JPS6355867A - Secondary cell - Google Patents
Secondary cellInfo
- Publication number
- JPS6355867A JPS6355867A JP61200583A JP20058386A JPS6355867A JP S6355867 A JPS6355867 A JP S6355867A JP 61200583 A JP61200583 A JP 61200583A JP 20058386 A JP20058386 A JP 20058386A JP S6355867 A JPS6355867 A JP S6355867A
- Authority
- JP
- Japan
- Prior art keywords
- libf4
- dme
- concentration
- discharge
- secondary cell
- 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.)
- Pending
Links
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 20
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 229920000767 polyaniline Polymers 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- 229910000573 alkali metal alloy Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 13
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000003115 supporting electrolyte Substances 0.000 abstract description 4
- -1 aniline compound Chemical class 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229920000775 emeraldine polymer Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910004039 HBF4 Inorganic materials 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 2
- DWJXWSIJKSXJJA-UHFFFAOYSA-N 4-n-[4-(4-aminoanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC(C=C1)=CC=C1NC1=CC=C(N)C=C1 DWJXWSIJKSXJJA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000763 leucoemeraldine polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 241001474791 Proboscis Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002932 luster Substances 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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- IDIXOSREORKJTN-UHFFFAOYSA-N nonylhydrazine Chemical compound CCCCCCCCCNN IDIXOSREORKJTN-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- DTLKWZKUAHYQGX-UHFFFAOYSA-N polyanine Natural products CC1CCC2(NC1)OC3CC4C5CCC6CC(CCC6(C)C5CCC4(C)C3C2C)OC7OC(CO)C(O)C(OC8OCC(O)C(O)C8O)C7OC9OCC(O)C(O)C9O DTLKWZKUAHYQGX-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、エネルギー密度が高く、自己放電が小さく、
サイクル寿命が長く、かつ充、放゛電効率（クーロン効
率）の良好な二次電池に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention has high energy density, low self-discharge,
This invention relates to a secondary battery with a long cycle life and good charging and discharging efficiency (Coulomb efficiency).
主鎖に共役二重結合を有する高分子化合物を電極に用い
た、いわゆるポリマー電池は、１ａ工ネルギー密度二次
電池として期待されている。ポリマー電池に関してはす
でに多くの報告がなされており、例えば、ビー・ジェー
・ナイグレイ等、ジャーナル・オブ・ザ・ケミカル・ソ
ザイアディ、ケミカル・コミュニケーション、１９７９
年、第５９４頁（Ｐ、 Ｊ、 Ｎ ｉｇｒｃｙ等、Ｊ、
Ｃ，Ｓ、 、 Ｃｈｅｍ、 ＣｏＩＩｌｍｕｎ、 、
ユ９７９５９４） 、ジ１１−ナル・エレクトロケミカ
ル・ソサ゛イアティ、１９８１年、第１６５１頁（Ｊ、
Ｅｌｅｃｔｒｏｃｈｅｍ。A so-called polymer battery using a polymer compound having a conjugated double bond in its main chain as an electrode is expected to be a 1A energy density secondary battery. Many reports have already been made regarding polymer batteries, for example, BJ Nigley et al., Journal of the Chemical Society, Chemical Communication, 1979.
, p. 594 (P, J, Nigrcy et al., J.
C,S, , Chem, CoIIlmun, ,
979594), General Electrochemical Society, 1981, p. 1651 (J,
Electrochem.
ＳＯＣ，、１９８１，１６！１１） 、特開昭５６−１
３６４６９号、同５７−１２１１６８号、同５９−３８
７０号、同５９−３８７２号、同５９−３８７３号、同
５９−１９６５６６丹、同 ５９−１９６５７３号、
同５９−２０３３６８号、同５９−２０３３６９号等を
その一部としてあげることができる。SOC,, 1981, 16!11), JP-A-56-1
No. 36469, No. 57-121168, No. 59-38
No. 70, No. 59-3872, No. 59-3873, No. 59-196566, No. 59-196573,
No. 59-203368, No. 59-203369, etc. can be mentioned as some of them.
また、アニリンを電解酸化重合して得られるポリアニン
を水溶液系または非水溶媒系の電池の電極として用いる
提案もずでになされている〔エイ・ジー・マツクダイア
ーミド等、ポリ十−・プレプリンツ、第２５巻、ナンバ
ー２．第２４８頁（ｉ９８４年） （Ａ、Ｇ、Ｈａｃ
ＤｉａｒＩＩｌｉｄ ａｔ ａｌ、ＰｏｌｙｍｅｒＰｒ
ａｐｒｉｎｔＳ、 亘 Ｎ（ｉ２，２４８（ｉ９８４
） ） 、佐々木等、電気化学協会第５１大会要旨集、
１２３ （ｉ９８３）、電気化学協会第５１大会要旨集
、２２８ （ｉ９８４） ）。In addition, proposals have been made to use polyanine obtained by electrolytic oxidation polymerization of aniline as an electrode for aqueous or non-aqueous batteries [A.G. Matsuku Diamide et al., Polyten Preprints, Volume 25, number 2. Page 248 (i984) (A, G, Hac
DiarIIlid at al, PolymerPr
aprintS, Wataru N(i2,248(i984
) ), Sasaki et al., Abstracts of the 51st Conference of the Electrochemical Society,
123 (i983), Proceedings of the 51st Conference of the Electrochemical Society, 228 (i984)).
しかし、従来公知のポリマーを電極に用いたポリマー電
池では、（ｉ）高エネルギー密度、Ｑｉ）低自己放電、
０高充・放電効率および（ｉｖ）長サイクル寿命を同時
に満足するものは得られていなかった。However, in polymer batteries using conventionally known polymers for electrodes, (i) high energy density, Qi) low self-discharge,
0.No one has been obtained that simultaneously satisfies high charge/discharge efficiency and (iv) long cycle life.
本発明者等は、上記４つの電池性能を同時に満足する電
極材料について種々検討した結果、ポリアニリン系化合
物を正極に用い、電解液がＬｉＢＦ４およびプロピレン
カーボネート（ＰＣ）と１・２−ジメトキシエタン（Ｄ
ＭＥ）の混合溶媒からなる二次電池において、充・放電
時のｕＢＦ４１度によって電池性能が改善されることを
発見した。As a result of various studies on electrode materials that simultaneously satisfy the above four battery performances, the present inventors found that a polyaniline compound was used for the positive electrode, and the electrolyte was made of LiBF4, propylene carbonate (PC), and 1,2-dimethoxyethane (D
It has been discovered that in a secondary battery made of a mixed solvent of ME), battery performance is improved by uBF of 41 degrees during charging and discharging.
本発明は上記の発見に基づいて開発されたもので、上記
４つの電池性能が同時に満足される二次電池を提供する
ことを目的とする。The present invention was developed based on the above discovery, and an object of the present invention is to provide a secondary battery that satisfies the above four battery performances at the same time.
本発明は上記の目的を達成すべくなされたもので、その
要旨は、正極がポリアニリン系化合物、負極が（ｉ）ア
ルカリ金属、（ｎ）アルカリ金属合金、（至）電導性高
分子、或いは（ｉｖ）電導性高分子とアルカリ金属また
はアルカリ金属合金との複合体、から選ばれた物質で、
かつ電解液が１１８ Ｆ ４およびプロピレンカーボネ
ートと１・２−ジメトキシエタンの混合溶媒からなる二
次電池において、該電解液中のＬＩ Ｂ Ｆ ａの濃度
が放電終了時に４ｍｏｌ／ｌ以上で、充電終了時に１ｍ
ｏｌ／ｌ以下である二次電池にある。The present invention has been made to achieve the above object, and its gist is that the positive electrode is made of a polyaniline compound, and the negative electrode is made of (i) an alkali metal, (n) an alkali metal alloy, (to) a conductive polymer, or ( iv) A substance selected from a complex of a conductive polymer and an alkali metal or an alkali metal alloy,
In a secondary battery in which the electrolytic solution is made of 118 F 4 and a mixed solvent of propylene carbonate and 1,2-dimethoxyethane, charging is completed when the concentration of LI B Fa in the electrolytic solution is 4 mol/l or more at the end of discharging. sometimes 1m
It is found in secondary batteries with ol/l or less.
（発明の具体的構成および作用〕 以下本発明の詳細な説明する。(Specific structure and operation of the invention) The present invention will be explained in detail below.
本発明の二次電池の正極に用いられるポリアニリン系化
合物は、下記の一般式（ｉ）と（２）から選ばれた少な
くとも−・種のアニリン系化合物を酸化重合または酸化
共重合することによって（ｑられる。The polyaniline compound used in the positive electrode of the secondary battery of the present invention can be obtained by oxidative polymerization or oxidative copolymerization of at least - species of aniline compounds selected from the following general formulas (i) and (2). be qed.
（但し、式中、Ｒ＋ 、Ｒ２は炭素数が５以下のアル１
ル基または炭素数が５以下のアルコキシ基、Ｘ、Ｙは０
．１または２である。〕
一般式が（ｉ）または（２）で表わされるアニリン化合
物としては、例えばアニリン、２−メト１シ−アニリン
、２．５−ジメチルアニリン、２−メト１シーアニリン
、２．５−ジメト１シーアニリン、Ｏ−ノ１ニレンジア
ミン、Ｓ３−メチル−１゜２−ジアミノ−ベンゼン等が
あげられる１、これらのうちでｌ’（ましいものとして
は、）Ｉニリン、〇−ノ１ニレンジアミンがあげらｒし
、１！■に好ましいものとしてはアニリンがあげられる
、。(However, in the formula, R+ and R2 are Al1 having 5 or less carbon atoms.
or an alkoxy group having 5 or less carbon atoms, X and Y are 0
．． 1 or 2. ] As the aniline compound represented by the general formula (i) or (2), for example, aniline, 2-metho-1-cy-aniline, 2,5-dimethylaniline, 2-metho-1-cyaniline, 2,5-dimetho-1 Examples include cyaniline, O-no-1 nylene diamine, S3-methyl-1゜2-diamino-benzene, etc. 1 Among these, l' (preferably) I-niline, 0-no 1 nylene diamine are mentioned. Rashi, 1! Aniline is preferable for (1).
上記ポリアニリン系化合物は、電気化学的重合または化
学的重合のいずれの方法でも製造することができる。The above polyaniline compound can be produced by either electrochemical polymerization or chemical polymerization.
電気化学的重合法を用いる場合、アニリン系化合物の重
合は陽極酸化により行われるが、そのためには例えば０
．１〜２０ ｍ Ａ ／ ｃｄの電流密度が用いられ、
多くは１〜３００ボルトの゛心任が印加される。重合は
好ましくはアニリン系化合物が可溶な補助液体の存在下
で行われ、そのためには水または極性有機溶剤が使用で
きる。水と混合しうる溶剤を使用するときは少バ１の水
を添加してもよい。優れた有機溶剤は、アルコール、ニ
ーデル例えばジオキサンまたはテトラヒドロフラン、ア
セトンまたはアセトニトリル、ベンゾニトリル、ジメチ
ルホルムアミドまたはＮ−メチルピロリドンである。When electrochemical polymerization is used, the polymerization of aniline compounds is carried out by anodic oxidation, for example, 0
．． A current density of 1-20 mA/cd was used,
In many cases, a voltage of 1 to 300 volts is applied. The polymerization is preferably carried out in the presence of an auxiliary liquid in which the aniline compound is soluble, for which water or a polar organic solvent can be used. When using a solvent that is miscible with water, one part water may be added. Suitable organic solvents are alcohols, needles such as dioxane or tetrahydrofuran, acetone or acetonitrile, benzonitrile, dimethylformamide or N-methylpyrrolidone.
重合は支持電解質の存在下で行われる。これは、アニオ
ンとして８Ｆａ−、ＡＳＦ４−。Polymerization takes place in the presence of a supporting electrolyte. This is 8Fa-, ASF4- as anions.
ＡＳＦｅ −＋ ５ｂＦｓ−，５ｂＣＪ−、ＰＦｓ −
。ASFe −+ 5bFs−, 5bCJ−, PFs −
.
ＣｌＯ２−＋ Ｈ３Ｏ４−、５ＯＡ２−およびこれら
の塩は、カチオンとじて例えばプロ１−ン［１”）、４
ｉ＆アンモニウムイオン、リチウムイオン、ナトリウム
イオンまたＧ、Ｌカリウムイオンを含有する。この種の
化合物の使用は既知であって、本発明の対象ではない。ClO2-+ H3O4-, 5OA2- and their salts are cations such as pro1-[1''), 4
Contains ammonium ions, lithium ions, sodium ions, and G and L potassium ions. The use of compounds of this type is known and is not the subject of the present invention.
これらの化合物は、通常はポリアニリン系化合物がアニ
オンを１０〜１００モル％含有するｆｌＬ′ｃ用いられ
る。These compounds are usually polyaniline compounds containing 10 to 100 mol % of anions.
ポリアニリン系化合物を化学的方法で製造するには、例
えば、アニリン系化合物を水溶液中で強酸、例えば塩酸
および無機の過酸化物、例えば過硫酸カリウムにより重
合させることができる。この方法によると、ポリアニリ
ン系化合物が微粉末状で得られる。これらの方法におい
てｂ塩が存在するので、ポリアニリン系化合物は対応す
るアニオンにより錯化合物になっている。重合してｊＩ
Ｉらねたｉ；１化したポリアニリン系化合物は予めアン
モニア、 Ｋ ＯＨ、Ｎ ａ ＯＨ秀のアルカリ（・処
！’！！ シてアンドープしてＡｓ＜ことがりｉ’；ｌ
：Ｌい。To produce polyaniline compounds by chemical methods, for example, aniline compounds can be polymerized in aqueous solution with strong acids, such as hydrochloric acid, and inorganic peroxides, such as potassium persulfate. According to this method, a polyaniline compound is obtained in the form of a fine powder. In these methods, since the b salt is present, the polyaniline compound becomes a complex compound with the corresponding anion. Polymerize and jI
The monomerized polyaniline compound is preliminarily treated with ammonia, KOH, NaOH, and alkali.
:L.
、１、た、脱ドーピングまたは脱１０トン化７る他の方
法としＣ’ ｆ、１１００へ一３００１’、Ｑ加熱処理
・）るｌｊ法、二したは電気化学的ｌＪ法をあげること
が出来る。また、アルカリ処理ｉＰの前、また＋、１後
に低分子ト？）部分を除去するため、４：ｉ機溶媒で洗
浄または抽１１１することが好ましいが、この処理を行
なわなくとも差し支えない。脱ドーピングまたは脱ドー
ピングされたポリアニリン系化合物は、ポリアニリンを
例にとれば下式（３）のエメラルディン構造を多く含有
する。, 1.Other methods for dedoping or de10tonization7 include C' f, 1100 to 3001', Q heat treatment, lj method, and second, electrochemical lj method. . In addition, before the alkali treatment iP, and after + and 1, low molecular weight treatment? ) is preferably washed or extracted with a 4:i solvent, but this treatment may be omitted. Taking polyaniline as an example, a dedoped or dedoped polyaniline compound contains a large amount of the emeraldine structure of the following formula (3).
脱ドープまたは脱プロトン化されたポリアニリン系化合
物はさらにヒドラジン、ノ１ニルヒドラジン、三塩化チ
タン等の還元削ぐ還元したｂのを用いた方がより好まし
い。還元８れたポリアニリン系化合物は、ポリアニリン
を例にとれば下式（４）のルイ〕■メラルディン↑ｌ’
４ ）’！’ｊを多く含イｉ′Ｊる。As the dedoped or deprotonated polyaniline compound, it is more preferable to use a reduced compound such as hydrazine, nonylhydrazine, titanium trichloride, or the like. Taking polyaniline as an example, the reduced polyaniline compound has the following formula (4): Louis] ■ Meraldine ↑l'
4)'! Contains a lot of 'j'i'Jru.
説ドープ、１だは股ブ［Ｊトン化したポリアニリン系化
合物は１１Ｊ１αプロトン酸で錯化したものを用いた方
がより好ましい。It is more preferable to use a polyaniline compound complexed with a 11J1α protonic acid.
（３）式のエメラルディン構造のものを酸化剤により酸
化して、ニグラニリン構Ｙａ （り）またはパーニグラ
ニリン構造（６ンのものに変換し、次いでプロトン酸で
錯化したものり用い（も良い。The emeraldine structure of formula (3) is oxidized with an oxidizing agent to convert it to the nigraniline structure (Ya (ri)) or the pernigraniline structure (6), and then a resin complexed with a protonic acid may also be used.
錯化する方法は特に制限は無いが、通常はアニオンを含
むＯＬ＋が３以下の酸性水溶液を１と触さける方２人が
用いられる、。There are no particular restrictions on the method for complexing, but usually two people are used who touch one and two acidic aqueous solutions containing anions and having an OL+ of 3 or less.
錯化剤どしではｌ−１ｃｆ、 ＨＦ、 Ｈｌｌｒの如き
ハ【１グン化水木、ＨＦ３Ｆ４の如き第■Ωａ元素のハ
１１き過塩素酸、及びＨ２Ｓ ０４ 、 ＨＮ Ｏ３等
ｔｆｉ ’４ ケられるが、プロトン酸でポリアニリン
系化合物に錯化するものであれば特に制限は無い。これ
等のプロトン酸のうちでもＨＢＦ４ 、ＨＰＦａ 。Among complexing agents, there are perchloric acids such as l-1cf, HF, Hllr, perchloric acid of the Ωa element such as HF3F4, and tfi '4 such as H2S 04 and HN O3. There are no particular limitations as long as the polyaniline compound is complexed with a protonic acid. Among these protic acids, HBF4, HPFa.
ＨＣ１０４が好ましく、ｌ−Ｉ Ｂ Ｆ ４及びＨＰＦ
ｓが特に好ましい。これらのプロトン酸のアニオンは、
本発明の二次電池の電解液中のアニオンと異なっていて
も一向に差し支えないが、同一である方がより好ましい
。HC104 is preferred, l-I B F 4 and HPF
s is particularly preferred. The anions of these protonic acids are
Although there is no problem even if the anion is different from the anion in the electrolytic solution of the secondary battery of the present invention, it is more preferable that the anion is the same.
前記のアルカリ処理、有機溶媒洗浄、酸化及びプロトン
酸での錯化処理のいずれも、ボリアニリ電極として使用
しうる成形体は、種々の方法に□より得られる。例えば
アニリン系化合物の陽Ｍｉ化の場合は、アニオンににり
錯化合物化され、そして使用陽極の形を呈するポリアニ
リン系化合物が形成される。陽極が平らな形状ならば、
ポリアニリン系化合物の平らな位が形成される。ポリア
ニリン系化合物微粉末の製法を利用するとぎは、この微
粉末を既知方法により加圧および加熱下に成形体に圧縮
成形することができる。多くの場合室温〜３００℃の温
度および１０〜ｉｏ、ｏｏ。Any of the above-mentioned alkali treatment, organic solvent washing, oxidation, and protonic acid complexing treatment can yield a molded body that can be used as a borianylene electrode by various methods. For example, in the case of positive Mi conversion of an aniline compound, the anion is converted into a complex compound, and a polyaniline compound having the shape of the anode used is formed. If the anode is flat,
A flat layer of polyaniline compound is formed. When the method for producing a polyaniline compound fine powder is used, this fine powder can be compression molded into a molded body by a known method under pressure and heat. Temperatures often from room temperature to 300°C and from 10 to io, oo.
Ｋｙ ／ ｃｄの圧力が用いられる。アニオン性の錯化
合物化したポリアニリン系化合物を製造するためのこの
既知方法によれば、任意の形の成形体を得ることができ
る。即ち、例えばＮＷＡ、板または立体形態の成形物が
用いられる。A pressure of Ky/cd is used. According to this known method for producing anionic complexed polyaniline compounds, molded bodies of arbitrary shapes can be obtained. That is, for example, NWA, plate or three-dimensional moldings are used.
本発明の二次電池に用いられる負極は（ｉ）アルカリ金
属、（ｉ＋）アルカリ金属合金、０電導性高分子または
（ｉｖ）アルカリ金属もしくはアルカリ土類合金と電導
性高分子との複合体である。The negative electrode used in the secondary battery of the present invention is (i) an alkali metal, (i+) an alkali metal alloy, a conductive polymer, or (iv) a composite of an alkali metal or an alkaline earth alloy and a conductive polymer. be.
（ｉ）アルカリ金属としては、Ｌｌ、Ｎａ、に等があげ
られ、（ｉ）アルカリ金属合金としては、Ｌｌ／Ｍ合金
、Ｌｌ／Ｈ（Ｊ合金、Ｌｌ ／ Ｚ ｎ合金、Ｌｌ ／
Ｃｄ合金、Ｌｌ／、５ｎ合金、Ｌｌ ／ ｐ ｂ合金
およびこれらの合金に用いられたアルカリ金属を含む３
種以上の金属の合金、例えばＬｌ／＃／ＭＣＩ、 Ｌｌ
／ＡＪ／Ｓｎ、 Ｌｌ／Ａｊ／ Ｐ ｂ 、 Ｌｉ ／
な、１／ Ｚ ｎ 、 Ｌｉ／／Ｖ／ ＨＣ１等があげ
られる。(i) Examples of alkali metals include Ll, Na, etc. (i) Examples of alkali metal alloys include Ll/M alloy, Ll/H (J alloy, Ll/Z n alloy, Ll/
3 including Cd alloy, Ll/, 5n alloy, Ll/pb alloy and alkali metals used in these alloys.
Alloys of more than one metal, such as Ll/#/MCI, Ll
/AJ/Sn, Ll/Aj/Pb, Li/
, 1/Z n , Li//V/ HC1, etc.
これらの合金は電気化学的方法および化学的方法のいず
れの方法で製造したものでもよいが、電気化学的に合金
化したものの方がより好ましい。These alloys may be manufactured by either an electrochemical method or a chemical method, but those alloyed electrochemically are more preferable.
また、０電導性高分子としては、ポリピロール、ポリピ
ロール誘導体、ポリチオフェン、ポリチオフェン誘導体
、ポリキノリン、ボリアセン、ポリバラフェニレン、ポ
リバラフェニレン誘導体、ポリアセチレン等があげられ
る。さらに、（ｉｖ）アルカリ金属もしくはアルカリ土
類合金と電導性高分子との複合体としては、Ｌｌ／Ａ＃
合金と上記各種電導性高分子、例えばポリパラフェニレ
ンまたはポリアセチレンとの複合体があげられる。これ
らのうちで好ましいものとしては、例えばポリアセチレ
ン、ポリバラフェニレン、ＬＩＯＮ合金、Ｌｌ／＃／Ｍ
ｏ合金、Ｌ１／Ｍ合金とボリアセンまたはポリバラフェ
ニレンとの複合体があげられる。ここでいう複合体とは
、アルカリ金属またはアルカリ金属合金と電導性高分子
の均一な混合物、積層休むよび基体となる成分を他の成
分で修飾した修飾体を意味する。Furthermore, examples of the zero-conductivity polymer include polypyrrole, polypyrrole derivatives, polythiophene, polythiophene derivatives, polyquinoline, boriacene, polyvaraphenylene, polyvaraphenylene derivatives, polyacetylene, and the like. Furthermore, (iv) as a composite of an alkali metal or alkaline earth alloy and a conductive polymer, Ll/A#
Examples include composites of alloys and the various conductive polymers mentioned above, such as polyparaphenylene or polyacetylene. Among these, preferred are, for example, polyacetylene, polyvaraphenylene, LION alloy, Ll/#/M
o alloy, a composite of L1/M alloy and boriacene or polyvaraphenylene. The term "composite" as used herein refers to a homogeneous mixture of an alkali metal or an alkali metal alloy and a conductive polymer, or a modified product in which a component serving as a laminate or a base is modified with another component.
本発明の二次電池の電極に用いられるポリアニリン系化
合物、電導性高分子および層間化合物には、当該業者に
よく知られているように他の適当な導電材料、例えばノ
コ−ボンブラック、アセチレンブラック、金属粉、金属
Ｉ！帷、炭素繊維等を混合してもよい。The polyaniline compound, conductive polymer, and interlayer compound used in the electrode of the secondary battery of the present invention may include other suitable conductive materials, such as Nocobon black and acetylene black, as well known to those skilled in the art. , metal powder, metal I! A cloth, carbon fiber, etc. may be mixed.
また、ポリエチレン、変性ポリエチレン、ポリプロピレ
ン、ポリテトラフルオロエチレン、エチレンープロピレ
ンージエンーターボリマ−（ＥＰＤＭ）、スルホン化Ｅ
ＰＤＭ等の熱可塑性樹脂で補強してもよい。In addition, polyethylene, modified polyethylene, polypropylene, polytetrafluoroethylene, ethylene-propylene-diene ether polymer (EPDM), sulfonated E
It may be reinforced with thermoplastic resin such as PDM.
本発明の二次電池に用いられる電解液は支持電解質とし
てＬＩＢＦａを、溶媒としてＰＣとＤＭＥの混合溶媒を
用いたものであり、電解液の聞及びＬｉ Ｂ Ｆ ４
（ｉ） ’ＣＢ Ｇｅｔ、放’ａｊｌＩ了時（７）Ｌｉ
Ｂ Ｆａ （ｉ）５度が４ｚｏｌ／−ｆ以上で、充電
終了時のＬＩ Ｆ３ Ｆ ４の濃度が１ｍｏｌ／ｌ以下
になるように制御されたものである。Ｐ Ｃ、！： Ｄ
Ｍ Ｅの混合割合は特に限定はないが、通常、ＰＣが
１０〜９０容積％、ＤＭＥが９０〜１０容積％で、好ま
しくはＰＣが３０〜７０容積％、ＤＭＥが７０〜３０容
積％である。The electrolytic solution used in the secondary battery of the present invention uses LIBFa as a supporting electrolyte and a mixed solvent of PC and DME as a solvent.
(i) 'CB Get, release'ajlI completed (7) Li
B Fa (i) 5 degrees is 4 zol/-f or more, and the concentration of LI F3 F 4 at the end of charging is controlled to be 1 mol/l or less. PC,! :D
The mixing ratio of ME is not particularly limited, but is usually 10 to 90% by volume of PC and 90 to 10% by volume of DME, preferably 30 to 70% by volume of PC and 70 to 30% by volume of DME. .
前記した鞘囲内での支持電解質及び混合溶媒を用いるこ
とによって、電解液量を著しく低減することができ、電
池のエネルーに一密度を著しく高めることができ、工業
的に非常に有用である。By using the above-mentioned supporting electrolyte and mixed solvent within the sheath, the amount of electrolyte can be significantly reduced, and the energy density of the battery can be significantly increased, which is very useful industrially.
本発明の二次電池において、ポリアニリン系化合物にド
ープされるドーパントの闇は、酸化重合体中のＮ原子１
原子に対して０．２〜１．５モルであり、好ましくは０
．２〜１．５モルである。In the secondary battery of the present invention, the darkness of the dopant doped into the polyaniline compound is due to the fact that 1 N atom in the oxidized polymer
0.2 to 1.5 mol per atom, preferably 0
．． It is 2 to 1.5 moles.
ドー７１は、電解の際に流れた°眉気聞を測定すること
によって自由にｉｌｉ＋Ｊ Ｗすることができる。−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ってもよい
。Do 71 can freely perform ili+JW by measuring the amount of air flowing during electrolysis. - The doping can be carried out either under constant current or under constant voltage or under conditions of varying current and voltage.
本発明においては、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Ｍ紙を隔
膜として用いても差し支えない。In the present invention, if necessary, a porous membrane made of synthetic resin such as polyethylene or polypropylene or natural fiber M paper may be used as the diaphragm.
また、本発明の二次電池に用いられる電極のある種のも
のは、酸素または水と反応して電池の性能を低下させる
場合もあるので、電池は密閉式にして実質的に無酸素お
よび無水の状態であることが望ましい。In addition, some of the electrodes used in the secondary battery of the present invention may react with oxygen or water and reduce the performance of the battery, so the battery should be sealed and substantially oxygen-free and water-free. It is desirable that the condition is as follows.
以下、実施例および比較例を示して本発明をさらに詳細
に説明する。Hereinafter, the present invention will be explained in more detail by showing Examples and Comparative Examples.
実施例１
くポリアニリン電極の製造〉
予め脱酸素した蒸留水４００ｄと４２重氾％ＨＢＦ４水
溶液１００ｍを１ノの三つロフラスコに入れ、撹拌下約
１時間、窒素ガスをバブリングさせた。その後、系内を
窒素ガス雰囲気にし、温度計、コンデンサーを取り付【
プ、次いでフラスコを水と氷で、冷却して溶液温度を１
５℃にした。これに、アニリン２０ｇを加えた。モノマ
ーが溶解した後、過硫酸アンモニウム２２Ｑを一度に加
え、撹拌下、内温を２５℃以下に保ちながら、５時間反
応さ「た。反応終了後、緑褐色の反応液を）濾過し、真
空乾燥して濃緑色の生成物１５ｇを得た。Example 1 Production of Polyaniline Electrode> 400 d of distilled water that had been previously deoxygenated and 100 ml of a 42% HBF4 aqueous solution were placed in a three-necked flask, and nitrogen gas was bubbled through the flask for about 1 hour while stirring. After that, create a nitrogen gas atmosphere inside the system, and install a thermometer and condenser [
The flask was then cooled with water and ice to bring the solution temperature to 1.
The temperature was set at 5°C. To this was added 20 g of aniline. After the monomer was dissolved, ammonium persulfate 22Q was added all at once, and the reaction was continued for 5 hours while stirring and keeping the internal temperature below 25°C. After the reaction was completed, the greenish-brown reaction liquid was filtered and dried under vacuum. 15 g of a dark green product was obtained.
この生成物１ｇに対してアセトン１００ＣＣを加え、室
温で３時間撹拌後、スラリー液を１濾過し、固形分を回
収した。次いで、新たに１００ＣＣのアヒトンを加え上
記と同じ操作を繰り返した。この操作を３回繰り返した
ところ、）１液の着色は殆んどなくなった。得られたポ
リアニリンをアンモニア水溶液で処理して前記した式（
３）のエメラルディン構造のポリアニリン粉末を得た。100 cc of acetone was added to 1 g of this product, and after stirring at room temperature for 3 hours, the slurry liquid was filtered to collect the solid content. Next, 100 CC of ahitone was newly added and the same operation as above was repeated. When this operation was repeated three times, the coloring of liquid 1 had almost disappeared. The obtained polyaniline was treated with an aqueous ammonia solution to obtain the formula (
3) Polyaniline powder having an emeraldine structure was obtained.
このポリアニリン粉末に１０重間％のポリテトラフロロ
エチレンと１０重け％のカーボン・ブラックを添加し、
室温で５００に！Ｊ／ｃｄの圧力で加圧成型して電極を
作製した。Adding 10% by weight of polytetrafluoroethylene and 10% by weight of carbon black to this polyaniline powder,
500 at room temperature! An electrode was produced by pressure molding at a pressure of J/cd.
〈膜状アセチレン高重合体の製造〉
窒素雰囲気で内容積５００成のガラス製反応容器に１．
７ｍのチタニウムテトラブトキサイドを加え、３０７！
のアニソールに溶かし、次いで２．７１ｎｌのトリエチ
ルアルミニウムを撹拌しながら加えて触媒溶液を調整し
た。<Production of film-like acetylene polymer> 1.
Add 7m of titanium tetrabutoxide, 307!
of anisole and then 2.71 nl of triethylaluminum was added with stirring to prepare a catalyst solution.
この反応溶液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、この反応溶液を一７８
℃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ぎ込んだ。This reaction solution was cooled with liquid nitrogen, and the nitrogen gas in the system was evacuated using a vacuum pump. Next, this reaction solution was diluted with
After cooling to 0.degree. C. and keeping the catalyst solution stationary, purified acetylene gas at a pressure of 1 atmosphere was bubbled through.
直ちに、触媒溶液表面で重合が起り、膜状のアセチレン
、￥Ｊｉ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ｔＪＪ各で除去した
後、−７８℃に保ったまま生成トルエン１００Ｉｎ１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、フィブリルが密に絡み合った均一な膜
状膨潤物であった。Immediately, polymerization occurred on the surface of the catalyst solution, producing a film of acetylene and \Ji polymer. Thirty minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. After removing the catalyst solution by pouring tJJ each time under a nitrogen atmosphere, it was repeatedly washed 5 times with 100 Inl of generated 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 intertwined.
次いで、この膨潤物を真空乾燥して金属光沢を有づ゛る
赤紫色の厚さ１８０μｍで、シス含［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０．３０（Ｊ／ＣＣであり、その電気
伝導度（直流四端子法）は２０℃で３．２Ｘ１０’Ω−
１・α−１であった。Next, this swollen product was vacuum-dried to obtain a cis-containing [98%] membranous acetylene polymer having a reddish-purple color and a thickness of 180 μm and having a metallic luster. In addition, the bulk density of this film-like acetylene polymer is 0.30 (J/CC), and its electrical conductivity (DC four-probe method) is 3.2X10'Ω- at 20°C.
It was 1.α-1.
〈電池試販〉
前記の方法で１ｑられたポリアニリン電極（直径２０ｍ
の円板状物）および前記膜状アセチレン高重合体から切
り抜いた直径２０ｒＮＲの円板状のものを、それぞれ正
極および負極の活物質として、電池を構成した。<Battery trial sale> Polyaniline electrode (diameter 20 m) prepared by the above method.
A battery was constructed using a disk-shaped object (disk-shaped object) and a disk-shaped object with a diameter of 20 rNR cut out from the film-like acetylene polymer as active materials for the positive and negative electrodes, respectively.
第１図は、本発明の一興体例である二次電池の特性測定
用電池セルの断面概略図で、図中１は負極用白金リード
線、２は直径２０ｍｍ、８０メツシユの負極白金網集電
体、３は直径２０ｍｍの円板状負極、４は直径２０＃ｌ
ｌＩ＋の円形の多孔性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２０ｍの円
板状正極、６は直径２０ｍ、８０メツシユの正極白金網
集電体、７はリード線、８はねじ込み式ポリテトラフ［
１０エチレン製容器を示す。FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a secondary battery, which is an example of the present invention. In the figure, 1 is a platinum lead wire for the negative electrode, and 2 is a negative electrode platinum wire mesh current collector with a diameter of 20 mm and 80 meshes. body, 3 is a disc-shaped negative electrode with a diameter of 20 mm, 4 is a diameter of 20 #l
lI+ circular porous polypropylene diaphragm with a thickness sufficient to be impregnated with electrolyte; 5 is a disk-shaped positive electrode with a diameter of 20 m; 6 is a positive electrode platinum wire mesh current collector with a diameter of 20 m and 80 mesh; 7 is a Lead wire, 8 is a screw-in polyte trough [
10 ethylene container is shown.
まず、前記、正極白金網集電体６を容器８の凹部の下部
に入れ、さらに正極５を、正極白金網集電体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（（、負４ｆＡ３を重ね、さら
にその上に負極白金編集７ｒ１体２を載置し、容器８を
締めつけて電池を作製した。First, the positive electrode platinum wire mesh current collector 6 is placed in the lower part of the recess of the container 8, and the positive electrode 5 is stacked on the positive electrode platinum wire mesh current collector 6, and the porous polypropylene diaphragm 4 is stacked on top of it. −
The electrolytic solution was sufficiently impregnated ((, negative 4fA3 was stacked, and the negative electrode platinum edited 7r1 body 2 was further placed on top of it, and the container 8 was tightened to produce a battery.
電解液としては、常法に従って蒸留脱水したブロビレン
カーボネートと１．２−ジメトキシエタン〈体積比が１
＝１）混合溶媒に溶解したＬｉＢＦ４の５ｍｏｌ／ｊ溶
液０．７ｃｃを用いた。The electrolyte was brobylene carbonate and 1,2-dimethoxyethane (volume ratio: 1), which had been distilled and dehydrated according to a conventional method.
=1) 0.7 cc of a 5 mol/j solution of LiBF4 dissolved in a mixed solvent was used.
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（２，０ｍＡ／ｃｉ）で正極および負
極へのドーピングｈ１がそれぞれ４８ｍｏ１％および６
ＩｌｌＯ１％に相当する電気量を流して充電した。充電
終了時の電解液中のＬｌ’ＢＦ４の濃度は０．５ｍｏｌ
／ｌであった。充電終了後、直ちに一定電流下（３゜
５ ｍ Ａ ／ ｃｉ ）で、放電を行ない電池電圧が
０．１０Ｖになっ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ったところ、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（サイクル寿命）は、６３５回を記録した。Using the thus prepared battery, doping h1 to the positive and negative electrodes was 48 mo1% and 6 mo1%, respectively, under constant current (2.0 mA/ci) in an argon atmosphere.
It was charged by flowing an amount of electricity equivalent to 1% IllO. The concentration of Ll'BF4 in the electrolyte at the end of charging is 0.5 mol
/l. Immediately after charging, the battery was discharged under a constant current (3°5 mA/ci), and when the battery voltage reached 0.10V, the battery was charged again under the same conditions as above.A repeated charge/discharge test was conducted. However, the number of repetitions of charging and discharging (cycle life) was recorded as 635 times before the charging and discharging efficiency decreased to 50%.
また繰り返し回数５回目のエネルギー密度は、電極活吻
質及び電解液の重量当り、１１０Ｗ−ｈｒ／Ｋｙで、最
高充・放電効率は１００％であった。Furthermore, the energy density at the fifth repetition was 110 W-hr/Ky per weight of electrode active proboscis and electrolyte, and the maximum charge/discharge efficiency was 100%.
また、充電したままで７５時間放置したところ、その自
己放電率は２．０％であった。When the battery was left charged for 75 hours, its self-discharge rate was 2.0%.
比較例１
実施例１の電池実験において用いた５ｍｏｌ／ｌのＬＩ
Ｂ Ｆ ４ ／ Ｐ Ｃ＋ Ｄ Ｍ Ｅの電解液の代
りに１ｍｏｌ／ｌの電解液を用いた他は実施例と同じ条
件で電池試験を行なった。その結果、サイクル寿命は５
９回、エネルギー密度は、１１０Ｗ−ｈｒ／に９で、最
高充・放電効率は７２％、自己放電率は３９．４％であ
った。Comparative Example 1 5 mol/l LI used in the battery experiment of Example 1
A battery test was conducted under the same conditions as in the example except that a 1 mol/l electrolyte was used instead of the B F 4 /P C+ D M E electrolyte. As a result, the cycle life is 5
In the 9th cycle, the energy density was 110 W-hr/9, the highest charge/discharge efficiency was 72%, and the self-discharge rate was 39.4%.
比較例２
電池実験において用いた５ｍｏｌ／ｌのＬＩＢＦ４／Ｐ
Ｃ＋ＤＭＥの電解液を１，５ｄ用いた他は実施例１と全
く同じ条件で電池試験を行なった。充電終了時のＬＩ
Ｂ Ｆ ４のｏｒｘは２．７ｍｏｌ ／ｉであった。そ
の結果、ナイクル寿命は６０９回、エネルギー密度は、
９６Ｗ −ｈ ｒ／Ｋｙ−（：、最高充・放電効率は１
００％、自己放電率は２．１％であった。Comparative Example 2 5 mol/l LIBF4/P used in battery experiment
A battery test was conducted under exactly the same conditions as in Example 1, except that 1.5 d of C+DME electrolyte was used. LI at the end of charging
The orx of B F 4 was 2.7 mol/i. As a result, the Nykle lifespan is 609 times, and the energy density is
96W -hr/Ky-(:, maximum charge/discharge efficiency is 1
00%, and the self-discharge rate was 2.1%.
実施例２
実施例１で得られたエメラルディン構造のポリアニリン
粉末をヒドラジン水溶液に浸漬して還元し、前記式（４
）の構造を持つルイコエメラルディンとした。このルイ
コエメラルディンに１１０ｆｆ１％のポリテトラフロロ
エヂレンと１０重覆％のカーボン・ブラックを添加し、
室温で５００Ｋｙ／ｄの圧力で加圧成型して電極を作成
した。Example 2 The polyaniline powder having an emeraldine structure obtained in Example 1 was reduced by immersing it in an aqueous hydrazine solution to obtain the formula (4).
) with the structure of leucoemeraldine. To this leucoemeraldine, 110ff1% polytetrafluoroethylene and 10% carbon black were added,
An electrode was prepared by pressure molding at a pressure of 500 Ky/d at room temperature.
この電極を正極に、負極にＬｌ−＃＝９４：６、（重量
比）合金を用い、６ｍｏｌ／ｌのＬＩＢＦ４／ＰＣ＋Ｄ
ＭＥ （ＰＣ： ＤＭＥ＝６０ ： ４０容量比）を０
．６ｍ用いた他は実施例１と全く同様な方法で電池実験
を行なった。充電終了時のＬＩ Ｂ Ｆ ４の濃度は０
．６５ｍｏｌ ／ノであった。この電池のサイクル寿命
は７７３回、エネルギー密度は、１３５Ｗ−ｈ ｒ／Ｋ
ｇテ、ｍ Ｓ 充・ｆｉｌｌ 電効率ハ１００％、自己
放電率は５．４％であった。This electrode was used as the positive electrode, Ll-#=94:6, (weight ratio) alloy was used as the negative electrode, and 6 mol/l LIBF4/PC+D
ME (PC: DME=60:40 capacity ratio) is 0
．． A battery experiment was conducted in exactly the same manner as in Example 1 except that 6 m was used. The concentration of LI B F 4 at the end of charging is 0
．． It was 65 mol/no. This battery has a cycle life of 773 cycles and an energy density of 135 W-hr/K.
gTe, mS Charge/fill The electric efficiency was 100%, and the self-discharge rate was 5.4%.
実施例３
実施例１で得られたエメラルディン構造のポリアニリン
粉末をｐＨ＝１のＨＢＦ４水溶液に浸；ｄして、ＨＢＦ
ａで錯化（プロトネーション）させた。得られた錯化ポ
リアニリンを正極に用いた他は実施例２と全く同様な方
法で電池実験を行なった。その結果、サイクル寿命は７
２９回、エネルギー密度は、１３０Ｗ−ｈｒ／Ｋｇで、
最高充・放電効率は１００％、自己放電率は６．７％で
あった。Example 3 The polyaniline powder with the emeraldine structure obtained in Example 1 was immersed in an aqueous solution of HBF4 at pH=1.
It was complexed (protonated) with a. A battery experiment was conducted in exactly the same manner as in Example 2, except that the obtained complexed polyaniline was used for the positive electrode. As a result, the cycle life is 7
29 times, the energy density was 130W-hr/Kg,
The highest charge/discharge efficiency was 100%, and the self-discharge rate was 6.7%.
実施例４
アセチレン高重合体の代りにアセチレン高重合体とＮの
１：１（重量比）の複合体を用いた他は、実施例１と全
く同じ方法で電池試験を行なった。Example 4 A battery test was conducted in exactly the same manner as in Example 1, except that a 1:1 (weight ratio) composite of acetylene polymer and N was used instead of the acetylene polymer.
その結果、サイクル寿命は７２１回、エネルギー密度は
、１１３Ｗ−ｈｒ／Ｋｇで、ｉ高充−放電効率は１００
％、自己放電率は４．９％であった。As a result, the cycle life was 721 times, the energy density was 113 W-hr/Kg, and the i-high charge-discharge efficiency was 100
%, and the self-discharge rate was 4.9%.
実施例１〜４、比較例１，２の結果を一括し第１表に示
す。The results of Examples 1 to 4 and Comparative Examples 1 and 2 are summarized in Table 1.
（発明の効果〕
本発明の二次電池は、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、自己放電率が小さ
く、放電時の電圧の平坦性が良好である。また、本発明
の二次電池は、軽Ｍ１小型で、かつ高いエネルギー密度
を有するからポータプル機器、電気自動車、ガソリン自
動車および電力貯蔵型バッテリーとして最適である。(Effects of the Invention) The secondary battery of the present invention has high energy density, high charge/discharge efficiency, long cycle life, low self-discharge rate, and good voltage flatness during discharge. Further, the secondary battery of the present invention is small in size and has a high energy density, so it is suitable for use in portable devices, electric vehicles, gasoline vehicles, and power storage batteries.
第１図は本発明の一具体例である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FIG. 1 is a schematic cross-sectional view of a battery cell for measuring characteristics of a 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 lead wire
Claims (1)
属、（ｉｉ）アルカリ金属合金、（ｉｉｉ）電導性高分
子、或いは（ｉｖ）電導性高分子とアルカリ金属または
アルカリ金属合金との複合体から選ばれた物質で、かつ
電解液がＬｉＢＦ＿４およびプロピレンカーボネートと
１・２−ジメトキシエタンの混合溶媒からなる二次電池
において、該電解液中のＬｉＢＦ＿４の濃度が放電終了
時に４ｍｏｌ／ｌ以上で、充電終了時に１ｍｏｌ／ｌ以
下であることを特徴とする二次電池。The positive electrode is a polyaniline compound, and the negative electrode is selected from (i) an alkali metal, (ii) an alkali metal alloy, (iii) a conductive polymer, or (iv) a composite of a conductive polymer and an alkali metal or an alkali metal alloy. In a secondary battery in which the electrolyte is made of LiBF_4 and a mixed solvent of propylene carbonate and 1,2-dimethoxyethane, charging is completed when the concentration of LiBF_4 in the electrolyte is 4 mol/l or more at the end of discharge. A secondary battery characterized in that the concentration is sometimes 1 mol/l or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61200583A JPS6355867A (en) | 1986-08-27 | 1986-08-27 | Secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61200583A JPS6355867A (en) | 1986-08-27 | 1986-08-27 | Secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6355867A true JPS6355867A (en) | 1988-03-10 |
Family
ID=16426754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61200583A Pending JPS6355867A (en) | 1986-08-27 | 1986-08-27 | Secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6355867A (en) |
-
1986
- 1986-08-27 JP JP61200583A patent/JPS6355867A/en active Pending
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