JPH0381909A - Material for ledox reaction pole of electrochemical element - Google Patents
Material for ledox reaction pole of electrochemical elementInfo
- Publication number
- JPH0381909A JPH0381909A JP1218817A JP21881789A JPH0381909A JP H0381909 A JPH0381909 A JP H0381909A JP 1218817 A JP1218817 A JP 1218817A JP 21881789 A JP21881789 A JP 21881789A JP H0381909 A JPH0381909 A JP H0381909A
- Authority
- JP
- Japan
- Prior art keywords
- redox
- reactive material
- ion
- reaction electrode
- conductive polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title abstract description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 4
- 239000011147 inorganic material Substances 0.000 claims abstract description 4
- 239000011368 organic material Substances 0.000 claims abstract description 4
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 4
- 238000006479 redox reaction Methods 0.000 claims description 21
- 229920001940 conductive polymer Polymers 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 12
- 230000004044 response Effects 0.000 abstract description 6
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 abstract description 4
- 229960003351 prussian blue Drugs 0.000 abstract description 4
- 239000013225 prussian blue Substances 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 description 11
- 239000010409 thin film Substances 0.000 description 10
- 229920000767 polyaniline Polymers 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000000178 monomer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- -1 polyparaphenylene Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、電気化学素子のレドックス反応極用材料に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a material for a redox reaction electrode of an electrochemical device.
従来の技術
レドックス活性点をもつレドックス反応性材料として、
既に多くの材料が知られている。例えば、ＷＯ３ｓ プ
ルシアンブルー、ポリアニリン等が例示される。これら
は、電池、エレクトロクロミック素子、センサー コン
デンサー等のレドックス反応極用材料に用いられている
。Conventional technologyAs a redox-reactive material with redox active sites,
Many materials are already known. For example, WO3s Prussian blue, polyaniline, etc. are exemplified. These are used as materials for redox reaction electrodes in batteries, electrochromic devices, sensors, capacitors, etc.
発明が解決しようとする課題
上記レドックス反応極用材料を使う電池ではエネルギー
密度の改善が、エレクトロクロミック素子では応答性の
改善が、あるいは、センサーでは感度の改善が強く望壕
れている。レドックス反応極において酸化還元反応がよ
り速やかに進行すれば、上記要望が満たせることになる
ので、これに沿って新規な反応極用材料を開発すべく研
究が進められている。しかし、期待に沿うような材料は
なかなか得られない。Problems to be Solved by the Invention There is a strong desire to improve the energy density of batteries that use the above redox reaction electrode materials, the responsiveness of electrochromic devices, and the sensitivity of sensors. If the oxidation-reduction reaction progresses more rapidly in the redox reaction electrode, the above requirements can be met, and research is being conducted to develop new materials for the reaction electrode in line with this. However, it is difficult to obtain materials that meet expectations.
この発明は、上記事情に鑑み、反応がより速やかに進行
する電気化学素子のレドックス反応極用材料を提供する
ことを課題とする。In view of the above circumstances, it is an object of the present invention to provide a material for a redox reaction electrode of an electrochemical device in which a reaction proceeds more quickly.
課題を解決するための手段
前記課題を解決するため、請求項１〜３の発明は、以下
のような構成をとるようにしている。Means for Solving the Problems In order to solve the problems described above, the inventions of claims 1 to 3 have the following configurations.
請求項１のレドックス反応極用材料は、レドックス反応
性材料とイオン導電性高分子を複合化するようにしてな
る材料である。The redox reaction electrode material according to claim 1 is a material formed by combining a redox-reactive material and an ion-conductive polymer.
請求項１のレドックス反応極用材料では、レドックス反
応性材料として、例えば、請求項２記載のレドックス反
応極用材料のように、遷移金属酸化物系無機材料や高分
子系有機材料が用いられる。In the redox reaction electrode material according to claim 1, for example, a transition metal oxide-based inorganic material or a polymer-based organic material is used as the redox-reactive material, as in the redox reaction electrode material according to claim 2.
レドックス反応性材料を、より具体的に挙げれば、ＷＯ
２，ＭｏＯ３，ＴｉＯ２等の遷移金属酸化物やプルシア
ンブルー等を始めとする無機材料、あるいは、ポリアニ
リン、ポリチオフェン、ポリピロール、ポリアセチレン
、ポリパラフェニレン等の各種の導電性高分子や、スチ
リル類似化合物、ビオロゲン誘導体等を始めとする有機
材料等がある。もちろん、これらの材料に限らないこと
はいう１でもない。More specifically, redox-reactive materials include WO
2. Inorganic materials such as transition metal oxides such as MoO3 and TiO2 and Prussian blue, various conductive polymers such as polyaniline, polythiophene, polypyrrole, polyacetylene, and polyparaphenylene, styryl-like compounds, and viologen. There are organic materials such as derivatives, etc. Of course, it is not limited to these materials.
請求項１または２のレドックス反応極用材料では、イオ
ン導電性高分子として、例えば、請求項３記載の発明の
ように、高分子−金属塩ハイブリッド体やポリカチオン
−ポリアニオン複合体を用いるようにしている。In the redox reaction electrode material according to claim 1 or 2, for example, as in the invention according to claim 3, a polymer-metal salt hybrid or a polycation-polyanion complex is used as the ion-conductive polymer. ing.
イオン導電性高分子を、より具体的に挙げれば、ポリエ
チレンオキシド、ポリエチレンオキシド−ＬｉＣＩＯ４
系化合物、易重合性リン酸エステルマクロマー−アルカ
リ金属塩系などの高分子−金属塩ハイブリッド体あるい
は、ポリカチオン−ポリアニオン複合体等がある。もち
ろん、これらの・・材料に限らないことはいう壕でもな
い。More specific examples of ion conductive polymers include polyethylene oxide, polyethylene oxide-LiCIO4
Examples include polymer-metal salt hybrids such as easily polymerizable phosphate ester macromer-alkali metal salt systems, and polycation-polyanion complexes. Of course, it is not limited to these materials.
レドックス反応性材料とイオン導電性高分子の複合化は
、例えば、イオン導電性高分子薄膜とレドックス反応性
材料を積層化したり、イオン導電性高分子とレドックス
反応性材料であるポリアニリンを渾然一体化したりする
こと等でなされる。Composites of redox-reactive materials and ion-conductive polymers include, for example, laminating ion-conductive polymer thin films and redox-reactive materials, or harmoniously integrating ion-conducting polymers and polyaniline, which is a redox-reactive material. This is done by doing things like
作 用
この発明のレドックス反応性材料で酸化反応が起こる場
合、レドックス活性点がカチオンとなり、その対イオン
としてのアニオンがイオン導電性高分子を通って速やか
にレドックス活性点の近くにくるようになる。Function When an oxidation reaction occurs in the redox-reactive material of the present invention, the redox active site becomes a cation, and the anion as a counter ion quickly comes close to the redox active site through the ionically conductive polymer. .
また、この発明のレドックス反応性材料で還元反応が起
こる場合、レドックス活性点がアニオンとなり、その対
イオンとしてのカチオンが、やはり酸化反応の場合と同
様、イオン導電性高分子を通って速やかにレドックス活
性点の近くにくるようになる。In addition, when a reduction reaction occurs with the redox-reactive material of this invention, the redox active site becomes an anion, and the cation as a counter ion quickly undergoes redox through the ion-conductive polymer, as in the case of an oxidation reaction. It comes close to the active point.
このように、この発明のレドックス反応極用材料では、
イオン導電性高分子の働きにより反応がより速やかに進
行するようになるのである。In this way, in the redox reaction electrode material of this invention,
The action of the ion-conductive polymer allows the reaction to proceed more quickly.
捷た、レドックス反応性材料が、例えば、プルシアンブ
ルーのように比較的イオンを通し易いような場合でも、
イオン導電性高分子を複合させることにより、より対イ
オンが通り易くなる。Even if the redox-reactive material is relatively permeable to ions, such as Prussian blue,
By combining an ion conductive polymer, counter ions can pass through more easily.
実施例 続いて、この発明の詳細な説明する。Example Next, the present invention will be explained in detail.
一実施例１−
電極基材表面に予めイオン導電性高分子であるポリエチ
レンオキシド薄膜を形成して訃いてから、レドックス反
応性材料であるポリアニリン薄膜を形成しレドックス反
応極用材料を得た。Example 1 - A thin film of polyethylene oxide, which is an ion-conductive polymer, was previously formed on the surface of an electrode base material, and then a thin film of polyaniline, which is a redox-reactive material, was formed to obtain a material for a redox reaction electrode.
薄膜の形成は電解重合法を用いて行うようにした。ポリ
エチレンオキシド薄膜形成の場合、ポリエチレンオキシ
ドのモノマーおよび／またはオリゴマーと支持電解質を
含む水溶液を用いて電解重合させ、ポリアニリン薄膜形
成の場合、ポリアニリンのモノマー訃よび／またはオリ
ゴマーと支持電解質を含む水溶液を用いて電解重合させ
るようにした。The thin film was formed using an electrolytic polymerization method. In the case of forming a polyethylene oxide thin film, electropolymerization is performed using an aqueous solution containing a polyethylene oxide monomer and/or oligomer and a supporting electrolyte, and in the case of forming a polyaniline thin film, an aqueous solution containing a polyaniline monomer and/or oligomer and a supporting electrolyte is used. Then, electrolytic polymerization was carried out.
上のことから分かるように、この実施例のレドックス反
応極用材料では、イオン導電性高分子薄膜とレドックス
反応性材料薄膜が積層されることにより複合化されてい
る。As can be seen from the above, the redox reaction electrode material of this example is made into a composite material by laminating an ion-conductive polymer thin film and a redox-reactive material thin film.
一実施例２−
電極基材表面にイオン導電性高分子であるポリエチレン
オキシドとレドックス反応性材料であるポリアニリンが
渾然と混じり合った状態の薄膜を形成しレドックス反応
極用材料を得た。Example 2 - A thin film in which polyethylene oxide, which is an ion-conductive polymer, and polyaniline, which is a redox-reactive material, are thoroughly mixed was formed on the surface of an electrode base material to obtain a material for a redox-reactive electrode.
この場合、薄膜の形成を電解重合法を用いて行うように
した。この場合には、ポリエチレンオキシドのモノマー
訃よび／またはオリゴマー、ポリアニリンのモノマー訃
よび／またはオリゴマー訃よび、支持電解質を含む水溶
液を用いて電解重合させるようにした。In this case, the thin film was formed using an electrolytic polymerization method. In this case, electrolytic polymerization was carried out using an aqueous solution containing a polyethylene oxide monomer and/or oligomer, a polyaniline monomer and/or oligomer, and a supporting electrolyte.
上のことから分かるように、この実施例のレドックス反
応極用材料では、イオン導電性高分子とレドックス反応
性材料が渾然と混じり合った状態となることにより複合
化されている。As can be seen from the above, in the redox reaction electrode material of this example, the ion-conductive polymer and the redox-reactive material are mixed harmoniously into a composite.
実施例１および実施例２のレドックス反応極用材料を使
ってエレクトロクロミック素子を作製し、その応答速度
を調べた。比較のために、実施例に釦いてイオン導電性
高分子を用いない他は同様にしてエレクトロクロミック
素子を作製し、その応答速度を調べた。Electrochromic devices were produced using the redox reaction electrode materials of Examples 1 and 2, and their response speeds were investigated. For comparison, an electrochromic device was prepared in the same manner as in the example except that the ion conductive polymer was not used, and its response speed was investigated.
そして、実施例と比較例の応答速度を比べた結果、この
発明の実施例のレドックス反応極用材料ヲ使ったエレク
トロクロミック素子の方が、約３０％程度、応答性が向
上していた。As a result of comparing the response speed of the example and the comparative example, it was found that the electrochromic element using the redox reaction electrode material of the example of the present invention had improved response by about 30%.
この発明は上記実施例に限らない。例えば、複合化がレ
ドックス反応性材料とイオン導電性高分子の一方を芯と
し、他方をこの芯を包む鞘とすることでなされていても
よい。また、この発明のレドックス反応極用材料は、電
池やセンサー コンデンサー等のエレクトロクロミック
素子以外の電気化学素子に用いることができることはい
う壕でもない。This invention is not limited to the above embodiments. For example, the composite may be made by using one of the redox-reactive material and the ion-conductive polymer as a core, and using the other as a sheath surrounding the core. Further, it is not implied that the redox reaction electrode material of the present invention can be used for electrochemical devices other than electrochromic devices such as batteries, sensors, and capacitors.
発明の効果
以上に述べたように、この発明の電気化学素子のレドッ
クス反応極用材料を用いた場合、反応が速やかに進行す
るため、応答速度の速いエレクトロクロミック素子、エ
ネルギー密度の高い電池、あるいは、感度が優れたセン
サ等が実現できるようになる。Effects of the Invention As mentioned above, when the material for the redox reaction electrode of an electrochemical device of the present invention is used, the reaction proceeds quickly, so it can be used for electrochromic devices with fast response speed, batteries with high energy density, or , sensors with excellent sensitivity can be realized.
Claims (3)
合されてなる電気化学素子のレドックス反応極用材料。(1) A material for a redox reaction electrode of an electrochemical device, which is a composite of a redox-reactive material and an ion-conductive polymer.
材料および高分子系有機材料のうちから選ばれている請
求項１記載の電気化学素子のレドックス反応極用材料。(2) The material for a redox reaction electrode of an electrochemical device according to claim 1, wherein the redox-reactive material is selected from transition metal oxide-based inorganic materials and polymer-based organic materials.
ッド体およびポリカチオン−ポリアニオン複合体のうち
から選ばれている請求項１または２記載の電気化学素子
のレドックス反応極用材料。(3) The material for a redox reaction electrode of an electrochemical device according to claim 1 or 2, wherein the ionically conductive polymer is selected from a polymer-metal salt hybrid and a polycation-polyanion complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1218817A JPH0381909A (en) | 1989-08-25 | 1989-08-25 | Material for ledox reaction pole of electrochemical element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1218817A JPH0381909A (en) | 1989-08-25 | 1989-08-25 | Material for ledox reaction pole of electrochemical element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0381909A true JPH0381909A (en) | 1991-04-08 |
Family
ID=16725812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1218817A Pending JPH0381909A (en) | 1989-08-25 | 1989-08-25 | Material for ledox reaction pole of electrochemical element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0381909A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1010733A2 (en) * | 1998-12-17 | 2000-06-21 | Samsung General Chemicals Co., Ltd. | Polymer composition for coatings with high refractivity conductivity and transparency |
| JP2012063525A (en) * | 2010-09-15 | 2012-03-29 | Sekisui Plastics Co Ltd | Composite particle, and manufacturing method and use of the same |
| CN103613759A (en) * | 2013-12-06 | 2014-03-05 | 东华大学 | Preparation method of MoO3/polyaniline coaxial nano heterojunction |
| WO2017111004A1 (en) * | 2015-12-25 | 2017-06-29 | 国立研究開発法人産業技術総合研究所 | Deformation sensor |
-
1989
- 1989-08-25 JP JP1218817A patent/JPH0381909A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1010733A2 (en) * | 1998-12-17 | 2000-06-21 | Samsung General Chemicals Co., Ltd. | Polymer composition for coatings with high refractivity conductivity and transparency |
| EP1010733A3 (en) * | 1998-12-17 | 2002-07-03 | Cheil Industries Inc. | Polymer composition for coatings with high refractivity conductivity and transparency |
| JP2012063525A (en) * | 2010-09-15 | 2012-03-29 | Sekisui Plastics Co Ltd | Composite particle, and manufacturing method and use of the same |
| CN103613759A (en) * | 2013-12-06 | 2014-03-05 | 东华大学 | Preparation method of MoO3/polyaniline coaxial nano heterojunction |
| WO2017111004A1 (en) * | 2015-12-25 | 2017-06-29 | 国立研究開発法人産業技術総合研究所 | Deformation sensor |
| CN108369085A (en) * | 2015-12-25 | 2018-08-03 | 国立研究开发法人产业技术综合研究所 | Deformation-sensor |
| JPWO2017111004A1 (en) * | 2015-12-25 | 2018-10-18 | 国立研究開発法人産業技術総合研究所 | Deformation sensor |
| US10788307B2 (en) | 2015-12-25 | 2020-09-29 | National Institute Of Advanced Industrial Science And Technology | Deformation sensor comprising an ion-conductive polymer layer |
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