JPS5948789A - Electrochromic display - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a display device (electrochromic display device, hereinafter referred to as ECD) that utilizes an electrochemical oxidation reaction.
This invention relates to the improvement of counter electrodes.

FIG. 1 is a sectional view showing an example of a conventional EOD. Reference numeral 1 denotes a transparent substrate made of glass or the like. On the transparent substrate 1, an electrode 2 made of tin nitride or the like is formed. On the transparent substrate 11, an electrochromic material made of tungsten trioxide or the like is formed. The layers are formed by a method such as steaming to form display electrodes 4-j4. Opposed 11 that exists opposite the display pole
A counter electrode layer 5 is formed on the electrode substrate 4 and is integrated with the transparent ψJ group &i with an adhesive 7 via a spacer 6. 8
is a white porous plate made of ceramic or the like, and faces the transparent substrate 1 to provide a white background. It is interposed between the 1L4 and 113 substrates 4.

Normally, a solution of oversalted purple 1j lithium in 11 lots 7t propylene carbonate is injected through the sealing port 10 and sealed with the sealing material 11. 12 is a voltage application terminal for the display 4111, and 13 is a voltage application terminal for the counter electrode.

When tungsten trioxide is used as the electrochromic material layer in the EOD constructed with 4+'+'I'', when a voltage is applied with the display electrode set to negative and the counter electrode set to positive, a chemical reaction occurs as expressed by the following formula. occurs, and the tungsten trioxide film turns blue.

WO, 1xM” +re -gM-TWO3(M”H,
It is said that the principle of coloring is that cations and electrons are injected into L i , N (Z , etc.), that is, tungsten 31F film, and tungsten bronze is formed. Conversely, by making the display electrode positive and the counter electrode negative, a completely opposite reaction can occur and the color can be erased. EC like this! A major feature of D is that ion movement is accompanied by nine color erasures. Therefore, in order to quickly and stably perform coloring and decoloring, it is necessary for the counter electrode to quickly and stably take in and release the charge accompanying the movement of ions. One of the things that has been considered as something that does not meet these conditions is the "Carpons" pole. Carbon has a large surface area and can accumulate a lot of charge in the form of ion adsorption.
7J quality. When electrodes are actually made from carbon, it is either press-molded or hardened with a polymer material. When a binder is used, the effective surface area of carbon is damaged and a sufficient 'itL loading capacity bi cannot be obtained. Transferable metal oxide free metal 1ii capable of performing a solubilization-reduction reaction
I-body was considered, but these are also in the form of powder, and when formed as an actual electrode on the same El as in the case of carbon,
It has many problems. Therefore, in order to eliminate such drawbacks, this product can make the 7[5-electrode] thinner without using a bonding material.
However, the electrode is made of manganese dioxide, which is porous and has a large surface area, and has electron conductivity.
・Spread the 4-compound serum into a 'gi cloth1. By firing, a thin layer of fritted metal 11:a I; The purpose is to

Porous manganese dioxide can be obtained by thermal decomposition or electrolytic film formation of manganese salt solution, and is widely used as electrodes for 1U ponds and solid electrolytic capacitors.

In addition, manganese trioxide itself is a bertholed compound,
In other words, it is said to be a substance that undergoes a reverse oxidation-reduction reaction, and that both cations and electrons can pass through the formation of crystals. As a method for forming a sapwood metal oxide on this manganese dioxide porous membrane, a method using generally known chain metal salts, chlorides, ammonium compounds, alkoxides, etc. Thermal decomposition of materials such as ff;H is effective.

The following is an example of the arrangement of the present invention, with one person per song. explain about.

Figure 21 is a cross section 11'' of an example of GJ Akira Honkabuto. Tin oxide J is placed on a transparent glass substrate 1.
Meiden 41'J32 is formed, and an electrochromic material layer made of tungsten trioxide is transparent to form an indicator electrode h'J with 4" waves 11 on the L'iiL electrode 2. The opposing electrode bases Ni 4 arranged opposite to each other are made of glass.G on the opposing electrode substrate 4 is a concentrated electrode 14 made of tin-11-gold, etc. for taking out the electrode terminals.
is formed. 15 is a manganese dioxide porous electrode, and after coating a 40% manganese nitrate aqueous solution on the collector electrode 14,
It is formed by firing in air at 150-200°C. Reference numeral 16 denotes a fugitive metal compound layer, which is used by immersing a transition metal compound solution on the porous electrode 14 and then firing it. Display electrode glass substrate 1
and the opposing ηL pole substrate 4 are integrated with a bonding agent 7 via a spacer 6. A ceramic white porous plate 8 is interposed between the glass substrate 1 and the counter electrode substrate 4. 9 is 't
tt fiJ (, 1 mo of perchlorine fK IJ lithium in liquid
A t/L propylene carbonate solution is injected through the sealing port 10 and sealed with a sealing material 11. 12 is a '#IL pressure applying terminal for the display electrode, and 13 is a voltage applying terminal for the counter electrode.

The above is the configuration of the KOD cell used in the present invention. An example will be described below regarding the method for manufacturing the opposed 'tff poles of the present invention.

(Example 1) Hexaphenoxytungsten was used as the compound 1.4 compound ζri J, and 10illi was also mixed with 1% toluene #
After immersing the liquid into manganese dioxide porous pulp chamber 4.lIj,
The potential-other flow curve hd of the counter electrode created using air is shown in FIG. The curve indicated by a in the figure is the potential-current curve of the counter electrode in Example 1, the curve indicated by S in the figure is the potential-current curve of only the manganese dioxide porous electrode, and the curve indicated by C in the figure is the potential-current curve of the acetylene black and binder. polystyrene as weight ratio 1;
In 1 (1', j), there is a potential of a certain counter electrode ', and a feedstock flow curve. Acetylene black counter electrode was used for comparison as an example of a conventional carbon counter electrode. Acetylene black itself was used as a manganese dioxide porous electrode. Although it has a comparable surface area, by using a binding agent, its effective surface area becomes extremely small, ihN, which causes a small current capacity t+i.On the other hand, manganese dioxide porous '1 The .lL pole does not have a large Table 1f capacity because it does not use an eyebrow agent, and also shows a large current capacity due to the contribution of the 1-so reduction tonne current of manganese dioxide itself. In the counter electrode in Example 1 of the invention, a metallurgical metal saponified thin film acting as an active material is formed on the manganese dinitride porous electrode, so that a larger current capacity can be obtained than that of the manganese dinitride porous electrode. ing.

In this way, an EOD using a counter electrode with a large current capacity has little potential fluctuation at the counter electrode when a current flows during coloring, and it is possible to apply an appropriate voltage to the display electrode. If the potential fluctuation at the counter electrode is large, the voltage applied to the display electrode will change over time and depending on the flowing 't4i current value. It becomes difficult to maintain. Further, the large drop in 'tli[iZ in the pair 18 means that a voltage applied to the output voltage is required in order to obtain a fast response speed, which is not preferable when battery-driven.

In the KOD using the counter electrode in Example 1, the color was erased with a constant contrast even when displaying different areas by applying a voltage of 1.5 cm, and a response speed of 0.5 seconds was obtained.

(Example 2) Using molybdic acid at 25% (per % ammonia water bath t (support)), a electrode was prepared as in Example 1, and EiOD cell/
When this was constructed, the same performance as in Example 1 was obtained.

(Example 5) A counter electrode was prepared as in Example 1 using dichromium enemy ammonium as a 10% water solution and a KOD cell was constructed. As a result, the same properties as in Example 1 were obtained.

(Example 4) A counter electrode was prepared as in Example 1 using a 10 ilj bi% ethanol solution of tetrabutoxytitanium, and 170D
When a cell was constructed, performance similar to that of Example 1 was obtained.

(Example 5) A counter electrode was prepared as in Example 1 using a 10% by weight 61% ethanol solution of triethyl vanadyl, and a KOD cell was constructed, and the same performance as in Example 1 was obtained.

(Example 6) A counter electrode was prepared as in Example 1 using pentaethoxytantalum as a 1oyH% ethanol solution, and an ECD cell (11
When J was prepared, the same performance as in Example 1 was obtained.

(Actual Li1i Example 7) When a counter electrode was prepared as in Example 1 using a 10jtbt% ethanol solution of pentabutoxyniophylfluoride and a KOD cell was constructed, the same performance as in Actual Li1i Example 1 was obtained.

(Example 8) A 10% by weight water bath solution containing ferric chloride was immersed in a manganese dioxide porous 1+L electrode, and after thermal separation at 200°C for 1 hour, a counter electrode was used which was partially dissolved in hydrogen at 200°C. ,EOD
When a cell was constructed, performance similar to that of Example 1 was obtained.

(Example 9) A counter electrode was prepared as in Example 1 using 5-fold 1f11% water-based cerium and an EOD cell was constructed, and the same performance as in Example 1 was obtained.

＼ As mentioned above, EOD using the opposite pole based on “hon-ori”
is 1 at constant voltage! It is possible to color the display poles of different display areas evenly even when the display is moved, and moreover, it exhibits a fast response with a low voltage. In particular, porous electrodes that do not use a binder and counter electrodes made of thin cut Japanese cedar metal are allowed to flow.
Since the potential is stable with respect to the current, a constant voltage can be applied to display electrodes having different display areas. Moreover, it goes without saying that the manufacturing method uses R10 rather than the pressing method.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing an example of a conventional EOD cell. FIG. 2 is a sectional view +d showing an example of an 0ECD cell according to the present invention. FIG. 6 is a diagram showing the ratio axis of the potential-current curve of one embodiment of the counter electrode of the present invention and the potential-current curve of the manganese dioxide porous electrode and the acetylene black+polystyrene counter electrode. 1...IJ substrate 2...Transparent electrode 3...Electrochromic 9 Free layer 4...
... Opposing 'magnetic pole substrate 5... Pair 4!1jj layer 9... Electrolyte 14... Transparent 8A electrode 15... Porous' electrode 16... Transition metal Oxide 1u or more Daisei Daidai Daini Seikosha Co., Ltd. J Seijin Patent Attorney Tsutomu Mogami

Claims (4)

[Claims] (1) A display electrode substrate consisting of a transparent first substrate, a transparent electrode formed on the transparent substrate, and an electrochromic material layer formed on the transparent electrode; An electrochromic display device comprising: a counter electrode substrate formed on a substrate, and an electrolytic solution containing ions capable of changing an electrochromic substance to X7 colors, sandwiched between the two electrode substrates; An electrochromic display device characterized in that the counter electrode layer is a multilayer film having a porous 1 (a multilayer film formed on an electrode and a thin film of a metal 1 bag formed on an electrode) having an exclusive electrical property. (2) A patent characterized in that the porous electrode with 446 properties is made of double-sided manganese: 4+! The electrochromic display device according to item 1 of the scope of requirements. (3) The transmissible metal oxide thin film formed on the porous electrode is a transmissible metal oxide V+'j obtained by applying a transmissible metal compound solution on the porous electrode and then firing it.
The electrochromic display device t-1' according to item 1 of the scope of the invention, characterized in that the electrochromic display device t-1' is characterized in that the electrochromic display device t-1' is characterized in that: (4) Electrochromic substance Ie (consisting of tungsten trioxide and 'electrolytic solution consisting of an electrolyte dissolved in an organic solvent) Special a'1/h blue water category 17Ji M'+ 1 term The electrochromic display device a(5) described above includes a tungsten compound, a molybdenum compound, a chromium compound, a titanium compound, a vanadium compound, a tanker compound, a niobium compound, an iron compound, and a cerium compound. Electrochromic display device 1゜ according to item 3 of the scope of patent N+'l, characterized in that it is one selected from