JP2934933B2 - Electrochromic display device - Google Patents
Electrochromic display deviceInfo
- Publication number
- JP2934933B2 JP2934933B2 JP5271251A JP27125193A JP2934933B2 JP 2934933 B2 JP2934933 B2 JP 2934933B2 JP 5271251 A JP5271251 A JP 5271251A JP 27125193 A JP27125193 A JP 27125193A JP 2934933 B2 JP2934933 B2 JP 2934933B2
- Authority
- JP
- Japan
- Prior art keywords
- electrochromic display
- electrochromic
- display device
- film
- bpdp
- 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
- 239000000463 material Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- OJTMBXWTXBFVQN-UHFFFAOYSA-N iron;1,10-phenanthroline Chemical compound [Fe].C1=CN=C2C3=NC=CC=C3C=CC2=C1 OJTMBXWTXBFVQN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 239000003115 supporting electrolyte Substances 0.000 description 5
- 229910020808 NaBF Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 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 description 3
- 229960003351 prussian blue Drugs 0.000 description 3
- 239000013225 prussian blue Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- -1 bathophenanthroline iron complex Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、電解析出法により成膜
が可能な鉄−フェナントロリン錯体を用い、その酸化還
元反応を利用した、赤と無色の表示が可能なエレクトロ
クロミック表示素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic display device capable of displaying red and colorless color using an oxidation-reduction reaction of an iron-phenanthroline complex which can be formed into a film by an electrolytic deposition method.
【0002】[0002]
【従来の技術】従来、赤色エレクトロクロミック材料で
あるフェノール基を有するバソフェナントロリン鉄錯体
は、図1に示す結合構造のトリス(バソフェナントロリ
ンジフェノール)鉄(II)錯体(以下Fe(BPDP)
3 と示す)であって、本出願人が先に提案した特開平4
−29220号に示されるように電解析出法により成膜
され、支持電解質として過塩素酸ナトリウム(NaCl
O4 )を0.1mol/lの濃度で含むアセトニトリル
電解液中において、プルシアンブルーを対向極として一
万回以上の色変化(赤と薄黄色)と0.5秒以下の応答
速度を達成することができた。2. Description of the Related Art Conventionally, a red electrochromic material, a bathophenanthroline iron complex having a phenol group, is a tris (basophenanthroline diphenol) iron (II) complex (hereinafter Fe (BPDP)) having a bonding structure shown in FIG.
3 ), which is disclosed in Japanese Patent Laid-Open No.
No.-29220, a film was formed by an electrolytic deposition method, and sodium perchlorate (NaCl) was used as a supporting electrolyte.
In an acetonitrile electrolyte containing O 4 ) at a concentration of 0.1 mol / l, a color change (red and pale yellow) of 10,000 times or more and a response speed of 0.5 seconds or less are achieved using Prussian blue as a counter electrode. I was able to.
【0003】しかしこのFe(BPDP)3 の膜は、図
2に示す様な片側に透明導電膜1、7を形成した透明基
板1、8のそれぞれの内側に表示極エレクトロクロミッ
ク材料4、対向極エレクトロクロミック材料6を設け
て、背景材5を介して対向させ、上下をシール材3で囲
んだ空間に電解液9を充填したエレクトロクロミック表
示素子において、駆動用電解液溶媒9にアセトニトリル
(接着剤の剥離液に使用される)を使用すると、それに
耐えられるシール材3が無いため、素子の構成が困難で
あるという問題があった。However, this Fe (BPDP) 3 film is composed of a display electrode electrochromic material 4 and a counter electrode inside each of transparent substrates 1 and 8 having transparent conductive films 1 and 7 formed on one side as shown in FIG. In an electrochromic display element in which an electrochromic material 6 is provided and opposed to each other with the background material 5 interposed therebetween, and a space surrounded by the sealing material 3 on the upper and lower sides is filled with an electrolyte 9, acetonitrile (adhesive However, there is no sealing material 3 that can withstand such a problem, and there is a problem that the configuration of the element is difficult.
【0004】この駆動用電解液の問題は、エレクトロク
ロミック表示素子を構成する上で非常に重要なポイント
である。一方電解液9に水溶液が使用できれば、様々な
接着剤(例えばUV硬化型)をシール材3として使用で
きるため、大きなメリットとなる。ところが以前の実験
では、表示極材料4であるFe(BPDP)3 は、対向
極材料6にプルシアンブルーを使用して塩化ナトリウム
(NaCl)を0.1mol/lの濃度に含む水溶液中
で駆動すると著しい特性劣化を起すことが確認されたた
め、駆動用電解液として水が使用できなかった。[0004] The problem of the driving electrolyte is a very important point in forming an electrochromic display element. On the other hand, if an aqueous solution can be used for the electrolytic solution 9, various adhesives (for example, UV curing type) can be used as the sealing material 3, which is a great merit. However, in the previous experiment, Fe (BPDP) 3 as the display electrode material 4 was driven in an aqueous solution containing sodium chloride (NaCl) at a concentration of 0.1 mol / l using Prussian blue for the counter electrode material 6. Since it was confirmed that remarkable deterioration of characteristics was caused, water could not be used as the driving electrolyte.
【0005】ところで、Fe(BPDP)3 膜は、鉄錯
体が2価から3価へ酸化されることにより赤色から薄黄
色に変化し、再還元されることにより元の赤色に戻る。
この一連の反応を化1に示す。[0005] The Fe (BPDP) 3 film changes from red to light yellow when the iron complex is oxidized from divalent to trivalent, and returns to the original red color by being reduced again.
This series of reactions is shown in Chemical formula 1.
【0006】[0006]
【化1】 Embedded image
【0007】上記化1式からわかるように、消色時のF
e(BPDP)3 膜は+に帯電しているため、その電荷
を補償するための−電荷すなわちアニオンを膜中に取り
込まなければならない。また着色時にはアニオンを電解
液へ放出しなければ元の赤色に戻れない。従って繰り返
し駆動の安定性は、アニオンの種類にかなりの影響を受
けるものと考えられる。As can be seen from the above formula 1, F
Since the e (BPDP) 3 film is positively charged, a − charge, ie, an anion, for compensating the charge must be incorporated into the film. In addition, during coloring, the color cannot be returned to the original red color unless anions are released into the electrolytic solution. Therefore, it is considered that the stability of repetitive driving is considerably affected by the type of anion.
【0008】[0008]
【発明が解決しようとする課題】解決しようとする課題
は、Fe(BPDP)3 を表示極材料として構成された
エレクトロクロミック表示素子の繰り返し駆動の安定性
向上のために、最適な支持電解質を見つけ出すことであ
る。The problem to be solved is to find an optimum supporting electrolyte in order to improve the stability of repetitive driving of an electrochromic display element composed of Fe (BPDP) 3 as a display electrode material. That is.
【0009】[0009]
【問題を解決するための手段】本発明は、Fe(BPD
P)3 に組み合わされる支持電解質を従来のNaClか
ら四フッ化ホウ素酸塩(NaBF4 )に変更すること
で、繰り返し駆動寿命の問題を改善するものである。SUMMARY OF THE INVENTION The present invention relates to Fe (BPD).
By changing the supporting electrolyte combined with P) 3 from conventional NaCl to tetrafluoroboronate (NaBF 4 ), the problem of the repeated driving life is improved.
【0010】[0010]
【実施例】以下に実施した実験例を実施例として述べ
る。検討した駆動用支持電解質は、カチオン(陽イオ
ン)をナトリウム(Na+ )、濃度を0.1mol/l
に固定し、アニオンの異なる支持電解質を用意した。こ
の電解質は、塩化ナトリウム(NaCl)、過塩素酸ナ
トリウム(NaClO4 )、硝酸ナトリウム(NaNO
3 )、四フッ化ホウ素酸ナトリウム(NaBF4 )の4
種類である。評価方法はFe(BPDP)3 膜を成膜し
た電極についてサイクリックボルタンメトリーを連続し
て測定し、得られたボルタモグラムのピーク電流値の変
化を追跡することによって繰り返し駆動の安定性を評価
した。サイクリックボルタンメトリーは3電極法にて実
施し、対極には白金そして参照電極には飽和カロメル電
極を使用した。また、この時の走査速度は20mV/s
ec、走査電位幅は0V←→+1.5Vvsにて実施し
た。EXAMPLES Examples of experiments performed below will be described as examples. The supporting electrolyte for driving examined was a cation (cation) of sodium (Na + ) and a concentration of 0.1 mol / l.
And supporting electrolytes having different anions were prepared. This electrolyte comprises sodium chloride (NaCl), sodium perchlorate (NaClO 4 ), sodium nitrate (NaNO).
3 ) 4 of sodium tetrafluoroborate (NaBF 4 )
Kind. In the evaluation method, cyclic voltammetry was continuously measured on the electrode on which the Fe (BPDP) 3 film was formed, and the change in peak current value of the obtained voltammogram was traced to evaluate the stability of repeated driving. Cyclic voltammetry was performed by a three-electrode method, using platinum as a counter electrode and a saturated calomel electrode as a reference electrode. The scanning speed at this time is 20 mV / s.
ec, the scanning potential width was set at 0 V ← → + 1.5 V vs.
【0011】その結果、図3に示されるように、ほとん
どの場合においてサイクリックボルタモグラムの電流値
が減少するなかでNaBF4 のみ低下率が少なく、繰り
返し寿命回数が数倍改善される結果が得られた。この時
Fe(BPDP)3 の繰り返し駆動に必要なイオンは陰
イオンであるため、BF4 塩であれば対陽イオンはナト
リウムに限定されるものではなく、H+ 、Li+ 、
K+ 、Rb+ などであっても問題ない。またNaBF4
の添加濃度は0.01mol/l〜1mol/lの範囲
内であれば問題なく駆動可能であるが、特に0.05m
ol/l〜0.5mol/lの範囲であることが望まし
い。As a result, as shown in FIG. 3, in most cases, while the current value of the cyclic voltammogram decreases, only NaBF 4 has a small decrease rate, and the result that the number of times of repeated life is improved several times is obtained. Was. At this time, the ion necessary for the repetitive driving of Fe (BPDP) 3 is an anion, so that the counter cation is not limited to sodium in the case of BF 4 salt, and H + , Li + ,
There is no problem even if it is K + , Rb + or the like. NaBF 4
Can be driven without any problem as long as the addition concentration is in the range of 0.01 mol / l to 1 mol / l.
It is desirably in the range of ol / l to 0.5 mol / l.
【0012】また今回は3電極法による評価によって発
明の効果を確認したが、例えばプルシアンブルーや酸化
タングステン(WO3 )あるいは金属フタロシアニンの
ように還元反応が安定なエレクトロクロミック材料を対
向極材料として使用すれば、容易に赤色表示可能なエレ
クトロクロミック表示部材の素子化が可能であることは
言うまでもない。In this case, the effect of the present invention was confirmed by the evaluation using the three-electrode method. For example, an electrochromic material such as Prussian blue, tungsten oxide (WO 3 ), or metal phthalocyanine, whose reduction reaction is stable, was used as the counter electrode material. If it does, it cannot be overemphasized that the electrochromic display member which can display red easily can be made into an element.
【0013】[0013]
【発明の効果】以上述べたように、電解析出法により得
られた鉄−フェナントロリン錯体を用いたエレクトロク
ロミック表示素子において、その駆動用電解液に四フッ
化ホウ素酸塩水溶液を使用した結果、繰り返し駆動寿命
が従来の水溶液系に比べて数倍改善される効果が得られ
た。このことによりエレクトロクロミック表示素子を構
成するためのシール剤として有機高分子系の接着剤が使
用できるようになり、従来困難であった赤色表示可能な
エレクトロクロミック表示素子の提供を実現できる。As described above, in an electrochromic display device using an iron-phenanthroline complex obtained by an electrolytic deposition method, as a result of using an aqueous solution of tetrafluoroboronate as a driving electrolyte, The effect that the repetition drive life was improved several times compared with the conventional aqueous solution system was obtained. As a result, an organic polymer-based adhesive can be used as a sealant for forming an electrochromic display element, and it is possible to provide an electrochromic display element capable of displaying red, which has been conventionally difficult.
【図1】Fe(BPDP)3 の構造式である。FIG. 1 is a structural formula of Fe (BPDP) 3 .
【図2】エレクトロクロミック表示素子の断面図であ
る。FIG. 2 is a sectional view of an electrochromic display element.
【図3】繰り返し駆動寿命の評価結果である。FIG. 3 is an evaluation result of a repetitive driving life.
1、8 透明基板 2、7 透明導電膜 3 シール材 4 表示極エレクトロクロミック材料 5 背景材 6 対向極エレクトロクロミック材料 9 電解液 1, 8 transparent substrate 2, 7 transparent conductive film 3 sealing material 4 display electrode electrochromic material 5 background material 6 counter electrode electrochromic material 9 electrolyte
───────────────────────────────────────────────────── フロントページの続き (72)発明者 英 謙二 長野県上田市常田3−15−1 信州大学 繊維学部機能高分子学科内 (72)発明者 白井 汪芳 長野県上田市常田3−15−1 信州大学 繊維学部機能高分子学科内 (58)調査した分野(Int.Cl.6,DB名) G02F 1/15 - 1/163 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenji Ei 3-15-1 Tsuneda, Ueda City, Nagano Prefecture Shinshu University, Department of Functional Polymer Science (72) Inventor Hiroyoshi Shirai 3-15-, Tsuneda, Ueda City, Nagano Prefecture 1 Shinshu University Faculty of Textile Science and Technology Department of Functional Polymers (58) Fields surveyed (Int. Cl. 6 , DB name) G02F 1/15-1/163
Claims (1)
ントロリン錯体を表示極エレクトロクロミック材料とし
て用い、その酸化還元反応を利用することにより赤と無
色の表示が可能なエレクトロクロミック表示素子におい
て、電解液に四フッ化ホウ素酸塩水溶液を使用したこと
を特徴とするエレクトロクロミック表示素子。An electrochromic display device capable of displaying red and colorless by utilizing an iron-phenanthroline complex capable of forming a film by an electrolytic deposition method as a display electrode electrochromic material and utilizing its oxidation-reduction reaction. An electrochromic display element, wherein an aqueous solution of tetrafluoroboronate is used as an electrolytic solution.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5271251A JP2934933B2 (en) | 1993-10-04 | 1993-10-04 | Electrochromic display device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5271251A JP2934933B2 (en) | 1993-10-04 | 1993-10-04 | Electrochromic display device |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07104321A JPH07104321A (en) | 1995-04-21 |
JP2934933B2 true JP2934933B2 (en) | 1999-08-16 |
Family
ID=17497474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5271251A Expired - Lifetime JP2934933B2 (en) | 1993-10-04 | 1993-10-04 | Electrochromic display device |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2934933B2 (en) |
-
1993
- 1993-10-04 JP JP5271251A patent/JP2934933B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH07104321A (en) | 1995-04-21 |
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