JPH0527232B2 - - Google Patents
Info
- Publication number
- JPH0527232B2 JPH0527232B2 JP59034175A JP3417584A JPH0527232B2 JP H0527232 B2 JPH0527232 B2 JP H0527232B2 JP 59034175 A JP59034175 A JP 59034175A JP 3417584 A JP3417584 A JP 3417584A JP H0527232 B2 JPH0527232 B2 JP H0527232B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- battery
- acetylene
- polymer compound
- doping
- 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.)
- Expired - Lifetime
Links
- 239000003792 electrolyte Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 37
- -1 aromatic nitrile compound Chemical class 0.000 claims description 33
- 239000002019 doping agent Substances 0.000 claims description 19
- 150000003863 ammonium salts Chemical class 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 38
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 37
- 229920000547 conjugated polymer Polymers 0.000 description 20
- 238000007599 discharging Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- 229910020366 ClO 4 Inorganic materials 0.000 description 5
- 229920000265 Polyparaphenylene Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910021115 PF 6 Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- COOSQAXLLKTSQO-UHFFFAOYSA-N trimethyl(2-methylpropyl)azanium Chemical compound CC(C)C[N+](C)(C)C COOSQAXLLKTSQO-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DNXUGBMARDFRGG-UHFFFAOYSA-N 3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound O=C1C=CC(=O)C(C#N)=C1C#N DNXUGBMARDFRGG-UHFFFAOYSA-N 0.000 description 1
- HDEXQZFQDZGFLQ-UHFFFAOYSA-N 4,5-dibromo-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound BrC1=C(Br)C(=O)C(C#N)=C(C#N)C1=O HDEXQZFQDZGFLQ-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- MPDDDPYHTMZBMG-UHFFFAOYSA-N butyl(triethyl)azanium Chemical compound CCCC[N+](CC)(CC)CC MPDDDPYHTMZBMG-UHFFFAOYSA-N 0.000 description 1
- GXHODIIDLMSKDU-UHFFFAOYSA-M butyl(triethyl)azanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CC)(CC)CC GXHODIIDLMSKDU-UHFFFAOYSA-M 0.000 description 1
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 1
- HNXHGBVDHPZIRM-UHFFFAOYSA-M butyl(trimethyl)azanium;trifluoromethanesulfonate Chemical compound CCCC[N+](C)(C)C.[O-]S(=O)(=O)C(F)(F)F HNXHGBVDHPZIRM-UHFFFAOYSA-M 0.000 description 1
- CIFCGXKXFRLSAF-UHFFFAOYSA-N butyl(tripropyl)azanium Chemical compound CCCC[N+](CCC)(CCC)CCC CIFCGXKXFRLSAF-UHFFFAOYSA-N 0.000 description 1
- OZHYULYUYJVOPW-UHFFFAOYSA-N butyl-ethyl-methyl-propylazanium Chemical compound CCCC[N+](C)(CC)CCC OZHYULYUYJVOPW-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 229940100060 combination of electrolytes Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- OATRZMUGANSNMU-UHFFFAOYSA-N diethyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](CC)(CC)C1=CC=CC=C1 OATRZMUGANSNMU-UHFFFAOYSA-N 0.000 description 1
- PJABQHODPAEOFU-UHFFFAOYSA-N diethyl(dipropyl)azanium Chemical compound CCC[N+](CC)(CC)CCC PJABQHODPAEOFU-UHFFFAOYSA-N 0.000 description 1
- MXTMXRYBYWOAGX-UHFFFAOYSA-N dimethyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C)(C)C1=CC=CC=C1 MXTMXRYBYWOAGX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- YZCTWRWJKAZUIJ-UHFFFAOYSA-N ethyl-methyl-dipropylazanium Chemical compound CCC[N+](C)(CC)CCC YZCTWRWJKAZUIJ-UHFFFAOYSA-N 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- ZRZKFGDGIPLXIB-UHFFFAOYSA-N fluoroform;sulfuric acid Chemical compound FC(F)F.OS(O)(=O)=O ZRZKFGDGIPLXIB-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XTPRURKTXNFVQT-UHFFFAOYSA-N hexyl(trimethyl)azanium Chemical compound CCCCCC[N+](C)(C)C XTPRURKTXNFVQT-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- SPJZSTLXABSXII-UHFFFAOYSA-N tert-butyl(trimethyl)azanium Chemical compound CC(C)(C)[N+](C)(C)C SPJZSTLXABSXII-UHFFFAOYSA-N 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- GCRCSLNXFKCFHB-UHFFFAOYSA-N triethyl(hexyl)azanium Chemical compound CCCCCC[N+](CC)(CC)CC GCRCSLNXFKCFHB-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- JJPVWQWOOQYHCB-UHFFFAOYSA-N triethyl(phenyl)azanium Chemical compound CC[N+](CC)(CC)C1=CC=CC=C1 JJPVWQWOOQYHCB-UHFFFAOYSA-N 0.000 description 1
- WGYXSYLSCVXFDU-UHFFFAOYSA-N triethyl(propyl)azanium Chemical compound CCC[N+](CC)(CC)CC WGYXSYLSCVXFDU-UHFFFAOYSA-N 0.000 description 1
- ACZOGADOAZWANS-UHFFFAOYSA-N trimethyl(pentyl)azanium Chemical compound CCCCC[N+](C)(C)C ACZOGADOAZWANS-UHFFFAOYSA-N 0.000 description 1
- BMTHNVMASXVELE-UHFFFAOYSA-N trimethyl(propan-2-yl)azanium Chemical compound CC(C)[N+](C)(C)C BMTHNVMASXVELE-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
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Description
【発明の詳細な説明】
本発明は、高エネルギー密度を有し、充・放電
効率が高く、サイクル寿命が長く、自己放電が小
さく、放電時の電圧の平坦性が良好な非水二次電
池に関する。
遷移金属化合物と有機金属化合物とからなる、
いわゆるチーグラー・ナツタ触媒を用いてアセチ
レンを重合して得られるアセチレン高重合体は、
その電気伝導度が半導体領域にあることにより、
電気・電子素子として有用な有機半導体材料であ
ることはすでに知られている。
アセチレン高重合体の実用的成形品を製造する
方法としては、
(イ) 粉末状アセチレン高重合体を加圧成形する方
法、および
(ロ) 特殊な重合条件下で重合と同時に膜状に成形
して、繊維状微結晶（フイブリル）構造を有
し、かつ機械的強度の大きい膜状アセチレン公
重合体を得る方法（特公昭48−32581号）が知
られている。
上記(イ)の方法で得られる粉末状アセチレン高重
合体成形品をBF3，BCl3，HCl，Cl2，SO2，
NO2，HCN，O2，NO等の電子受容性化合物
（アクセプター）で化学的に処理すると電気伝導
度が最高３桁上昇し、逆にアンモニアやメチルア
ミンのような電子供与性化合物（ドナー）で処理
すると電気伝導度が最高４桁低下することもすで
に知られている。
また、(ロ)の方法で得られる膜状アセチレン高重
合体にI2，Cl2，Br2，ICl，IBr，AsF5，SbF5，
PF6等の如き電子受容性化合物またはNa，Ｋ，
Liの如き電子供与性化合物を化学的にドープする
ことによつてアセチレン高重合体の電気伝導度を
10-8〜103Ω-1・cm-1の広い範囲にわたつて自由に
コントロールできることもすでに知られている。
このドープされた膜状アセチレン高重合体を一次
電池の正極の材料として使用するという考えもす
でに提案されている。
一方、前記の化学的にドーピングする手法以外
に、電気化学的にClO- 4，PF- 6，AsF- 6，AsF- 4，
CF3SO- 3，BF- 4等の如きアニオンおよびR′4N+
（R′はアルキル基で、しかも同時に同一の基であ
る。）の如きカチオンをアセチレン高重合体にド
ープしてｐ型およびｎ型の電導性アセチレン高重
合体を製造する方法もすでに開発されている。そ
して、(ロ)の方法で得られる膜状アセチレン高重合
体を用いて電気化学的ドーピングを利用した再充
電可能な電池が報告されている。この電池(ロ)の方
法で得られる例えば、0.1mmの厚さのアセチレン
高重合体フイルム二枚をそれぞれ正・負の電極と
し、ヨウ化リチウムを含むテトラハイドロフラン
溶液にこれを浸して9Vの直流電源につなぐとヨ
ウ化リチウムが電気分解され、正極のアセチレン
高重合体フイルムはヨウ素でドープされ、負極の
アセチレン高重合体フイルムはリチウムでドープ
される。この電解ドーピングが充電過程に相当す
ることになる。ドープされた二つの電極に負荷を
つなげばリチウムイオンとヨウ素イオンが反応し
て電力が取り出せる。この場合、開放端電圧
（Voc）は2.8V、短絡電流密度は5mA／cm2であ
り、電解液に過塩素酸リチウムのテトラハイドロ
フラン溶液を使用した場合、開放端電圧は2.5V、
短絡電流密度は約3mA／cm2であつた。
また、上記の(ロ)の方法で得られた厚さ0.1mmの
アセチレン高重合体フイルム２枚をそれぞれ別々
にリード線を取り出した白金メツシユに包み、１
モル／相当のテトラブチルアンモニウムパーク
ロレートを含むアセトニトリル溶液に浸漬し、
5mA／cm2の定電流で一定時間充電すると、テト
ラブチルアンモニウムイオンは、負極のアセチレ
ン高重合フイルムにドープされ、パークロレート
イオンは、正極のアセチレン高重合体フイルムに
ドープされる。この場合、電池の開放端電圧
（Voc）は2.5Vであつた。この電池を1mA／cm2で
電池電圧が1.0Vに低下するまで放電させると充
電電気量に対し、81％の効率で放電電気量が取り
出せる。
これらの電池は、電極材料として軽量化および
小型化が容易なアセチレン高重合体を用いている
ので、高エネルギー密度を有する軽量化、小型化
が容易で、かつ安価な電池として注目を集めてい
る。
しかしながら、これら既知の文献で用いられて
いるドーパントとしての電解質のほとんどは、比
較的安定電位範囲の広い溶媒に対して溶解度が低
いか、また、電解液としての電気伝導度が低い
か、または、電解質そのものあるいはその電気分
解物が比較的安定電位範囲の広い溶媒と反応性を
有するため、安定電位範囲の広い溶媒には、使用
できないという難点を有する。
例えば、リチウム金属は、比較的安定電位範囲
の広い溶媒とされているニトリル系溶媒とは反応
性を有し、リチウム金属をカチオン成分とするリ
チウム塩を電解質と使用するには難点を有する。
また、前記のようなテトラブチルアンモニウム塩
は、ニトリル系溶媒には比較的良く溶解し、電解
質として使用した場合、高い充・放電効率を得る
ことは可能であるが、エネルギー密度が充分満足
すべきものではない。
さらに、同じアルキルアンモニウム塩の一つで
あるテトラエチルアンモニウム塩を電解質として
使用する場合は、安定電位範囲の広いベンゾニト
リルに対してテトラエチルアンモニウム塩の溶解
度が低く、室温での飽和溶解度は１モル／に達
せず、従つてテトラエチルアンモニウム塩をベン
ゾニトリルに溶解した電解液はエネルギー密度の
点から考えると非常に不利であり、高エネルギー
密度を有する電池用電解液として適用しにくい。
従つて、比較的安定電位範囲の広い有機溶媒を
用いた場合、有機溶媒への溶解度が高く、モル分
子量が可能な限り小さく、かつ高電気伝導度を与
え、それ自身の電気化学的安定性がよく、電極と
して使用する主鎖に共役二重結合を有する高分子
化合物との反応性が小さい電解質、即ちドーパン
トを得ることは当該業者間で強く要求されてい
た。
本発明者らは、上記の点に鑑みて、高エネルギ
ー密度を有し、充・放電効率が高く、サイクル寿
命が長く、電圧の平坦性が良好で、自己放電率が
小さく、軽量化、小型化が容易で、かつ安価な非
水二次電池を得るべく種々検討した結果、電解質
としてカチオン成分が非対称第４級アンモニウム
イオンからなるアンモニウム塩を使用し、かつ電
解質の濃度が少なくとも２モル／の電解液を用
いることにより、良好な性能を有する非水二次電
池が得られることを見い出し、本発明を完成した
ものである。
即ち、本発明は、主鎖に共役二重結合を有する
高分子化合物、または該高分子化合物にドーパン
トをドープして得られる電導性高分子化合物を負
極、または正極と負極の両極に用いた非水二次電
池において、電解質としてカチオン成分が下記の
一般式で表わされる非対称第４級アンモニウムイ
オンからなるアンモニウム塩を使用し、かつ電解
質の濃度が少なくとも２モル／の電解液を用い
たことを特徴とする非水二次電池に関するもので
ある。
〔式中、R1，R2，R3およびR4は炭素数が１〜
16のアルキル基、またはアリール（aryl）基であ
る。但し、すべてのR1，R2，R3およびR4は同時
に同一の基であることはない。〕
本発明の非水二次電池は、従来公知のR′4N+
（R′はアルキル基で、しかも同時に同一の基であ
る）で表わされる対称第４級アンモニウムイオン
をカチオン成分とするアンモニウム塩やリチウム
塩を電解質として用いた二次電池に比較して
（）エネルギー密度が大きい、（）電圧の平坦
性が良好である、（）自己放電が少ない、（）
繰り返しの寿命が長い、という利点を有する。
本発明で用いられる主鎖に共役二重結合を有す
る高分子化合物（以下、共役高分子化合物と略称
する）の具体例としては、アセチレン高重合体
（ポリアセチレン）、ポリパラフエニレン、ポリメ
タフエニレン、ポリ（２，５−チエニレン）、ポ
リピロール、ポリキノリン、ポリフエニルアセチ
レン、ポリアセン、ポリアセンキノンラジカル重
合体、シツフ塩基構造を有するキナゾリンポリマ
ー、ポリアリーレンキノン類、ポリアクリルニト
リルやポリイミドの熱分解物等をあげることがで
きるが必ずしもこれ等に限定されるものではな
く、主鎖に共役二重結合を有する高分子化合物で
あればよい。またホモポリマーでも共重合体でも
一向に差し支えない。上記の共役高分子化合物の
うちでも好ましいものとしては、アセチレン高重
合体、ポリパラフエニレン、ポリ（２，５−チエ
ニレン）、ポリピロールをあげることができ、特
に好ましいものとしてはアセチレン高重合体をあ
げることができる。
本発明で好ましく用いられるアセチレン高重合
体の製造方法は特に制限はなく、いずれの方法で
も用いられるが、その具体例としていは特公昭48
−32581号、特公昭56−45365号、特開昭55−
129404号、同55−128419号、同55−142012号、同
56−10428号、同56−133133号、Trans.Farady
Soc.，64，823（1968），J.PolymerSci.，Ａ−１，
７，3419（1969），Makeromol.Chem.，Rapid
Comm.，１，621（1980），J.Chem.Phys.，69
（１），106（1978），Synthetic Metals，４，81
（1981）等の方法をあげることができる。
本発明においては、共役高分子化合物にグラフ
アイト、カーボンブラツク、アセチレンブラツ
ク、金属粉および炭素繊維等のごとき導電材料を
混合してもよく、また集電体として金属網等を入
れることも一向に差し支えない。
本発明では、共役高分子化合物ばかりでなく、
該高分子化合物にドーパントをドープして得られ
る電導性高分子化合物も電極として用いることが
できる。
共役高分子化合物へのドーパントのドーピング
方法は、化学的ドーピングおよび電気化学的ドー
ピングのいずれの方法を採用してもよい。
共役高分子化合物に化学的にドーピングするド
ーパントとしては、従来知られている種々の電子
受容性化合物および電子供与性化合物、即ち、
（）ヨウ素、臭素およびヨウ化臭素の如きハロ
ゲン、（）五フツ化ヒ素、五フツ化アンチモン、
四フツ化ケイ素、五塩化リン、五フツ化リン、塩
化アンモニウム、臭化アルミニウムおよびフツ化
アルミニウムの如き金属ハロゲン化物、（）硫
酸、硝酸、フルオロ硫酸、トリフルオロメタン硫
酸およびクロロ硫酸の如きプロトン酸、（）三
酸化イオウ、二酸化窒素、ジフルオロスルホニル
パーオキシドの如き酸化剤、（）AgClO4、
（）テトラシアノエチレン、テトラシアノキノ
ジメタン、クロラニール、２，３−ジクロル−
５，６−ジシアノパラベンゾキノン、２，３−ジ
ブロム−５，６−ジシアノパラベンゾキノン等を
あげることができる。
一方、共役高分子化合物に電気化学的にドーピ
ングするドーパントとしては、（）PF- 6，
SbF- 6，AsF- 6，SbCl- 6の如きVa族の元素のハロゲ
ン化物アニオン、BF- 4の如きａ族の元素のハロ
ゲン化物アニオン、I-（I- 3），Br-，Cl-の如きハロ
ゲンアニオン、ClO- 4の如き過塩素酸アニオンな
どの陰イオン・ドーパント（いずれもｐ型電導性
共役高分子化合物を与えるドーパントとして有
効）および（）Li+，Na+，K+の如きアルカリ
金属イオン、R4N+（Ｒ：炭素数１〜20の炭化水
素基）の如き４級アンモニウムイオンなどの陽イ
オン・ドーパント（いずれもｎ型電導性共役高分
子化合物を与えるドーパントとして有効）等をあ
げることができるが、必ずしもこれ等に限定され
るものではない。
但し、共役高分子化合物に予めドーパントをド
ープして得られる電導性高分子化合物を電極に用
いる場合は、負極に予備ドープされるドーパント
は、本発明において電池の電解質に用いられる非
対称第４級アンモニウムカチオンと同一のものが
望ましい。
また、本発明における電池のドープ量は電解の
際に流れた電気量を測定することによつて自由に
制御することができる。一定電流下でも一定電圧
下でもまた電流および電圧の変化する条件下のい
ずれの方法でドーピングを行なつてもよい。ドー
ピングの際の電流値、電圧値およびドーピング時
間等は、用いる共役高分子化合物の種類、嵩さ密
度、面積、ドーパントの種類、電解液の種類、要
求される電気伝導度によつて異なるので一概に規
定することはできない。
共役高分子化合物にドープされるドーパイント
の量は、共役高分子化合物の繰り返し単位１モル
に対して２〜40モル％であり、好ましくは４〜30
モル％、特に好ましくは５〜20モル％である。ド
ープしたドーパントの量が２モル％以下でも40モ
ル％以上でも放電容量の充分大きな非水二次電池
を得ることはできない。
共役高分子化合物の電気伝導度はドーピング前
において、10-5Ω-1・cm-1以下であり、ドーパン
トをドープして得られる電導性共役高分子化合物
の電気伝導度は約10-10〜104Ω-1・cm-1の範囲で
ある。
本発明において用いられる電池の電解質は、カ
チオン成分が前記一般式で表わされる非対称第４
級アンモニウムイオンからなるアンモニウム塩で
ある。
アンモニウム塩のカチオン成分の具体例として
は、トリメチルプロピルアンモニウム、トリメチ
ルブチルアンモニウム、トリメチルヘキシルアン
モニウム、トリメチルオキシルアンモニウム、ト
リメチルイソブチルアンモニウム、トリメチルタ
ーシヤリーブチルアンモニウム、トリメチルイソ
プロピルアンモニウム、トリメチルイソブチルア
ンモニウム、トリメチルヘキサデシルアンモニウ
ム、トリメチルペンチルアンモニウム、トリメチ
ルフエニルアンモニウム、トリエチルブチルアン
モニウム、トリエチルプロピルアンモニウム、ト
リエチルメチルアンモニウム、トリエチルヘキシ
ルアンモニウム、トリエチルフエニルアンモニウ
ム、トリプロピルブチルアンモニウム、トリブチ
ルメチルアンモニウム、トリブチルエチルアンモ
ニウム、ジプロピルジエチルアンモニウム、ジブ
チルジエチルアンモニウム、ジブチルジメチルア
モニウム、ジメチルジフエニルアンモニウム、ジ
エチルジフエニルアンモニウム、ジブチルエチル
メチルアンモニウム、ジプロピルエチルメチルア
ンモニウム、ブチルプロピルエチルメチルアンモ
ニウム等があげられる。
これらのカチオン成分とアンモニウム塩を構成
するアニオン成分の具体例としては、HF- 2，
ClO- 4，AlCl- 4，BF- 4，FeCl- 4，SnCl- 5，PF- 6，
PCl- 6，SiF- 4，SbF- 6，AsF- 6，CF3SO- 3等があげら
れる。
アンモニウム塩の具体例としては、トリエチル
ブチルアンモニウムテトラフルオロボレート、ト
リエチルブチルアンモニウムパークロレート、ト
リエチルブチルアンモニウムヘキサフルオロフオ
スフエート、トリメチルブチルアンモニウムトリ
フルオロメタンスルフオネート、トリメチルエチ
ルアンモニウムテトラフルオロボレート、トリメ
チルエチルアンモニウムヘキサルフルオロフオス
エート、ジブチルジエチルアンモニウムパークロ
レート、トリブチルエチルアンモニウムテトラフ
ルオロボレート、ブチルプロピルエチルメチルア
ンモニウムヘキサクロロフオスフエート、トリメ
チルフエニルテトラフルオロボレート、トリエチ
ルフエニルテトラフルオロボレート等をあげるこ
とができるが、これらに限定されるものではな
い。
これらのアンモニウム塩は、１種または２種以
上を混合して使用してもよい。
また、本発明のアンモニウム塩は、他のアルキ
ルアンモニウム塩、例えばテトラブチルアンモニ
ウム塩やテトラエチルアンモニウム塩との混合電
解質として用いても差し支えないし、またはアル
カリ金属塩、例えばリチウム塩、ナトリウム塩お
よびカリウム塩との混合電解質として用いても差
し支えない。
さらに、本発明のアンモニウム塩は、次式
（）で表わされるピリリウムまたはピリジウ
ム・カチオン：
〔式中、Ｘは酸素原子または窒素原子、R′は
水素原子または炭素数が１〜15のアルキル基、炭
素数６〜15のアリール（aryl）基、R″はハロゲ
ン原子または炭素数が１〜10のアルキル基、炭素
数が６〜15のアリール（aryl）基、ｍはＸが酸素
原子のとき０であり、Ｘが窒素原子のとき１であ
る。ｎは０または１〜５である。〕
または次式（）もしくは（）で表わされる
カルボニウム・カチオン：
または
〔式中、R1，R2，R3は水素原子（R1，R2，R3
は同時に水素原子であることはない）、炭素数１
〜15のアルキル基、アリル（allyl）基、炭素数
６〜15のアリール（aryl）基または−OR5基、但
しR5は炭素数が１〜10のアルキル基または炭素
数６〜15のアリール（aryl）基を示し、R4は水
素原子、炭素数が１〜15のアルキル基、炭素数６
〜15のアリール基である。〕
をカチオン成分として有する電解質と混合して使
用してもよい。
但し、本発明のカチオン成分が非対称第４級ア
ンモニウムイオンからなるアンモニウム塩と他の
電解質を混合して用いる場合は、アンモニウム塩
を等モル以上含有した形態で用いることが好まし
い。
本発明において用いられる電解液の有機溶媒は
芳香族ニトリル系化合物である。
この有機溶媒の具体例としては、ベンゾニトリ
ル、ｏ−トルニトリル、ｍ−トルニトリル、ｐ−
トルニトリル、ａ−トルニトリルがあげられる。
これらの溶媒は、混合溶媒として用いても一向に
差し支えない。
本発明の非水二次電池において用いられる電解
質の濃度は、少なくとも２モル／、好ましくは
３〜10モル／である。電解質の濃度が２モル／
未満では、非水二次電池の自己放電が比較的大
きいという欠点を有する。電解液は均一系でも不
均一系でも一向に差し支えないが通常は均一系で
用いられる。
本発明において、共役高分子化合物または該共
高分子化合物にドーパントをドープして得られる
電導性共役高分子化合物は、電池の（）負極ま
たは（）正極と負極の両極の活性物質として用
いることができるが、本発明の効果を最大限に発
揮するには（）のタイプの電池が好ましい。
例えば共役高分子化合物としてアセチレン高重
合体を用いた非水二次電池の場合、（）の例と
して、アセチレン高重合体を（CH）ｘとする
と、グラフアイト（正極）／（Et3BuN）+・
（ClO4）-（電解質）／（CH）x（負極）、（）の
例としては〔（CH）+ 0.024（ClO4）- 0.024〕x（正極）
／
（Me3BuN）+・（ClO4）-（電解質）／〔（Me3
BuN）+ 0.024（CH）- 0.024〕x（負極）、〔（CH）+ 0.06
（PF6）- 0.06〕x（正極）／（Bu3EtN）+・（PF6）-（電
解質）／〔（Bu3EtN）+ 0.06（CH）- 0.06〕x（負極）、
〔Et3BuN）+ 0.02〕x（正極）／（Et3BuN）+・（ClO4）
-（電解質）／〔（Et3BuN）+ 0.07（CH）- 0.07〕x（負
極）等をあげることができる。
ポリパラフエニレンの場合には前記の（CH）x
の代りに（C6H4）x、ポリ（２，６−チエニレン）
の場合には（CH）xの代りに（C4H2Ｓ）xを、ポリ
ピロールの場合には（C4H2Ｎ）xとして前記と同
じ型の非水二次電池として用いられる。
また、本発明では正極、負極にそれぞれ異なつ
た共役高分子化合物を用いることもでき、その具
体例としては（CH）x／Et3BuN・ClO4／（C6
H4）x、（CH）x／Me3BuN・BF4／（C4H2Ｓ）x、
（C6H4）x／Et2Bu2Ｎ・PF6・（C4H2Ｓ）x等をあげ
ることができる。
本発明において必要ならばポリエチレン、ポリ
プロピレンのごとき合成樹脂製の多孔質膜や天然
繊維紙を隔膜として用いても一向に差し支えな
い。
また、本発明において用いられる共役高分子化
合物の一部は、酸素によつて徐々に酸化反応をう
け、電池の性能が低下させる場合もあるので、電
池は密閉式にして実質的に無酸素の状態であるこ
とが必要である。
本発明の非水二次電池は、高エネルギー密度を
有し、充・放電効率が高く、サイクル寿命が長
く、特に自己放電率が小さい。また、本発明の非
水二次電池は、軽量、小型で、かつ高いエネルギ
ー密度を有するからポータブル機器、電気自動
車、ガソリン自動車および電力貯蔵用バツテリー
として最適である。
以下、実施例および比較例をあげて本発明をさ
らに詳細に説明する。
実施例 １
〔膜状アセチレン高重合体の製造〕
窒素雰囲気化で内容積500mlのガラス製反応容
器に1.7mlのチタニウムテトラブトキサイドを加
え、30mlのアニソールに溶かし、次いで2.7mlの
トリエチルアルミニウムを攪拌しながら加えて触
媒溶液を調製した。
この反応容器を液体窒素で冷却して、系中の窒
素ガスを真空ポンプで排気した。次いで、この反
応容器を−78℃に冷却し、触媒溶液を静止したま
まで、１気圧の圧力の精製アセチレンガスを吹き
込んだ。
直ちに、触媒溶液表面で重合が起り、膜状のア
セチレン高重合体が生成した。アセチレン導入
後、30分で反応容器系内のアセチレンガスを排気
して重合を停止した。窒素雰囲気下で触媒溶液を
注射器で除去した後、−78℃に保つたまま精製ト
ルエン100mlで５回繰り返し洗浄した。トルエン
で膨潤した膜状アセチレン高重合体は、フイブリ
ルが密に絡み合つた均一な膜状膨潤物であつた。
次いでこの膨潤物を真空乾燥して金属光沢を有す
る赤紫色の厚さ100μmで、シス含量98％の膜状ア
セチレン高重合体を得た。また、この膜状アセチ
レン高重合体の嵩さ密度は0.30g／c.c.であり、そ
の電気伝導度（直流四端子法）は20℃で3.2×
10-9Ω-1・cm-1であつた。
〔電池実験〕
前記の方法で得られた膜状アセチレン重合体か
ら、直径20mmの円板２枚を切り抜いて、それぞれ
を正極、負極の活物質として、電池を構成した。
図は、本発明の一具体例である非水二次電池の
特性測定用電池セルの断面概略図であり、１は負
極用白金リード線、２は直径20mm、80メツシユの
負極用白金網集電体、３は直径20mmの円板状負
極、４は直径20mmの円形の多孔質ポリプロピレン
製隔膜で、電解液を充分含浸できる厚さにしたも
の、５は直径20mmの円板状正極、６は直径20mm、
80メツシユの正極用白金網集電体、７は正極リー
ド線、８はねじ込み式テフロン製容器を示す。
まず、前記、正極用白金網集電体６をテフロン
製容器８の凹部の下部に入れ、更に正極５を正極
用白金網集電体６の上に重ね、その上に多孔性ポ
リプロピレン製隔膜４を重ね、電解液を充分含浸
させた後、負極３を重ね、更にその上に負極用白
金網集電体２を載置し、テフロン製容器８を締め
つけて電池を作製した。
電解液としては、常法に従つて蒸留脱水ベンゾ
ニトリルに溶解したEt3BuN・BF4の３モル／
溶液を用いた。
このようにして作製した電池を用いて、アルゴ
ン雰囲気中で、一定電流下（4.0mA／cm2）で15分
間充電を行なつた（ドーピング量５モル％に相当
する電気量）。充電終了後、直ちに一定電流下
（4.0mA／cm2）で、放電を行ない電池電圧が1Vに
なつたところで再度前記と同じ条件で充電を行な
う充・放電の繰り返し試験を行なつたところ、
充・放電効率が、50％に低下するまでに充・放電
の繰り返し回数は、893回を記録した。
また繰り返し回数５回目のエネルギー密度は、
140W・hr／Kgで、充・放電効率は99％であつた。
また、充電したままで48時間放置したところ、そ
の自己放電率は1.2％であつた。
比較例 １
実施例１において、電解液の電解質として用い
たEt3BuN・BF4の代りにBu4Ｎ・BF4を用いた以
外は実施例１と全く同様の方法で電池の充・放電
の繰り返し実験を行なつたところ、最高充・放電
効率は、96％であり、繰り返し回数479回目で放
電が不可能となつた。
また繰り返し回数５回目のエネルギー密度は
130W・hr／Kgで、充・放電効率は96％であつた。
また、充電したままで48時間放置したところ、そ
の自己放電率は4.9％であつた。
比較例 ２
実施例１において、電解質の濃度を３モル／
から１モル／に代えた以外は実施例１と全く同
様の方法で電池の充・放電の繰り返し実験を行な
つたところ、充・放電効率が50％に低下するまで
の充・放電の繰り返し回数は700回であつた。ま
た、繰り返し回数５回目のエネルギー密度は
140W・hr／Kgで、充・放電効率は99％であつた。
また、充電したままで48時間放置したところ、そ
の自己放電率は3.0％であつた。
比較例 ３
実施例１において、電解液の電解質として用い
たEt3BuN・BF4の代りにEt4Ｎ・BF4を等モル量
用いて試みたところ、Et4Ｎ・BF4はベンゾニト
リルに殆んど溶解せず、溶解しないEt4Ｎ・BF4
が沈殿したままの状態で実施例１と同様の方法で
電池の充・放電の繰り返し実験を行なつた。その
結果、最高、充・放電効率は72％であり、繰り返
し回数25回目で放電が不可能となつた。
比較例 ４
実施例１において、電解液の電解質として用い
たEt3BuN・BF4の代りにLiBF4を等モル量用い
て試みたところ、LiBF4はベンゾニトリルに完全
には溶解せず、一部、不溶解で沈殿したままの状
態で実施例１と同様の方法で電池の充・放電の繰
り返し実験を行なつた。結果は、最高充・放電効
率は24％であり、繰り返し回数12回目で放電が不
可能となつた。
また繰り返し回数５回目のエネルギー密度は
24W・hr／Kgで充・放電効率は18％であつた。
実施例 ２
窒素ガスで完全に置換した１のガラス製反応
容器に、ステンレス・スチールの100メツシユの
網を入れ、次いで重合溶媒として常法に従つて精
製したトルエン100ml、触媒としてテトラブトキ
シチタニウム4.41ミリモルおよびトリエチルアル
ミニウム11.01ミリモルを順次に室温で仕込んで
触媒溶液を調製した。触媒溶液は均一溶液であつ
た。次いで、反応器を液体窒素で冷却して系中の
窒素ガスを真空ポンプで排気した。−78℃に反応
器を冷却し、触媒溶液を静置した状態で１気圧の
圧力の精製アセチレンガスを吹き込んだ。アセチ
レンガスの圧力を１気圧に保つたままで10時間重
合反応をそのまま継続した。系は赤紫色を呈した
寒天状であつた。重合終了後、未反応のアセチレ
ンガスを除去し、系の温度を−78℃に保つたまま
200mlの精製トルエンで４回繰り返し洗浄し、ト
ルエンで膨潤した膜厚が約0.5cmのステンレス・
スチールの網を含むシート状膨潤アセチレン高重
合体を得た。この膨潤アセチレン高重合体は、
300〜500Åの径の繊維状微結晶（フイブリル）が
規則的に絡み合つた膨潤物であり、粉末状や塊状
のポリマーは生成していなかつた。
このステンレス・スチールの網を含むシート状
膨潤アセチレン高重合体をクロムメツキしたフエ
ロ板にはさみ、室温で100Kg／cm2の圧力で予備プ
レスし、次いで15ton／cm2の圧力でプレスして赤
褐色の金属光沢を持つた均一で可撓性のある膜厚
280μmの複合体を得た。この複合体を５時間室温
で真空乾燥した。この複合体は43重量％のステン
レス・スチールの網を含有していた。
〔電池実験〕
前記の方法で得られた複合体から、直径20mmの
円板２枚を切りぬいて正極活物質、負極活物質と
し、電解液としては蒸留脱水アセトニトリルに溶
解したEt3BuN・ClO4のモル／溶液を用い、実
施例１と全く同様のセルで充・放電実験を行なつ
た。充電電流密度は、5.0mA／cm2で15分間充電を
行なつた（ドーピング量は５モル％相当）。充電
終了後、直ちに放電電流密度5.0mA／cm2で放電を
行ない電池電圧が1Vになつたところで再度、前
記と同じ条件で充電を行なう充・放電の繰り返し
試験を行なつたところ、充・放電効率が50％に低
下するまでに充・放電の繰り返し回数は663回を
記録した。
この繰り返し実験での繰り返し回数５回目のエ
ネルギー密度は、152W・hr／Kgで、充・放電効
率は98％であつた。また、充電したままで48時間
放置したところ、その自己放電率は6.3％であつ
た。
比較例 ５
実施例２において、電解液の電解質の濃度を１
モル／とした以外は実施例２と全く同様の方法
で電池の充・放電の繰り返し実験を行なつたとこ
ろ、充・放電効率が50％に低下するまでの充・放
電の繰り返し回数は420回であつた。
また繰り返し回数５回目のエネルギー密度は、
152W・hr／Kgで充電・放電効率は、98％であつ
た。また、充電したままで48時間放置したとこ
ろ、その自己放電率は9.5％であつた。
実施例 ３
Bull.Chem.Soc.Japan.，51，2091（1978）に記
載されている方法で製造したポリ（パラフエニレ
ン）を1ton／cm2の圧力で20mmの円板状に成形し
たものを正極とした以外は実施例１と全く同じ方
法で〔電池実験〕を行なつた結果、充・放電の繰
返し試験313回まで第１回目の放電時の電圧特性
とほとんど同じであつた。充・放電効率が50％に
低下するまでの繰返し回数は417回を記録した。
この電池のエネルギー密度は166W・hr／Kgであ
り、充・放電効率は93％であつた。また、充電し
たままで48時間放置したところその自己放電率は
3.7％であつた。
実施例 ４
実施例３で用いたポリ（パラフエニレン）の代
りにJ.Polym.Sci.，Polym.Lets.，ed.，18，９
（1980）に記載されている方法で製造したポリ
（２，５−チエニレン）を用いた以外は実施例３
と全く同じ方法で〔電池実験〕を行なつた。その
結果充・放電効率が50％に低下するまでの繰返し
回数は505回を記録した。この電池のエネルギー
密度は158W・hr／Kgであり、充・放電効率は97
％であつた。また、充電したままで48時間放置し
たところその自己放電率は4.1％であつた。
実施例 ５〜11
実施例１において、電解質及び溶媒の組み合せ
を表のごとく変えた以外は実施例１と全く同様な
方法で充・放電の繰り返し実験を行なつた。結果
を表に示した。表中、エネルギー密度は繰り返し
回数５回目のものを示し、サイクル寿命は充・放
電効率が50％に低下するまでの繰り返し回数を示
した。また、自己放電量は、充電終了後48時間、
開回路で放置した後のものを示した。
【表】 Detailed Description of the Invention The present invention provides a nonaqueous secondary battery that has high energy density, high charge/discharge efficiency, long cycle life, low self-discharge, and good voltage flatness during discharge. Regarding. consisting of a transition metal compound and an organometallic compound,
Acetylene polymers obtained by polymerizing acetylene using a so-called Ziegler-Natsuta catalyst are
Because the electrical conductivity is in the semiconductor region,
It is already known that organic semiconductor materials are useful as electrical and electronic devices. Methods for producing practical molded products of acetylene high polymers include (a) pressure molding of powdered acetylene high polymers, and (b) molding into a membrane at the same time as polymerization under special polymerization conditions. A method for obtaining a membranous acetylene public polymer having a fibrous microcrystalline (fibril) structure and high mechanical strength (Japanese Patent Publication No. 32581/1983) is known. The powdered acetylene polymer molded product obtained by the method (a) above is mixed with BF 3 , BCl 3 , HCl, Cl 2 , SO 2 ,
Chemical treatment with electron-accepting compounds (acceptors) such as NO 2 , HCN, O 2 , and NO increases electrical conductivity by up to three orders of magnitude, and conversely, chemical treatment with electron-donating compounds (donors) such as ammonia and methylamine It is already known that the electrical conductivity decreases by up to four orders of magnitude when treated with . In addition, I 2 , Cl 2 , Br 2 , ICl, IBr, AsF 5 , SbF 5 ,
Electron accepting compounds such as PF 6 or Na, K,
The electrical conductivity of acetylene polymers can be improved by chemically doping them with electron-donating compounds such as Li.
It is already known that it can be freely controlled over a wide range of 10 -8 to 10 3 Ω -1 cm -1 .
The idea of using this doped film-like acetylene polymer as a material for the positive electrode of a primary battery has already been proposed. On the other hand, in addition to the chemical doping method described above, electrochemical doping of ClO - 4 , PF - 6 , AsF - 6 , AsF - 4 ,
Anions such as CF 3 SO - 3 , BF - 4 and R′ 4 N +
(R' is an alkyl group and is also the same group.) A method for producing p-type and n-type conductive acetylene polymers by doping them with cations such as There is. A rechargeable battery using electrochemical doping using a film-like acetylene polymer obtained by the method (b) has been reported. For example, two sheets of acetylene polymer film with a thickness of 0.1 mm obtained by the method of this battery (b) are used as positive and negative electrodes, respectively, and immersed in a tetrahydrofuran solution containing lithium iodide to generate a voltage of 9V. When connected to a DC power source, lithium iodide is electrolyzed, and the acetylene polymer film at the positive electrode is doped with iodine, and the acetylene polymer film at the negative electrode is doped with lithium. This electrolytic doping corresponds to the charging process. When a load is connected to the two doped electrodes, lithium ions and iodine ions react to generate electricity. In this case, the open circuit voltage (Voc) is 2.8 V and the short circuit current density is 5 mA/cm 2. When a tetrahydrofuran solution of lithium perchlorate is used as the electrolyte, the open circuit voltage is 2.5 V,
The short circuit current density was approximately 3 mA/cm 2 . In addition, two sheets of acetylene high polymer film with a thickness of 0.1 mm obtained by the method (b) above were each wrapped in a platinum mesh from which the lead wires were taken out separately.
immersed in an acetonitrile solution containing mol/equivalent of tetrabutylammonium perchlorate,
When charged at a constant current of 5 mA/cm 2 for a certain period of time, tetrabutylammonium ions are doped into the acetylene high polymer film of the negative electrode, and perchlorate ions are doped into the acetylene high polymer film of the positive electrode. In this case, the open circuit voltage (Voc) of the battery was 2.5V. When this battery is discharged at 1 mA/cm 2 until the battery voltage drops to 1.0 V, the amount of discharged electricity can be extracted with an efficiency of 81% relative to the amount of charged electricity. These batteries use acetylene polymer as the electrode material, which is easy to reduce weight and size, so they are attracting attention as batteries that have high energy density, are easy to reduce weight and size, and are inexpensive. . However, most of the electrolytes as dopants used in these known documents have low solubility in solvents with a relatively wide stable potential range, or have low electrical conductivity as electrolytes, or Since the electrolyte itself or its electrolyzed product has reactivity with a solvent having a relatively wide stable potential range, it has the disadvantage that it cannot be used with a solvent having a relatively wide stable potential range. For example, lithium metal is reactive with nitrile solvents, which are considered to have a relatively wide stable potential range, and there are difficulties in using lithium salts containing lithium metal as a cation component as electrolytes.
In addition, the above-mentioned tetrabutylammonium salt dissolves relatively well in nitrile solvents, and when used as an electrolyte, it is possible to obtain high charge/discharge efficiency, but the energy density must be sufficiently satisfied. isn't it. Furthermore, when using tetraethylammonium salt, which is one of the same alkylammonium salts, as an electrolyte, the solubility of tetraethylammonium salt is low in benzonitrile, which has a wide stable potential range, and the saturated solubility at room temperature is 1 mol/mole. Therefore, an electrolytic solution prepared by dissolving a tetraethylammonium salt in benzonitrile is very disadvantageous in terms of energy density, and is difficult to be applied as an electrolytic solution for batteries having a high energy density. Therefore, when an organic solvent with a relatively wide stable potential range is used, it has a high solubility in the organic solvent, a molar molecular weight as low as possible, high electrical conductivity, and its own electrochemical stability. There has been a strong demand among those in the industry to obtain an electrolyte, that is, a dopant, which has low reactivity with a polymer compound having a conjugated double bond in its main chain used as an electrode. In view of the above points, the present inventors have developed a battery that has high energy density, high charge/discharge efficiency, long cycle life, good voltage flatness, low self-discharge rate, light weight, and small size. As a result of various studies in order to obtain a non-aqueous secondary battery that is easy to produce and inexpensive, we found that an ammonium salt whose cation component is an asymmetric quaternary ammonium ion was used as the electrolyte, and the concentration of the electrolyte was at least 2 mol/min. The inventors have discovered that a non-aqueous secondary battery with good performance can be obtained by using an electrolytic solution, and have completed the present invention. That is, the present invention provides a non-conductive polymer that uses a polymer compound having a conjugated double bond in its main chain, or a conductive polymer compound obtained by doping the polymer compound with a dopant, for the negative electrode, or for both the positive and negative electrodes. A water secondary battery is characterized in that an ammonium salt consisting of an asymmetric quaternary ammonium ion whose cation component is represented by the following general formula is used as the electrolyte, and an electrolytic solution having an electrolyte concentration of at least 2 mol/min is used. This invention relates to a non-aqueous secondary battery. [In the formula, R 1 , R 2 , R 3 and R 4 have 1 to 1 carbon atoms
16 alkyl group or aryl group. However, all R 1 , R 2 , R 3 and R 4 are not the same group at the same time. ] The non-aqueous secondary battery of the present invention has a conventionally known R′ 4 N +
(R' is an alkyl group, and they are also the same group) Compared to a secondary battery using an ammonium salt or lithium salt as an electrolyte that has a symmetrical quaternary ammonium ion as a cation component, the energy () Large density, () Good voltage flatness, () Low self-discharge, ()
It has the advantage of long repeat life. Specific examples of polymer compounds having a conjugated double bond in the main chain (hereinafter referred to as conjugated polymer compounds) used in the present invention include acetylene polymers (polyacetylene), polyparaphenylene, and polymethaphenylene. Nylene, poly(2,5-thienylene), polypyrrole, polyquinoline, polyphenylacetylene, polyacene, polyacenequinone radical polymer, quinazoline polymer with Schiff base structure, polyarylenequinones, thermal decomposition products of polyacrylonitrile and polyimide, etc. Examples include, but are not necessarily limited to, any polymer compound having a conjugated double bond in its main chain. Further, there is no problem with either homopolymer or copolymer. Among the above conjugated polymer compounds, preferred are acetylene high polymer, polyparaphenylene, poly(2,5-thienylene), and polypyrrole, and particularly preferred is acetylene high polymer. I can give it to you. The method for producing the acetylene polymer preferably used in the present invention is not particularly limited, and any method can be used.
−32581, Special Publication No. 56-45365, Japanese Patent Publication No. 1983-
No. 129404, No. 55-128419, No. 55-142012, No. 55-128419, No. 55-142012, No.
No. 56-10428, No. 56-133133, Trans.Farady
Soc., 64, 823 (1968), J. Polymer Sci., A-1,
7, 3419 (1969), Makeromol.Chem., Rapid
Comm., 1 , 621 (1980), J.Chem.Phys., 69
(1), 106 (1978), Synthetic Metals, 4 , 81
(1981) and other methods. In the present invention, a conductive material such as graphite, carbon black, acetylene black, metal powder, carbon fiber, etc. may be mixed with the conjugated polymer compound, and there is no problem in adding a metal net or the like as a current collector. do not have. In the present invention, not only conjugated polymer compounds but also
A conductive polymer compound obtained by doping the polymer compound with a dopant can also be used as an electrode. The method for doping the conjugated polymer compound with a dopant may be either chemical doping or electrochemical doping. As dopants to be chemically doped into the conjugated polymer compound, there are various conventionally known electron-accepting compounds and electron-donating compounds, i.e.,
() Halogens such as iodine, bromine and bromine iodide; () arsenic pentafluoride; antimony pentafluoride;
metal halides such as silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, ammonium chloride, aluminum bromide and aluminum fluoride; () protonic acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid; () Oxidizing agents such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl peroxide, () AgClO 4 ,
() Tetracyanoethylene, tetracyanoquinodimethane, chloranil, 2,3-dichloro-
Examples include 5,6-dicyanoparabenzoquinone and 2,3-dibromo-5,6-dicyanoparabenzoquinone. On the other hand, dopants to be electrochemically doped into a conjugated polymer compound include ()PF - 6 ,
Halide anions of group Va elements such as SbF - 6 , AsF - 6 , SbCl - 6 , halide anions of group A elements such as BF - 4 , I - (I - 3 ), Br - , Cl - Anion dopants such as halogen anions such as ClO - 4 and perchlorate anions such as ClO - 4 (both are effective as dopants to provide p-type conductive conjugated polymer compounds); and alkalis such as ()Li + , Na + , K + Metal ions, cations and dopants such as quaternary ammonium ions such as R 4 N + (R: hydrocarbon group having 1 to 20 carbon atoms) (both are effective as dopants that provide n-type conductive conjugated polymer compounds), etc. Examples include, but are not necessarily limited to. However, when a conductive polymer compound obtained by doping a conjugated polymer compound with a dopant in advance is used for the electrode, the dopant pre-doped into the negative electrode is the asymmetric quaternary ammonium compound used in the battery electrolyte in the present invention. The same as the cation is desirable. Furthermore, the amount of doping in the battery of the present invention can be freely controlled by measuring the amount of electricity flowing during electrolysis. The doping may be carried out either under constant current, constant voltage or under conditions of varying current and voltage. The current value, voltage value, doping time, etc. during doping vary depending on the type of conjugated polymer compound used, bulk density, area, type of dopant, type of electrolyte, and required electrical conductivity. cannot be specified. The amount of dopant doped into the conjugated polymer compound is 2 to 40 mol%, preferably 4 to 30 mol%, based on 1 mol of repeating units of the conjugated polymer compound.
mol %, particularly preferably 5 to 20 mol %. Even if the amount of the doped dopant is less than 2 mol % or more than 40 mol %, a non-aqueous secondary battery with a sufficiently large discharge capacity cannot be obtained. The electrical conductivity of a conjugated polymer compound is 10 -5 Ω -1 cm -1 or less before doping, and the electrical conductivity of a conductive conjugated polymer compound obtained by doping with a dopant is approximately 10 -10 ~ It is in the range of 10 4 Ω -1 cm -1 . The battery electrolyte used in the present invention has a cationic component represented by the above general formula.
It is an ammonium salt consisting of class ammonium ions. Specific examples of the cation component of the ammonium salt include trimethylpropylammonium, trimethylbutylammonium, trimethylhexylammonium, trimethyloxylammonium, trimethylisobutylammonium, trimethyltertiarybutylammonium, trimethylisopropylammonium, trimethylisobutylammonium, trimethylhexadecylammonium, Trimethylpentylammonium, trimethylphenylammonium, triethylbutylammonium, triethylpropylammonium, triethylmethylammonium, triethylhexylammonium, triethylphenylammonium, tripropylbutylammonium, tributylmethylammonium, tributylethylammonium, dipropyldiethylammonium, dibutyldiethyl Examples include ammonium, dibutyldimethylammonium, dimethyldiphenylammonium, diethyldiphenylammonium, dibutylethylmethylammonium, dipropylethylmethylammonium, butylpropylethylmethylammonium, and the like. Specific examples of these cationic components and anionic components constituting the ammonium salt include HF - 2 ,
ClO - 4 , AlCl - 4 , BF - 4 , FeCl - 4 , SnCl - 5 , PF - 6 ,
Examples include PCl - 6 , SiF - 4 , SbF - 6 , AsF - 6 , CF 3 SO - 3 and the like. Specific examples of ammonium salts include triethylbutylammonium tetrafluoroborate, triethylbutylammonium perchlorate, triethylbutylammonium hexafluorophosphate, trimethylbutylammonium trifluoromethanesulfonate, trimethylethylammonium tetrafluoroborate, trimethylethylammonium hexal Examples include fluorophosate, dibutyldiethylammonium perchlorate, tributylethylammonium tetrafluoroborate, butylpropylethylmethylammonium hexachlorophosphate, trimethylphenyltetrafluoroborate, triethylphenyltetrafluoroborate, etc. It is not limited. These ammonium salts may be used alone or in combination of two or more. The ammonium salt of the present invention may also be used as a mixed electrolyte with other alkylammonium salts, such as tetrabutylammonium salts and tetraethylammonium salts, or with alkali metal salts, such as lithium salts, sodium salts, and potassium salts. It may be used as a mixed electrolyte. Furthermore, the ammonium salt of the present invention is a pyrylium or pyridium cation represented by the following formula (): [In the formula, ~10 alkyl group, aryl group having 6 to 15 carbon atoms, m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom. n is 0 or 1 to 5. ] Or a carbonium cation represented by the following formula () or (): or [In the formula, R 1 , R 2 , R 3 are hydrogen atoms (R 1 , R 2 , R 3
is not a hydrogen atom at the same time), carbon number is 1
-15 alkyl group, allyl group, aryl group having 6 to 15 carbon atoms or -OR 5 group, provided that R 5 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms (aryl) group, R 4 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and 6 carbon atoms.
~15 aryl groups. ] may be used in combination with an electrolyte having as a cationic component. However, when the cation component of the present invention is a mixture of an ammonium salt consisting of an asymmetric quaternary ammonium ion and another electrolyte, it is preferable to use the ammonium salt in a form containing equal moles or more of the ammonium salt. The organic solvent of the electrolyte used in the present invention is an aromatic nitrile compound. Specific examples of this organic solvent include benzonitrile, o-tolnitrile, m-tolnitrile, p-
Examples include tolnitrile and a-tolnitrile.
These solvents may be used as a mixed solvent without any problem. The concentration of the electrolyte used in the nonaqueous secondary battery of the present invention is at least 2 mol/, preferably 3 to 10 mol/. Electrolyte concentration is 2 mol/
If it is less than 1, the disadvantage is that the self-discharge of the non-aqueous secondary battery is relatively large. The electrolyte may be either homogeneous or heterogeneous, but it is usually used as a homogeneous electrolyte. In the present invention, the conjugated polymer compound or the conductive conjugated polymer compound obtained by doping the co-polymer compound with a dopant can be used as an active material for the () negative electrode or () both the positive and negative electrodes of a battery. However, in order to maximize the effects of the present invention, batteries of the type () are preferred. For example, in the case of a non-aqueous secondary battery using an acetylene polymer as a conjugated polymer compound, as an example of (), if the acetylene polymer is (CH)x, graphite (positive electrode)/(Et 3 BuN) +・
(ClO 4 ) - (electrolyte)/(CH) x (negative electrode), an example of () is [(CH) + 0.024 (ClO 4 ) - 0.024 ] x (positive electrode)
/
(Me 3 BuN) +・(ClO 4 ) - (electrolyte)/[(Me 3
BuN) + 0.024 (CH) - 0.024 〕 x (negative electrode), [(CH) + 0.06
(PF 6 ) - 0.06 ] x (positive electrode) / (Bu 3 EtN) +・(PF 6 ) - (electrolyte) / [(Bu 3 EtN) + 0.06 (CH) - 0.06 ] x (negative electrode),
[Et 3 BuN) + 0.02 ] x (positive electrode) / (Et 3 BuN) +・(ClO 4 )
- (electrolyte) / [(Et 3 BuN) + 0.07 (CH) - 0.07 ] x (negative electrode), etc. In the case of polyparaphenylene, the above (CH) x
instead of (C 6 H 4 ) x , poly(2,6-thienylene)
In the case of (CH) x , (C 4 H 2 S) x is used instead of (C 4 H 2 S) x, and in the case of polypyrrole, (C 4 H 2 N) x is used in the same type of non-aqueous secondary battery as above. Furthermore, in the present invention, different conjugated polymer compounds can be used for the positive electrode and the negative electrode, and a specific example thereof is (CH) x /Et 3 BuN・ClO 4 /(C 6
H 4 ) x , (CH) x ／Me 3 BuN・BF 4 ／(C 4 H 2 S) x ,
(C 6 H 4 ) x /Et 2 Bu 2 N・PF 6・(C 4 H 2 S) x etc. can be given. In the present invention, if necessary, a porous membrane made of synthetic resin such as polyethylene or polypropylene or natural fiber paper may be used as the diaphragm. Furthermore, some of the conjugated polymer compounds used in the present invention undergo gradual oxidation reactions due to oxygen, which may reduce the performance of the battery. It is necessary to be in the state. The nonaqueous secondary battery of the present invention has high energy density, high charge/discharge efficiency, long cycle life, and particularly low self-discharge rate. Furthermore, the non-aqueous secondary battery of the present invention is lightweight, compact, and has a high energy density, making it ideal for use in portable devices, electric vehicles, gasoline vehicles, and power storage batteries. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 [Production of film-like acetylene polymer] 1.7 ml of titanium tetrabutoxide was added to a glass reaction vessel with an internal volume of 500 ml under a nitrogen atmosphere, dissolved in 30 ml of anisole, and then 2.7 ml of triethylaluminum was stirred. A catalyst solution was prepared by adding the mixture in parallel. This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. The reaction vessel was then cooled to −78° C. and purified acetylene gas at a pressure of 1 atmosphere was bubbled through while the catalyst solution remained stationary. Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acetylene high polymer. Thirty minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. After the catalyst solution was removed with a syringe under a nitrogen atmosphere, it was washed five times with 100 ml of purified toluene while keeping the temperature at -78°C. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product in which fibrils were tightly entangled.
This swollen product was then vacuum-dried to obtain a reddish-purple film with a metallic luster, a thickness of 100 μm, and a cis content of 98%. In addition, the bulk density of this film-like acetylene polymer is 0.30 g/cc, and its electrical conductivity (DC four-terminal method) is 3.2× at 20°C.
It was 10 -9 Ω -1 cm -1 . [Battery Experiment] Two disks with a diameter of 20 mm were cut out from the film-like acetylene polymer obtained by the above method, and a battery was constructed by using the disks as active materials for a positive electrode and a negative electrode, respectively. The figure is a schematic cross-sectional view of a battery cell for measuring the characteristics of a nonaqueous secondary battery, which is a specific example of the present invention, in which 1 is a platinum lead wire for the negative electrode, and 2 is a collection of platinum wire mesh for the negative electrode with a diameter of 20 mm and 80 meshes. Electric body, 3 is a disc-shaped negative electrode with a diameter of 20 mm, 4 is a circular porous polypropylene diaphragm with a diameter of 20 mm, and is thick enough to be sufficiently impregnated with electrolyte, 5 is a disc-shaped positive electrode with a diameter of 20 mm, 6 is 20mm in diameter,
80 mesh platinum wire mesh current collector for the positive electrode, 7 a positive electrode lead wire, and 8 a screw-in Teflon container. First, the platinum wire mesh current collector 6 for the positive electrode is placed in the lower part of the concave portion of the Teflon container 8, and then the positive electrode 5 is stacked on the platinum wire mesh current collector 6 for the positive electrode, and the porous polypropylene diaphragm 4 is placed on top of the platinum wire mesh current collector 6 for the positive electrode. After stacking them and sufficiently impregnating them with the electrolytic solution, the negative electrode 3 was stacked, and the platinum wire mesh current collector 2 for the negative electrode was further placed thereon, and the Teflon container 8 was tightened to produce a battery. The electrolyte was 3 moles of Et 3 BuN・BF 4 dissolved in distilled and dehydrated benzonitrile according to a conventional method.
A solution was used. Using the battery thus produced, charging was performed for 15 minutes at a constant current (4.0 mA/cm 2 ) in an argon atmosphere (amount of electricity corresponding to a doping amount of 5 mol %). Immediately after charging, the battery was discharged under a constant current (4.0mA/cm 2 ), and when the battery voltage reached 1V, it was charged again under the same conditions as above.A repeated charge/discharge test was performed.
The number of charging/discharging cycles recorded was 893 before the charging/discharging efficiency decreased to 50%. Also, the energy density at the fifth repetition is
At 140W・hr/Kg, the charge/discharge efficiency was 99%.
Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 1.2%. Comparative Example 1 A battery was charged and discharged in exactly the same manner as in Example 1, except that Bu 4 N BF 4 was used instead of Et 3 BuN BF 4 used as the electrolyte in the electrolytic solution. After repeated experiments, the highest charging/discharging efficiency was 96%, and discharging became impossible after the 479th repetition. Also, the energy density at the 5th repetition is
At 130W・hr/Kg, the charge/discharge efficiency was 96%.
Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 4.9%. Comparative Example 2 In Example 1, the electrolyte concentration was changed to 3 mol/
An experiment of repeatedly charging and discharging the battery was conducted in the same manner as in Example 1 except that the ratio was changed from 1 mol/.The number of times charging and discharging was repeated until the charging and discharging efficiency decreased to 50% was was 700 times. Also, the energy density at the fifth repetition is
At 140W・hr/Kg, the charge/discharge efficiency was 99%.
Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 3.0%. Comparative Example 3 In Example 1, an attempt was made to use equimolar amounts of Et 4 N BF 4 instead of Et 3 BuN BF 4 used as the electrolyte in the electrolytic solution, and as a result, Et 4 N BF 4 was converted into benzonitrile. Hardly dissolves, does not dissolve Et 4 N・BF 4
The battery was repeatedly charged and discharged in the same manner as in Example 1 while the precipitated state was maintained. As a result, the maximum charging/discharging efficiency was 72%, and discharging became impossible after the 25th repetition. Comparative Example 4 In Example 1 , when an attempt was made to use an equimolar amount of LiBF 4 instead of Et 3 BuN・BF 4 used as the electrolyte in the electrolyte, LiBF 4 did not completely dissolve in benzonitrile and A battery was repeatedly charged and discharged in the same manner as in Example 1, with the remaining undissolved and precipitated. As a result, the maximum charge/discharge efficiency was 24%, and discharging became impossible after the 12th repetition. Also, the energy density at the 5th repetition is
The charging/discharging efficiency was 18% at 24W・hr/Kg. Example 2 A 100-mesh mesh of stainless steel was placed in a glass reaction vessel 1 that was completely purged with nitrogen gas, and then 100 ml of toluene purified according to a conventional method was used as a polymerization solvent, and 4.41 mmol of tetrabutoxytitanium was used as a catalyst. and 11.01 mmol of triethylaluminum were sequentially charged at room temperature to prepare a catalyst solution. The catalyst solution was a homogeneous solution. Next, the reactor was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. The reactor was cooled to −78° C., and purified acetylene gas at a pressure of 1 atmosphere was blown into the reactor while the catalyst solution was left standing. The polymerization reaction was continued for 10 hours while maintaining the pressure of the acetylene gas at 1 atm. The system was agar-like with a reddish-purple color. After polymerization, unreacted acetylene gas was removed and the system temperature was maintained at -78℃.
After repeated washing with 200ml of purified toluene four times, the stainless steel film was swollen with toluene and had a film thickness of about 0.5cm.
A sheet-like swollen acetylene polymer containing a steel mesh was obtained. This swollen acetylene polymer is
It was a swollen product in which fibrous microcrystals (fibrils) with a diameter of 300 to 500 Å were regularly intertwined, and no powder or lump-like polymer was produced. This sheet-like swollen acetylene polymer containing a stainless steel mesh was sandwiched between chromium-plated ferro plates, pre-pressed at room temperature at a pressure of 100 kg/cm 2 , and then pressed at a pressure of 15 ton/cm 2 to form a reddish-brown metal. Uniform and flexible film thickness with gloss
A 280 μm composite was obtained. This composite was vacuum dried for 5 hours at room temperature. This composite contained 43% by weight stainless steel mesh. [Battery experiment] From the composite obtained by the above method, two disks with a diameter of 20 mm were cut out and used as a positive electrode active material and a negative electrode active material.Et 3 BuN ClO dissolved in distilled and dehydrated acetonitrile was used as an electrolyte. A charge/discharge experiment was conducted using a cell exactly the same as in Example 1 using 4 mol/solution. Charging was carried out for 15 minutes at a charging current density of 5.0 mA/cm 2 (doping amount equivalent to 5 mol %). Immediately after charging, the battery was discharged at a discharge current density of 5.0 mA/cm 2 , and when the battery voltage reached 1 V, the battery was charged again under the same conditions as above. The number of charging/discharging cycles was recorded 663 times before the efficiency dropped to 50%. The energy density at the fifth repetition of this repeated experiment was 152 W·hr/Kg, and the charge/discharge efficiency was 98%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 6.3%. Comparative Example 5 In Example 2, the concentration of electrolyte in the electrolytic solution was reduced to 1
An experiment was conducted in which the battery was repeatedly charged and discharged in the same manner as in Example 2, except that the charging and discharging efficiency decreased to 50%.The number of times that charging and discharging was repeated was 420 times. It was hot. Also, the energy density at the fifth repetition is
The charging/discharging efficiency was 98% at 152W・hr/Kg. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 9.5%. Example 3 Poly(paraphenylene) produced by the method described in Bull.Chem.Soc.Japan., 51 , 2091 (1978) was molded into a 20 mm disk shape at a pressure of 1 ton/ cm2 , and a positive electrode was used. [Battery experiment] was carried out in exactly the same manner as in Example 1 except that the voltage characteristics were almost the same as the first discharge up to 313 repeated charging/discharging tests. The number of repetitions until the charging/discharging efficiency decreased to 50% was recorded as 417 times.
The energy density of this battery was 166 W·hr/Kg, and the charging/discharging efficiency was 93%. Also, when left charged for 48 hours, the self-discharge rate was
It was 3.7%. Example 4 Instead of poly(paraphenylene) used in Example 3, J.Polym.Sci., Polym.Lets., ed., 18 , 9
Example 3 except that poly(2,5-thienylene) produced by the method described in (1980) was used.
I conducted a [battery experiment] in exactly the same way. As a result, the number of repetitions until the charging/discharging efficiency decreased to 50% was recorded as 505 times. The energy density of this battery is 158W・hr/Kg, and the charge/discharge efficiency is 97
It was %. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 4.1%. Examples 5 to 11 In Example 1, repeated charging/discharging experiments were conducted in exactly the same manner as in Example 1, except that the combinations of electrolytes and solvents were changed as shown in the table. The results are shown in the table. In the table, the energy density indicates the 5th repetition, and the cycle life indicates the number of repetitions until the charge/discharge efficiency drops to 50%. In addition, the self-discharge amount is 48 hours after the end of charging.
Shown after being left open circuit. 【table】
図は本発明の一具体例である非水二次電池の特
性測定用電池セルの断面概略図である。
１……負極用白金リード線、２……負極用白金
網集電体、３……負極、４……多孔性ポリプロピ
レン製隔膜、５……正極、６……正極用白金網集
電体、７……正極リード線、８……テフロン製容
器。
The figure is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous secondary battery, which is a specific example of the present invention. 1... Platinum lead wire for negative electrode, 2... Platinum wire mesh current collector for negative electrode, 3... Negative electrode, 4... Porous polypropylene diaphragm, 5... Positive electrode, 6... Platinum wire mesh current collector for positive electrode, 7... Positive electrode lead wire, 8... Teflon container.
Claims (1)
たは該高分子化合物にドーパントをドープして得
られる電導性高分子化合物を負極、または正極と
負極の両極に用いた非水二次電池において、電解
液の電解質としてカチオン成分が下記の一般式で
表わされる非対称第４級アンモニウムイオンから
なるアンモニウム塩を用い、かつ電解質の濃度が
少なくとも２モル／であつて、電解液の溶媒と
して芳香族ニトリル系化合物を用いたことを特徴
とする非水二次電池。 ［式中、R1，R2，R3およびR4は炭素数が１〜
16のアルキル基、またはアリール基である。但
し、すべてのR1，R2，R3およびR4は同時に同一
の基であることはない。］[Scope of Claims] 1. Non-containing polymers in which a polymer compound having a conjugated double bond in the main chain or a conductive polymer compound obtained by doping the polymer compound with a dopant are used for the negative electrode or both the positive and negative electrodes. In a water secondary battery, an ammonium salt consisting of an asymmetric quaternary ammonium ion whose cation component is represented by the following general formula is used as the electrolyte of the electrolytic solution, and the concentration of the electrolyte is at least 2 mol/ A nonaqueous secondary battery characterized by using an aromatic nitrile compound as a solvent. [In the formula, R 1 , R 2 , R 3 and R 4 have a carbon number of 1 to
16 alkyl group or aryl group. However, all R 1 , R 2 , R 3 and R 4 are not the same group at the same time. ]
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59034175A JPS60180072A (en) | 1984-02-27 | 1984-02-27 | Nonaqueous secondary battery |
| US06/663,540 US4537843A (en) | 1983-10-26 | 1984-10-22 | Secondary battery |
| CA000466056A CA1242483A (en) | 1983-10-26 | 1984-10-22 | Secondary battery |
| DE8484112784T DE3473387D1 (en) | 1983-10-26 | 1984-10-23 | Secondary battery |
| EP84112784A EP0141371B1 (en) | 1983-10-26 | 1984-10-23 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59034175A JPS60180072A (en) | 1984-02-27 | 1984-02-27 | Nonaqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60180072A JPS60180072A (en) | 1985-09-13 |
| JPH0527232B2 true JPH0527232B2 (en) | 1993-04-20 |
Family
ID=12406864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59034175A Granted JPS60180072A (en) | 1983-10-26 | 1984-02-27 | Nonaqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60180072A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2601776B2 (en) * | 1988-12-28 | 1997-04-16 | 鐘紡株式会社 | Organic electrolyte battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835874A (en) * | 1981-08-27 | 1983-03-02 | Kao Corp | Chemical cell |
| JPS58121569A (en) * | 1982-01-14 | 1983-07-19 | Hitachi Ltd | Plastic secondary battery |
-
1984
- 1984-02-27 JP JP59034175A patent/JPS60180072A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835874A (en) * | 1981-08-27 | 1983-03-02 | Kao Corp | Chemical cell |
| JPS58121569A (en) * | 1982-01-14 | 1983-07-19 | Hitachi Ltd | Plastic secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60180072A (en) | 1985-09-13 |
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