JPH01651A - Active materials for batteries - Google Patents
Active materials for batteriesInfo
- Publication number
- JPH01651A JPH01651A JP62-92551A JP9255187A JPH01651A JP H01651 A JPH01651 A JP H01651A JP 9255187 A JP9255187 A JP 9255187A JP H01651 A JPH01651 A JP H01651A
- Authority
- JP
- Japan
- Prior art keywords
- batteries
- polymer
- thienyl
- active material
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011149 active material Substances 0.000 title claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- AYBFWHPZXYPJFW-AATRIKPKSA-N 2-[(e)-2-thiophen-2-ylethenyl]thiophene Chemical compound C=1C=CSC=1/C=C/C1=CC=CS1 AYBFWHPZXYPJFW-AATRIKPKSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- -1 polyphenylene Polymers 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- BOJMHHBWYPDQQH-UHFFFAOYSA-N 3-ethenylthiophene Chemical compound C=CC=1C=CSC=1 BOJMHHBWYPDQQH-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- FDRNXKXKFNHNCA-UHFFFAOYSA-N 4-(4-anilinophenyl)-n-phenylaniline Chemical compound C=1C=C(C=2C=CC(NC=3C=CC=CC=3)=CC=2)C=CC=1NC1=CC=CC=C1 FDRNXKXKFNHNCA-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 １４分！ 本発明は電池用の新規な高分子活物質に関する。[Detailed description of the invention] 14 minutes! The present invention relates to novel polymeric active materials for batteries.
従速４０支４
近年、共役２重粘合を有する高分子材料を活物質として
用いた有機２次電池が種々提案されている０例えばＪ
、Ｃｈｅｍ、 Ｓｏｃ、 Ｃｈｅ＋ｍ、 Ｃｏｍｍｕｎ
、。Speed-driven 40 supports 4 In recent years, various organic secondary batteries using polymeric materials with conjugated double viscosity as active materials have been proposed.
, Chem, Soc, Che+m, Commun
,.
３１７（１９８１） ； Ｊ 、 Ｅｌｅｃｔｒｏｃｈ
ｅｍ、 Ｓｏｃ、、 １２８．１６５１（１９８１）等
にはポリアセチレンを用いた電池が。317 (1981); J. Electroch.
EM, Soc, 128.1651 (1981), etc. contain batteries using polyacetylene.
Ｊ 、 ＣｈｅＩｌ、 Ｓｏｃ、 Ｃｈｅｗ、 Ｃｏｍ
＋ｍｕｎ、、 ３６１（１９８２）にはポリフェニレン
を用いた電池が、特開昭６１−２１６４７０号にはポリ
ピロールを用いた電池が、またフランス特許第２５５３
５８１号にはポリアニリンを用いた電池が提案されてい
る。J,CheIl,Soc,Chew,Com
+mun,, 361 (1982) describes a battery using polyphenylene, JP-A-61-216470 discloses a battery using polypyrrole, and French Patent No. 2553 discloses a battery using polypyrrole.
No. 581 proposes a battery using polyaniline.
且−一旌
本発明の目的は従来のポリアセチレン、ポリフェニレン
等の高分子材料と同様に電池用活物質として使用できる
新規な電池用高分子活物質を提供することである。An object of the present invention is to provide a novel polymer active material for batteries that can be used as an active material for batteries in the same way as conventional polymer materials such as polyacetylene and polyphenylene.
盪−一處
本発明の電池用活物質は１，２−ジ（２−チエニル）エ
テン及びその誘導体の重合体よりなるものである。(2) The active material for batteries of the present invention is composed of a polymer of 1,2-di(2-thienyl)ethene and its derivatives.
本発明者らは一般式■
（ｎは自然数、ＲはＨ又は炭素数１〜
３のアルキル基）
で示される化合物が共鳴構造を持つことやチオフェン骨
格に２カ所のα位が存在することから電気化学的重合が
容易である可能性のあること、更にはポリチオフェンや
ポリアセチレンと同様。The present inventors discovered that the compound represented by the general formula (where n is a natural number and R is H or an alkyl group having 1 to 3 carbon atoms) has a resonance structure and that there are two α-positions in the thiophene skeleton. Possibly easy to electrochemically polymerize, even similar to polythiophene and polyacetylene.
一般式■の化合物の重合体が共役系高分子として電池用
活物質としての可能性があることから一般式Ｉの化合物
について種々重合し、その活物質特性を調べた。その結
果、一般式Ｉ中ｎが１である１、２−ジ（２−チエニル
）エテン及びｎが１で、Ｒがメチル基である１−（４−
メチル−２−チエニル）−２−（２−チエニル）エテン
の重合体が優れた電池用活物質であることを見出し、本
発明に到達した。Since the polymer of the compound of the general formula (1) has the possibility of being used as a conjugated polymer as an active material for batteries, various compounds of the general formula (I) were polymerized and the properties of the active materials were investigated. As a result, 1,2-di(2-thienyl)ethene in the general formula I where n is 1 and 1-(4-thienyl)ethene where n is 1 and R is a methyl group.
It has been discovered that a polymer of methyl-2-thienyl)-2-(2-thienyl)ethene is an excellent active material for batteries, and the present invention has been achieved.
本発明の重合体は前述のように電気化学的方法によって
容易に製造できる。この電気化学的方法は一般的には例
えばＪ、Ｅｌｅｃｔｒｏｃｈｅｍ、 Ｓａｃ。The polymer of the present invention can be easily produced by electrochemical methods as described above. This electrochemical method is generally described, for example, in J. Electrochem, Sac.
Ｖｏｌ、１３０．Ｎｏ’７．１５０６〜１５０９（１９
８３） ； Ｅｌｅｃｔｒｏｃｈｉｍｉｃａ Ａｃｔａ
Ｖｏｌ、２７． Ｎｏ １．６１〜６５（１９８２）
； Ｊ、Ｃｈｅｍ。Vol, 130. No'7.1506-1509 (19
83) ; Electrochimica Acta
Vol, 27. No. 1.61-65 (1982)
; J, Chem.
Ｓｏｃ、、Ｃｈｅ＋ａ、Ｃｏ＋ａｍｕｎ、１１９９ （
１９８４）等に示されるものであるが、本発明において
は単量体と電解質とを溶媒に溶解した液を電解槽中で陽
極酸化による電解重合反応させることにより行なわれる
。この場合、電解質としてはＬｉＰＦ、 、 Ｌｉ５ｂ
Ｆ、 。Soc,, Che+a, Co+amun, 1199 (
In the present invention, a monomer and an electrolyte are dissolved in a solvent and subjected to an electrolytic polymerization reaction by anodic oxidation in an electrolytic bath. In this case, the electrolyte is LiPF, , Li5b
F.
ＬｉＡｓＦ、 、 ＬｉＣｍ Ｏ４，ＮａＣ１０，：
ＫＩ、ＫＰＦ、 、 ＫＳｂＦ４゜ＫＡｓＦ、、 ＫＣ
ＱＯ，、ＡｇＢＦ４． ＮａＢＦ４． ＮａＡｓＦ、、
ＮａＰＦ、。LiAsF, , LiCm O4, NaC10,:
KI, KPF, , KSbF4゜KAsF,, KC
QO,,AgBF4. NaBF4. NaAsF...
NaPF,.
（（ｎ−Ｃ４Ｈり４Ｎ）” −（Ａ８Ｆｓ）−ｔ （（
ｎ−Ｃ４Ｈ９）Ｎ）” −ＣＱＯｌ−、ＬｉＡＱＣＱ、
、或いはＦｅＣＱａ、ＡＱＣＱ３゜ＺｎＣＱ、、 ＡＱ
Ｂｒ、、 ＢＦ、等のフリーデルクラフト反応用触媒等
が使用できる。また溶媒としてはアセトニトリル、ベン
ゾニトリル、プロピレンカーボネート、γ−ブチロラク
トン、ジクロルメタン、ジオキサン、ジメチルホルムア
ミド、又はニトロメタン、ニトロエタン、ニトロプロパ
ン、ニトロベンゼン等のニトロ系溶媒が使用できる。な
お陽極酸化用の電極を構成する材料としては例えばＡｕ
、Ｐｔ、Ｎｉ等の金属−１ＳｎＯ，。((n-C4Hri4N)" -(A8Fs)-t ((
n-C4H9)N)” -CQOl-, LiAQCQ,
, or FeCQa, AQCQ3゜ZnCQ,, AQ
Friedel-Crafts reaction catalysts such as Br, BF, etc. can be used. As the solvent, acetonitrile, benzonitrile, propylene carbonate, γ-butyrolactone, dichloromethane, dioxane, dimethylformamide, or nitro solvents such as nitromethane, nitroethane, nitropropane, and nitrobenzene can be used. The material constituting the electrode for anodic oxidation is, for example, Au.
, Pt, Ni, etc.-1SnO,.
Ｉｎ、０３等の金属酸化物、又はそれらの複合体或いは
被覆物等が使用できる。Metal oxides such as In and 03, or composites or coatings thereof can be used.
電解法としては定電圧電解、定電流電解及び定電位電解
のいずれも可能であるｈ＜、定電圧及び定電流電解が適
しており、特に量産の面からは定電流電解が好ましい、
また電流密度の調整は膜のモルフオロジーに大きな影響
を与えるので重要であり、電解液の成分の組合せによっ
て微妙に変化させる必要がある０本発明高分子材料の場
合、この電流密度は１．０〜２．０ｍＡ／’ａｊの範囲
が好ましい。As the electrolytic method, any of constant voltage electrolysis, constant current electrolysis, and constant potential electrolysis are possible. Constant voltage and constant current electrolysis are suitable, and constant current electrolysis is particularly preferable from the standpoint of mass production.
In addition, adjusting the current density is important as it has a large effect on the morphology of the membrane, and it is necessary to change it delicately depending on the combination of components of the electrolyte.In the case of the polymer material of the present invention, this current density is 1.0. A range of ~2.0 mA/'aj is preferred.
しかし本発明の高分子材料の製造法は以上のように電気
化学的に重合できるが、製法については特に制限される
ものではない。However, although the method for producing the polymer material of the present invention allows electrochemical polymerization as described above, the production method is not particularly limited.
いずれにしてもこうして得られる１、２−ジ（２−チエ
ニル）エテン及びその誘導体の重合体の重合度は１０以
上であることが好ましい。In any case, the degree of polymerization of the polymer of 1,2-di(2-thienyl)ethene and its derivatives thus obtained is preferably 10 or more.
以上のようにして得られる本発明の重合体材料は電池用
の活物質として使用されるが、本発明の活物質を正極に
用いた場合、この正極活物質に対して用いられる負極活
物質としてはＬｉ。The polymer material of the present invention obtained as described above is used as an active material for batteries, but when the active material of the present invention is used as a positive electrode, it is used as a negative electrode active material for this positive electrode active material. is Li.
Ｚｎ、Ｃｕ、Ａｇ等の金属やアセチレン、ベンゼン、チ
オフェン、ジフェニルベンジジン等の有機物質を原料と
した有機高分子材料が挙げられる。いずれにしても電池
の電圧は正極と負極との電位の差として表わされるため
、正極及び負極の活物質としては夫々適切な電位を持つ
ものを選択して組合せる必要がある。Examples include organic polymer materials made from metals such as Zn, Cu, and Ag, and organic substances such as acetylene, benzene, thiophene, and diphenylbenzidine. In any case, since the voltage of a battery is expressed as the difference in potential between the positive electrode and the negative electrode, it is necessary to select and combine active materials for the positive and negative electrodes each having an appropriate potential.
以上のような電池用高分子正極活物質は電解゛液中の電
解質を構成するアニオンによってドープされてエネルギ
ーを貯え、脱ドープによって外部回路を通してエネルギ
ーを放出するものである。このようなアニオンドーパン
トとしてはＰＦｓ−ｔ ＳｂＦ、−、ＡｓＦ、−、５ｂ
ＣＱ、−等のＶａ族元素のハロゲン化物アニオン： Ｂ
Ｆ４−のようなｍａ族元素のハロゲン化物アニオン；Ｃ
ｉ、−のような過塩素酸塩アニオン等が挙げられる。ま
たこれらドーパントを与える化合物（電池の電解液中の
電解質）の具体例としてはＬｉＰＦ、、 Ｌｉ５ｂＦ４
゜ＬｉＡｓＦ、、 ｔ、ｉｃｇｏ、、 ＮａＣＱ０４．
ＫＩ、 ＫＰＦ、、 ＫＳｂＦ４゜ＫＡｇＦ、、 Ｋ
ＣＱＯ４，［（ｎ−Ｃ４Ｈ，） ４Ｎ］” ・ＡｓＦ、
−。The polymer positive electrode active material for batteries as described above is doped with anions constituting an electrolyte in an electrolytic solution to store energy, and releases energy through an external circuit by dedoping. Such anion dopants include PFs-t SbF, -, AsF, -, 5b
Halide anion of Va group element such as CQ, -: B
Halide anion of ma group element such as F4-;C
i, perchlorate anions such as -, and the like. Specific examples of compounds that provide these dopants (electrolytes in battery electrolytes) include LiPF, Li5bF4
゜LiAsF,, t, icgo,, NaCQ04.
KI, KPF,, KSbF4゜KAgF,, K
CQO4, [(n-C4H,) 4N]” ・AsF,
−.
（（ｎ−Ｃ４Ｈ，）、Ｎ）”・ＣＩＩ Ｏ４−、ＬｉＡ
ｆＡ ＣＱ ４． ＬｉＢＦ４等がある。((n-C4H,), N)"・CII O4-, LiA
fA CQ 4. There are LiBF4 etc.
また電池の電解液の溶媒としては非プロトン性で、且つ
誘電率の大きい極性非プロトン性溶媒と云われるものが
好ましい、具体的には例えばケトン類、ニトリル類、エ
ステル類、エーテル類、カーボネート類、ニトロ化合物
、スルホラン系化合物、或いはそれらの混合物等が挙げ
られるが、これらの中でもニトリル類、カーボネート類
、スルホラン系化合物が好ましい。これらの代表例とし
てはアセトニトリル、プロピオニトリル、ブチロニトリ
ル、バレロニトリル、ベンゾニトリル、エチレンカーボ
ネート、プロピレンカーボネート、γ−ブチロラクトン
、スルホラン、３−メチルスルホラン等が挙げられる。In addition, as the solvent for the battery electrolyte, it is preferable to use a polar aprotic solvent that is aprotic and has a high dielectric constant, such as ketones, nitriles, esters, ethers, and carbonates. , nitro compounds, sulfolane compounds, and mixtures thereof, among which nitriles, carbonates, and sulfolane compounds are preferred. Typical examples of these include acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, ethylene carbonate, propylene carbonate, γ-butyrolactone, sulfolane, 3-methylsulfolane, and the like.
以下に本発明を実施例によって説明する。The present invention will be explained below by way of examples.
実施例
１．２−ジ（２−チエニル）エテン２０Ｂ及びテトラフ
ルオロ硼酸元トラブチルアンモニウム６６０ｍｇをアセ
トニトリル２０ＩＩＱに溶解した電解液に、陽極として
ネサガラス（３０Ω／ｄ）、陰極としてＮｉ板を浸漬し
、３．５ｖの定電圧電解を行なってネサガラス上に１，
２−ジ（２−チエニル）エテン重合体を製造した。Example 1. Nesa glass (30 Ω/d) as an anode and a Ni plate as a cathode were immersed in an electrolytic solution in which 2-di(2-thienyl)ethene 20B and 660 mg of original trabutylammonium tetrafluoroborate were dissolved in acetonitrile 20IIQ, Perform constant voltage electrolysis at 3.5V and apply 1,
A 2-di(2-thienyl)ethene polymer was produced.
次に重合体が付着したネサガラスを第１図に示すように
正極１（２はネサガラス、３は前記重合体）とし、また
Ｌｉを負極４としてＬＭ−ＬｉＢ Ｆ４炭酸プロピレン
溶液からなる電解液５中で１，２−ジ（２−チエニル）
エテン重合体の充放電特性を充放電測定装置６で測定し
た。その結果を第２図に示す。また下記方法により開放
電圧、クーロン効率及びエネルギー効率を測定したとこ
ろ、夫々３．８Ｖ、８０％、７４％の結果が得られた。Next, as shown in FIG. 1, Nesa glass with the polymer attached was used as a positive electrode 1 (2 is Nesa glass, 3 is the above polymer), and Li was used as a negative electrode 4 in an electrolytic solution 5 consisting of LM-LiB F4 propylene carbonate solution. 1,2-di(2-thienyl)
The charge/discharge characteristics of the ethene polymer were measured using a charge/discharge measuring device 6. The results are shown in FIG. Further, when the open circuit voltage, coulomb efficiency, and energy efficiency were measured by the following methods, results of 3.8 V, 80%, and 74% were obtained, respectively.
開放電圧：
両電極端子間電圧を充電して１０分間放置後について測
定。Open circuit voltage: Measure the voltage between both electrode terminals after charging and leaving for 10 minutes.
クーロン効率、エネルギー効率：
定電流（０，１ｍＡ／ａ＃）により充放電を行なって測
定。Coulomb efficiency, energy efficiency: Measured by charging and discharging with constant current (0.1 mA/a#).
なおこの構成の電池の充放電の可能な繰返し回数は数千
回以上であった。The battery with this configuration could be charged and discharged several thousand times or more.
羞−一果
以上の如く本発明の１．２−ジ（２−チエニル）エテン
系重合体は第２図の充放電特性曲線から判るように、電
池用活物質としての性能を備えている。As can be seen from the charge-discharge characteristic curve of FIG. 2, the 1,2-di(2-thienyl)ethene polymer of the present invention has performance as an active material for batteries.
第１図は実施例で作った電池の充放電特性を測定するた
めの装置図、第２図は本発明の１，２−ジ（２−チエニ
ル）エテン重合体の充放電特性曲線図である。
１・・・ネサガラス２に本発明の重合体３を付着した正
極
４・・・Ｌｉ負極 ５・・・電解液６・・・充放
電測定装置
煽穂１
Ｊ１−
帛１ 図
用２図
埒間（介）Fig. 1 is a diagram of an apparatus for measuring the charge/discharge characteristics of the battery made in the example, and Fig. 2 is a diagram of the charge/discharge characteristic curve of the 1,2-di(2-thienyl)ethene polymer of the present invention. . DESCRIPTION OF SYMBOLS 1... Positive electrode 4... Li negative electrode 5... Electrolyte solution 6... Charge/discharge measuring device 1 (Intermediate)
Claims (1)
る電池用活物質。A battery active material comprising a 1,1,2-di(2-thienyl)ethene polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092551A JP2536865B2 (en) | 1987-03-24 | 1987-04-15 | Battery active material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6777387 | 1987-03-24 | ||
| JP62-67773 | 1987-03-24 | ||
| JP62092551A JP2536865B2 (en) | 1987-03-24 | 1987-04-15 | Battery active material |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH01651A true JPH01651A (en) | 1989-01-05 |
| JPS64651A JPS64651A (en) | 1989-01-05 |
| JP2536865B2 JP2536865B2 (en) | 1996-09-25 |
Family
ID=26408987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62092551A Expired - Lifetime JP2536865B2 (en) | 1987-03-24 | 1987-04-15 | Battery active material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2536865B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4519269A (en) * | 1981-06-19 | 1985-05-28 | Clarion Co., Ltd. | Transmission system in a cam mechanism |
| CN114649509A (en) * | 2022-04-07 | 2022-06-21 | 楚能新能源股份有限公司 | Method for preparing anode of lithium ion battery |
-
1987
- 1987-04-15 JP JP62092551A patent/JP2536865B2/en not_active Expired - Lifetime
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