JPS5987431A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPS5987431A JPS5987431A JP57196999A JP19699982A JPS5987431A JP S5987431 A JPS5987431 A JP S5987431A JP 57196999 A JP57196999 A JP 57196999A JP 19699982 A JP19699982 A JP 19699982A JP S5987431 A JPS5987431 A JP S5987431A
- Authority
- JP
- Japan
- Prior art keywords
- soln
- electrolyte
- electrode
- solvent
- display 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
- G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (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
Description
【発明の詳細な説明】
本発明は、タングステン酸化物Ｗｏ３ を表示極に用い
たエレクトロクロミック表示素ボ以下ＥＣＤと略称する
）に関する１、
ψ
従来例の構成と問題点
ＷＯ３を表示極に用いたＥＣＤでは、ＷＯ３の耐水性が
弱く溶解し易いため一般に有機溶剤を用い過塩素酸リチ
ウム（ＬｉＣＩＯ４）などを電解質とする電解液を用い
ている。一方この電解液を用いた場合もＷＯ３がエレク
トロクロミック反応を示すためには若干の水分は必要と
されている。しかしながらその若干の水分によりＷＯ３
表示極の劣化が起こり、長期保存の後には所定の表示濃
度が得られないという状況にある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic display element (hereinafter abbreviated as ECD) using tungsten oxide Wo3 as a display electrode. In ECD, since WO3 has weak water resistance and is easily dissolved, an electrolytic solution using an organic solvent and lithium perchlorate (LiCIO4) or the like as an electrolyte is generally used. On the other hand, even when this electrolyte is used, a small amount of water is required for WO3 to exhibit an electrochromic reaction. However, due to some moisture, WO3
The situation is such that the display electrode deteriorates and a predetermined display density cannot be obtained after long-term storage.
一方フルオロ錯塩を電解液中に存在さぜると、ｗｏ３表
示極の劣化を防止することができることが知られている
。しかしながら、一般にフルオロ錯塩ばその製法−に、
遊離の酸を含有するものが多い。On the other hand, it is known that when a fluoro complex salt is present in the electrolytic solution, deterioration of the WO3 display electrode can be prevented. However, in general, the manufacturing method of fluoro complex salts is
Many contain free acids.
またこの含有量の少ないものでも、例えば、Ｌ Ｉ Ｂ
Ｆ ４＋ Ｈ２０＜ Ｌ ｉＢ Ｆ ３（ＯＨ）
十ＨＦであられされる如く、水分が存在すると酸を遊離
するものが多くこの結果、強い酸性となり、通常ＰＨが
２．６〜３．５で平衡するものがほとんどである。そし
て、プロピレンカーボネイトは強い酸性溶液に接触する
と極めて分解し易く、さらに水分が存在すると一層激し
い反応上する。したがって」二連の様にＷＯ３表示極を
保獲する作用を有していても溶媒を劣化させ、この結果
ＥＣＤとしての寿命が短かなものになってし甘うという
問題があった。Moreover, even if this content is small, for example, L I B
F 4+ H20< L iB F 3(OH)
As shown in 10HF, when water is present, many of them liberate acid, and as a result, they become strongly acidic, and most of them usually have an equilibrium pH of 2.6 to 3.5. Furthermore, propylene carbonate is extremely easy to decompose when it comes into contact with a strongly acidic solution, and the presence of moisture causes an even more violent reaction. Therefore, even if it has the effect of retaining the WO3 display electrode like a double series, it deteriorates the solvent, resulting in a problem that the life of the ECD is shortened.
発明の目的
本発明はＷＯ３表示極の劣化を防ぐとともに電解液の劣
化をも防ぎ、これにより耐久性のすぐれたＥＣＤが容易
に得られるようにすることを目的とする。OBJECTS OF THE INVENTION It is an object of the present invention to prevent deterioration of a WO3 display electrode and also prevent deterioration of an electrolytic solution, thereby making it possible to easily obtain an ECD with excellent durability.
発明の構成
本発明は、ＷＯ３表示極とその表示極に対向する対極間
に介在させる電解液として、微量の水分を含むポリプロ
ピレンカーボネイトを溶媒とし過塩素酸塩を電解質とす
る電解液を用いるとともに、水溶液のＰＨが４．５ 以
」二となるようなフルオロ錯塩を上記電解液中に存在せ
しめたものである。。Structure of the Invention The present invention uses an electrolytic solution in which polypropylene carbonate containing a trace amount of water is used as a solvent and perchlorate is used as an electrolyte, as an electrolytic solution interposed between a WO3 display electrode and a counter electrode facing the display electrode. A fluoro complex salt such that the pH of the aqueous solution is 4.5 or higher is present in the electrolyte. .
本発明によると、上述のように水溶液のＰＨが４．５以
上となるようなフルオロ錯塩を電解液中に存在せしめる
ことにより、ＷＯ３表示極の劣化を防ぐとともに溶媒の
劣化をも防止するものである。According to the present invention, as described above, by allowing a fluoro complex salt such that the pH of the aqueous solution is 4.5 or higher to be present in the electrolytic solution, deterioration of the WO3 display electrode is prevented and also deterioration of the solvent is prevented. be.
実施例の説明
図は本発明によるＥＣＤの断面図で、１は蒸発により形
成されたＷＯ３よりなる表示電極、２はカーボンからな
る対向電極、３は対向電極２に接続された電圧印加端子
、４は透明電極、５はガラス基板、６は表示電極１に接
続された電圧印加端子、アは背面容器、８は電解液、９
は多孔性アルミナからなる反射板である。The explanatory diagram of the embodiment is a sectional view of the ECD according to the present invention, in which 1 is a display electrode made of WO3 formed by evaporation, 2 is a counter electrode made of carbon, 3 is a voltage application terminal connected to the counter electrode 2, and 4 is a display electrode made of WO3 formed by evaporation. 5 is a transparent electrode, 5 is a glass substrate, 6 is a voltage application terminal connected to display electrode 1, A is a rear container, 8 is an electrolytic solution, 9
is a reflector made of porous alumina.
本実施例における電解液としては、プロピレンカーボネ
イトに０．１ｍｏｌ／ｌの水を含まぜた溶媒に電解質と
してＬｉＣｌＯ４を０．２ｍｏｌ／ｌ溶解し、さらにＬ
ｉ５ＡＩＦ６の微粉末を野濁飽和させたものを用いた。The electrolytic solution in this example was prepared by dissolving 0.2 mol/l of LiClO4 as an electrolyte in a solvent containing propylene carbonate and 0.1 mol/l of water, and further adding L
A finely saturated i5AIF6 powder was used.
なおとのＬｉ５ＡＩＦ６は純水に懸濁飽和させた溶液の
ＰＨ値が６．６であった。Naoto's Li5AIF6 was suspended and saturated in pure water, and the pH value of the solution was 6.6.
なおここで本発明によるＥＣＤと比較するため以下のよ
うな従来例を試作した。Here, in order to compare with the ECD according to the present invention, the following conventional example was prototyped.
（従来例１）
電解液がプロピレンカーボネイトにＯ，，１ｍｏｌ／４
の水を含み、Ｌ ｉ Ｃ７０４０，２ｍｏｌ／ｌ溶解し
た溶液で、他は本発明実施例と同じであるＥＣＤ。(Conventional example 1) The electrolyte is propylene carbonate with O, 1 mol/4
ECD is a solution containing 2 mol/l of Li C7040, and is otherwise the same as the example of the present invention.
（従来例２）
電解液が、プロピレンカーボネイトに、０．１ ｍｏ
ｌ／ｌの水を含み、Ｌ ｉ ＣｌＯ４０、２ｍｏ ｌ／
ＩＪとＬ Ｉ Ｂ Ｆ２Ｏ、０６ｍｏｌ ／ＩＪ 溶
解した溶液で、他は本発明実施例と同じＥＣＤｏ
なお、このＬ １ＢＦ４は純水にｏ、ｏｓｍｏｌ／ｌ
溶方イした場合ＱＰＨ値が３．１であった。(Conventional Example 2) The electrolyte is propylene carbonate at a concentration of 0.1 mo
Contains l/l water, Li ClO40, 2mol/
IJ and L I B F2O, 06 mol/IJ Dissolved solution, other than this, the same ECDo as in the example of the present invention. Note that this L 1BF4 was added to pure water at o, osmol/l.
When melted, the QPH value was 3.1.
本発明によるＥＣＤと、従来例のＥＣＤとを７０°Ｃの
環境下に保存し、１０００時間経過後初期の特性と比較
した。この結果、従来例１では表示極を構成するＷＯ３
がほとんど溶解し機能を失なっていた。１だ従来例２Ｎ
は、内部で溶媒が分解し、ガス発生し一部漏液を生じて
いる素子もあり、寸だ他のものは極めて書込、消去反応
の応答性が悪くなっていた。これに対し本発明によるも
のではほとんど変化が認められなかった。The ECD according to the present invention and the conventional ECD were stored in an environment of 70° C., and after 1000 hours, their initial characteristics were compared. As a result, in Conventional Example 1, the WO3 constituting the display pole
had almost completely dissolved and lost its functionality. 1 Conventional example 2N
In some devices, the solvent decomposed internally, generating gas and causing some liquid leakage, and in others, the responsiveness of writing and erasing reactions was extremely poor. In contrast, almost no change was observed in the case of the present invention.
なお本発明を実施する場合のフルオロ錯塩の添加方法と
しては、電解液に直接添加するだけに限らず、電解液と
接触状態にして、究極的に電解液に溶解または分散する
ような状態に存在させても良いことは自明である。When carrying out the present invention, the method of adding fluoro complex salts is not limited to directly adding them to the electrolyte solution, but also by bringing them into contact with the electrolyte solution so that they are present in a state where they are ultimately dissolved or dispersed in the electrolyte solution. It is obvious that it is okay to do so.
発明の効果
本発明によれば、ＷＯ３表示極の劣化を防止した上で電
解液の劣化を防止し、これにより耐久性にすぐれたＥＣ
Ｄを容易じ得ることができる。Effects of the Invention According to the present invention, it is possible to prevent the deterioration of the WO3 display electrode and also the deterioration of the electrolyte, thereby providing an EC with excellent durability.
D can be easily obtained.
図は本発明によるエレクトロクロミック表示素子の断面
図である。
１・・・・・・表示電極、２・・・・・・対向電極、５
・・・・・基板、８・・・・・・電解液。The figure is a cross-sectional view of an electrochromic display element according to the present invention. 1...Display electrode, 2...Counter electrode, 5
...Substrate, 8... Electrolyte.
Claims (1)
むポリプロピレンカーボネイトを溶媒とし過塩素酸塩を
電解質とする電解液を介して対極が対向し、かつ水溶液
のＰＨが４．６以上となるようなフルオロ錯塩が上記電
解液中に存在していることを特徴とするエレクトロクロ
ミンク表示素子。A display electrode made of tungsten oxide is opposed to a counter electrode via an electrolytic solution containing polypropylene carbonate containing a trace amount of water as a solvent and perchlorate as an electrolyte, and the pH of the aqueous solution is 4.6 or higher. An electrochromic display element characterized in that a fluoro complex salt is present in the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57196999A JPS5987431A (en) | 1982-11-10 | 1982-11-10 | Electrochromic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57196999A JPS5987431A (en) | 1982-11-10 | 1982-11-10 | Electrochromic display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5987431A true JPS5987431A (en) | 1984-05-21 |
Family
ID=16367134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57196999A Pending JPS5987431A (en) | 1982-11-10 | 1982-11-10 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5987431A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265830A2 (en) * | 1986-10-25 | 1988-05-04 | Hitachi Maxell Ltd. | Electrochromic display device |
-
1982
- 1982-11-10 JP JP57196999A patent/JPS5987431A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265830A2 (en) * | 1986-10-25 | 1988-05-04 | Hitachi Maxell Ltd. | Electrochromic display device |
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