JPS6039623A - Electrochromic display element - Google Patents

Electrochromic display element

Info

Publication number
JPS6039623A
JPS6039623A JP58147646A JP14764683A JPS6039623A JP S6039623 A JPS6039623 A JP S6039623A JP 58147646 A JP58147646 A JP 58147646A JP 14764683 A JP14764683 A JP 14764683A JP S6039623 A JPS6039623 A JP S6039623A
Authority
JP
Japan
Prior art keywords
acid
display
electrode
electrolyte
ecd
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
Application number
JP58147646A
Other languages
Japanese (ja)
Inventor
Shigeo Kondo
繁雄 近藤
Yasuo Mizuno
水野　康男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP58147646A priority Critical patent/JPS6039623A/en
Publication of JPS6039623A publication Critical patent/JPS6039623A/en
Pending legal-status Critical Current

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

Abstract

PURPOSE:To obtain an ECD low in change with time during high temp. storage, that is, deterioration of electric display amt. after storage by using an org. acid for the solvent of an electrolyte between a display member and an opposite electrode. CONSTITUTION:A display member 3 and an insulator 4 are formed on the transparent electrode 2 of a galss base plate 1. An electrolyte 8 is filled between the display member 3 and an opposite electrode 5, and the solvent to be used for it 8 is an org. acid, such as acrylic, methacrylic, n-valeric, i-valeric, propionic, linolic, and butyric acids, and acetic anhydride, etc., and the electrolyte 8 is prepared by dissolving LiClO4 in 0.8M/l in said acidic org. solvent is used.

Description

【発明の詳細な説明】 産業上の利用分野 本発明はエレクトロクロミック表示素子に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to electrochromic display elements.

従来例の構成とその問題点 エレクトロミック表示素子（以下ＥＣＤと略記する）は
一般に第１図に示したように構成されている。即ち、透
明基板（１）に薄膜透明電極（２）を設け、ｉらにその
上に酸化タングステン、酸化モリブデン等の表示体（３
）および表示極用リード部位に電解液が直接接触するの
をさけるための絶縁物（４）を設けて表示極とする。対
向電極（５）はカーボン粉末と対向電極活物質（例えば
、二酸化マンガン、プルシアンブルー、酸化タングステ
ン等の還元体が用いられる）をフッ素樹脂粉末をバイン
ダーとして集電体（５′）に接触するようにして形成さ
れる。表示体（３）と対向電極（５）との間にはアルミ
ナ等の多孔性の反射極（６）を介在させ、これらをガラ
ス製容器（７）内に配置し、接着材（ロ）で表示極とガ
ラス製容器とを接着した後、セル内に電解液（８）を注
入して構成される。ここで使用される電解液としては、
プロピレンカーボネート、γ−ブチロラクトン、アセト
ニトリル、ニトロメタン等の極性溶媒が一般に用いられ
、該溶媒に過塩葉酸リチウム（ＬｉＣ１０４）をほぼＬ
Ｍ／ＩＩの割合に溶解させ、電解液として用いられる。Conventional Structure and its Problems An electromic display element (hereinafter abbreviated as ECD) is generally structured as shown in FIG. That is, a thin film transparent electrode (2) is provided on a transparent substrate (1), and a display material (3) of tungsten oxide, molybdenum oxide, etc. is placed thereon.
) and an insulator (4) to prevent the electrolyte from coming into direct contact with the display electrode lead portion to form a display electrode. The counter electrode (5) is made of carbon powder and a counter electrode active material (for example, a reduced material such as manganese dioxide, Prussian blue, tungsten oxide, etc. is used) with fluororesin powder as a binder and is brought into contact with the current collector (5'). It is formed by A porous reflective electrode (6) made of alumina or the like is interposed between the display body (3) and the counter electrode (5), and these are placed in a glass container (7) and bonded with an adhesive (b). After bonding the display electrode and the glass container, an electrolytic solution (8) is injected into the cell. The electrolyte used here is
Polar solvents such as propylene carbonate, γ-butyrolactone, acetonitrile, and nitromethane are generally used, and lithium perchlorate folate (LiC104) is added to the solvent to approximately
It is dissolved in a ratio of M/II and used as an electrolyte.

（９）　ＯＯはそれぞれ表示体（３）、対向電極（５）
への電圧印加端子である。(9) OO are display body (3) and counter electrode (5), respectively.
This is the voltage application terminal for the

このようなＥＣＤを駆動するには、対向電極（５）に対
して、表示体（３）が負となるような電圧を印加するこ
とにより表示され、表示体（３）が正となるような電圧
を印加することにより消去される。表示体（３）として
、例えば酸化タングステン（ＷＯａ）を用いた場合の表
示反応は（１）式のように進行するとされている。To drive such an ECD, a voltage is applied to the counter electrode (5) so that the display body (3) becomes negative, and a voltage that becomes positive on the display body (3) is displayed. It is erased by applying a voltage. When, for example, tungsten oxide (WOa) is used as the display material (3), the display reaction is said to proceed as shown in equation (1).

ＷＯ３＋ｘＨ”＋ｘｅ≠ＨｘＷＯｓ　・・・・・・・・
・・・・・・・・・・・・・（１）（無色）　（青色） すなわち、酸化タングステンを電気化学的に還元を行う
ことで、青色のタングステンブロンズ（ＨｘＷＯ３）状
態とし、青色表示を行うものである。WO3+xH"+xe≠HxWOs...
・・・・・・・・・・・・・・・(1) (colorless) (blue) In other words, by electrochemically reducing tungsten oxide, it becomes a blue tungsten bronze (HxWO3) state, and a blue display is produced. It is something to do.

このような電気化学的ディスプレーにおいて、特に酸化
タングステン、酸化モリブデン等の遷移金属酸化物を表
示体としたＥＣＤにおいては、素子を高温保存すること
により、素子を駆動した際、表示のコントラスト低下現
象が存在していた。In such electrochemical displays, especially in ECDs that use transition metal oxides such as tungsten oxide and molybdenum oxide as display materials, by storing the elements at high temperatures, there is a reduction in display contrast when the elements are driven. It existed.

発明の目的 本発明は、高温保存時における表示コントラストの経時
変化の少ないＥＣＤを提供することを目的とするもので
ある。OBJECTS OF THE INVENTION It is an object of the present invention to provide an ECD with little change in display contrast over time during high-temperature storage.

発明の構成 本発明は、表示極と対向ｍ極間に電解液を介在させてな
るＥＣＤにおいて、前記電解液を構成する溶媒として有
機酸からなる溶媒を用いるものである。Structure of the Invention The present invention is an ECD in which an electrolytic solution is interposed between a display electrode and an opposing m-electrode, in which a solvent made of an organic acid is used as a solvent constituting the electrolytic solution.

すなわち、本発明は、ＥＣＤの高温保存後素子を駆動し
た際の表示コントラスト低下現象の原因が表示体自身に
よるものであり、その原因が、表示体自身がカチオンの
交換反応によって、即ち表示体内からプロトンが放出さ
れ、かわりにリチウムがトラップされる結果、電極自身
の抵抗の増大現象が生じているものと判断し、カチオン
の交換反応を阻止する方法として、電解液自身全酸性状
態にして用いることが望ましいと推察し、表示体特性の
優れた酸性溶媒を種々探索した結果、種々のカルボン酸
がその効果を極めて発揮することを見い出したものであ
る。That is, the present invention shows that the cause of the display contrast reduction phenomenon when the ECD element is driven after high-temperature storage is due to the display itself, and that the cause is that the display itself causes cation exchange reaction, that is, from within the display body. It was determined that protons were released and lithium was trapped instead, resulting in an increase in the resistance of the electrode itself, and as a way to prevent the cation exchange reaction, the electrolyte was used in a fully acidic state. As a result of searching for various acidic solvents with excellent display properties, they discovered that various carboxylic acids exhibit the most effective effects.

実施例の説明 以下本発明の一実施例を図面に基づいて説明する。本発
明のＥＣＤは、電解液を除く他は第１図で示した従来の
ＥＣＤと同様の構造で構成される７（１）はガラス基板
よりなる透明基板、（２）は酸化スズよりなる透明電極
で、約２０９の面抵抗のものを使用した。（３）は透明
電極（２）上に酸化タングステンを約８０００人の厚さ
になるよう電子ビーム蒸着法により蒸着した表示体で、
つづいて、ＳｉＯよりなる絶縁物（４）を設けて表示極
とした。対向電極（５）としては、グラファイト粉末に
フッ素樹脂を少しの重量比で混合し、チタンネット集電
体（５′）を中心にして１ｔｏｎ　／　ｃｄの圧力で加
圧成型したものを用いた。電解液としては、酸性有機溶
媒に０．８Ｍ　／　ＩＩとなるようにＬｉＣ１０＋を溶
解させたものを使用した。DESCRIPTION OF EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. The ECD of the present invention has the same structure as the conventional ECD shown in FIG. 1 except for the electrolyte. 7 (1) is a transparent substrate made of a glass substrate, and (2) is a transparent substrate made of tin oxide. The electrode used had a sheet resistance of about 209. (3) is a display body in which tungsten oxide is deposited on the transparent electrode (2) to a thickness of approximately 8,000 yen by electron beam evaporation.
Subsequently, an insulator (4) made of SiO was provided to serve as a display electrode. As the counter electrode (5), a mixture of graphite powder and fluororesin in a small weight ratio was used, and the mixture was press-molded with a titanium net current collector (5') at a pressure of 1 ton/cd. The electrolyte used was an acidic organic solvent in which LiC10+ was dissolved at a concentration of 0.8 M/II.

第１表は酸性有機溶媒を用いた各種実施例１〜９と、従
来の溶媒としてプロピレンカーボネート、γ−ブチロラ
クトンを用いたＥＣＤについて、７０°Ｃ１１０００時
間保存後、ＥＣＤを駆動した際のコントラスト変化を表
示に使われる電気量でもって表わしたものである。該電
気量は１ｖ・１　ｓｅｃの定電圧を第１表 表示極一対向電極間端子に印加した際に単位表示面積に
流れる電流を積分したものである。Table 1 shows the contrast changes when ECD was operated after storage at 70°C for 11,000 hours for various Examples 1 to 9 using acidic organic solvents and ECD using propylene carbonate and γ-butyrolactone as conventional solvents. It is expressed by the amount of electricity used for display. The quantity of electricity is obtained by integrating the current flowing in a unit display area when a constant voltage of 1 v·1 sec is applied to the terminal between the first display electrode and the opposite electrode.

上記の実施例から明白なごとく、本発明のＥＣＤにおい
て、高温保存後０ＥＣＤに対する表示に使用される電気
量低下が少ないことが分る。As is clear from the above examples, in the ECD of the present invention, the decrease in the amount of electricity used for displaying 0 ECD after high temperature storage is small.

発明の効果 以上のように本発明のＥＣＤでは、高温保存における素
子のコントラスト低下に関する経時変化を少なくでき、
ＥＣＤの信頼性を極めて高いものとすることができるも
のである。Effects of the Invention As described above, the ECD of the present invention can reduce changes over time related to the decrease in contrast of the element during high-temperature storage.
This makes it possible to make the reliability of the ECD extremely high.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は一般ＥＣＤの縦断面図である。 （１）・・・透明基板、（２）・・・透明電極、（３）
・・・表示体、（４）・・・絶縁物、（５）・・・対向
電極、（５′）・・・集電体、（８）・・・電解液 代理人　森本義弘 第１図FIG. 1 is a longitudinal sectional view of a general ECD. (1)...Transparent substrate, (2)...Transparent electrode, (3)
... Display body, (4) ... Insulator, (5) ... Counter electrode, (5') ... Current collector, (8) ... Electrolyte agent Yoshihiro Morimoto Figure 1

Claims (1)

【特許請求の範囲】 １、遷移金属を表示体とする表示極と対向電極との間に
電解液を介在させてなるエレクトロクロミック表示素子
であって、前記電解液を構成する溶媒が有機酸よりなる
エレクトロクロミック表示素子。 １　電解液を構成する有機酸溶媒はアクリル酸、メタク
リル酸、吉草酸、プロピオン酸、リノール酸、酪酸、無
水酢酸から選ばれるカルボン酸であることを特徴とする
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。[Scope of Claims] 1. An electrochromic display element comprising an electrolytic solution interposed between a display electrode and a counter electrode using a transition metal as a display material, wherein the solvent constituting the electrolytic solution is an organic acid. An electrochromic display element. 1. The organic acid solvent constituting the electrolytic solution is a carboxylic acid selected from acrylic acid, methacrylic acid, valeric acid, propionic acid, linoleic acid, butyric acid, and acetic anhydride. Electrochromic display element.
JP58147646A 1983-08-11 1983-08-11 Electrochromic display element Pending JPS6039623A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58147646A JPS6039623A (en) 1983-08-11 1983-08-11 Electrochromic display element

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58147646A JPS6039623A (en) 1983-08-11 1983-08-11 Electrochromic display element

Publications (1)

Publication Number Publication Date
JPS6039623A true JPS6039623A (en) 1985-03-01

Family

ID=15435043

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58147646A Pending JPS6039623A (en) 1983-08-11 1983-08-11 Electrochromic display element

Country Status (1)

Country Link
JP (1) JPS6039623A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0253249A2 (en) * 1986-07-08 1988-01-20 Hitachi Maxell Ltd. Electrochromic display device
US5956184A (en) * 1996-09-04 1999-09-21 Nikon Corporation Zoom lens system having high zoom ratio

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0253249A2 (en) * 1986-07-08 1988-01-20 Hitachi Maxell Ltd. Electrochromic display device
US5956184A (en) * 1996-09-04 1999-09-21 Nikon Corporation Zoom lens system having high zoom ratio

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