JPS62226568A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPS62226568A JPS62226568A JP61069880A JP6988086A JPS62226568A JP S62226568 A JPS62226568 A JP S62226568A JP 61069880 A JP61069880 A JP 61069880A JP 6988086 A JP6988086 A JP 6988086A JP S62226568 A JPS62226568 A JP S62226568A
- Authority
- JP
- Japan
- Prior art keywords
- group
- battery
- oxidizing agent
- secondary battery
- electrode
- 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
- -1 pyrrole compound Chemical class 0.000 claims abstract description 38
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004065 semiconductor Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims description 8
- 150000003233 pyrroles Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229920000128 polypyrrole Polymers 0.000 description 18
- 238000007599 discharging Methods 0.000 description 15
- 239000007774 positive electrode material Substances 0.000 description 13
- 239000007772 electrode material Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 229920001940 conductive polymer Polymers 0.000 description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- 229920001197 polyacetylene Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000004698 Polyethylene Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- CTWQGTOWGFCWNW-UHFFFAOYSA-N 1,3-dimethylpyrrole Chemical compound CC=1C=CN(C)C=1 CTWQGTOWGFCWNW-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- VPUAYOJTHRDUTK-UHFFFAOYSA-N 1-ethylpyrrole Chemical compound CCN1C=CC=C1 VPUAYOJTHRDUTK-UHFFFAOYSA-N 0.000 description 1
- GEZGAZKEOUKLBR-UHFFFAOYSA-N 1-phenylpyrrole Chemical compound C1=CC=CN1C1=CC=CC=C1 GEZGAZKEOUKLBR-UHFFFAOYSA-N 0.000 description 1
- WAUGGYPDCQZJKK-UHFFFAOYSA-N 1h-pyrrol-3-amine Chemical compound NC=1C=CNC=1 WAUGGYPDCQZJKK-UHFFFAOYSA-N 0.000 description 1
- IMKVMBSERNTJBM-UHFFFAOYSA-N 3-bromo-1-methylpyrrole Chemical compound CN1C=CC(Br)=C1 IMKVMBSERNTJBM-UHFFFAOYSA-N 0.000 description 1
- ZZHFDFIWLDELCX-UHFFFAOYSA-N 3-bromo-1h-pyrrole Chemical compound BrC=1C=CNC=1 ZZHFDFIWLDELCX-UHFFFAOYSA-N 0.000 description 1
- UUUOHRSINXUJKX-UHFFFAOYSA-N 3-chloro-1h-pyrrole Chemical compound ClC=1C=CNC=1 UUUOHRSINXUJKX-UHFFFAOYSA-N 0.000 description 1
- VWSSZZBNUPLYAT-UHFFFAOYSA-N 3-ethylsulfanyl-1h-pyrrole Chemical compound CCSC=1C=CNC=1 VWSSZZBNUPLYAT-UHFFFAOYSA-N 0.000 description 1
- OTODBDQJLMYYKQ-UHFFFAOYSA-N 3-methoxy-1h-pyrrole Chemical compound COC=1C=CNC=1 OTODBDQJLMYYKQ-UHFFFAOYSA-N 0.000 description 1
- VQFUAJORKBIYKB-UHFFFAOYSA-N 3-methyl-1-naphthalen-1-ylpyrrole Chemical compound C1=C(C)C=CN1C1=CC=CC2=CC=CC=C12 VQFUAJORKBIYKB-UHFFFAOYSA-N 0.000 description 1
- UAHOVFOZEICOPL-UHFFFAOYSA-N 3-methyl-1-phenylpyrrole Chemical compound C1=C(C)C=CN1C1=CC=CC=C1 UAHOVFOZEICOPL-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- WRAPYPVHEAQARO-UHFFFAOYSA-N 3-methylsulfanyl-1h-pyrrole Chemical compound CSC=1C=CNC=1 WRAPYPVHEAQARO-UHFFFAOYSA-N 0.000 description 1
- LOJNBPNACKZWAI-UHFFFAOYSA-N 3-nitro-1h-pyrrole Chemical compound [O-][N+](=O)C=1C=CNC=1 LOJNBPNACKZWAI-UHFFFAOYSA-N 0.000 description 1
- BNQPUGPPVNNKBK-UHFFFAOYSA-N 3-phenoxy-1h-pyrrole Chemical compound C=1C=CC=CC=1OC=1C=CNC=1 BNQPUGPPVNNKBK-UHFFFAOYSA-N 0.000 description 1
- LJDRAKFYYGCAQC-UHFFFAOYSA-N 3-phenyl-1h-pyrrole Chemical compound N1C=CC(C=2C=CC=CC=2)=C1 LJDRAKFYYGCAQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000001814 trioxo-lambda(7)-chloranyloxy group Chemical group *OCl(=O)(=O)=O 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は二次電池に関し、詳しくは、有機材料よりな
る導電体を電極材料として用いた非水系の二次電池に関
するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a secondary battery, and more particularly to a non-aqueous secondary battery using a conductor made of an organic material as an electrode material.
〈従来の技術〉
近年、各種有機材料からなる導電性ポリマーを電極材料
とした二次電池が提案されている。<Prior Art> In recent years, secondary batteries using conductive polymers made of various organic materials as electrode materials have been proposed.
この種の二次電池の電極材料となる導電性ポリマーは、
通常は導電性はわずかであるが、各種アニオンやカチオ
ンの如きドーパントをドーピング並びにアンド−ピング
処理することが可能でおり、ドーピングにより導電性が
飛躍的に上昇する。そして、アニオンがドーピングされ
る導電性ポリマーを正極材料として、またカチオンがド
ーピングされる導電性ポリマーを負極材料として各々使
用すると共に上記ドーパントを含有する溶液を電解液と
して用い、ドーピング及びアンド−ピングを電気化学的
に可逆的に行なうことにより充放電可能な電池が構成さ
れる。The conductive polymer that serves as the electrode material for this type of secondary battery is
Normally, the conductivity is slight, but it is possible to perform doping and undoping treatment with dopants such as various anions and cations, and doping dramatically increases the conductivity. Then, a conductive polymer doped with anions is used as a positive electrode material, a conductive polymer doped with cations is used as a negative electrode material, and a solution containing the dopant is used as an electrolytic solution to perform doping and undoping. A battery that can be charged and discharged is constructed by electrochemically performing the process reversibly.
このような導電性ポリマーとしては従来よりポリアセチ
レン、ポリチオフェン、ポリピロールなどが知られてお
り、ポリアセチレンを例に採れば、ポリアセチレンを正
極または負極の少なくとも一方の電極材料として用い、
ＢＦ４−１ＣλＯ’−１ＳｂＦ −１ＰＦ６−等のア
ニ第ン、またはＬｌ 、Ｎａ 、Ｒ４Ｎ （Ｒは
アルキル基を表わす）等のカチオンを電気化学的に可逆
的にドーピング、アンド−ピングする構成が採られてい
る。Polyacetylene, polythiophene, polypyrrole, etc. are conventionally known as such conductive polymers. Taking polyacetylene as an example, polyacetylene is used as an electrode material for at least one of the positive electrode and the negative electrode,
A configuration is adopted in which electrochemically reversible doping and doping is performed with ananidine such as BF4-1CλO'-1SbF-1PF6-, or cations such as Ll, Na, R4N (R represents an alkyl group). ing.
ところで、この種の導電性ポリマー、例えばポリアセチ
レンは、ドーピング及びアンド−ピング状態において空
気中の酸素によって非常にたやすく酸化され易いという
欠点をもつ。このため、これを電極材料とした場合、電
極作製環境の管理が重大となり、電極作製作業が困難且
つ煩雑化し、また電極自身の保存性が悪い等という不都
合がある。更に、電池内に組込んだ場合、微量の酸素や
水分が存在するだけで変成あるいは分解を起こして電池
特性劣化を引き起す他、過充電を行なうとポリマーが変
成２分解する可能性が必る等の欠点がおり、充電電圧の
急上昇、充放電効率の低下や電池サイクル寿命の減少等
を招くことから、電極材料としてはあまり好ましくない
。However, this type of conductive polymer, such as polyacetylene, has the disadvantage that it is very easily oxidized by oxygen in the air in doped and undoped conditions. For this reason, when this is used as an electrode material, it becomes important to control the electrode manufacturing environment, making the electrode manufacturing work difficult and complicated, and there are disadvantages such as poor storage stability of the electrode itself. Furthermore, when incorporated into a battery, even the presence of trace amounts of oxygen or moisture can cause denaturation or decomposition, leading to deterioration of battery characteristics, and overcharging can also cause the polymer to undergo denaturation and decomposition. It is not very desirable as an electrode material because it causes a sudden increase in charging voltage, a decrease in charging and discharging efficiency, and a shortened battery cycle life.
一方、上記の各種導電性ポリマーのうちポリピロールは
、ポリアセチレンに較べて、空気中での安定性が良好で
酸化劣化が極めて少なくて取扱い易いという特徴がある
。従ってポリピロールを電池の電極材料として用いた時
には、ポリアセチレンの場合のような欠点がなく、作製
容易で保存性のよい電極を得ることができる。On the other hand, among the above-mentioned various conductive polymers, polypyrrole has better stability in air than polyacetylene, has extremely little oxidative deterioration, and is easy to handle. Therefore, when polypyrrole is used as a battery electrode material, it does not have the disadvantages of polyacetylene, and it is possible to obtain an electrode that is easy to produce and has good storage stability.
このようなポリピロールとしては、従来、■ピロールを
電気化学的に酸化重合（電解重合）したもの、■酸化剤
を使用してピロールを化学的に酸化重合したもの、等が
知られている。そして、■の場合は電解陽極上にポリピ
ロールがフィルム状に析出し、析出後に同極上から剥離
することによりフィルム状のポリピロールが得られる。Conventionally known examples of such polypyrrole include (1) pyrrole produced by electrochemical oxidative polymerization (electrolytic polymerization), and (2) pyrrole produced by chemical oxidative polymerization of pyrrole using an oxidizing agent. In the case of (2), polypyrrole is deposited in the form of a film on the electrolytic anode, and after the deposition is peeled off from the anode, polypyrrole in the form of a film is obtained.
また■の場合、酸化剤として過硫酸カリウムや過硫酸ア
ンモニウムなどの過酸化物、硝酸や硫Ｖおるいはクロム
酸などの酸、塩化第二鉄や塩化ルテニウムや塩化タング
ステンあるいは塩化モリブデンなどのルイス酸などを使
用して酸化重合したり、あるいは、有＠溶媒中で過塩素
酸第二鉄を酸化剤に使用してピロールの酸化重合を行な
い（Ｍｏｌ、 Ｃｒｙｓｔ、 ＬｉＱ。In the case of Alternatively, oxidative polymerization of pyrrole is carried out using ferric perchlorate as an oxidizing agent in a solvent (Mol, Cryst, LiQ, etc.).
ＣｒｙＳｔ、誌 １９８５年 ｖｏｌ １１Ｂの第１４
９〜１５３頁）、粉末状のポリピロールが得られている
。CrySt, magazine 1985 vol 11B no. 14
9-153), powdered polypyrrole was obtained.
〈発明が解決しようとする問題点〉
しかしながら、上記従来のポリピロールのうち■のもの
は、製造方法が煩雑で、電池コスト高の原因となるばか
りか、ポリピロールが電解陽極面上で生成するので得ら
れるポリピロールの形状や大きさがその電極板の寸法に
規制され、このため電池品種に応じた自由な寸法に成形
するのが難しいという問題がある。更に、均一な厚さで
膜厚のものが再現性よく得にくいので、工業用の電池用
材料としては膜厚の薄いものしか利用できず、このため
電池電極自体並びに電池の充放電容量が制限を受けて容
量増大が極めて困難でおるという問題もある。<Problems to be Solved by the Invention> However, among the conventional polypyrroles mentioned above, the method of manufacturing method (2) is complicated, which not only causes high battery costs, but also makes it difficult to obtain benefits because the polypyrrole is generated on the surface of the electrolytic anode. The shape and size of the polypyrrole to be used are restricted by the dimensions of the electrode plate, and this poses a problem in that it is difficult to mold the polypyrrole into a size that suits the type of battery. Furthermore, it is difficult to obtain a film with a uniform thickness with good reproducibility, so only thin films can be used as materials for industrial batteries, which limits the battery electrode itself and the charge/discharge capacity of the battery. Another problem is that it is extremely difficult to increase capacity.
一方、上記■で得られたポリピロールを用いた場合は上
記のような問題はない。しかしながら、■のポリピロー
ルはその電気伝導度が極めて小さいので、これを電極材
料として二次電池を作製した場合、電池の内部抵抗が増
大すると共に充放電反応が電極各部で不均一になってし
まう。このため、充放電サイクルを繰返すと充電電圧が
上昇し易く、充電電圧の上昇に伴って電解液の分解が起
こって電池特性の著しい劣化を招き易いという問題があ
る。On the other hand, when the polypyrrole obtained in the above (1) is used, the above-mentioned problem does not occur. However, the electrical conductivity of the polypyrrole (3) is extremely low, so when a secondary battery is manufactured using it as an electrode material, the internal resistance of the battery increases and the charging/discharging reaction becomes non-uniform in each part of the electrode. Therefore, when charging and discharging cycles are repeated, the charging voltage tends to increase, and as the charging voltage increases, the electrolytic solution tends to decompose, resulting in a problem that the battery characteristics tend to deteriorate significantly.
〈問題点を解決するための手段〉
本発明者は、上記従来のピロール系ポリマーの如き欠点
のないピロール系の導電性ポリマーを電極材料として用
いることで上記問題点を解決せんと研究し、特定の第二
鉄化合物とピロール系化合物とを反応させて得られる有
機半導体を用いた場合には所期の目的を達成できること
を知得してこの発明を完成した。即ち、この発明の二次
電池は、ピロール系化合物と酸化剤とを反応させて得ら
れる有機半導体を正極または負極の少なくとも一方の電
極として用いてなる二次電池であって、該酸化剤が、一
般式％式％）
（式中、ＸはＣｌＯ４’−１ＡＳＦ
−、ＰＦ６−．５ｂＦ６−１ＣＨ３Ｃ６Ｈ４５０３−
１
ＣＲ３ＳＯ３−、Ｚ ｒ Ｒ６−１
Ｔ ｒ Ｒ６−またはｓ ｒ Ｒ６−を表わし、ｍ及び
ｎは１〜３の整数を表わす。）
で示される第二鉄化合物でおることを要旨とする二次電
池に存する。<Means for Solving the Problems> The present inventor has conducted research to solve the above problems by using a pyrrole-based conductive polymer, which does not have the drawbacks of the conventional pyrrole-based polymers, as an electrode material, and has identified This invention was completed after learning that the intended purpose could be achieved by using an organic semiconductor obtained by reacting a ferric compound with a pyrrole compound. That is, the secondary battery of the present invention is a secondary battery that uses an organic semiconductor obtained by reacting a pyrrole compound and an oxidizing agent as at least one of the positive electrode and the negative electrode, wherein the oxidizing agent is General formula % formula %) (wherein, X is ClO4'-1ASF -, PF6-.5bF6-1CH3C6H4503-
1 CR3SO3-, Z r R6-1 T r R6- or s r R6-, and m and n represent integers of 1 to 3. ) The secondary battery consists of a ferric compound shown in the following.
上記のような有機半導体は、単一または異なる二種類以
上の後述する如きピロール系化合物を出発物質に用い、
これと、単一または異なる二種類以上の後述する第二鉄
化合物とを反応させて１ｑることができる。The above organic semiconductor uses a single or two or more different pyrrole compounds as described below as a starting material,
1q can be produced by reacting this with a single or two or more different ferric compounds described below.
本発明で使用される上記ピロール系化合物と゛しては、
例えば、一般式
（式中、Ｒ及びＲ２は水素原子、アルキル基、アルコキ
シ基、アリール基、アリロキシ基、アルキルチオ基、ア
ミン基、ハロゲン原子、シアノ基またはニトロ基を表わ
し、Ｒ３は水素原子、アルキル基またはアリール基を表
わす。）
で示される化合物でが挙げられる。The above-mentioned pyrrole compounds used in the present invention include:
For example, the general formula (where R and R2 represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an alkylthio group, an amine group, a halogen atom, a cyano group, or a nitro group, and R3 represents a hydrogen atom, an alkyl group or aryl group).
上記一般式（２）で示されるピロール系化合物において
、ピロール環骨格構造の２，５位置に置換基をもたない
ピロール系化合物が好ましい。Among the pyrrole compounds represented by the general formula (2) above, pyrrole compounds having no substituents at the 2 and 5 positions of the pyrrole ring skeleton structure are preferred.
また、詳しくは、Ｒ１−Ｒ２は水素原子、メチル基、エ
チル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル
基、イソブチル基、ｓｅｃ −ブチル基、ｔｅｒｔ−ブ
チル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、
イソプロポキシ基、ｎ−ブトキシ基、フェニル基、トル
イル基、ナフチル基、フェノキシ基、メチルフェノキシ
基、ナフトキシ基、メチルチオ基、エチルチオ基、アミ
ノ基、フッ素原子、塩素原子、臭素原子、沃素原子、シ
アノ基、ニトロ基を表わし、Ｒ３は水素原子、メチル基
、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブ
チル基、イソブチル基、５ｅｃ−ブ≠ル基、ｔｅｒｔ−
ブチル基、フェニル基、１−ルイル基、ナフチル基を表
わす。In addition, in detail, R1-R2 are hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, methoxy groups, ethoxy groups, n-propoxy group,
Isopropoxy group, n-butoxy group, phenyl group, tolyl group, naphthyl group, phenoxy group, methylphenoxy group, naphthoxy group, methylthio group, ethylthio group, amino group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, R3 represents a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5ec-butyl group, tert-
Represents a butyl group, a phenyl group, a 1-ruyl group, and a naphthyl group.
このようなピロール系化合物としては、具体的にはピロ
ール、Ｎ−メチルピロール、Ｎ−エチルピロール、Ｎ−
フェニルピロール、３−メチルピロール、Ｎ−メチル−
３−メチルピロール、３−クロルピロール、３．４−ジ
クロルピロール、３−ブロムピロール、Ｎ−メチル−３
−ブロムピロール、３−メトキシピロール、３−フェノ
キシピロール、３−フェニルピロール、３−メチルチオ
ピロール、３−エチルチオピロール、３−アミノピロー
ル、３−ニトロピロール、Ｎ−フェニル−３−メチルピ
ロール、Ｎ−ナフチル−３−メチルピロールなどが挙げ
られる。Specific examples of such pyrrole compounds include pyrrole, N-methylpyrrole, N-ethylpyrrole, and N-
Phenylpyrrole, 3-methylpyrrole, N-methyl-
3-methylpyrrole, 3-chloropyrrole, 3.4-dichloropyrrole, 3-bromopyrrole, N-methyl-3
-bromopyrrole, 3-methoxypyrrole, 3-phenoxypyrrole, 3-phenylpyrrole, 3-methylthiopyrrole, 3-ethylthiopyrrole, 3-aminopyrrole, 3-nitropyrrole, N-phenyl-3-methylpyrrole, N -naphthyl-3-methylpyrrole and the like.
前記一般式（１）で示される第二鉄化合物は、具体的に
は、Ｆｅ （Ｃｆ、４）３、
Ｆｅ （ＢＦ４ ）３ 、Ｆｅ （ＡｓＦ６ ）３．１
”ｅ （ＰＦ６ ）３ 、Ｆｅ （ＳｂＦ６ ）３、Ｆ
ｅ （ＣＨ３Ｃ６Ｈ４３０３＞３、
Ｆｅ（ＣＦ３Ｓ０３）３、
Ｆｅ２ （Ｚｒ Ｆ６ ）３ 、Ｆｅ２ （Ｔｔ Ｆ
６ ）３、Ｆｅ２ （ＳｉＦ６）３であり、これらは通
常結晶水をもつ化合物もしくは水溶液として使用される
。Specifically, the ferric compound represented by the general formula (1) is Fe (Cf,4)3, Fe (BF4)3, Fe (AsF6)3.1
”e (PF6)3, Fe (SbF6)3, F
e (CH3C6H4303>3, Fe(CF3S03)3, Fe2 (Zr F6 )3, Fe2 (Tt F
6)3, Fe2 (SiF6)3, and these are usually used as compounds with water of crystallization or as aqueous solutions.
使用量はピロール系化合物１モルに対してｏ、 ｏｉ〜
１００ミル１００倍モルましくは０．１〜５０倍モルで
ある。The amount used is o, oi~ per mole of pyrrole compound.
100 mils is 100 times the mole or 0.1 to 50 times the mole.
前記一般式（１）で示される第二鉄化合物と例えば前記
一般式（２）で示されるピロール系化合物との反応は固
相、液相、気相の任意の相で実施することができるが、
両者が溶解する任意の溶媒の存在下、液相で反応させる
のが好ましい。このような溶媒としては、上記第二鉄化
合物並びに上記ピロール系化合物と直接反応しないもの
なら適宜選択できる。両者を溶解する溶媒として、水、
メタノール、エタノール等のアルコール類、極性有機系
溶媒、具体的にはアセトニトリル、テトラヒドロフラン
、ジオキサン、ニトロメタン、酢酸、プロピレンカーボ
ネートなどが使用される。The reaction between the ferric compound represented by the general formula (1) and the pyrrole compound represented by the general formula (2), for example, can be carried out in any phase including solid phase, liquid phase, and gas phase. ,
Preferably, the reaction is carried out in a liquid phase in the presence of any solvent in which both are soluble. Such a solvent can be appropriately selected as long as it does not directly react with the ferric compound and the pyrrole compound. As a solvent for dissolving both, water,
Alcohols such as methanol and ethanol, polar organic solvents, and specifically acetonitrile, tetrahydrofuran, dioxane, nitromethane, acetic acid, propylene carbonate, and the like are used.
尚、上記溶媒として上記の極性有機系溶媒を用いた場合
、これら極性有機系溶媒は前記酸化剤、例えば過塩素酸
第二鉄の溶解度が水溶液中に較へて非常に小さいため、
有機半導体の伍産性の面で製造上制約を受けて不利であ
り電池コスト高を招く原因となると共に、溶解度の減少
分だけ溶媒中における前記ドーピング剤の濃度が低下す
るため、生成するポリピロールの電気伝導度が小さくな
り易く、電池特性劣化の度合が大きい等という欠点があ
る。また、上記アルコール類を用いた場合もこの傾向が
ある。よって、上記溶媒としてはこのような欠点のない
水を用いることが好ましい。In addition, when the above-mentioned polar organic solvent is used as the above-mentioned solvent, the solubility of the oxidizing agent, such as ferric perchlorate, in these polar organic solvents is very low compared to that in an aqueous solution.
This is disadvantageous due to manufacturing constraints due to the low productivity of organic semiconductors, which causes high battery costs, and the concentration of the doping agent in the solvent decreases by the amount of decreased solubility, so that the resulting polypyrrole There are drawbacks such as the electrical conductivity tends to be low and the degree of deterioration of battery characteristics is high. This tendency also exists when the above-mentioned alcohols are used. Therefore, it is preferable to use water, which does not have such drawbacks, as the solvent.
また、反応温度は一５０°Ｃ〜１５０℃であり、好まし
くは一２０℃〜１００℃である。反応時間は反応温度と
関連するが通常０．５〜２００時間、好ましくは１．０
〜１００時間でおる。Further, the reaction temperature is -50°C to 150°C, preferably -20°C to 100°C. The reaction time is related to the reaction temperature, but is usually 0.5 to 200 hours, preferably 1.0 hours.
~100 hours.
反応生成物は暗褐色〜黒色の粉末状物質であり、上記溶
媒存在下での反応では反応終了後溶媒を通常の方法で除
去するか、水、アルコール中などに移し生成物を枦取す
ることができる。The reaction product is a dark brown to black powdery substance, and in the case of the reaction in the presence of the above solvent, after the reaction is completed, the solvent must be removed in the usual manner, or the product can be collected by transferring it to water, alcohol, etc. I can do it.
この反応生成物は実施例において述べる如く導電性を有
する。本発明では、かかる反応生成物を加圧成形の如き
公知の方法で所要形状に成形加工し、二次電池の電極と
して使用する。この際、かかる反応生成物を単独で使用
することも可能であるが、電極の機械的強度を高めると
共に、導電性を上昇させて電池特性向上を図るために熱
可塑性樹脂や適宜な導電性部材等を添加するのが好まし
い。このような熱可塑性樹脂としては、電池の電解液に
対して実質的に不溶のものであれば特に制限なく用いる
ことができる。通常、分子箔１万以上のものが用いられ
、具体例としては、ポリエチレン、ポリプロピレン、エ
チレン−プロピレン共重合体、エチレンーテｌ〜ラフル
オロエチレン共重合体、ポリテトラフルオロエチレン、
ポリトリフルオロエチレン、ポリジフルオロエチレン、
四フッ化エチレンーパーフルオロアルキルビニルエーテ
ル共重合体、四フッ化エチレンー六フッ化プロピレン共
重合体、ポリ三フッ化塩化エチレン、ポリフッ化ごニリ
デン、四フッ化エチレンーエチレン共重合体、クロロト
リフルオロエチレン−エチレン共重合体、ポリアミド、
ポリエステル、ポリカーボネート、及び、変成ポリオレ
フィン等が挙げられる。This reaction product has electrical conductivity as described in the Examples. In the present invention, the reaction product is molded into a desired shape by a known method such as pressure molding, and used as an electrode for a secondary battery. At this time, it is possible to use such a reaction product alone, but in order to increase the mechanical strength of the electrode and increase the conductivity to improve battery characteristics, thermoplastic resin or an appropriate conductive material may be used. It is preferable to add the like. As such a thermoplastic resin, any thermoplastic resin can be used without particular limitation as long as it is substantially insoluble in the electrolyte of the battery. Usually, molecular foils of 10,000 or more are used, and specific examples include polyethylene, polypropylene, ethylene-propylene copolymer, ethylenetetrafluoroethylene copolymer, polytetrafluoroethylene,
polytrifluoroethylene, polydifluoroethylene,
Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polytrifluorochloroethylene, polynylidene fluoride, tetrafluoroethylene-ethylene copolymer, chlorotrifluoro Ethylene-ethylene copolymer, polyamide,
Examples include polyester, polycarbonate, and modified polyolefin.
また、導電性部材としては充放電を繰り返しても溶解し
ない材質のもの、例えばステンレス鋼、金、白金、ニッ
ケル、銅、モリブデン、チタン等の金属、カーボン、炭
素繊維等の部材からなるものならば特に制限はないが、
特に、軽量且つ高導電性のものが好ましい。具体的には
、そのような金属からできた金属網、あるいは、金属メ
ッキ繊維、金属蒸着繊維、金属含有合成繊維、更には炭
素繊維、炭素複合繊維等からなる網や織布および不織布
が挙げられる。In addition, the conductive member may be made of a material that does not dissolve even after repeated charging and discharging, such as stainless steel, metals such as gold, platinum, nickel, copper, molybdenum, titanium, carbon, carbon fiber, etc. There are no particular restrictions, but
In particular, those that are lightweight and highly conductive are preferred. Specifically, examples include metal nets made of such metals, metal-plated fibers, metal-deposited fibers, metal-containing synthetic fibers, and nets, woven fabrics, and non-woven fabrics made of carbon fibers, carbon composite fibers, etc. .
このような熱可塑性樹脂及び導電性部材の添加伍は反応
生成物（有機半導体） １００重田部に対して熱可塑
性樹脂０．０２〜ｉ ｏｏｏ重伍部、導電性部材２〜１
００重量部使用することが好ましい。The addition of such a thermoplastic resin and a conductive member is a reaction product (organic semiconductor), and the thermoplastic resin is 0.02 to 100 parts.
It is preferable to use 00 parts by weight.
本発明の二次電池には、かかる反応生成物を電極材料と
して用いてなる電極を正負両極に使用する場合と、一方
の電極のみにこの電極を使用し、他の電極には、金属や
金属酸化物あるいは他の無機化合物更には本発明の反応
生成物以外の公知の導電性重合体や有機化合物および有
機金属化合物等を電極材料として使用する場合とがある
。正極にのみこの反応生成物を用いた電極を使用し、負
極の電極材料として金属を使用する場合を例にとれば、
負極を構成する金属として電気陰性度が１．６以下のも
のを用いるのが好ましく、このような金属の例としては
Ｌｌ。In the secondary battery of the present invention, there are cases in which electrodes made of such reaction products as electrode materials are used for both positive and negative electrodes, and cases in which this electrode is used only for one electrode and metals or metals are used for the other electrodes. Oxides or other inorganic compounds, as well as known conductive polymers, organic compounds, and organometallic compounds other than the reaction products of the present invention may be used as electrode materials. For example, if an electrode using this reaction product is used only for the positive electrode, and a metal is used as the negative electrode material,
It is preferable to use a metal having an electronegativity of 1.6 or less as the metal constituting the negative electrode, and an example of such a metal is Ll.
Ｎａ、に、Ｍｇ、Ａ、Ｃあるいはそれらの合金等が挙げ
られ、ｌｉおよびｌｉ金合金好ましい。Examples of Na include Mg, A, C, and alloys thereof, with Li and Li gold alloys being preferred.
一方、本発明の二次電池に用いられる電解液としては、
例えば、電解質を有機溶剤に溶解した溶液が使用される
。かかる電解質としては、電気陰性度が１．６以下の金
属の陽イオンや有機カチオン等の陽イオン及び陰イオン
との塩を挙げることができる。オニウムイオンの例とし
て、４級アンモニウムイオン、カルボニウムイオン、オ
キソニウムイオン等が挙げられる。また、陰イオンとし
ては、ＢＦ −１Ｃλ０４−１ＰＦ６−、ＢＦ４６−
１ＣＦ ｓｏ ＋、Ｉ−１Ｂｒ−１Ｃ，１２” 、
Ｆ−等が挙げられる。そして、このような電解質の具体
例としては、テトラフルオロホウ酸リチウム（ＬｉＢＦ
４）、過塩素酸リチウム（ＬｉＣλ０４．）、ヘキサフ
ルオロリン酸リチウム（ＬｉＰＦ６）、テトラクロロア
ルミン酸リチウム（Ｌ ｉ ＡＪ！ ＣＪ！４ ） 、
テトラフルオロホウ酸テトラエチルアンモニウム（Ｅｔ
４ＮＢＦ４ ＞、過塩素酸テトラｎ−７チルアンモニウ
ム（ｎＢｕ４ＮＣぶ０４）、トリフルオロメタンスルホ
ン酸リチウム
（Ｌ ！ ＣＦ３３０３ ） 、ヨウ化リチウム（Ｌｉ
Ｉ）、臭化リチウム（ＬｉＢｒ）等が挙げることかでき
るが、これらに限定されるものではない。そして、正負
両極に本発明の有機半導体を用い、ＬｉＢＦ４を電解質
として溶解しでなる電解液を用いて構成される電池を例
にとれば、充電時には、正極内の有機半導体に電解液中
のＢＦ４−が、また負極内の有機半導体には電解液中の
１１ が夫々ドーピングされる。On the other hand, the electrolyte used in the secondary battery of the present invention is as follows:
For example, a solution in which an electrolyte is dissolved in an organic solvent is used. Examples of such electrolytes include salts with cations and anions such as metal cations and organic cations having an electronegativity of 1.6 or less. Examples of onium ions include quaternary ammonium ions, carbonium ions, oxonium ions, and the like. In addition, as anions, BF -1Cλ04-1PF6-, BF46-
1CF so +, I-1Br-1C, 12",
F- etc. are mentioned. A specific example of such an electrolyte is lithium tetrafluoroborate (LiBF).
4), lithium perchlorate (LiCλ04.), lithium hexafluorophosphate (LiPF6), lithium tetrachloroaluminate (L i AJ! CJ!4),
Tetraethylammonium tetrafluoroborate (Et
4NBF4>, tetra n-7 tylammonium perchlorate (nBu4NC 04), lithium trifluoromethanesulfonate (L! CF3303), lithium iodide (Li
I), lithium bromide (LiBr), etc., but are not limited to these. For example, if a battery is constructed using the organic semiconductor of the present invention in both the positive and negative electrodes and an electrolytic solution containing LiBF4 dissolved as an electrolyte, during charging, the organic semiconductor in the positive electrode is mixed with BF4 in the electrolytic solution. - is doped, and the organic semiconductor in the negative electrode is doped with 11 in the electrolyte.
一方、放電時には、正、負極にドーピングされたＢＦ
”、Ｌｌ が夫々電解液中に放出される。On the other hand, during discharge, BF doped into the positive and negative electrodes
”, Ll are released into the electrolyte, respectively.
また、電解質を溶解する有機溶剤としては、高誘電率で
非プロトン性のものが好ましく、ニトリル、カーボネー
ト、エーテル、ニトロ化合物、アミド、含硫黄化合物、
塩素化炭化水素、ケトン、エステル等を用いることがで
きる。また、このような溶剤は二種以上を混合して用い
ることもできる。これらの代表例として、アセトニトリ
ル、プロピオニトリル、ブチロニトリル、ベンゾニトリ
ル、プロピレンカーボネート、エチレンカーボネート、
テトラヒドロフラン、ジオキソラン、１，４−ジオキサ
ン、ニトロメタン、Ｎ、Ｎ−ジメチルホルムアミド、ジ
メチルスルホキシド、スルホラン、１，２−ジクロロエ
タン、γ−ブチロラクトン、１，２−ジメトキシエタン
、リン酸メチル、リン酸エチル等を挙げることができる
が、これらに限定されるものではない。In addition, as the organic solvent for dissolving the electrolyte, it is preferable to use an aprotic one with a high dielectric constant, such as nitrile, carbonate, ether, nitro compound, amide, sulfur-containing compound,
Chlorinated hydrocarbons, ketones, esters, etc. can be used. Moreover, two or more kinds of such solvents can also be used in combination. Representative examples of these include acetonitrile, propionitrile, butyronitrile, benzonitrile, propylene carbonate, ethylene carbonate,
Tetrahydrofuran, dioxolane, 1,4-dioxane, nitromethane, N,N-dimethylformamide, dimethylsulfoxide, sulfolane, 1,2-dichloroethane, γ-butyrolactone, 1,2-dimethoxyethane, methyl phosphate, ethyl phosphate, etc. These include, but are not limited to.
そして、本発明の電解液の濃度は、通常ｏ、ｏｏｉ〜１
０モル／Ｊ２．で用いられ、好ましくは０．１〜３モル
／ぶで用いられる。The concentration of the electrolytic solution of the present invention is usually o, ooi~1
0 mol/J2. It is preferably used in an amount of 0.1 to 3 mol/bu.
このような電解液は注液の他、予め本発明の有機半導体
を用いた電極に含液させて用いることもできる。In addition to being injected, such an electrolytic solution can also be used by impregnating an electrode using the organic semiconductor of the present invention in advance.
また、以上では有機半導体にドーピング処理をすること
なくそのまま電極に成形加工する方法について説明した
が、ドーパントを予め有機半導体にドーピングせしめ、
しかる後、単独あるいはこれと上記した如き導電性材料
及び又は熱可塑性樹脂を用いて、電極に成形加工して使
用することもできる。In addition, although the method for forming an electrode as it is without doping the organic semiconductor has been described above, it is also possible to dope the organic semiconductor with a dopant in advance.
Thereafter, it can be used alone or together with the conductive material and/or thermoplastic resin described above to form an electrode.
更に、本発明に於て、電解質中で電極を固定するために
、スノコ状または孔を有するガラス、テフロン、ポリエ
チレン、板等を用いて電極を被覆する構成としてもよい
。Further, in the present invention, in order to fix the electrode in the electrolyte, the electrode may be covered with a slat-like or holed glass, Teflon, polyethylene, plate, or the like.
また、本発明の電池においては、ガラスフィルター濾紙
、テフロン、ポリエチレン、ポリプロピレン、ナイロン
等の多孔質膜をセパレータとして用いてもよい。Further, in the battery of the present invention, a porous membrane such as glass filter paper, Teflon, polyethylene, polypropylene, nylon, etc. may be used as the separator.
く作 用〉
上記の如き有職半導体は、耐酸化性が優れていることは
勿論、前記従来のポリピロールの如き問題なく、製造容
易で電気伝導度が大きい。Effects> The above-mentioned skilled semiconductors not only have excellent oxidation resistance, but also have no problems like the conventional polypyrrole, are easy to manufacture, and have high electrical conductivity.
このため、この有機半導体を電極材料とした場合、電極
作製環境の管理が非常に容易化し、また電極自身の保存
性が向上する等のことは勿論、電池電極並びに電池の充
放電容量が制限をうけることもなく、また電極各部の充
放電反応の不均一などに起因する電池の特性劣化の度合
も非常に小ざく、電池のサイクル特性が大幅に改善され
る。For this reason, when this organic semiconductor is used as an electrode material, it is extremely easy to manage the electrode manufacturing environment, and the storage stability of the electrode itself is improved. Furthermore, the degree of deterioration in battery characteristics due to non-uniform charging and discharging reactions at various electrode parts is extremely small, and the cycle characteristics of the battery are greatly improved.
〈実施例〉 以下に実施例を挙げて本発明を具体的に説明する。<Example> The present invention will be specifically described below with reference to Examples.
五町土豆狭り翌童■ユ
１βの丸底フラスコにＦｅ （（ｄｏ４）３・８Ｈ２０
を７４．９ｇ （０，１５ｍｏｌ）採り、脱塩水６０
０ｍＮを加えて窒素雰囲気下で攪拌しながら溶解させる
。この水溶液に、室温（２５℃）、窒素気流下でピロー
ル１０．１ｇを滴下した。滴下とともに反応液は黒色に
変化し、２時間攪拌を継続した後、室温で一夜放置した
ところ、黒色の粉末状沈澱が反応液の下部に認められた
。濾過後、枦残をメタノール２００ｍＮで３回洗浄を繰
返した後、更に水２００ｍρで２回、トルエン２（）Ｏ
ｍ［で２回、メタノール２００ｍ１ｌで２回ずつ洗浄を
繰返した。洗浄後６０’Ｃ減圧下で乾燥すると、６．０
（ｌの黒色粉末状物質が得られた。得られた黒色物の元
素分析は Ｃ５０，６５％、）（２，８３％、Ｎ １
４．４５％、（，２９，２９％であり、炭素を４．０と
仮定すると、Ｃ４，０、Ｈ２，７、Ｎ１．Ｏ１Ｃλ。、
２５に相当するものを得た。また別途、鉄の含有量を分
析した結果、炭素４．０に対して鉄０．００１であった
。これはピロールに対してＦｅ （Ｃ，１２０４）３が
反応したものであり、殊にそのアニオン部分が付加した
ものであることを示している。Fe in the round bottom flask of Gomachi Tozu Narrow Dou ■ Yu 1β ((do4) 3・8H20
Take 74.9g (0.15mol) of
Add 0 mN and dissolve while stirring under nitrogen atmosphere. To this aqueous solution, 10.1 g of pyrrole was added dropwise at room temperature (25° C.) under a nitrogen stream. The reaction solution turned black as it was added dropwise, and after continued stirring for 2 hours, it was left to stand overnight at room temperature, and a black powdery precipitate was observed at the bottom of the reaction solution. After filtration, the residue was washed three times with 200 mN of methanol, and then washed twice with 200 mN of water and washed with toluene 2()O.
Washing was repeated twice with 200 ml of methanol and twice with 200 ml of methanol. After washing and drying at 60'C under reduced pressure, the result is 6.0
(l of black powdery substance was obtained. The elemental analysis of the black material obtained was C50,65%,) (2,83%, N1
4.45%, (,29,29%, assuming carbon is 4.0, C4,0, H2,7, N1.O1Cλ.,
The equivalent of 25 was obtained. Separately, the iron content was analyzed and found to be 4.0 carbon and 0.001 iron. This shows that Fe (C, 1204) 3 reacts with pyrrole, and in particular, the anion portion thereof is added.
この反応生成物について２端子法による電気伝導度の測
定を行なった結果、７．６ｘ １Ｑ−２３ｃｍ−１を得
、半導体領域の伝導度をもつ有機半導体であることがわ
かった。As a result of measuring the electrical conductivity of this reaction product by a two-probe method, it was found to be 7.6x 1Q-23cm-1, indicating that it is an organic semiconductor with conductivity in the semiconductor region.
有機半導体の製造例２
ピロールの代りにＮ−メチルピロール１２．２（Ｊを使
用したほかは実施例１と同様にして実験を行なった結果
、７．３ｇの黒色粉末状物質を得た。Production Example 2 of Organic Semiconductor An experiment was conducted in the same manner as in Example 1 except that N-methylpyrrole 12.2 (J) was used instead of pyrrole, and as a result, 7.3 g of a black powdery substance was obtained.
得られた黒色物の元素分析はＣ５９，５８％、Ｈ４，７
７％、Ｎ １３．９０％、Ｃ，ｆｆｉ ７．７５％で
あり、炭素を５．０と仮定すると、Ｃ５，Ｏ、Ｈ４，８
、Ｎ１．ｏ、Ｃλｏ、２２に相当するものを得た。Elemental analysis of the black substance obtained was C59.58%, H4.7
7%, N 13.90%, C,ffi 7.75%, and assuming carbon is 5.0, C5, O, H4,8
, N1. o, Cλo, equivalent to 22 was obtained.
これはＮ−メチルピロールに対して
Ｆｅ （Ｃ２Ｏ４）３が反応したものでめり、殊にその
アニオン部分が付加したものであることを示している。This indicates that Fe (C2O4)3 reacts with N-methylpyrrole, and in particular, the anion portion thereof is added.
この黒色物の電気伝導度は３．５×１０−１０−３８Ｃ
であった。The electrical conductivity of this black object is 3.5×10-10-38C
Met.
有機半導体の製造例３〜１４
各種のピロール系化合物を使用し、これらと各種第二鉄
化合物との反応を実施例１と同様に行なった。１ｑられ
た暗褐色〜黒色粉末の検討結果を第１表に示した。Production Examples 3 to 14 of Organic Semiconductors Various pyrrole compounds were used, and reactions between these and various ferric compounds were performed in the same manner as in Example 1. Table 1 shows the results of the investigation of the dark brown to black powder obtained by 1q.
電池の実施例
上記製造例１て１ｄだ有機半導体を正極材料として用い
、・これとアセチレンブラック（導電剤）、並びにポリ
テトラフルオロエチレン（結着剤）とを重量比８５：１
０：５の割合で混合した後、ディスク状に加圧成形した
ものを正極とした。Example of a battery The above production example 1 1d organic semiconductor was used as a positive electrode material, and acetylene black (conducting agent) and polytetrafluoroethylene (binder) were mixed in a weight ratio of 85:1.
After mixing at a ratio of 0:5, the mixture was press-molded into a disk shape and used as a positive electrode.
また、リチウムを所定寸法に打ち後いたものを負極とし
た。In addition, a negative electrode was prepared by punching lithium into a predetermined size.
次いで、第１図に示すように、上記の負極２を負極集電
体８を介して負極化７の底面に圧着させてなる負極部分
と、上記の正極１を正極集電体６を介して正極缶５の底
面に密着させてなる正極部分とを、ポリプロピレン不織
布からできたセパレータ３を介して組合せ、また、過塩
素酸リチウム（電解質）をプロピレンカーボネー１〜（
溶媒）に溶解してなる電解液を用いて、本発明に係る電
池（本発明品△）を作製した。Next, as shown in FIG. 1, a negative electrode part formed by pressing the negative electrode 2 onto the bottom surface of the negative electrode 7 via a negative electrode current collector 8, and a negative electrode part formed by pressing the above negative electrode 2 onto the bottom surface of the negative electrode 7 through a negative electrode current collector 6, and a negative electrode part formed by pressing the above negative electrode 2 onto the bottom surface of the negative electrode 7 through a negative electrode current collector 6, The positive electrode part that is in close contact with the bottom surface of the positive electrode can 5 is combined with the separator 3 made of polypropylene nonwoven fabric, and lithium perchlorate (electrolyte) is mixed with propylene carbonate 1 to (
A battery according to the present invention (product of the present invention △) was produced using an electrolytic solution dissolved in a solvent).
尚、第１図において４は絶縁ガスケットでおる。In addition, in FIG. 1, 4 is an insulating gasket.
また、上記製造例２で得た有機半導体を正極材料として
用い、これとアセチレンブラック、並びにポリテトラフ
ルオロエチレンとを重量比８５：１０：５の割合で混合
しディスク状に加圧成形したものを正極とした他は本発
明品△と同様にして、本発明に係る電池（本発明品Ｂ）
を作製した。In addition, the organic semiconductor obtained in Production Example 2 above was used as a positive electrode material, and this was mixed with acetylene black and polytetrafluoroethylene at a weight ratio of 85:10:5, and the mixture was pressure-molded into a disk shape. A battery according to the present invention (present invention product B) was prepared in the same manner as the present invention product △ except that the positive electrode was used.
was created.
一方、正極材料としてポリアセチレン粉末を用い、これ
とアセチレンブラック、並びにポリテトラフルオロエチ
レンとを重量比８５：１０：５の割合で混合しディスク
状に加圧成形したものを正極とし、他は本発明品Ａと同
様にして比較用の電池（比較量Ｃ）を作製した。On the other hand, polyacetylene powder was used as the positive electrode material, and the positive electrode was prepared by mixing this with acetylene black and polytetrafluoroethylene at a weight ratio of 85:10:5 and press-molding it into a disk shape. A comparative battery (comparative quantity C) was produced in the same manner as Product A.
更に以下の手順で比較用の電池（比較量Ｄ）を作製した
。Furthermore, a comparative battery (comparative quantity D) was produced according to the following procedure.
５００ｍＪ２の丸底フラスコにＦｅＣｌ３−６１−（２
０を４０．６（１（０，１５ｍｏｌ）採り、脱塩水３０
０ｍＩ！を加えて窒素雰囲気下で滑拌しながら溶解させ
る。この水溶液に室温（２５°Ｃ）窒素気流下でピロー
ルｉｏ、ｉｇを滴下した。次いで、６時間攪拌を継続し
た後、室温で一日放置したところ、黒色の粉末状沈澱が
反応液の下部に認められた。濾過後、枦残をメタノール
２００ｍｆ！で３回洗浄を繰返した後、更に水２００１
で２回、トルエン２００ｍ１ｌで２回、メタノール２０
０ｍＮで２回洗浄を繰返した。洗浄後６０℃減圧下で乾
燥すると黒色粉末状物質が得られた。FeCl3-61-(2
Take 40.6 (1 (0.15 mol)) of 0 and add 30 mol of demineralized water.
0mI! Add and dissolve while stirring under a nitrogen atmosphere. Pyrrole io and ig were added dropwise to this aqueous solution at room temperature (25°C) under a nitrogen stream. Next, after stirring was continued for 6 hours, a black powdery precipitate was observed at the bottom of the reaction solution when it was left to stand at room temperature for one day. After filtration, methanol 200mf to remove the residue! After washing 3 times with water, add water 2001
2 times with 200ml of toluene, 200ml of methanol
Washing was repeated twice at 0 mN. After washing, a black powdery substance was obtained by drying at 60° C. under reduced pressure.
このようにして、上記塩化鉄を酸化剤としてピロールを
化学的に重合させて作製した有機半導体（ポリピロール
）を正極材料として用い、これとアセチレンブラック、
並びにポリテトラフルオロエチレンとを重量比８５：１
０：５の割合で混合し、ディスク状に加圧成形したもの
を正極とした他は本発明品Ａと同様にして、比較用の電
池（比較量Ｄ）を作製した。In this way, an organic semiconductor (polypyrrole) prepared by chemically polymerizing pyrrole using iron chloride as an oxidizing agent was used as a positive electrode material, and this and acetylene black,
and polytetrafluoroethylene in a weight ratio of 85:1.
A comparative battery (comparative quantity D) was prepared in the same manner as inventive product A, except that the positive electrode was prepared by mixing the components at a ratio of 0:5 and press-molding them into a disk shape.
以上の４つの電池について、１ ｍＡの電流で５時間
充電した後、１ ｍＡの電流で電池電圧が２．５ｖに
なるまで放電するという一連の充放電サイクルを繰り返
し行なった時の充放電効率（％）のサイクル変化を調べ
た。結果は第２図に示す通りである。The charge/discharge efficiency of the above four batteries was determined by repeating a series of charge/discharge cycles in which the batteries were charged with a current of 1 mA for 5 hours and then discharged with a current of 1 mA until the battery voltage reached 2.5 V. %) was investigated. The results are shown in FIG.
同図より、比較量Ｃは２０サイクル当たりまでは充放電
効率が低いが、本発明品Ａ、Ｂではサイクル初期から高
い充放電効率を維持している。このように本発明品Ａ、
Ｂがサイクル初期から高い充放電効率を示すのは、上記
製造例１及び２で得られた有機半導体が予め過塩素酸イ
オンがドープされたものであるためと考えられる。また
比較量りもサイクル初期から高い充放電効率を維持する
ものの、本発明品Ａ、Ｂに較べて劣っているのは、ドー
プされているイオンが過塩素酸イオンでなく塩素イオン
であるためである。From the figure, comparative amount C has a low charging and discharging efficiency until about the 20th cycle, but products A and B of the present invention maintain a high charging and discharging efficiency from the beginning of the cycle. In this way, the invention product A,
The reason why B shows high charge/discharge efficiency from the early stage of the cycle is considered to be because the organic semiconductors obtained in Production Examples 1 and 2 were doped with perchlorate ions in advance. In addition, although the comparative weigher maintains high charge/discharge efficiency from the beginning of the cycle, it is inferior to the products A and B of the present invention because the doped ions are chlorine ions rather than perchlorate ions. .
また、比較量Ｃは５０サイクルをすぎるあたりから充放
電効率の急激な低下がみられるのに対し、本発明品Ａ、
Ｂでは、全サイクルを通じて比較量Ｃより高い充放電効
率を示すのみならず８０サイクルをすぎても９０％以上
の高い充放電効率を維持し続けることがわかる。尚、第
８０サイクル目における本発明品Ａ、Ｂの充放電効率は
夫々９９％、９５％でおるのに対し、比較量Ｃ及び比較
量りの場合は夫々２５％及び５５％と僅かでめった。比
較量Ｃのサイクル特性がこのように劣悪であるのは、ポ
リアセチレン粉末に完全に除去されずに吸着おるいは付
着していた水や酸素、並びに電解液中の溶存酸素や微量
水分によって、正極材料であるポリアセチレン粉末が材
質劣化したことに依るものと思われる。本発明品Ａ、Ｂ
の場合は、正極材料である有機半導体が優れた耐酸化性
をもつことから電解液中の溶存酸素や微量水分による材
質劣化がなく、良好なサイクル特性が得られる訳である
。また、比較量りのサイクル特性が悪いのは、その正極
材料として用いた従来の化学的に酸化重合して得たポリ
ピロールの電気伝導度が小さい他、正極材料中にドーパ
ントとして塩素イオンが存在し、このためにサイクル中
に塩素ガスが発生し、この塩素ガスと負極との反応等が
起こるためと考えられる。本発明品Ａ、Ｂの場合は、正
極材料として用いたポリピロールの電気伝導性が優秀で
あり、またサイクル中に塩素イオンが存在する可能性は
殆んどないので上記負極における副反応が生じることは
なく、良好なサイクル特性が得られる。In addition, with comparison amount C, a rapid decrease in charging and discharging efficiency was observed after 50 cycles, whereas inventive product A,
It can be seen that B not only shows a higher charge/discharge efficiency than Comparative Amount C throughout all cycles, but also continues to maintain a high charge/discharge efficiency of 90% or more even after 80 cycles. Incidentally, at the 80th cycle, the charging and discharging efficiencies of the products A and B of the present invention were 99% and 95%, respectively, whereas in the case of the comparative amount C and the comparative weight, the efficiency was only 25% and 55%, respectively. The reason why the cycle characteristics of Comparative Amount C are so poor is that the positive electrode This seems to be due to the material deterioration of the polyacetylene powder. Invention products A and B
In this case, since the organic semiconductor that is the positive electrode material has excellent oxidation resistance, there is no material deterioration due to dissolved oxygen or trace moisture in the electrolyte, and good cycle characteristics can be obtained. In addition, the reason for the poor cycle characteristics of the comparative example is that the electrical conductivity of polypyrrole obtained by conventional chemical oxidative polymerization used as the positive electrode material is low, and chlorine ions are present as a dopant in the positive electrode material. This is thought to be because chlorine gas is generated during the cycle, and a reaction between this chlorine gas and the negative electrode occurs. In the case of products A and B of the present invention, the electrical conductivity of the polypyrrole used as the positive electrode material is excellent, and there is almost no possibility that chlorine ions will be present during the cycle, so there is no possibility that side reactions will occur at the negative electrode. Good cycle characteristics can be obtained.
また、第８０ザイクル目における充電及び放電時の夫々
の電池電圧の経時変化を第３図に示す。尚、同図におい
て実線は充電時の、点線は放電時の電圧変化である。第
３図より、本発明品Ａ、Ｂは充電時における電圧の急激
な立ち上がりもなく、また比較量Ｃ，Ｄに較べて放電電
圧の平坦性が非常に良いことがわかる。Further, FIG. 3 shows the temporal changes in the battery voltage during charging and discharging in the 80th cycle. In the figure, the solid line represents the voltage change during charging, and the dotted line represents the voltage change during discharging. From FIG. 3, it can be seen that the products A and B of the present invention do not have a sudden rise in voltage during charging, and the flatness of the discharge voltage is very good compared to the comparative products C and D.
更に、第４図に保存中における電池の自己放電特性を示
す。同図より、本発明品Ａ、Ｂは比較量Ｃ，Ｄに較べて
自己放電が小さく、保存性が良好であることがわかる。Furthermore, FIG. 4 shows the self-discharge characteristics of the battery during storage. From the figure, it can be seen that the products A and B of the present invention have smaller self-discharge and better storage stability than the comparative products C and D.
比較量Ｃに較べて本発明品Ａ、Ｂの保存性がよいのは、
本発明品Ａ、Ｂで正極材料として用いた有機半導体が優
れた耐酸化性をもつために、電解液中の溶存酸素や微量
水分による材質劣化がないことによると考えられる。ま
た、比較量りの場合、予め塩素がドープされた正極材料
を用いており、このドーパントと電池反応によってドー
プされるドーパント（過塩素酸イオン）とが異なってい
るため、電池系内に塩素イオンなる不純物が存在するこ
ととなり、このためその自己放電が大きいものと考えら
れる。本発明品Ａ、Ｂの場合は、電池系内に塩素イオン
のような不純物が存在する可能性は少ないためにこのよ
うなことはなく、比較量Ｃより保存性がよいのである。The reason why the products A and B of the present invention have a better shelf life than the comparative amount C is that
This is thought to be due to the fact that the organic semiconductor used as the positive electrode material in products A and B of the present invention has excellent oxidation resistance, so that there is no material deterioration due to dissolved oxygen or trace moisture in the electrolytic solution. In addition, in the case of comparative weighing, a positive electrode material that has been doped with chlorine in advance is used, and since this dopant and the dopant (perchlorate ion) doped by the battery reaction are different, chlorine ions may be present in the battery system. It is thought that impurities are present, which is why the self-discharge is large. In the case of products A and B of the present invention, this problem does not occur because there is little possibility that impurities such as chlorine ions exist in the battery system, and the storage stability is better than that of comparative product C.
尚、以上は正極材′ｌＩにのみ有機半導体を用いたもの
について説明したが、負極材料、あるいは正負極材料に
本発明に係る有機半導体を用いた場合も同様の効果が得
られることは明らかである。Although the above description has been made regarding the use of an organic semiconductor only in the positive electrode material, it is clear that similar effects can be obtained when the organic semiconductor according to the present invention is used in the negative electrode material or the positive and negative electrode materials. be.
〈発明の効果〉
以上のように構成されるこの発明の二次電池によれば、
電極作！！！環境の管理が非常に容易化しまた電極自身
の保存性が向上することは勿論、電極並びに電池の充放
電容量が制限をうけることもなく、また電池内における
電極各部の充放電反応の不均一などに起因する電池の特
性劣化も僅かで充放電効率並びにザイクル寿命などの特
性向上が図れるといった効果を奏する。<Effects of the Invention> According to the secondary battery of the present invention configured as described above,
Electrode creation! ! ! Not only does environmental management become much easier and the storage life of the electrode itself improves, but the charging and discharging capacity of the electrode and battery is not limited, and the charging and discharging reactions of each part of the electrode within the battery are not uniform. The deterioration of battery characteristics caused by this is also slight, and it is possible to improve characteristics such as charging and discharging efficiency and cycle life.
第１図は本発明の実施例等の電池構造を示した断面図、
第２図は本発明品及び比較量のサイクル特性を示したグ
ラフ、第３図は同じく充放電における電池電圧の経時変
化を示したグラフ、第４図は本発明品及び比較量の自己
放電特性を示したグラフである。
１・・・正極、２・・・負極、３・・・セパレータ、５
・・・正極缶、７・・・負極缶。FIG. 1 is a sectional view showing a battery structure according to an embodiment of the present invention,
Figure 2 is a graph showing the cycle characteristics of the inventive product and comparative amount, Figure 3 is a graph showing the change in battery voltage over time during charging and discharging, and Figure 4 is the self-discharge characteristics of the inventive product and comparative amount. This is a graph showing 1...Positive electrode, 2...Negative electrode, 3...Separator, 5
...Positive electrode can, 7...Negative electrode can.
Claims (1)
有機半導体を正極または負極の少なくとも一方の電極と
して用いてなる二次電池であって、該酸化剤が、一般式 Ｆｅ＿ｍＸ＿ｎ……（１） （式中、ＸはＣｌＯ＿４＾−、ＢＦ＿４＾−、ＡＳＦ＿
６＾−、ＰＦ＿６＾−、ＳｂＦ＿６＾−、ＣＨ＿３Ｃ＿
６Ｈ＿４ＳＯ＿３＾−、 ＣＦ＿３ＳＯ＿３＾−、ＺｒＦ＿６＾−＾−、ＴｉＦ＿
６＾−＾−またはＳｉＦ＿６＾−＾−を表わし、ｍ及び
ｎは１〜３の整数を表わす。） で示される第二鉄化合物であることを特徴とする二次電
池。 ２、ピロール系化合物が、一般式 ▲数式、化学式、表等があります▼……（２） （式中、Ｒ＾１及びＲ＾２は水素原子、アルキル基、ア
ルコキシ基、アリール基、アリ ロキシ基、アルキルチオ基、アミノ基、 ハロゲン原子、シアノ基またはニトロ基 を表わし、Ｒ＾３は水素原子、アルキル基 またはアリール基を表わす。） で示される化合物であることを特徴とする特許請求の範
囲第１項記載の二次電池。 ３、ピロール系化合物と酸化剤との反応を水溶液中で行
なうことを特徴とする特許請求の範囲第１項または第２
項記載の二次電池。[Claims] 1. A secondary battery using an organic semiconductor obtained by reacting a pyrrole compound and an oxidizing agent as at least one of a positive electrode and a negative electrode, wherein the oxidizing agent has the general formula Fe_mX_n...(1) (In the formula, X is ClO_4^-, BF_4^-, ASF_
6^-, PF_6^-, SbF_6^-, CH_3C_
6H_4SO_3^-, CF_3SO_3^-, ZrF_6^-^-, TiF_
6^-^- or SiF_6^-^-, m and n represent integers from 1 to 3. ) A secondary battery characterized by being a ferric compound represented by: 2. Pyrrole compounds have the general formula▲mathematical formula, chemical formula, table, etc.▼...(2) (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, and allyloxy groups. , an alkylthio group, an amino group, a halogen atom, a cyano group, or a nitro group, and R^3 represents a hydrogen atom, an alkyl group, or an aryl group. The secondary battery according to item 1. 3. Claim 1 or 2, characterized in that the reaction between the pyrrole compound and the oxidizing agent is carried out in an aqueous solution.
Secondary batteries listed in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069880A JPH0722025B2 (en) | 1986-03-28 | 1986-03-28 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069880A JPH0722025B2 (en) | 1986-03-28 | 1986-03-28 | Secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62226568A true JPS62226568A (en) | 1987-10-05 |
| JPH0722025B2 JPH0722025B2 (en) | 1995-03-08 |
Family
ID=13415524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61069880A Expired - Lifetime JPH0722025B2 (en) | 1986-03-28 | 1986-03-28 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722025B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6319763A (en) * | 1986-07-09 | 1988-01-27 | Mitsubishi Chem Ind Ltd | Battery |
| FR2685122A1 (en) * | 1991-12-13 | 1993-06-18 | Alsthom Cge Alcatel | SUPERCONDENSOR BASED ON CONDUCTIVE POLYMER. |
| JP2008135371A (en) * | 2006-10-27 | 2008-06-12 | Denso Corp | Secondary battery active substance and secondary battery |
| CN111235595A (en) * | 2020-01-20 | 2020-06-05 | 常州大学 | TEMPO-based polypyrrole for mixed liquid flow battery cathode and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62119860A (en) * | 1985-11-20 | 1987-06-01 | Mitsubishi Chem Ind Ltd | Secondary cell |
-
1986
- 1986-03-28 JP JP61069880A patent/JPH0722025B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62119860A (en) * | 1985-11-20 | 1987-06-01 | Mitsubishi Chem Ind Ltd | Secondary cell |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6319763A (en) * | 1986-07-09 | 1988-01-27 | Mitsubishi Chem Ind Ltd | Battery |
| FR2685122A1 (en) * | 1991-12-13 | 1993-06-18 | Alsthom Cge Alcatel | SUPERCONDENSOR BASED ON CONDUCTIVE POLYMER. |
| US5442197A (en) * | 1991-12-13 | 1995-08-15 | Alcatel Alsthom Compagnie Generale D'electricite | Super-capacitor comprising positive and negative electrodes made of a p-doped electron conductive polymer and an electrolyte containing an organic redox compound |
| JP2008135371A (en) * | 2006-10-27 | 2008-06-12 | Denso Corp | Secondary battery active substance and secondary battery |
| CN111235595A (en) * | 2020-01-20 | 2020-06-05 | 常州大学 | TEMPO-based polypyrrole for mixed liquid flow battery cathode and preparation method |
| CN111235595B (en) * | 2020-01-20 | 2021-05-25 | 常州大学 | TEMPO-based polypyrrole for mixed liquid flow battery cathode and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0722025B2 (en) | 1995-03-08 |
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