JPH0466331B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an all-solid-state electrochromic display element. [Prior art] A conventional electrochromic display element has a second
They are classified into liquid phase electrolyte type as shown in the figure and solid electrolyte type as shown in Figure 3. The liquid phase electrolyte type has excellent response speed because the electrolyte ions move quickly, but drawbacks can be pointed out, such as problems such as liquid leakage and the complexity of the processing steps to prevent such problems. In addition, in Figure 2, the most common display electrode (color tone changing material) in this type of electrochromic display element is
Taking as an example a case where WO ₃ and a propylene carbonate solution of lithium perchlorate are used as the electrolyte solution, color development due to voltage application is expressed by formula (2). At this time, an oxidation reaction should occur on the counter electrode side, and is expressed, for example, by formula (3). y・WO ₃ (transparent) + x・Li ⁺ +xe ^- → Li ⁺ _x・(WO ₃ ) ^x- _y (blue) (2) x・ClO4￣−xe ^- →x・ClO4〓 (3) The resulting ClO4 〓 or the decomposition products induced therefrom deteriorate the electrolyte solution and the counter electrode, shortening the life of the product. formula
Although it is not as pronounced as the reaction in (3), it is easy to predict that ClO4￣ itself, which has lost its countercation, will have considerable reactivity, which will still lead to the deterioration and shortened lifespan as described above. . In the solid electrolyte type, the movement of electrolyte ions is slow, so there remains a problem with response speed, but there are no problems such as leakage, and the processing process for manufacturing products is easy. In Figure 3, the most common solid electrolyte in this type of electrochromic display element is
Taking Li ₃ N as an example and using WO ₃ as the color tone changing substance, color development by voltage application is in the same format as equation (2). At this time, it is thought that an oxidation reaction as shown in equation (4) is occurring on the solid electrolyte side. Li ₃ N−x・Li ⁺ −xe ⁻ →(Li _3−x N) ^x+ (4) In the coloring reaction of equation (2), most of the response speed is determined by the resistance value of the solid electrolyte layer. be.
Generally, this problem can be solved by making the solid electrolyte layer extremely thin, but doing so will inevitably reduce the amount of Li ⁺ that contributes to the reaction in equation (2), which will reduce the color development. The color becomes lighter. Therefore, the thickness of the solid electrolyte layer cannot be made thinner than 0.1 to several μm, which results in a slow color development rate. Furthermore, it is thought that the decoloring reaction (returning to the original color tone) after the voltage application is removed can be expressed by equation (5). Li ⁺ _x・(WO ₃ ) ^x- _y →y・WO ₃ +x・Li ⁺ +xe
^{- (} _{WO 3} ^{side )} _{_ _} ^_ _{_} It then moves through the lattice defects and free volume on the Li ₃ N side, and (Li _3-x N) ^x+
This results in a very energetically unfavorable diffusion. Therefore, the recovery time to return to the original color after the voltage application is removed is:
In fact, it is longer than the time required for color development, and attempts have even been made to speed up this process by, for example, applying a reverse voltage. [Object of the Invention] Accordingly, the object of the present invention is to use a polymer-alkali metal salt hybrid solid electrolyte having a thickness of 0.1 μm or less and 100 Å or more and having a high alkali ion conductivity of 10 ^-6 s/cm or more. All-solid-state electrochromium is composed of the basic structure of metal electrode] / [solid electrolyte] / [color tone changing substance], and the color tone changes at a speed of 100 milliseconds or less by applying a voltage of about 4.5 volts or less or removing the voltage. An object of the present invention is to provide a light display element. [Structure of the Invention] The present invention uses an alkali metal selected from lithium, sodium, and potassium as one electrode, 80 to 95 parts by weight of a phosphate ester macromer represented by formula (1) as a solid electrolyte, and the alkali metal electrode. Salts of the same kind of alkali metal ions, including lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium hexafluorophosphate, and hexafluoroborate. Sodium fluorophosphate, potassium hexafluorophosphate, lithium trifluoroacetate, sodium trifluoroacetate, potassium trifluoroacetate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, lithium toluenesulfonate, toluene A hybrid ion conductor made by polymerizing a mixture of 20 to 5 parts by weight of an alkali metal salt selected from sodium sulfonate, potassium toluenesulfonate, lithium thiocyanate, sodium thiocyanate, and potassium thiocyanate was used as the other electrode. , a thin film of a substance whose color tone changes due to the inflow and outflow of alkali metal ions accompanying redox is formed on a transparent conductive substrate, and these are pressed together to form an [alkali metal electrode]/[solid electrolyte]. This is an all-solid-state electrochromic display element characterized by having the following structure: /[color tone changing substance-transparent conductive substrate]. However, in formula (1), 4≦n≦22, 1≦a≦2,
2≧b≧1, a+b=3, R is a straight chain or branched alkylene group having 2 to 4 carbon atoms, and R' is hydrogen or a methyl group. The solid electrolyte is formed into a thin film of 0.1 μm to 100 Å after or during polymerization of a homogeneous mixture of 20 to 5 parts by weight of the alkali metal salt and 80 to 95 parts by weight of the phosphate ester macromer of formula (1). It is. If the basic form of a color tone changing substance is the shape before the color tone changes due to voltage application, then the basic form is M ⁺ _x・
( _WO3 ) ^x- _y (M ⁺ is an alkali metal ion, 0.5≦x/y≦1.0), _M4・_Fe4 [Me(CN) ₆ ] ₃ (Me is iron, osmium, or ruthenium),
It is a compound represented by M ₃ ⁺・(octacyanophthalocyanine) ^3- , etc. The alkali metal electrode may be one cut into a thin plate from a metal block, but it can be placed on a conductive substrate made of platinum, gold, glassy carbon, graphite, etc.
A thin film formed by vapor deposition or the like to a thickness of about 10 ⁴ Å is preferable. The color tone changing material layer is preferably formed as a thin film with a thickness of 0.05 to 0.5 μm on a transparent conductive substrate such as SnO ₂ Nesa Glass, Indium Tin Oxide Nesa Glass, TiO ₂ Nesa Glass, etc., and most preferably 0.075 μm thick.
~0.15μm thick. In M ⁺ _x・(WO ₃ ) ^x- _y ,
A thin film of WO ₃ is formed by sputtering to the thickness described above, and when the electrochromic display element of the present invention is constructed as described later, M ⁺ _x・(WO ₃ ) ^x- _y
Changes to For M ₃ ⁺ /(octacyanophthalocyanine) ^3- , octacyanophthalocyanine is prepared by spin coating or casting on the conductive substrate described above from a dimethylformamide or N-methylpyrrolidone solution with a concentration of 0.5 to 1.0 mg/ml. When a thin film is formed to the thickness described above and an electrochromic display element of the present invention is constructed as described later, it changes to M ₃ ⁺ (octacyanophthalocyanine) ^{3 -} . The synthesis method for octacyanophthalocyanine is described by D. Wohrle et al., Macromolecular Chemistry (D. Wohrle et al.,
Markromol.Chem.), 181 2127 (1980). For M ₄ / Fe ₄ [Me(CN) ₆ ] ₃ , the above-mentioned transparent conductive substrate was prepared in an aqueous solution containing 1 to 100 mM each of ferric chloride and [Me(CN) ₆ ] ^3- salt. is the working electrode and 0.5 volts (vs.
When the electrochromic display element of the present invention is constructed by performing electrolytic polymerization using a Fe ₄ [Me(CN) ₆ ] ₃ thin film having the thickness described above, as described below, , changes to _M4・_Fe4 [Me(CN) ₆ ] ₃ . The solid electrolyte used in the present invention is synthesized from the aforementioned phosphate ester macromer and alkali metal salt. The method for producing the phosphate ester macromer will be described in detail with reference examples. The phosphate ester macromer and the alkali metal salt are mixed in an aprotic organic solvent such as THF, dioxane, chloroform, acetonitrile, etc., preferably THF, in the proportions described above.
Most of the solvent is distilled off under reduced pressure to obtain a viscous liquid. Cast this onto a Teflon plate
Polymerization is carried out at 60 to 80° C. for 8 to 20 hours under a vacuum of 0.1 torr or less to obtain a flexible membrane, which is then stretched with a Teflon roller to obtain a solid electrolyte thin film with a thickness of 0.05 to 0.1 μm. This thin film has excellent adhesive strength with the alkali metals and color-changing substances used in the present invention, and has an adhesive strength of 80 to 110 dyne/cm with smooth lithium electrodes, for example.
That's about it. If this thin film is placed between the already mentioned alkali metal electrode and the transparent conductive electrode supporting the color tone changing substance, and is crimped with a pressure of about 2 to 10 kg/cm ² and provided with terminals, etc., as shown in Figure 1. The basic structure of the all-solid-state electrochromic display element of the present invention shown in FIG. When thinning the film by roller stretching, it may be difficult to form a thin film within the above-mentioned range. This mainly occurs when a macromer with 2≧b≧1.5 is used in formula (1). In such a case, apply a solution of the aprotic organic solvent mentioned above or a viscous liquid obtained by distilling off the solvent under reduced pressure directly to the surface of the thin layer of the color tone changing substance, and apply it under the conditions mentioned above. perform polymerization
Form a solid electrolyte layer with a thickness of 100 Å to 0.1 μm,
If this is further pressed against an alkali metal electrode under the pressure described above, the basic structure of the all-solid-state electrochromic display element of the present invention shown in FIG. 1 is completed. The all-solid-state electrochromic display element of the present invention has basically the same structure as an alkali metal secondary battery. For example, Fe ₄ [Me(CN) ₆ ] ₃ has a reduction potential of 0.2 volts (vs. SEC electrode, hereinafter the same), octacyanophthalocyanine has a reduction potential of −0.6 volts, while the reducing power of alkali metals is −2.8 to −
Ranging to 2.5 volts. In the case of WO ₃ , the reduction potential cannot be clearly identified, but it is completely reduced at at least -0.8 volts. Therefore, in FIG. 1, when switch 8 is connected to the lower terminal to directly connect terminals 7 and 7', the alkali metal electrode discharges and releases M ⁺ to the solid electrolyte layer, transferring electrons from 7 to 7. '→transparent conductive layer 5→color tone changing material thin layer 4, and as a result, the reactions of formulas (6) to (8) occur, and the color tone changing material layer becomes the basic type described above. M ⁺ (from the collective electrolyte layer) +e ^- +WO ₃ (colorless) → M ⁺ (WO ₃ ) ^- (blue) (6) 4M ⁺ +4e ^- + Fe ₄ [Me(CN) ₆ ] ₃ Fe ₄ [Me(CN) ) ₆ 〕 ₃ (Me=Fe; blue, Os: red-purple, Ru: blue-purple) → M ⁺ ₄・
{Fe ₄ [Me(CN) ₆ ] ₃ } ^4- (colorless) (7) 3M ⁺ +3e ^- + octacyanophthalocyanine (
Green) →M ⁺ ₃・[Octacyanophthalocyanine] ^3- (Blue) (8) Therefore, in the electrochromic display element of the present invention, as shown in formulas (6) to (8), the backtone is blue and colorless, respectively. , is blue. Next, when the switch 8 is connected upward so that the color tone changing substance layer is oxidized by a DC power supply, the reactions in the opposite directions of equations (6) to (8) proceed, resulting in colorless, blue to reddish purple, respectively. ~The color tone changes from blue-purple to green. The voltage required at this time is approximately 3.5 volts or more,
Preferably in the range of 3.5 to 5 volts, most preferably
It is 4.5 volts. After this, when switch 8 is placed in the neutral state, this color tone is maintained, and when switch 8 is connected downward, the original blue, colorless, and blue color tone is quickly restored by the reactions of equations (6) to (8) again. to recover. [Effects of the Invention] The characteristics of the all-solid-state electrochromic display element of the present invention are summarized as follows: 1. The color tone changes rapidly within 100 milliseconds or less by applying a voltage of about 4.5 volts. 2. If you change the color tone to an open circuit state, the color tone will be maintained for a long time. 3. After the color tone has changed, if the state is changed to short circuit, the original color tone will be quickly restored in a short time of less than 100 milliseconds. As described above, according to the present invention, it is possible to obtain an all-solid-state electrochromic display element whose color tone changes in a short time of 100 milliseconds or less by applying a voltage of about 4.5 volts or less or by removing the applied voltage. [Explanation of Examples] Next, the all-solid-state electrochromic display element of the present invention will be explained using Examples. , the manufacturing method of the color tone changing material layer, etc. will be explained using reference examples. Reference Example 1 Manufactured by Poly Sciences Inc. (USA), 35 g (0.1 mol) of oligoethylene oxide of one-terminated methyl ether with a molecular weight of 350, 6.5 g (0.05 mol) of 2-hydroxyethyl methacrylate, and 18.4 g of triethylamine ( 0.165 mol)
Dissolve in 150ml dehydrated THF. Equipped with a condenser with a drying tube, a stirrer, a dropping funnel, and a nitrogen introduction tube.
8.43g of phosphorus oxychloride in a 500ml 4-necked flask
(0.055 mol) in 150 ml of dehydrated THF, and while cooling with ice and stirring and passing dry nitrogen through the mixture, the above mixed solution was added from the dropping funnel over 1 hour. After the dropwise addition was completed, the mixture was reacted at room temperature for 13 hours. The solution was concentrated under reduced pressure at a temperature below 20°C, and added dropwise to the dehydrated ethyl acetate in step 2 with stirring. The resulting white precipitate was filtered off, and the filtrate was concentrated under reduced pressure while adding CHCl ₃ to finally obtain a concentrated solution of CHCl ₃ . The mixture was placed in a basic alumina (Merck #1076) column of φ10 cm x 45 cm, and CHCl ₃ was used as a solvent to flow out. The first and second outflow portions with Rf = 0.65 and Rf = 0.42 were distilled off under reduced pressure to obtain 2.6 g (7.8 g) of di(2-hydroxyethyl methacrylate) mono(oligoethylene oxide) phosphate triester
% (calculated assuming 0.05 mol as 100% yield), 29.6 g (67.7%) of mono(2-hydroxyethyl methacrylate) di(oligoethylene oxide) phosphoric acid triester (abbreviation) was obtained. IR (cm ^-1 ): ν _c=p 1705, ν _c=c 1630, δ CH ₂ 1440, 1445, 1450, ν P−0 and P=0 1260, 1190, ν _cpc 1200 NMR (δ, ppm): Methacrylic-CH ₃ 1.9 (6H),
Methacryl vinyl = DH ₂ 5.6, 6.1 (4H), ethylene oxide terminal -CH ₃ 3.34 (3H), -P-O
−CH ₂ and −C00−CH ₂ −4.1 to 4.4 (10H), other −CH ₂ −3.62 (26.8H) IR (cm ^-1 ): The same as NMR (δ, ppm): Exactly the same except that the intensities of δ CH ₂ and ν _cpc are about twice as strong, but the numbers of protons are 3H, 2H, 6H, 8H, and 53.6, respectively. H (same order) Reference Example 2 The same operation as in Reference Example 1 was performed. However, 17.5 g (0.05 mol) of oligoethylene oxide having a molecular weight of 350 and having a methyl ether at one end and 13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate were used. Column separation was carried out in the same manner as Reference Example 1, and 24.5 g of
(73.5%), 4.2g (9.6%) of the product was obtained. Reference Example 3 The same operation as in Reference Example 1 was performed. However, the molecular weight manufactured by Poly Sciences Inc.
Using 55 g (0.1 mol) of oligoethylene oxide containing methyl ether at one end of 550 and 6.46 g (0.05 g) of 2-hydroxypropyl acrylate, the dropwise addition under ice-cooling took 1.5 hours, and the reaction at room temperature took 16 hours.
Column separation was carried out in the same manner as in Reference Example 1, and di(2-hydroxypropyl acrylate) mono(oligoethylene oxide) phosphate triester (and 4.6 g (10.8%) of mono(2-hydroxypropyl acrylate) di(oligoethylene oxide) phosphate triester (abbreviated)
g (71.0%) was obtained. IR (cm ^-1 ): Very similar to , but the intensity of δ CH ₂ and ν _cpc is about 20% larger. NMR (δ, ppm): Isopropylene-CH ₃ 1.8
(6H), acrylic vinyl = CH ₂ 5.5, 6.0 (4H),
Acrylic vinyl=CH and isopropylene-
CH4.9~5.3 (4H), -P-O-CH2 _4.2 (6H),
Ethylene oxide terminal -CH ₃ 3.34 (3H), other -CH ₂ 3.62 (45.2H) IR (cm ^-1 ): Exactly the same except that it has about twice the intensity of δ CH ₂ and ν _cpc . NMR (δ, ppm): Isopropylene-CH ₃ 1.82
(3H), acrylic vinyl = CH ₂ 5.5, 6.0 (2H),
Acrylic vinyl=CH and isopropylene-
CH4.9~5.3 (2H), P-O- _CH2 4.2~4.4
(6H), ethylene oxide terminal - CH ₃ 3.34
(3H), other -CH ₂ 3.62 (90.4H) Reference Example 4 Using exactly the same apparatus as Reference Example 1, oligoethylene oxide of one-terminal methyl ether with a molecular weight of 750 manufactured by Poly Sciences Inc. (USA) was prepared.
37.5g (0.05mol), 4-hydroxybutyl methacrylate 15.8g (0.1mol), pyridine 14.2g
(0.18 mol) and 150 ml of THF were added dropwise from a dropping funnel to 150 ml of THF in a stirred container cooled to 0 to 5°C over a period of about 1.2 hours. Allowed time to react. After this, column separation was carried out in exactly the same manner as in Reference Example 1.
First outlet (Rf=0.53), second outlet (Rf=0.29)
and 33.2% each of di(4-hydroxybutyl methacrylate) mono(oligoethylene oxide) phosphoric acid triester (abbreviated) and mono(4-hydroxybutyl methacrylate) di(oligoethylene oxide) phosphoric acid triester (abbreviated). g (59.8%), 6.3 g (7.4%) were obtained. IR (cm ^-1 ): Very similar to δ CH ₂ , ν _cpc has approximately 1.5 times the intensity. NMR (δ, ppm): Methacrylic-CH ₃ 1.9 (6H),
Methacryl vinyl=CH ₂ 5.6, 6.1 (4H), methacrylic-COO-C-CH ₂ -2.6 (4H), methacrylic-COO-C-C-CH ₂ -2.2 (4H), ethylene oxide terminal -CH ₃ 3.34 (3H) ), -P-O
−CH ₂ − and −COO−CH ₂ −4.05 to 4.4
(1OH), other −CH ₂ (63.2H) IR (cm ^-1 ): Same as δ CH ₂ , ν _cpc except that it has about twice the intensity. NMR (δ, ppm): Methacrylic-CH ₃ 1.9 (3H),
Methacryl vinyl = _CH2 5.6, 6.1 (2H), methacryl-COO-C- _CH2 2.6 (2H), methacryl-COO-C-C- _CH2 2.15 (2H), ethylene oxide terminal _-CH3 3.34 (6H), -P-
O- _CH2- and -COO- _CH2-4.05 to 4.4
(8H), other -CH ₂ (126.4H) Reference example 5 Triethylene glycol monomethyl ether
Di(2-hydroxyethyl methacrylate) mono( Oligoethylene oxide) phosphate triester (abbreviated), 2.1g (10.6%),
Mono(2-hydroxyethyl methacrylate)
15.2 g (53.1%) of di(oligoethylene oxide) phosphoric acid triester (abbreviation) was obtained. IR (cm ^-1 ): ν _c=p 1703, ν _c=c 1630, δ CH ₂ 1440, 1445, 1450, ν P−0 and P=0 1260, 1190, ν _cpc 1205 NMR (δ, ppm): Methacrylic - CH ₃ 1.9 (6H),
Methacryl vinyl = CH ₂ 5.6, 6.1 (4H), ethylene oxide terminal -CH ₃ 3.34 (3H), -P-O
−CH ₂ − and −COO−CH ₂ −4.1 to 4.4 (10H),
Other −CH ₂ −3.62 (10H) IR (cm ^-1 ): Same as δ CH ₂ , ν _cpc has approximately twice the intensity. NMR (δ, ppm): Methacrylic-CH ₃ 1.9 (3H),
Methacryl vinyl = CH ₂ 5.6, 6.1 (2H), ethylene oxide terminal -CH ₃ 3.32 (6H), -P-O
−CH ₂ − and −COO−CH ₂ −4.1 to 4.4 (8H),
Other −CH ₂ −3.60 (20H) Reference example 6 Ferric chloride and potassium ferricyanide, respectively
A surface area of 1
cm ² , sheet resistance of 10 Ω/sq., indium tin oxide Nesaglass, platinum plate, and SCE were installed as the working electrode, counter electrode, and reference electrode, respectively, and electrolytic reduction polymerization was performed at 0.5 V for 20 seconds in a nitrogen atmosphere, followed by water washing. It was then vacuum dried to obtain an electrode in which a thin film with a thickness of 700 Å having the composition formula Fe ₄ [Fe(CN) ₆ ] ₃ was formed. Reference Examples 7 and 8 Electrolytic polymerization was carried out in the same manner as in Reference Example 6, but for 15 seconds and 35 seconds to obtain electrodes in which thin films with thicknesses of 500 Å and 1300 Å were formed, respectively. Reference Examples 9 and 10 The same operations as in Reference Example 6 were performed. However, K ₃ [Os(CN) ₆ ] and K ₃ [Ru(CN) ₆ ] were used instead of potassium ferricyanide. A thin film with a composition of Fe ₄ [Os(CN) ₆ ] ₃ and a thickness of 850 Å with a composition of Fe ₄ [Ru(CN) ₆ ] ₃ were obtained, respectively. Reference example 11 D. Wo¨rhle et al., Macromol.Chem.
181 2127 (1980) in N-methylpyrrolidone solution with a ^{concentration} of 0.75 mg/ml.
The electrode was developed on a 100Ω/cm ² SnO ₂ Nesa glass, and the solvent was evaporated at room temperature to form an electrode with a thin film of 850 Å thick. Example 1 Approximately 1 mm of the edge of the transparent electrode having the thin film of the color tone changing substance obtained in Reference Example 6 was scratched to expose the indium tin oxide layer. Obtained in reference example 1 is 1.74
g, dehydrate 0.26 g of lithium perchlorate to 2.5 ml THF
Dissolve in and apply 10μ onto the color tone changing material layer, being careful not to touch the exposed area.
After evaporating THF, under vacuum below 0.1 torr at 80℃
The mixture was heated and polymerized for 14 hours to create a solid electrolyte layer with a thickness of 0.075 μm. Metallic lithium is deposited on one side of a platinum plate with a surface area of 2 cm ² and a thickness of 0.5 mm, and the thickness is 650 mm.
A thin layer of .ANG. was formed. After that, under a dry argon atmosphere, the electrode with the structure of the transparent electrode/color tone changing material layer/solid electrolyte and this metal lithium vapor-deposited electrode were bonded together in a dry argon atmosphere, making sure that the exposed parts were not covered.
By pressing at a pressure of Kg/cm ² , an electrochromic display element whose basic configuration is shown in FIG. 1 was produced.
When I connected the terminal from the exposed part to the terminal from the platinum side, the color tone instantly changed from blue to white (nothing). Next, connect each terminal to a DC constant voltage power supply so that the oxidation reaction occurs on the color tone changing material layer side.
4.5 volts direct current was applied for 10 ms, 50 ms, 75 ms, and 100 ms. Immediately thereafter, the reflection spectrum was measured using a visible spectrophotometer under an open circuit condition. As a result, 100
In the case of milliseconds, the color tone changes to blue, and if the relative absorption intensity is 1, then it is 0.96 and 0.99 for 50 milliseconds and 75 milliseconds, respectively, and 0.35 for 10 milliseconds. It was also found that the intensity of this tone only decreased by 94% after at least 2 hours after open circuit. Next, for 1 second in advance
Each terminal of the display element, which had been given a 4.5 volt direct current to change the color tone, was directly short-circuited for 100 milliseconds, 200 milliseconds, and 500 milliseconds using a relay. As a result, in both cases, it returned to colorless when observed with the naked eye, and if the relative absorption intensity of the reflection spectrum was 0 before the color change occurred, and when it was completely caused,
Assuming 1.0, the value for 100 milliseconds was 0.02, and the other values were at least 0.01 or less. From the above, the electrochromic display element of the present invention undergoes almost complete color tone change within 50 milliseconds when 4.5 volts DC is applied. After changing the color tone, if it is placed in an open circuit state, the color tone will be maintained for a long time. After the color tone changes, when the short circuit condition is used, the original color tone is almost completely restored within 100 milliseconds. It is understood that it has characteristics. Regarding the future, regarding the color tone change time, which is the DC application time for the relative absorption intensity to reach 90%, the relative absorption intensity of the color after the open circuit will be 50% of the original color.
Regarding the decay time, which is the time required to return to %,
The time required for the relative absorption intensity to return to 90% of the original color tone will be referred to as the recovery time, and the following examples will be explained using this time. 1.74g of Example 2, 0.26g of lithium hexafluorophosphate
An electrochromic display element was constructed in exactly the same manner as in Example 1, except that 10 µm of 10 g dissolved in 2.5 ml of THF was used. By applying 4.2 volts of DC, it instantly changed from colorless to blue, and the color change time was less than 75 milliseconds. Also DC 4.2
When the voltage was applied for 1 second and then the circuit was immediately turned into an open circuit, the decay time was 7.5 hours, and the recovery time after the short circuit was about 80 milliseconds. After this, after applying 4.2 volts and running the short circuit 10,000 times for 1 second each, the color tone change time was
The decay time and recovery time were measured, and the results were exactly the same as those described above. Examples 3 to 21 Alkali metal thin films were created by vapor deposition as shown in Table 1 in the same manner as in Example 1, and phosphate ester macromer xg and alkali metal salt yg were added to 2.5 ml of THF as shown in Table 1. Using 10μ of the dissolved solution,
As shown in Table 1, Z
The color tone change time, decay time, and recovery time were determined in the same manner as in Example 1, except that an electrochromic display element was produced by pressure bonding at a pressure of Kg/cm ² . Results first
Shown in the table. [Table] [Table] Example 22 Color tone-changing substance-supported electrode in which WO ₃ was made into a thin film of 650 Å on indium tin oxide Nesa glass with a surface area of 1.0 cm ² and a sheet resistance of 30 Ω/sq. (Matsuzaki Vacuum Co., Ltd.)
An electrochromic display element was constructed in exactly the same manner as in Example 1, except that the electrochromic display element was used. Tone change time is 85 ms, decay time is 7.5 hours, recovery time is 95
It was hot in milliseconds.

[Brief explanation of the drawing]

FIG. 1 is a drawing showing the basic configuration of an all-solid-state electrochromic display element of the present invention, and FIG.
The figure is a diagram showing the basic configuration of a typical conventional liquid-phase electrolyte type electrochromic display element.
FIG. 3 is a drawing showing the basic structure of a typical conventional solid electrolyte electrochromic display element. 1... Conductive substrate, 2... Alkali metal thin layer,
3... solid electrolyte thin layer, 4... color tone changing substance thin layer, 5... transparent conductive layer, 6... glass substrate, 7,
7'... Connection terminal, 8... Switch, 11... Transparent substrate, 12... Spacer, 13... Color tone changing material layer, 14... Counter electrode, 15... Electrolyte solution injection port (later sealed), 16... Electrolyte solution,
21... Solid electrolyte layer, 22... Color tone changing material layer, 23... Transparent conductive substrate, 24... Glass substrate, 25... Connection terminal.

Claims (1)

[Scope of Claims] 1. As one electrode, an alkali metal selected from lithium, sodium, and potassium is used, and as a solid electrolyte, 80 to 95 parts by weight of a phosphate ester macromer represented by formula (1) and the same type as the alkali metal electrode are used. Salts of alkali metal ions, including lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium hexafluorophosphate, hexafluoroline sodium acid, potassium hexafluorophosphate, lithium trifluoroacetate, sodium trifluoroacetate,
Potassium trifluoroacetate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, lithium toluenesulfonate, sodium toluenesulfonate, potassium toluenesulfonate, lithium thiocyanate, sodium thiocyanate, thiocyanic acid A substance whose color tone changes according to the inflow and outflow of alkali metal ions associated with redox, using a hybrid ion conductor made by polymerizing a mixture of 20 to 5 parts by weight of an alkali metal salt selected from potassium as the other electrode. An all-solid-state type having a composition of [alkali metal electrode]/[solid electrolyte]/[color tone changing substance-transparent conductive substrate], which is formed by forming a thin film on a transparent conductive substrate and press-bonding these. Electrochromic display element. However, in formula (1), 4≦n≦22, 1≦a≦2,
2≧b≧1, a+b=3, R is a straight chain or branched alkylene group having 2 to 4 carbon atoms, and R' is hydrogen or a methyl group. 2 The structure of the color tone changing substance before the color tone change occurs due to the application of voltage is M _x (WO ₃ ) _y (where M is an alkali metal ion, 0.5≦x/y≦1.0), and the unit composition is M ₄ Fe ₄ [M′(CN) ₆ ] ₃ (M′ is iron, osminium or ruthenium)
2. The electrochromic display element according to claim 1, which is a coordination polymer of M3.(octacyanophthalocyanine) _3- ⁽ M is an alkali metal ion).