) When the block copolymer (P) is in a solid form other than powder, a step of impregnating the block copolymer (P) with a solid form other than powder is impregnated. According to the process, the polymer electrolyte gel composition for a secondary battery in which the block copolymer (P) is swollen with an electrolyte and gelled can be obtained.
In addition, as such a solid shape, what is necessary is just a shape required suitably according to the shape calculated | required with respect to the polymer electrolyte gel composition for secondary batteries, for example, cast block copolymer (P) It may be a film shape obtained by film formation, melt extrusion film formation, or the like.
（ｉｉｉ）ブロック共重合体（Ｐ）が、有機溶媒により溶解された液状である場合、電解液と、液状のブロック共重合体（Ｐ）とを相溶させる工程が挙げられ、この相溶工程の後、有機溶媒を蒸発させ、それに伴いブロック共重合体（Ｐ）が電解液で膨潤しゲル化した二次電池用高分子電解質ゲル組成物を得ることができる。
この場合も、相溶物に対して所定の形状を付与することにより、得られる二次電池用高分子電解質ゲル組成物を成形加工してもよい。
(Iii) In the case where the block copolymer (P) is in a liquid state dissolved in an organic solvent, a step of compatibilizing the electrolytic solution and the liquid block copolymer (P) can be mentioned. Thereafter, the organic solvent is evaporated, and accordingly, the polymer electrolyte gel composition for a secondary battery in which the block copolymer (P) is swollen with the electrolyte and gelled can be obtained.
Also in this case, the obtained polymer electrolyte gel composition for a secondary battery may be molded by applying a predetermined shape to the compatible material.
なお、有機溶媒としては、ブロック共重合体（Ｐ）を溶解することのできるものであれば特に制限はなく、例えば、メタノール、エタノール、プロパノール等のアルコール；アセトン、メチルエチルケトン、シクロヘキサノン等のケトン；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド等のアミド；ジオキサン、テトラヒドロフラン等のエーテル；メチレンクロライド、クロロホルム等の塩素化炭化水素；トルエン、キシレン、スチレン、ピリジン等の芳香族炭化水素；ジメチルスルホキシド等のスルホキシド；酢酸等のカルボン酸などが挙げられる。 The organic solvent is not particularly limited as long as it can dissolve the block copolymer (P). Examples thereof include alcohols such as methanol, ethanol and propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; N Amides such as N, N-dimethylacetamide and N, N-dimethylformamide; ethers such as dioxane and tetrahydrofuran; chlorinated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as toluene, xylene, styrene and pyridine; dimethyl sulfoxide And carboxylic acids such as acetic acid.
これらの中うち、簡便でより均一な二次電池用高分子電解質ゲル組成物が得られることから、接触工程として、上記（ｉ）の電解液と粉粒状のブロック共重合体（Ｐ）とを混合する方法が好ましい。 Among these, since a simpler and more uniform polymer electrolyte gel composition for a secondary battery can be obtained, as the contacting step, the electrolytic solution (i) and the granular block copolymer (P) are used. A method of mixing is preferred.
電解液とブロック共重合体（Ｐ）とを接触させるにあたっては、割合（ＭＯＨ／ＭＬｉ）が上述した範囲内になるように両成分の配合割合を適宜調整するのが好ましい。上記製造方法によって、本発明の二次電池用高分子電解質ゲル組成物を容易に製造することができる。 In bringing the electrolytic solution into contact with the block copolymer (P), it is preferable to appropriately adjust the blending ratio of both components so that the ratio (M OH / M Li ) is within the above-described range. By the said manufacturing method, the polymer electrolyte gel composition for secondary batteries of this invention can be manufactured easily.
本発明の二次電池用高分子電解質ゲル組成物を用いたリチウムイオン二次電池の構成に特に制限はなく、例えば、一対の電極、セパレータおよび各電極とセパレータの間に配設された上記二次電池用高分子電解質ゲル組成物を有するものが挙げられる。各電極には、通常、活物質が含まれる。リチウムイオン二次電池における上記二次電池用高分子電解質ゲル組成物の形状は、目的とするリチウムイオン二次電池の形状やその製造方法等にもよるが、例えば、厚さ１〜５００μｍの薄膜状や、あるいは、一対の電極とその間に配設されたセパレータにおける各隙間やこれらの周囲に溶融状態の二次電池用高分子電解質ゲル組成物が連続的に入り込んだ後に固化して形成される形状などが挙げられる。 The configuration of the lithium ion secondary battery using the polymer electrolyte gel composition for a secondary battery of the present invention is not particularly limited. For example, a pair of electrodes, a separator, and the above-described second disposed between each electrode and the separator. What has a polymer electrolyte gel composition for secondary batteries is mentioned. Each electrode usually contains an active material. The shape of the polymer electrolyte gel composition for a secondary battery in a lithium ion secondary battery depends on the shape of the target lithium ion secondary battery, the manufacturing method thereof, etc., but for example, a thin film having a thickness of 1 to 500 μm Or a solid polymer electrolyte gel composition for a secondary battery in a molten state is continuously solidified and formed in each gap between the electrode and the separator disposed between the electrode and the periphery thereof. Examples include shape.
以下に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらの実施例によってなんら限定されるものではない。なお、以下の実施例および比較例において採用された、高分子電解質ゲル組成物のイオン伝導度・含水率の測定または算出方法を以下に示す。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. In addition, the measurement or calculation method of the ionic conductivity and the moisture content of the polymer electrolyte gel composition employed in the following examples and comparative examples is shown below.
［イオン伝導度］
２０３２型コインセルを作製して評価した。すなわち、正極ケース内側にガスケットを置き、「テフロン（登録商標）」製のリング状スペーサー（内径１４ｍｍ、厚み１ｍｍ）を置き、高分子電解質ゲル組成物をその中にいれ、さらにステンレス製電極板（φ１６ｍｍ、厚み０．５ｍｍ）をかぶせて、金属製ワッシャをのせ、負極ケースをかぶせ、かしめ機でかしめてコインセルを作製した。このコインセルを電池ホルダーにセットし、リード線で周波数応答アナライザー（Ｓｏｌａｒｔｒｏｎ社製１２５０型）につなぎ、交流インピーダンス法により、２５℃にて、交流５０ｍＶ、１〜６５ｋＨｚの範囲で、インピーダンスを測定した。コインセル中の高分子電解質ゲル組成物の面積Ｓ［ｃｍ２］、厚みｄ［ｃｍ］、得られたインピーダンスＲ［Ω］から、計算式（σ＝（１／Ｒ）×（ｄ／ｓ））により、イオン伝導度σ［Ｓ／ｃｍ］を算出した。
[Ionic conductivity]
A 2032 type coin cell was prepared and evaluated. That is, a gasket is placed inside the positive electrode case, a ring-shaped spacer (inner diameter: 14 mm, thickness: 1 mm) made of “Teflon (registered trademark)” is placed, the polymer electrolyte gel composition is placed therein, and a stainless steel electrode plate ( A coin cell was manufactured by covering with a metal washer, covering with a negative electrode case, and caulking with a caulking machine. This coin cell was set in a battery holder, connected to a frequency response analyzer (Model 1250 made by Solartron) with a lead wire, and impedance was measured in the range of AC 50 mV and 1 to 65 kHz at 25 ° C. by the AC impedance method. From the area S [cm 2 ], the thickness d [cm], and the obtained impedance R [Ω] of the polymer electrolyte gel composition in the coin cell, a calculation formula (σ = (1 / R) × (d / s)) Was used to calculate ionic conductivity σ [S / cm].
［ブロック共重合体中の含水量］
(株）三菱化学アナリテック製卓上型 電量法水分計ＣＡ−２００および水分気化装置ＶＡ−２００を用いて、カールフィッシャー法にて測定した。
[Water content in block copolymer]
Using a Karl Fischer method, a tabletop coulometric moisture meter CA-200 and a moisture vaporizer VA-200 manufactured by Mitsubishi Chemical Analytech Co., Ltd. were used.
［製造例１］
共重合体（Ｐ’−１）
還流冷却管、攪拌翼を備え付けた５００ｍＬの四つ口セパラブルフラスコに、イオン交換水２１２ｇ、（株）クラレ製ポバールＭ−１０５（平均重合度５００、けん化度９８．５モル％の末端ＳＨ化ＰＶＡ）を５０．０ｇとＡＧＣセイミケミカル（株）製ビニルベンジルトリメチルアンモニウムクロライドを６．２ｇ仕込み、攪拌下９０℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に２，２'-アゾビス[２−メチル−Ｎ−（２−ヒドロキシエチル）−２−プロピオンアミド]の２．０％水溶液５．６ｍＬを１．５時間かけて逐次的に添加して重合を進行させた後、系内温度を９０℃に４時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールとポリビニルベンジルトリメチルアンモニウムクロライドのブロック共重合体Ｐ’−１の水溶液（固形分濃度２０％）を作製した。水溶液の一部を乾燥した後、重水に溶解し、５００ＭＨｚでの１Ｈ−ＮＭＲ測定に付した結果、ビニルベンジルトリメチルアンモニウムクロライド単位の変性量は２．５モル％であった。
[Production Example 1]
Copolymer (P'-1)
A 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade was charged with 212 g of ion-exchanged water and POVAL M-105 manufactured by Kuraray Co., Ltd. 50.0 g of PVA) and 6.2 g of vinylbenzyltrimethylammonium chloride manufactured by AGC Seimi Chemical Co., Ltd. were charged and dissolved while bubbling nitrogen by heating to 90 ° C. with stirring. After nitrogen substitution, 5.6 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. And the polymerization is further continued by maintaining the system temperature at 90 ° C. for 4 hours, followed by cooling to block copolymer P′− of polyvinyl alcohol and polyvinylbenzyltrimethylammonium chloride. 1 aqueous solution (solid content concentration 20%) was prepared. A part of the aqueous solution was dried, dissolved in heavy water, and subjected to 1H-NMR measurement at 500 MHz. As a result, the modified amount of vinylbenzyltrimethylammonium chloride unit was 2.5 mol%.
[製造例２]
共重合体（Ｐ’−２）
製造例１のイオン交換水を２３２ｇ、セイミケミカル製ビニルベンジルトリメチルアンモニウムクロライドを１１．５ｇ、２，２'-アゾビス[２−メチル−Ｎ−（２−ヒドロキシエチル）−２−プロピオンアミド]の２．０％水溶液を１１．５ｍＬに変えた以外は同様の操作を行い、共重合体Ｐ’−２の水溶液（固形分濃度２０％）を作製した。ビニルベンジルトリメチルアンモニウムクロライド単位の変性量は５．０モル％であった。
[Production Example 2]
Copolymer (P'-2)
232 g of ion-exchange water of Production Example 1, 11.5 g of vinylbenzyltrimethylammonium chloride made by Seimi Chemical, 2 of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] A similar operation was performed except that the 0.0% aqueous solution was changed to 11.5 mL, to prepare an aqueous solution of copolymer P′-2 (solid content concentration 20%). The amount of modification of the vinylbenzyltrimethylammonium chloride unit was 5.0 mol%.
[製造例３]
共重合体（Ｐ’−３）
製造例１のイオン交換水を２５２ｇ、セイミケミカル製ビニルベンジルトリメチルアンモニウムクロライドを１９．５ｇ、２，２'-アゾビス[２−メチル−Ｎ−（２−ヒドロキシエチル）−２−プロピオンアミド]の２．０％水溶液を１７．７ｍＬに変えた以外は同様の操作を行い、共重合体Ｐ’−３の水溶液（固形分濃度２０％）を作製した。ビニルベンジルトリメチルアンモニウムクロライド単位の変性量は７．５モル％であった。
[Production Example 3]
Copolymer (P'-3)
252 g of ion-exchanged water of Production Example 1, 19.5 g of vinylbenzyltrimethylammonium chloride made by Seimi Chemical, 2 of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] A similar operation was performed except that the 0.0% aqueous solution was changed to 17.7 mL to prepare an aqueous solution (solid content concentration 20%) of copolymer P′-3. The amount of modification of the vinylbenzyltrimethylammonium chloride unit was 7.5 mol%.
[製造例４]
共重合体（Ｐ’−４）
製造例１のイオン交換水を２７３ｇ、セイミケミカル製ビニルベンジルトリメチルアンモニウムクロライドを２６．７ｇ、２，２'-アゾビス[２−メチル−Ｎ−（２−ヒドロキシエチル）−２−プロピオンアミド]の２．０％水溶液を２４．３ｍＬに変えた以外は同様の操作を行い、共重合体Ｐ’−４の水溶液（固形分濃度２０％）を作製した。ビニルベンジルトリメチルアンモニウムクロライド単位の変性量は１０．０モル％であった。
[Production Example 4]
Copolymer (P'-4)
273 g of ion-exchanged water of Production Example 1, 26.7 g of vinylbenzyltrimethylammonium chloride made by Seimi Chemical, 2 of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] A similar operation was performed except that the 0.0% aqueous solution was changed to 24.3 mL to prepare an aqueous solution of copolymer P′-4 (solid content concentration 20%). The amount of modification of the vinylbenzyltrimethylammonium chloride unit was 10.0 mol%.
［製造例５]
還流冷却器、温度計、イカリ型撹拌翼を備えた５００リットルガラス製容器に、製造例１で得られた共重合体（Ｐ’−１）水溶液（固形分２０％）２００ｇを仕込み、内温９０℃に維持し２５０ｒｐｍで撹拌しながら、完全に溶解した。この水溶液を２５０ｒｐｍで撹拌下、４０℃まで冷却した後、ｎ−ブチルアルデヒド２２．７ｇを添加した。さらに１２℃まで冷却した後、２０質量％の塩酸２６．７ｍＬを１２分かけて添加し、１０分間攪拌した。その後、１１６分かけて７３℃まで昇温し、１２０分間攪拌後、室温まで冷却した。析出した樹脂をろ過して２００ｍＬのイオン交換水で５回洗浄した後、１．０Ｍのリチウムビストリフルオロメチルスルホンイミド水溶液１００ｍＬに５時間浸漬した後にろ過・乾燥して、共重合体（Ｐ−１）を得た。得られた共重合体（Ｐ−１）のブチラール化度は８０モル％であった。
[Production Example 5]
A 500 liter glass container equipped with a reflux condenser, a thermometer, and a squid type stirring blade was charged with 200 g of the aqueous copolymer (P′-1) solution (solid content 20%) obtained in Production Example 1, and the internal temperature The solution was completely dissolved while maintaining at 90 ° C. and stirring at 250 rpm. The aqueous solution was cooled to 40 ° C. with stirring at 250 rpm, and 22.7 g of n-butyraldehyde was added. After further cooling to 12 ° C., 26.7 mL of 20 mass% hydrochloric acid was added over 12 minutes and stirred for 10 minutes. Thereafter, the temperature was raised to 73 ° C. over 116 minutes, stirred for 120 minutes, and then cooled to room temperature. The precipitated resin was filtered and washed 5 times with 200 mL of ion exchange water, then immersed in 100 mL of 1.0 M lithium bistrifluoromethylsulfonimide aqueous solution for 5 hours, filtered and dried to obtain a copolymer (P-1 ) The degree of butyralization of the obtained copolymer (P-1) was 80 mol%.
［製造例６］
製造例５の共重合体（Ｐ’−１）の代わりに共重合体（Ｐ’−２）を用い、ｎ−ブチルアルデヒドの使用量を２０．８ｇ、２０質量％の塩酸の使用量を２３．９ｇに変えた以外は同様の操作を行い、共重合体（Ｐ−２）を得た。得られた共重合体（Ｐ−２）のブチラール化度は８０モル％であった。
[Production Example 6]
The copolymer (P′-2) was used in place of the copolymer (P′-1) of Production Example 5, the amount of n-butyraldehyde used was 20.8 g, and the amount of 20 mass% hydrochloric acid was 23. A copolymer (P-2) was obtained in the same manner as described above except that the amount was changed to 9 g. The degree of butyralization of the obtained copolymer (P-2) was 80 mol%.
［製造例７］
製造例５の共重合体（Ｐ’−１）の代わりに共重合体（Ｐ’−３）を用い、ｎ−ブチルアルデヒドの使用量を１８．８ｇ、２０質量％の塩酸の使用量を２２．６ｇに変えた以外は同様の操作を行い、共重合体（Ｐ−３）を得た。得られた共重合体（Ｐ−３）のブチラール化度は８０モル％であった。
[Production Example 7]
The copolymer (P′-3) was used in place of the copolymer (P′-1) of Production Example 5, the amount of n-butyraldehyde used was 18.8 g, and the amount of 20 mass% hydrochloric acid was 22 A copolymer (P-3) was obtained in the same manner as described above except that the amount was changed to 0.6 g. The degree of butyralization of the obtained copolymer (P-3) was 80 mol%.
［製造例８］
製造例５の共重合体（Ｐ’−１）の代わりに共重合体（Ｐ’−４）を用い、ｎ−ブチルアルデヒドの使用量を１７．０ｇ、２０質量％の塩酸の使用量を１９．６ｇに変えた以外は同様の操作を行い、共重合体（Ｐ−４）を得た。得られた共重合体（Ｐ−４）のブチラール化度は８０モル％であった。
[Production Example 8]
The copolymer (P′-4) was used in place of the copolymer (P′-1) of Production Example 5, the amount of n-butyraldehyde used was 17.0 g, and the amount of 20 mass% hydrochloric acid was 19 A copolymer (P-4) was obtained in the same manner as described above except that the amount was changed to 0.6 g. The degree of butyralization of the copolymer (P-4) obtained was 80 mol%.
［製造例９］
特許文献５（特開２０１２−１１３８４９）に記載の方法で、（株）クラレ製ポリビニルアルコール（平均重合度：１０００、けん化度：９８モル％）を用いて、ポリビニルブチラールＰＶＢ−１を得た。ＰＶＢ−１のブチラール化度は８０モル％であった。
[Production Example 9]
Polyvinyl butyral PVB-1 was obtained by the method described in Patent Document 5 (Japanese Patent Application Laid-Open No. 2012-113849) using Kuraray Co., Ltd. polyvinyl alcohol (average polymerization degree: 1000, saponification degree: 98 mol%). The degree of butyralization of PVB-1 was 80 mol%.
［製造例１０］
特許文献６の製造例１（ＷＯ２０１１／０８７０２９Ａ１）に記載の方法で、カチオン変性のランダム共重合体Ｑ−１を得た。Ｑ−１のブチラール化度は８０モル％で、酢酸ビニル単位の含有率は２モル％で、（３−メタクリルアミドプロピル）トリメチルアンモニウムクロリド変性量は５％であった。
[Production Example 10]
A cation-modified random copolymer Q-1 was obtained by the method described in Production Example 1 (WO2011 / 0887029A1) of Patent Document 6. The degree of butyralization of Q-1 was 80 mol%, the content of vinyl acetate units was 2 mol%, and the amount of (3-methacrylamidopropyl) trimethylammonium chloride modification was 5%.
［実施例１］
炭酸エチレンと炭酸ジメチルとを炭酸エチレン：炭酸ジメチル＝３：７の質量比で混合してなる非水系溶媒に、電解質としてビス（トリフルオロメタンスルホニル）イミドリチウムを０．７９ミリモル／ｇの濃度で溶解した電解液を調製した。なお、電解液の調製に使用した上記各原料は十分に乾燥されたものを用いた。次いで、調製した電解液と共重合体（Ｐ−１）とを［電解液の質量］／［共重合体（Ｐ−１）］＝９５／５となる割合で混合し、５０℃で加熱しながら撹拌し、充分均一になった後に室温まで冷却して高分子電解質ゲル組成物を作製した。得られた高分子電解質ゲル組成物を用いて、上記した方法によりイオン伝導度を測定した。結果を表１に示した。
[Example 1]
Dissolve bis (trifluoromethanesulfonyl) imidolithium as an electrolyte at a concentration of 0.79 mmol / g in a non-aqueous solvent obtained by mixing ethylene carbonate and dimethyl carbonate in a mass ratio of ethylene carbonate: dimethyl carbonate = 3: 7. An electrolyte solution was prepared. In addition, the said each raw material used for preparation of electrolyte solution used what was fully dried. Next, the prepared electrolytic solution and copolymer (P-1) were mixed at a ratio of [electrolytic solution mass] / [copolymer (P-1)] = 95/5 and heated at 50 ° C. Then, the mixture was sufficiently homogenized and then cooled to room temperature to prepare a polymer electrolyte gel composition. Using the obtained polymer electrolyte gel composition, the ionic conductivity was measured by the method described above. The results are shown in Table 1.
［実施例２］
実施例１において共重合体（Ｐ−１）の代わりに共重合体（Ｐ−２）を使用したこと以外は実施例１と同様の方法により、高分子電解質ゲル組成物を作製した。得られた高分子電解質ゲル組成物を用いて、上記した方法によりイオン伝導度を測定した。結果を表１に示した。
[Example 2]
A polymer electrolyte gel composition was prepared in the same manner as in Example 1 except that the copolymer (P-2) was used instead of the copolymer (P-1) in Example 1. Using the obtained polymer electrolyte gel composition, the ionic conductivity was measured by the method described above. The results are shown in Table 1.
［実施例３］
実施例１において共重合体（Ｐ−１）の代わりに共重合体（Ｐ−３）を使用したこと以外は実施例１と同様の方法により、高分子電解質ゲル組成物を作製した。得られた高分子電解質ゲル組成物を用いて、上記した方法によりイオン伝導度を測定した。結果を表１に示した。
[Example 3]
A polymer electrolyte gel composition was prepared in the same manner as in Example 1 except that the copolymer (P-3) was used instead of the copolymer (P-1) in Example 1. Using the obtained polymer electrolyte gel composition, the ionic conductivity was measured by the method described above. The results are shown in Table 1.
［実施例４］
実施例１において共重合体（Ｐ−１）の代わりに共重合体（Ｐ−４）を使用したこと以外は実施例１と同様の方法により、高分子電解質ゲル組成物を作製した。得られた高分子電解質ゲル組成物を用いて、上記した方法によりイオン伝導度を測定した。結果を表１に示した。
[Example 4]
A polymer electrolyte gel composition was prepared in the same manner as in Example 1 except that the copolymer (P-4) was used instead of the copolymer (P-1) in Example 1. Using the obtained polymer electrolyte gel composition, the ionic conductivity was measured by the method described above. The results are shown in Table 1.
［比較例１］
実施例１において共重合体（Ｐ−１）の代わりにＰＶＢ−１を使用したこと以外は実施例１と同様の方法により、高分子電解質ゲル組成物を作製した。得られた高分子電解質ゲル組成物を用いて、上記した方法によりイオン伝導度を測定した。結果を表１に示した。
[Comparative Example 1]
A polymer electrolyte gel composition was prepared in the same manner as in Example 1 except that PVB-1 was used instead of the copolymer (P-1) in Example 1. Using the obtained polymer electrolyte gel composition, the ionic conductivity was measured by the method described above. The results are shown in Table 1.
[比較例２]
実施例１において共重合体（Ｐ−１）の代わりに共重合体（Ｑ−１）を使用したこと以外は実施例１と同様の方法により、高分子電解質ゲル組成物を作製した。得られた高分子電解質ゲル組成物を用いて、上記した方法によりイオン伝導度を測定した。結果を表１に示した。
[Comparative Example 2]
A polymer electrolyte gel composition was prepared in the same manner as in Example 1 except that the copolymer (Q-1) was used instead of the copolymer (P-1) in Example 1. Using the obtained polymer electrolyte gel composition, the ionic conductivity was measured by the method described above. The results are shown in Table 1.
表１の結果からも明らかなように、実施例１〜４では原料としてビニルブチラール重合体成分と特定のイオン性重合体成分から構成されるブロック共重合体を用いて二次電池用高分子電解質ゲル組成物を作製しているため、得られる二次電池用高分子電解質ゲル組成物はイオン伝導度が高く、充放電特性に優れた二次電池を与えることができる。 As is apparent from the results in Table 1, in Examples 1 to 4, a polymer electrolyte for a secondary battery using a block copolymer composed of a vinyl butyral polymer component and a specific ionic polymer component as raw materials. Since the gel composition is produced, the obtained polymer electrolyte gel composition for a secondary battery has a high ionic conductivity and can provide a secondary battery excellent in charge / discharge characteristics.
一方、比較例１は、イオン性重合体成分を有していないビニルブチラール重合体であるため、実施例１〜４と比べるとイオン伝導度が低減している。また、特許文献６の製造例１の方法により得られたランダム共重合体を用いている比較例２についても、実施例１〜４と比べ、イオン伝導度は低減している。 On the other hand, since the comparative example 1 is a vinyl butyral polymer which does not have an ionic polymer component, compared with Examples 1-4, ionic conductivity is reducing. Moreover, also in Comparative Example 2 using the random copolymer obtained by the method of Production Example 1 of Patent Document 6, the ionic conductivity is reduced as compared with Examples 1 to 4.
本発明によれば、イオン伝導度が高く、充放電特性に優れた二次電池を与え得る二次電池用高分子電解質ゲル組成物とその製造方法を提供することができ、充放電特性に優れたリチウムイオン二次電池を製造することができる。 According to the present invention, it is possible to provide a polymer electrolyte gel composition for a secondary battery that can provide a secondary battery having high ionic conductivity and excellent charge / discharge characteristics, and a method for producing the same. A lithium ion secondary battery can be manufactured.
Claims (6)
下記一般式（１）
で示されるビニルブチラール重合体成分とイオン性重合体成分から構成されるブロック共重合体（Ｐ）と、
で少なくとも構成された二次電池用高分子電解質ゲル組成物。 An electrolyte containing bis (trifluoromethanesulfonyl) imidolithium and a non-aqueous solvent;
The following general formula (1)
A block copolymer (P) composed of a vinyl butyral polymer component and an ionic polymer component represented by:
A polymer electrolyte gel composition for a secondary battery comprising at least
８０≦（ａ＋ｃ）／（ａ＋ｂ＋ｃ）×１００≦９９．９９であり、
５０≦ｃ／（ａ＋ｂ＋ｃ）×１００≦９５であり、および
１≦ｄ／（ａ＋ｂ＋ｃ＋ｄ）×１００≦３０である二次電池用高分子電解質ゲル組成物。 The polymer electrolyte gel composition for a secondary battery according to claim 1, wherein the block copolymer (P) represented by the formula (1):
80 ≦ (a + c) / (a + b + c) × 100 ≦ 99.99,
A polymer electrolyte gel composition for a secondary battery, wherein 50 ≦ c / (a + b + c) × 100 ≦ 95, and 1 ≦ d / (a + b + c + d) × 100 ≦ 30.
前記ブロック共重合体（Ｐ）が電解液で膨潤し、ゲル化した二次電池用高分子電解質ゲル組成物を得るゲル化工程と、
を少なくとも備える、請求項１〜５のいずれか一項に記載の二次電池用高分子電解質ゲル組成物の製造方法。 Contacting an electrolytic solution containing bis (trifluoromethanesulfonyl) imide lithium and a non-aqueous solvent with a block copolymer (P) composed of a vinyl butyral polymer component and an ionic polymer component;
A gelation step of obtaining a polymer electrolyte gel composition for a secondary battery in which the block copolymer (P) is swollen and gelled with an electrolyte;
The manufacturing method of the polymer electrolyte gel composition for secondary batteries as described in any one of Claims 1-5 provided with at least.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013067928A JP6090919B2 (en) | 2013-03-28 | 2013-03-28 | Polymer electrolyte gel composition for secondary battery and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013067928A JP6090919B2 (en) | 2013-03-28 | 2013-03-28 | Polymer electrolyte gel composition for secondary battery and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014192074A true JP2014192074A (en) | 2014-10-06 |
| JP6090919B2 JP6090919B2 (en) | 2017-03-08 |
Family
ID=51838131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013067928A Expired - Fee Related JP6090919B2 (en) | 2013-03-28 | 2013-03-28 | Polymer electrolyte gel composition for secondary battery and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6090919B2 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6430179A (en) * | 1987-07-27 | 1989-02-01 | Nippon Telegraph & Telephone | Electrolyte for lithium battery |
| JP2001200125A (en) * | 2000-01-17 | 2001-07-24 | Toyo Ink Mfg Co Ltd | Ionically conductive composition |
| JP2002313135A (en) * | 2001-04-10 | 2002-10-25 | Mitsubishi Paper Mills Ltd | Nonaqueous gel composite and electrochemical element using same |
| US20050084760A1 (en) * | 2003-09-26 | 2005-04-21 | Hwang Duck-Chul | Rechargeable lithium ion battery |
| WO2010110333A1 (en) * | 2009-03-25 | 2010-09-30 | 株式会社クラレ | Anion exchange membrane and method for producing same |
| JP2012113849A (en) * | 2010-11-22 | 2012-06-14 | National Institute Of Advanced Industrial & Technology | Polymer electrolyte gel composition for secondary battery |
| JP2013012322A (en) * | 2011-06-28 | 2013-01-17 | Kuraray Co Ltd | Ion exchange double-layered film for reverse electrodialysis power generation |
-
2013
- 2013-03-28 JP JP2013067928A patent/JP6090919B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6430179A (en) * | 1987-07-27 | 1989-02-01 | Nippon Telegraph & Telephone | Electrolyte for lithium battery |
| JP2001200125A (en) * | 2000-01-17 | 2001-07-24 | Toyo Ink Mfg Co Ltd | Ionically conductive composition |
| JP2002313135A (en) * | 2001-04-10 | 2002-10-25 | Mitsubishi Paper Mills Ltd | Nonaqueous gel composite and electrochemical element using same |
| US20050084760A1 (en) * | 2003-09-26 | 2005-04-21 | Hwang Duck-Chul | Rechargeable lithium ion battery |
| JP2005108835A (en) * | 2003-09-26 | 2005-04-21 | Samsung Sdi Co Ltd | Rechargeable lithium-ion secondary battery |
| WO2010110333A1 (en) * | 2009-03-25 | 2010-09-30 | 株式会社クラレ | Anion exchange membrane and method for producing same |
| JP2012113849A (en) * | 2010-11-22 | 2012-06-14 | National Institute Of Advanced Industrial & Technology | Polymer electrolyte gel composition for secondary battery |
| JP2013012322A (en) * | 2011-06-28 | 2013-01-17 | Kuraray Co Ltd | Ion exchange double-layered film for reverse electrodialysis power generation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6090919B2 (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huo et al. | Challenges of polymer electrolyte with wide electrochemical window for high energy solid‐state lithium batteries | |
| TWI498376B (en) | Polymer electrolyte gel composition | |
| JP4370079B2 (en) | Lithium polymer battery | |
| JP5462949B2 (en) | Electrolyte, electrolytic solution, gel electrolyte, electrolyte membrane, method for producing gel electrolyte battery, and lithium ion secondary battery | |
| JP5487458B2 (en) | Lithium ion secondary battery | |
| JP2020074476A (en) | Lithium ion capacitor | |
| Ab Aziz et al. | Magnesium ion-conductive poly (ethylene carbonate) electrolytes | |
| CN110212242B (en) | Porous gel polymer electrolyte and preparation method thereof | |
| JP2012018909A (en) | Electrolyte and electrolyte film | |
| TW201108488A (en) | Electrolyte compositions and methods of making and using the same | |
| EP3086337B1 (en) | Lithium ion capacitor | |
| JP7152429B2 (en) | Solid polymer electrolyte for batteries | |
| Zhong et al. | Polyhedral oligomeric silsesquioxane-modified gel polymer electrolyte based on matrix of poly (methyl methacrylate-maleic anhydride) | |
| Koliyoor et al. | An insight into the suitability of magnesium ion-conducting biodegradable methyl cellulose solid polymer electrolyte film in energy storage devices | |
| JP6090919B2 (en) | Polymer electrolyte gel composition for secondary battery and method for producing the same | |
| JP4985959B2 (en) | Organic solid electrolyte and secondary battery using the same | |
| JP5758214B2 (en) | Electrolyte and electrolyte membrane | |
| JP2014175203A (en) | Polymer gel electrolyte, and manufacturing method thereof | |
| WO2014084182A1 (en) | Electricity storage device, electrode used therein, and porous sheet | |
| CN104362373A (en) | Ion liquid doped solid polymer electrolyte material and preparation method thereof | |
| JP2012113849A (en) | Polymer electrolyte gel composition for secondary battery | |
| WO2021256467A1 (en) | Binder suitable for electricity storage device electrodes, binder solution for electricity storage device electrodes, electricity storage device electrode slurry, electricity storage device electrode, and electricity storage device | |
| WO2014077226A1 (en) | Power storage device, and electrode and porous sheet used in same | |
| CN113745648A (en) | Electrochemical energy storage polymer electrolyte and preparation method thereof | |
| Mahmud et al. | MG49-KOH-PC alkaline gel polymer electrolytes membrane for supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160112 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151224 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160913 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160920 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161109 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170117 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170203 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6090919 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |