JPS58203417A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPS58203417A JPS58203417A JP57086744A JP8674482A JPS58203417A JP S58203417 A JPS58203417 A JP S58203417A JP 57086744 A JP57086744 A JP 57086744A JP 8674482 A JP8674482 A JP 8674482A JP S58203417 A JPS58203417 A JP S58203417A
- Authority
- JP
- Japan
- Prior art keywords
- counter electrode
- display element
- electrochromic display
- potential
- electrode
- 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
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
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】
本発明はエレクトロクロミック表示素子に関し、とくに
エレクトロクロミック表示素子（以下ＥＣＤと略す）の
対向電極の構成材料に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic display element, and particularly to a constituent material of a counter electrode of an electrochromic display element (hereinafter abbreviated as ECD).
ＥＣＤの構成は一般に第１図のようなっており、１はガ
ラス基板、２は背面容器、３は透明導電膜、４はＥＣ（
エレクトロクロミック）材料、６は多孔質板、６は対向
電極、７は電解液、８は接着剤、９は対向電極リードで
ある。The configuration of an ECD is generally as shown in Figure 1, where 1 is a glass substrate, 2 is a rear container, 3 is a transparent conductive film, and 4 is an EC (
6 is a porous plate, 6 is a counter electrode, 7 is an electrolytic solution, 8 is an adhesive, and 9 is a counter electrode lead.
２ベージ
ＥＣＤは対向電極９と表示電極３との間に電圧を印加す
ることにより、ＥＣ材料４を酸化、還元し、それにより
発色、消色を可逆的に行なう表示素子である。The two-base ECD is a display element that oxidizes and reduces the EC material 4 by applying a voltage between the counter electrode 9 and the display electrode 3, thereby reversibly coloring and decoloring.
ＥＣ材料は例えばＷＯ３のようなブロンズ構造をとりう
る材料が選ばれ、
ＷＯ＋ｘＭ＋＋ｘｅ 、２ＭｘＷＯ３（Ｍ：Ｈ、Ｌ
ｉ 、Ｎａ。For the EC material, a material that can take a bronze structure, such as WO3, is selected, and WO+xM++xe, 2MxWO3 (M:H, L
i, Na.
Ａｑなど）
なる酸化還元反応が起こりやすいアモルファス構造の薄
膜が用いられる。 、
一方対向電極は表示電極の酸化還元反応と逆の酸化還元
反応が起こる。従って対向電極は酸化還元反応が起こり
やすい材料で構成しなければならない。また対向電極の
電位が変動すると一定の電圧を表示電極と対向電極との
間に印加しても、酸化還元反応の電位は一定であるため
、反応が起りにくくなったり、他の反応が起ったりする
ことがある。更に電圧を印加していない場合の電位は安
定していても、電圧を印加して電流が流れるとき、に対
向電極の電位が移動することがある。A thin film with an amorphous structure in which redox reactions such as Aq) are likely to occur is used. , On the other hand, an oxidation-reduction reaction occurs at the counter electrode, which is the opposite of the oxidation-reduction reaction at the display electrode. Therefore, the counter electrode must be made of a material that easily undergoes redox reactions. Furthermore, if the potential of the counter electrode changes, even if a constant voltage is applied between the display electrode and the counter electrode, the potential of the redox reaction remains constant, so the reaction may become difficult to occur or other reactions may occur. Sometimes. Furthermore, even if the potential is stable when no voltage is applied, the potential of the opposing electrode may shift when a voltage is applied and a current flows.
３、。−０
対向電極に要求される性能として、酸化還元反応前後の
電位変化が小さいこと、対向電極の電位が表示電極の電
位と大きく異ならず安定していること、対向電極の構成
材料が電解液と反応したり溶解したりしないことがあげ
られる。3. -0 The performance required of the counter electrode is that the change in potential before and after the redox reaction is small, the potential of the counter electrode is stable and does not differ greatly from the potential of the display electrode, and the constituent material of the counter electrode is not mixed with the electrolyte. One example is that it does not react or dissolve.
ところが従来の対向電極では電位が安定し、表示に十分
な電流を流しうる材料は得られなかった。However, with conventional counter electrodes, the potential is stable and it has not been possible to obtain a material that can flow sufficient current for display.
本発明は安定な電位と十分な電流を得る目的で陽イオン
を層間に保有しうる層状の結晶構造をもち、かつ電解液
に安定である元素周期律表中の第４族すの元素のカルコ
ゲン化合物、ＭＩ２（ＭはＴｉ、Ｚｒ、Ｈｆのうちの少
なくとも一種、ＸはＳ、Ｓｅ、Ｔｅのうち少なくとも一
種）および第５族すの元素のカルコゲン化合物ＮＸ２（
Ｎは■。The present invention is a chalcogen of an element of Group 4 in the Periodic Table of Elements, which has a layered crystal structure capable of holding cations between layers and is stable in electrolyte solutions for the purpose of obtaining a stable potential and sufficient current. Compound, MI2 (M is at least one of Ti, Zr, Hf, X is at least one of S, Se, Te) and a chalcogen compound of group 5 element NX2 (
N is ■.
Ｎｂ、Ｔａのうちの少なくとも一種、ＸはＳ。At least one of Nb and Ta, and X is S.
Ｓｅ、Ｔｅのうちの少なくとも一種）及びこれらＭＩ２
．ＮＸ２と同じ結晶構造を有するＭＩ ＋Ｘ＼２゜Ｎ１
＋ｘｘ２（ｏくｘ〈１）を対向電極材料として用いるこ
とにより、前記従来の問題を解決しまう以下に本発明の
詳細な説明する。At least one of Se, Te) and these MI2
．． MI +X\2゜N1 which has the same crystal structure as NX2
The present invention will be described in detail below, in which the above-mentioned conventional problems are solved by using +xx2(oxx<1) as the counter electrode material.
実施例１
１５ｍｍＸ １５肛×０．１爺のＴｉ金属板を陽極とし
、陰極として黒鉛を用い、含水硫化ナトリウム（Ｎａ２
Ｓ・９Ｈ２０）融液を電解液として９ｏ０Ｃで＋７Ｖの
直流電解を２時間性々つだ。これを対向電極とし、表示
電極にＷＯ３，電解液にはＬｉＣ１○４ト電解質とした
プロピレンカーボネートを用いてＥＣＤを構成した。Example 1 A 15mm x 15mm x 0.1mm Ti metal plate was used as an anode, graphite was used as a cathode, and hydrated sodium sulfide (Na2
S・9H20) Using the melt as an electrolyte, conduct +7V DC electrolysis at 9o0C for 2 hours. An ECD was constructed using this as a counter electrode, WO3 as a display electrode, and propylene carbonate as an electrolyte with LiC1*4 as an electrolyte.
表示電極の面積は５繍×５諭−２５−であり、作成直後
、印加電圧−１ｖ、印加時間１秒で２５Ｃで書込電気量
を測定した結果５．５ｍＣ／ｃｒｌであった。このＥＣ
Ｄを７０Ｃに放置したものの書込電気量の変化を第２図
の曲線１として示す。The area of the display electrode was 5 cm x 5 cm -25 cm, and the amount of write electricity was measured at 25 C with an applied voltage of -1 V and an application time of 1 second immediately after creation, and the result was 5.5 mC/crl. This EC
Curve 1 in FIG. 2 shows the change in the amount of electricity written when D was left at 70C.
実施例２
Ｚｒ金属粉末２．３ｇ、Ｓｅ粉末４ｑを石英管中に真空
封入し、７０ＯＣで２４０時間保持した。Example 2 2.3 g of Zr metal powder and 4 q of Se powder were vacuum sealed in a quartz tube and held at 70OC for 240 hours.
これを粉砕し、６ｑのアセチレンブラックと４９のフッ
素樹脂粉末とを混合し、Ｔｉ金属製のネットを中間に入
れ、１５ｗｎＸ１６ｒｒｒｍｘｏ、３＝に加圧５ページ
成型して対向電極とした。This was pulverized, 6q of acetylene black and 49 of fluororesin powder were mixed, a Ti metal net was placed in the middle, and the mixture was molded under pressure for 5 pages to a size of 15wn x 16rrrmxo, 3= to form a counter electrode.
実施例１と同様にＥＣＤを構成し、測定した結果を第２
図の曲線２として示す。Configure the ECD in the same manner as in Example 1, and use the measured results in the second
It is shown as curve 2 in the figure.
実施例３
Ｔａ粉末４．５ｇ、Ｔｅ粉末６．４ｑを十分粉砕混合し
１５爺Ｘ１５胴Ｘ０．３ａに加圧成型したものを石英管
中に真空封入し９００Ｃで４００時間保持したのち、さ
らに５００Ｃで１５０時間焼鈍したのち室温まで放冷し
た焼結板を対向電極とし実施例１と同様にＥＣＤを構成
し、測定した結果を第２図の曲線３として示す。Example 3 4.5 g of Ta powder and 6.4 q of Te powder were thoroughly ground and mixed and pressure-molded into a 15 x 15 x 0.3 a cylinder, which was vacuum sealed in a quartz tube and held at 900C for 400 hours, then further heated at 500C. An ECD was constructed in the same manner as in Example 1 using a sintered plate that was annealed for 150 hours and then allowed to cool to room temperature as a counter electrode, and the measured results are shown as curve 3 in FIG.
第２図には実施例１と同様に構成したアセチレンブラッ
クのみの対向電極を曲線４．実施例２においてＺｒ５０
２に替えてＴｌＯ２粉末を用いた対向電極により構成し
たＥＣＤの測定結果を曲線６として示す。FIG. 2 shows a counter electrode made of only acetylene black, constructed in the same manner as in Example 1, with curve 4. In Example 2, Zr50
Curve 6 shows the measurement results of an ECD configured with a counter electrode using TlO2 powder instead of TlO2 powder.
初期より７０Ｃ１２時間放置後の書込電気量の変化以後
は本発明にかかる対向電極は従来例に比べ安定している
ことから対向電極として適切であることが分かる。It can be seen that the counter electrode according to the present invention is more stable than the conventional example from the initial stage to the change in the write electricity amount after being left at 70C for 12 hours, and is suitable as a counter electrode.
６ページ
この３例からも本発明に係る層状化合物は対向電極材料
としてぼれている。Page 6 These three examples also show that the layered compound according to the present invention can be used as a counter electrode material.
以上の説明により明らかなように本発明によると性能の
安定したＥＣＤを容易に得ることができる。As is clear from the above description, according to the present invention, an ECD with stable performance can be easily obtained.
第１図はエレクトロクロミック表示素子の構成を示す図
、第２図は本発明の詳細な説明するためのもので、単位
表示面積あたりの書込電気量の変化を示す図である。
１ ・・・・・ガラス基板、２・・・・・・背面容器、
３・表示電極、４・・・・・エレクトロクロミック材料
、５・・・・・・多孔質板、６・・・・・対向電極、７
・・・・・電解液、８・・・・・・接着剤、９・・・・
・対向電極リード。FIG. 1 is a diagram showing the structure of an electrochromic display element, and FIG. 2 is a diagram for explaining the present invention in detail, and is a diagram showing changes in the amount of electricity written per unit display area. 1...Glass substrate, 2...Back container,
3. Display electrode, 4... Electrochromic material, 5... Porous plate, 6... Counter electrode, 7
... Electrolyte, 8 ... Adhesive, 9 ...
・Counter electrode lead.
Claims (2)
４族す及び第５族すの元素のカルコゲン化合物のうち層
状の結晶構造を有する化合物を含有するこトラ特徴とす
るエレクトロクロミック表示素子。(1) An electrochromic display element characterized in that it contains a compound having a layered crystal structure among chalcogen compounds of elements of Groups 4 and 5 in the Periodic Table of Elements as a constituent material of the counter electrode.
されたことを特徴とする特許請求の範囲第１項記載のエ
レクトロクロミック表示素子。(2) The electrochromic display element according to claim 1, characterized in that carbon is mixed into a compound having a layered crystal structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57086744A JPS58203417A (en) | 1982-05-21 | 1982-05-21 | Electrochromic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57086744A JPS58203417A (en) | 1982-05-21 | 1982-05-21 | Electrochromic display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58203417A true JPS58203417A (en) | 1983-11-26 |
Family
ID=13895295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57086744A Pending JPS58203417A (en) | 1982-05-21 | 1982-05-21 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58203417A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6940485B2 (en) * | 2003-01-15 | 2005-09-06 | Xerox Corporation | Flexible micron-thin display device |
-
1982
- 1982-05-21 JP JP57086744A patent/JPS58203417A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6940485B2 (en) * | 2003-01-15 | 2005-09-06 | Xerox Corporation | Flexible micron-thin display device |
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