JPH03231229A - Electrochemical color developing element - Google Patents

Abstract

PURPOSE:To obtain an electrochemical color developing element not causing a soln. leak and having high ionic conductivity and superior adhesion to a counter electrode by forming a layer of an ionic conductive material with a material obtd. by combining a mixture of polymers each having a structure composed of arbitrarily arranged specified segments with ions causing solvation. CONSTITUTION:This element is composed of a transparent substrate 1, a transparent electrode 2, an electrochromic layer 3, a nonflowable polyelectrolyte 4, a counter electrode 5, a spacer 6 and a counter substrate 7. In this device, a layer of the ionic conductive material is formed with a material obtd. by combining a mixture of polymers each having a structure composed of arbitrarily arranged segments represented by formulae I-VI with ions causing solvation. In the formulae I-VI, M is a monovalent element such as Li, Na or K, each of h and k is the average number of repeating ethylene oxide units, 0<=h<=22.5, 0<=k<=15, each of l, m and n is 0 or a positive integer and 3<=l+m+n<=20,000. A soln. leak is not caused and high ionic conductivity and improved adhesion to the counter electrode are ensured.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an improved electrochemical coloring element, and more particularly to a display using an essentially leak-free all-solid electrochemical coloring element. It is related to the device.

(Prior art) The ion conductive material (electrolyte) layer in an electrochemical coloring element using a transition metal oxide as an electrochromic material layer is roughly divided into those related to liquid electrolyte layer and those related to solid electrolyte layer. . For the liquid electrolyte layer, an electrolytic solution mainly containing acids with high cation mobility such as sulfuric acid is used in order to increase the color development/discoloration reaction rate and obtain high foundation stability, but it has the following problems. have. That is, when used for a long period of time, the electrolyte tends to leak from the element, so strict sealing is required in the production of the element, making the process complicated and reducing work efficiency. On the other hand, in the solid electrolyte layer, the target ion mobility within the solid layer is low, and the adhesion of the interface between the solid electrolyte layer and the electrochromic layer is poor, making it difficult for ions to move smoothly at this interface. As a result, the response speed for developing and decoloring becomes slow.

Furthermore, electrochemical elements such as a* that utilize Bronton conduction generate hydrogen as a side reaction, and this hydrogen reduces the metal oxide that is the transparent electrode, such as SnO2, In, and O, and When using for a period of time,
There are also problems in that the display portion of the device unevenly changes to brown or black, resulting in a decline in functionality.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide an electrochemical coloring element that essentially has high ionic conductivity without leakage and has excellent adhesion with the opposite electrode. be.

Another object of the present invention is to provide an electrochemical coloring element which has a high response speed for color development and fading and which does not cause any deterioration in the function of the display part of the element even when used for a long period of time.

(Means for Solving the Problems) The present invention provides an electrochemical dye element comprising an electrochromic material layer made of a transition metal oxide and an ion conductive material layer in contact with the electrochromic material layer, wherein the ion conductive material layer has the following formula (
The present invention relates to an electrochemical coloring element characterized by being made of a polymer represented by h1 structure in which the segments of 1) to (6) are arbitrarily arranged, or a mixture thereof, and a complex of solvated ions.

0(CH:CH20)hCH3 M is a monovalent element selected from lithium, sodium, potassium, copper, silver, and hydrogen, 11 and k are the average repeating numbers of ethyleneoxy units, respectively, 0≦h≦2
2. A real value in the range of 5.0≦≦15, 1. m and n mean 0 or a positive integer value in the range of 3≦/10+*+n≦20000.

The electrochemical coloring element of the present invention is an electrochemical coloring display element using a non-flowing and non-proton conducting polymer electrolyte.

The device of the present invention has an electrochromic layer made of a transition metal oxide and a polymer electrolyte in contact with the electrochromic layer sandwiched between opposing electrodes, at least one of which is transparent.

Figure #In1 shows a cross section of an example of the structure of an element according to the present invention, which includes a transparent substrate (1), a transparent electrode (2), an electrochromic layer (3), and a non-flowing polymer electrolyte (4).
), a counter-polar electrode (5), a spacer (6), and a 9-transparent electrode (2) that is S* from the opposite 'IIL electrode (7) is made of an electronically conductive material such as a metal oxide, such as 5n02, In2O3 or polypyrrole. The film and electrochromic layer (3) are transition metal oxides such as WOL, Mob, and ■201, and the electrolyte (4) is a polymer having an IfI structure in which the segments of (1) to (6) above are arbitrarily arranged. The counter electrode (5) is a non-fluid highly ion conductive material that is a composite of ions solvated in - transition force lucodenide such as V2O9 containing -4f, lithium 7-erythiumide, lithium alloy, and V l -i They can each be constructed from a doped carbon material or the like.

The non-flowable polymer electrolyte according to the present invention is prepared by adding monovalent metal salts that have been dissociated and solvated with a solvent with a large number of donors or a substance with high coordination ability, and if necessary, applying ultrasonic irradiation, etc. It can be obtained by performing a '11 synthesis.

The solvated ion composite 'KiM' obtained in this way has already undergone ion dissociation compared to the one obtained by simply adding salt to the polymer, so it is possible to have a high ion concentration inside the electrolyte. Not only can high ion conductivity be achieved, but also ion exchange can be quickly performed at the interface of the electrochromic layer due to the action of the solvated substance.Therefore, the interfacial impedance can be lowered. The coloring/fading response time of the device can be shortened.Such high donor number solvents include water, alfur, triethylamine, birinone, nomethoxyethane, tetrahydro7rane, propylene carbonate, dimethyl sulfoxide, and oligoethylene glycol. , oligopropionate esters, etc., and substances with high coordination ability include crown ether, cryptand, tris(
methoxyethoxyethyl)amine, etc. -valent metal salts include alkali metals such as lithium, perchlorates such as silver and copper, trifluoromethylsulfonates,
Examples include BF, salt, PF6 salt, AsF5 salt, and the like. When preparing and applying the present composite electrolyte material I4, the presence of an excessive amount of solvate has no adverse effect as long as it is non-flowing, and may even be beneficial.

(Effects of the Invention) The electrochemical dye element using the present PI electrolyte does not leak even when used for a long period of time, and the appearance of the display part of the element is less likely to deteriorate.

Furthermore, since the electrochromic layer has good adhesion with the opposing electrode, flexibility can be imparted by selecting the electrode material, and it is easy to mold it into any size and shape. The device manufacturing process can also be simplified.
Ru.

(Example) The present invention will be explained below with reference to Examples.

Example 1 0(CH,C1(,O)l+cH.

-(N=P)1-
(1) 8g of a polymer with an average molecular weight of about 1 million, represented by ○(CH2CH20)hcH3 [
After adding 4 g of a 50% ether solution of Li.(nomethoxyethane)2doCtO,- and mixing, the ether is removed to prepare a composite solid electrolyte. on the other hand,〃
A TTO transparent electrode was fabricated on a lath substrate, and a thickness of 50 mm was placed on top of this.
00A WO3 is vapor deposited, and a 7% linium elycyanide film is separately deposited on the metal electrode! imitate These two were laminated with the previously prepared composite electrolyte to construct an electrochemical dye element.

When a DC voltage of 3 cm was applied between the transparent electrode and the counter electrode of the electrochemical dye element with the transparent electrode used as a cathode, a clear deep blue color was observed, and the color disappeared when the polarity was reversed. The response time for color development/decolorization was approximately 1#+, and no change was observed in the element state after 10,000 repetitions of color development/decolorization test with 3V applied, and the initial function and quality were maintained.

Example 2 25% in polyethylene glycol with an average molecular weight of 300
Add the same amount of formula (
Add the polymer shown in 1) and heat and melt;
R and electrolyte i11! Manufactured. Using this electrolyte, a device was assembled in the same manner as in Example 1, and tlV was generated by applying 3.
When a color test was conducted, good response speed and repeat durability were obtained as in Example 1.

Example 3 Polymer in which the segments of formulas (1) to (6) are arbitrarily arranged.
After adding 4 g of 0q6 ether solution and 2 g of lithium titanate fisker and mixing well, ultrasonication was performed for 30 minutes to remove the ether and transform the electrolyte into i1! l
Manufactured. And instead of WO3, I knee V2O5 TT
On the O electrode, and in place of lithium 7-elycyanide, Li
o, a・v20. The device was assembled and tested in the same manner as in Example 1, except that it was fabricated on a metal electrode, and the same results as in Example 1 were obtained.

[Brief explanation of drawings]

FIG. 1 shows a cross section of an example of the structure of an element according to the present invention, in which a transparent substrate (1), a transparent electrode (2), an electrochromic layer (3), a non-flowing polymer electrolyte (4), an opposing A pole (5), a spacer (6), and a counter electrode () are shown. (Above) Applicant: Otsuka Chemical Co., Ltd.

Claims (1)

[Claims] (1) In an electrochemical dye element comprising an electrochromic material layer made of a transition metal oxide and an ion conductive material layer in contact with the electrochromic material layer, the ion conductive material layer has the following formula (1
1. An electrochemical coloring element characterized by comprising a polymer having a structure in which the segments of () to (6) are arbitrarily arranged, or a mixture thereof, combined with a solvated ion. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( 4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(5) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(6) M is a monovalent element selected from lithium, sodium, potassium, copper, silver, hydrogen, h layer and k are the average repeating numbers of ethyleneoxy units, respectively, 0≦h≦22.5;
Real numbers in the range 0≦k≦15, l, m, n are 3≦l+m
It means 0 or a positive integer value in the range of +n≦20,000.