JPS62270925A - Electrochromic element provided with conductive clip - Google Patents

Abstract

PURPOSE:To improve the responsiveness of an electrochromic element (ECD), to generate no uneven coloring and quenching, and to improve the connection workability of an external wiring and the reliability of the ECD, by attaching in advance a conductive clip to a taking-out part of an electrode of the ECD. CONSTITUTION:An ITO electrode layer is formed on the whole surface of a rectangular glass substrate S, and a groove is formed between a taking-out part F for the upper electrode A and the lower electrode B. The taking-out part F, the rectangular lower electrode B isolated therefrom, and a taking-out part B1 continued therefrom are formed. Subsequently, a reversible electrolytic oxidation layer C consisting of a mixture of iridium oxide and tin oxide, a tantalum oxide layer D and a tungsten oxide layer E are formed in order. Next, Al is vapor-deposited as the upper electrode A, and in this case, Al is formed so that its one end contacts the taking-out part F which has been formed on the substrate S already. A chip H is installed to short side sides of the substrate, respectively, so that a fragment H1 of the clip welds by pressure the taking-out parts F, B1.

Description

[Detailed description of the invention] 3. Detailed description of the invention [Industrial application field] The present invention relates to improvements in electrochromic elements.

Hereinafter, electrochromic will be abbreviated as rEcj and EC
The element is abbreviated as rEcDJ.

[Conventional technology]

When a voltage is applied, a reversible electrolytic oxidation or reduction reaction occurs, resulting in reversible coloring. This phenomenon is called electrochromism. Using an electrochromic (hereinafter abbreviated as EC) material that exhibits such a phenomenon, we create an EC element (hereinafter abbreviated as ECD) that changes color and decolors by voltage manipulation, and use this ECD as a light amount control element (for example, Attempts have been made for more than 20 years to use this technology in numeric display devices using 7-segment mirrors and 7-segment display devices. For example, on a glass substrate, a transparent electrode film (scratching), tungsten trioxide (Al)
l! An ECD (see Japanese Patent Publication No. 52-46098) in which an insulating film such as silicon dioxide and an electrode film (anode) are sequentially laminated is known as an all-solid-state ECD. This ECD
When a voltage is applied to , the tungsten trioxide (WO3) thin film is colored blue.

Then, when a reverse voltage is applied to this ECD, W O3
The blue color of the thin film disappears and it becomes colorless. Although the mechanism of coloring and decoloring has not been elucidated in detail, a small amount of water contained in the WO1 thin film and insulating film (ion conductive layer) causes W○,
It is understood that it controls the coloring and decoloring of The reaction formula for coloring is estimated as follows.

Cathode side: I (□O-H'+ 0H- WO3+nH" +ne-→H, WOt (S color transparent)
(Blue) Anode side: OH--1/2 H20+1/402 ↑+1/2e-
By the way, at least one of the pair of electrode layers that directly or indirectly determines the ECN must be transparent in order to show the coloring and fading of the EC layer to the outside. Particularly in the case of a transmission type ECD, both must be transparent. At present, S n Ox % I nz is used as a transparent electrode material.
Os, I To (mixture of S n Ox and In, O, IJ), Zn○, etc. are known, but these materials have relatively poor brightness and must be made thinner.
For this and other reasons, ECDs are usually formed on a substrate such as glass or plastic, and an example of the structure of such an ECD is shown in FIG.

In Figure 4, (A) is the upper transparent electrode, (B) is the lower transparent electrode, and (E) is the reduction coloring EC layer (for example, WO3).
, (D) represents an ion conductive layer, and (C) represents a reversible electrolytic oxidation layer or an oxidatively colored EC layer (e.g., iridium oxide or hydroxide), and is basically a stack of these (A) to (B). The structure alone constitutes the ECD, but as described above, these ECDs are formed on the substrate (S).

(R) is an ECD sealing material such as epoxy resin;
G) is a protective sealing substrate.

In order to supply external power to the electrodes (A) and (B) of such an ECD, an extraction electrode section is required,
External wiring (LA), (L,) was connected here by soldering.

[Problems to be Solved by the Invention] Conventionally, the extraction portion has been formed using the same material and manufacturing method as the upper and lower electrodes, and therefore has not been formed using vacuum thin film forming techniques such as vacuum evaporation, ion blating, and sputtering. (a) ITO or other oxide thin film, or (
b) Ae and other metal thin films were used.

However, in both cases (a) and (b), the lead-out part is very thin, so there is a problem that the soldering work efficiency is low.
Since the resistance is relatively high, if the external wiring is soldered directly, the external wiring with low resistance and the lead-out part with high resistance are in contact at one point, so the charge supplied from the external wiring to the whole electrode through the lead-out part is reduced. There were problems in that the supply speed was slow, resulting in poor response and uneven coloring and decoloring.Furthermore, there was a problem in that the external wiring peeled off from the outlet when subjected to the hot water test. .

In the case of (b), there was a problem in that the take-out portion peeled off from the substrate when subjected to a hot water infiltration test.

Therefore, an object of the present invention is to solve these problems, to prevent peeling even when subjected to a hot water immersion test, and to ensure that the supply speed of charge supplied from the external wiring to the entire electrode through the lead-out portion is not slow. An object of the present invention is to provide an ECD that has good responsiveness and does not cause uneven coloring or decoloring.

[Means for solving problems]

For this reason, in the ECD of the present invention, a low-resistance conductive clip is attached to the extraction portion, and external wiring is connected to this.

[Effect]

FIG. 5 is a perspective view showing an example of a conductive clip used in the present invention, and as shown in FIG. 6, this clip is approximately gutter-shaped with a substantially U-shaped cross section. .

This clip consists of a piece H+ that contacts the take-out part, a piece H2 that presses the board, and a connecting plate part H3 that connects the two pieces. Then, the periphery of the substrate, in which the extraction portion is formed on the surface of the periphery, is sandwiched between the old fragment and the fragment H2. Therefore, to prevent the clip from coming off the board after being pinched, it is preferable that the pieces H and H2 firmly grip the base 1, as shown in FIG. , and the fragment H2 is narrow near the entrance and widens as it approaches the connecting plate H3, and is preferably made of a metal having spring properties.Metals can also be soldered well. Therefore, it is preferable. Phosphor bronze is a preferable metal having elasticity, but steel and the like may also be used.The metal clip is made of a relatively soft metal such as tin, indium, It may be coated with solder, mixtures thereof, or other conductive materials, such that the lip will have the best contact with the outlet.

This is because metal surfaces generally have subtle irregularities when viewed under a microscope, and mere pressure contact does not provide the best possible contact with the extraction portion. Furthermore, tin plating on phosphor bronze clips has the advantage of improving corrosion resistance.

There is no limit to the length of the clip, so use one that has the length necessary to match the strip-shaped extraction section. In this way, the contact area between the extraction part and the clip will be very large, the electrical resistance between the two will be reduced, and since the clip is made of a low-resistance material, it will not be possible to connect it to the external wiring at a single point. Also, the supply of charge from the external wiring to the electrode through the lead-out part is smooth, the responsiveness is improved, and there is no uneven coloring or decoloring.

Furthermore, since the clip always presses the extraction part against the substrate, there is no risk that the modified part will peel off from the substrate even if it is subjected to a hot water immersion test. However, when attaching the clip, there is a risk that the take-out part may be used accidentally, so it is preferable that the take-out part itself is made of a strong IT○ or other oxide-based electrode material. However, if you pay close attention to the installation process, the fear of damage to the parts can be eliminated.

As mentioned earlier, the overall shape of the clip is approximately V-shaped, but E
It may be curved in the length direction to match the shape of the CD. For example, even if the ECD has a rectangular base, the saw board has an R along the circumferential surface of the cylinder as a whole, or the board is not a rectangle but a circle with two parallel straight lines. If it has the shape shown in Figure 7, which is obtained by cutting it off, or the shape of a television screen, as shown in Figure 8,
The clip may have a shape that matches the shape of the periphery of such a substrate.

If the ECD is an all-solid-state 111m type, the thickness of the ECD itself, excluding the substrate, is very thin (e.g., O
, 01mm or less), whereas clips are generally thick, 0.05 to 2IIIm, due to the cost of 1,000 mm.
When attached to D, as shown in FIG. 9, the clip segment H is thicker than the ECD, and therefore a step is created at the border between the display section of the ECD and the segment H. Therefore, if this level difference is used to position the sealing glass, the positioning work can be done easily and accurately.

In order to make this positioning work easier and more accurate,
As shown in the figure, the abutting piece H4 may be provided by standing the tip of the clip fragment H+ vertically. When the clinop is curved in the length direction, it is easier to curve the abutment piece H4 by making wedge-shaped slits (splits) here and there in advance. Furthermore, the abutment piece H4 does not need to be erected on the entire edge of the tip of the fragment H1, and may be partially erected.

As shown in No. 9-, if the end of the sealing glass is in contact with the clip and there is no gap between them, the ejecting part will not be able to be removed even when the ejecting part is made of a metal that is easily corroded such as Ap. The parts are not easily corroded. If a gap exists,
Even if the take-out part is sealed with a sealant such as Evokin resin, the take-out part is susceptible to corrosion due to the influence of moisture that penetrates through the sealant. However, when the sealing material is covered with the sealing glass and the clip to cut off contact with the outside world, the ejection portion corrodes and becomes silica. Therefore, the electrode A7! Even when the ECD is made of a metal that is easily corroded, such as ECD, there is no need to change only the extraction part or the surrounding area to ITO or other oxide-based material that is resistant to corrosion, which reduces the manufacturing cost of the ECD.

The conductive clip, which is a feature of the present invention, may also serve as a shielding material or a decorative material for the periphery of the electrochromic element. In particular, in the case of an anti-glare mirror (one in which the amount of reflected light is electrically controlled) where the ECD is viewed from the board side, it is desirable for aesthetics to make the area of the display part as large as possible and the peripheral part thin, so it can be used for both purposes. It is advantageous to do so.

The clip can be attached to the ECD before or after the sealing, but if it is attached before sealing, the sealing material is applied to the sealing glass and the ECD is pasted, and then the sealing material is cured. , the sealing material enters through the invisible minute gap between the take-out part and the fragment H, and fills the relatively large gap between the substrate end surface and the clip (No. 111i!).
(see J). In this case, compared to when the clip is attached after sealing and the sealing material does not fill the gap, the sealing material makes it difficult for external moisture to enter the extraction portion, making the extraction portion less susceptible to corrosion. Further, since the sealing material that has entered the gap adheres the substrate and the clip, there is an advantage that the clip is difficult to detach from the substrate.

If the clip is made of a material that can be soldered, soldering is sufficient when connecting external wiring to the clip, but if the clip is made of metal, crimp or crimping may be used instead of soldering. It may last for a long time due to pressure 1.

As a method of crimping or clamping, when a metal clip is used, for example, +11 a method of simply sandwiching the exposed external wiring between the end of the clip (particularly fragment H3) and the board; a modification thereof is a method of using a clip. A method of making a hole, groove, or slit in the middle of the length direction, inserting the exposed end of the external wiring through this hole or groove, and inserting it between the clip (particularly fragment H1) and the wire. As a modified example, two holes, grooves, or slits (splits) are made in the middle of the length direction of the clip, and the tip of the exposed external wiring is inserted through the first hole, groove, or slit (splits). 2 hole or groove or slit (split)
Clip the exposed external wiring (
(2) Using a long clip, inserting the exposed end of the external wiring into the clip protruding from the ECD, and then pushing the clip in. 3) At the middle or end of the length of the clip, for example, as shown in FIG.
Examples include a method in which a crimping piece Hs shaped like a letter "J" is provided, and the tip of the exposed external wiring (L) is crimped between the crimping pieces Hs. Alternatively, the crimp piece H6 may be created by bending a part of the piece H.

When the external wiring is connected to the clip by soldering, it is preferable to connect the external wiring to the clip before attaching it to the ECD. This way, the ECD will not be exposed to the heat of soldering and there will be no risk of injury due to heat.

Since the connection between the external wiring and the clip is physically and chemically weak, it is preferable to seal it. This seal is an ECD
It is particularly preferable to carry out the sealing process simultaneously with the sealing process, since a separate sealing process is not required.

On the other hand, although the laminated structure of the ECD in the present invention is not particularly limited, examples of the structure of the solid-state ECD include (i) electrode layer/EC layer/ion conductive layer/electrode layer; Examples include a four-layer structure, and a five-layer structure such as (2) electrode layer/reduction colored EC layer/ion conductive layer/reversible electrolytic oxidation layer or oxidation colored ECC layer multi-electrode layer.

Examples of the material for the transparent electrode include SnO2, In,
O,, I'r○, etc. are used. Such an electrode layer is generally formed by vacuum thin film forming techniques such as vacuum evaporation, ion blasting, and sputtering. (Reduction coloring property) WOl, MoO2, etc. are generally used as EC5.

As the ion conductive layer, for example, silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, magnesium fluoride, etc. are used. These substances Tjil
'J is an insulator with respect to electrons due to the manufacturing method, but is a good conductor with respect to protons (H') and hydroxy ions (OH-). Cations are required for the coloring and decoloring reaction of the EC layer, and it is necessary to contain H'ions and Li'ions in the EC layer and other parts. It is no longer necessary that the H' ions are ions from the beginning; it is sufficient that H° ions are generated when a voltage is applied. Therefore, water may be contained instead of the H' ions. Very little of this water is sufficient, and often even moisture that naturally enters from the atmosphere will discolor.

The EC layer and the ion conductive layer may be placed either side up or down. Furthermore, a reversible electrolytic oxidation layer (or oxidation-colored EC layer) or a catalyst layer may be provided with an ion-conductive layer interposed between the EC layer and the EC layer.

Such layers include, for example, iridium oxide or hydroxide, nickel, chromium, vanadium, ruthenium, rhodium, and the like. These substances may be dispersed in the ion conductive layer or the transparent electrode, or may be dispersed therein.

The opaque electrode layer may also serve as a reflective layer, and for example, metals such as gold, silver, aluminum, chromium, tin, zinc, nickel, ruthenium, rhodium, and stainless steel are used.

Hereinafter, the present invention will be explained in detail with reference to Examples with reference to FIGS. 1 to 3.

〔Example〕

An ITO electrode layer is formed on the entire surface of a rectangular glass substrate (S), and then a groove is formed between the extraction part (F) for the upper electrode (A) and the lower electrode (B) by photoetching or laser cutting. was formed. A lead-out part (F), a rectangular lower electrode (B) isolated from the lead-out part (F), and a lead-out part (Bl) of the lower electrode continuously following the lead-out part (B) were formed (see FIGS. 2 and 3).

Note that these patterns may be directly formed by mask vapor deposition of +1'O.

Next, a reversible electrolytic oxidation layer (C) made of a mixture of iridium oxide and tin oxide, a tantalum oxide layer (D), and a tungsten oxide layer (E) were formed in this order. Next, the upper electric current i (
As A), Al1 was mounted, and at this time Affi was formed so that one end was in contact with the take-out part (F) already formed on the substrate (S).

Two conductive clips (H) made of phosphor bronze were prepared in advance, and external wiring (L, ) or (Lll) was connected to each with solder or reverse conductive adhesive.

Attach this clip (H) to each short side of the board,
As a result, the clip fragment H, is removed from the extraction section (F) and (B).
1) was crimped.

The shape and dimensions of this four-electrode clip (I) are set so that the sealing glass plate (G) can be positioned and the non-display area around the ECD can be masked.

Finally, lay the sealing glass plate (G) coated with a large amount of epoxy resin sealant (R) on top of the ECD, and place the glass plate (G) between the two opposing holes. I paid it. Since the distance between the two clips and the length of one glass (C) are approximately the same, positioning of the glass plate (G) can be easily and easily achieved by placing the glass plate (G) between the clips. It was done quickly.

If the sealing material (R) is left until it hardens, the excess sealing material (R) will cover the extraction part, part of the clip, and the external wiring connection part, and will cover the gap between the base +7i (S) and the knob. and sealed them. This made the clip firmly adhered to the board and could not be removed.

In this way, the ECD of this example was produced. A vertical section of this ECD is shown in FIG. This figure is partially deformed and does not have accurate dimensional ratios.

Coloring voltage (+1.3
When a voltage of 5V) is applied, the reflectance decreases to 15% for light (L) with a wavelength of 633 nm incident from the left plate (S) side (after 10 seconds), and this reflectance remains unchanged even after the voltage application is stopped. , was held for a while. When a decoloring voltage (-1.35 V) was applied this time, the reflectance recovered to 65% (after 10 seconds).

Therefore, the ECD of this embodiment is useful as an anti-glare mirror for automobiles and other vehicles, and when a strong light from a car approaching from behind hits the mirror, the driver will not be dazzled by applying a voltage to reduce the reflectance.

In this embodiment, the upper electrode and the lower electrode each have one extraction portion on the short side of the substrate, but an extraction portion may also be provided at the terminal portion, and charges may be supplied from both. In this case, the extraction portions of one electrode are provided on both short sides of the substrate, the extraction portions of the other electrode are provided on both long sides of the substrate, and the clips are provided on all four sides of the substrate.

〔Effect of the invention〕

As described above, according to the present invention, since a conductive clip is attached in advance to the electrode extraction part of the ECD and external wiring is connected through this, the responsiveness of the [11E CD] is improved, and coloring/decolorization is achieved. (2) The connection workability of external wiring is improved, and (3) the lead-out part from the board does not peel off from the board or the connection part with external wiring does not peel off even when subjected to a hot water immersion test. ECD's (octavertability improves.

[Brief explanation of drawings]

FIG. 1 is a schematic vertical sectional view of an ECD according to Example 1 of the present invention. FIG. 2 is a schematic plan view of the substrate (S) on which the electrodes according to the first embodiment are formed. FIG. 3 is a sectional view taken along the arrow in FIG. 2. FIG. 4 is a schematic vertical cross-sectional view of a conventional ECD. FIG. 5 is a perspective view showing an example of a conductive clip. FIG. 6 is a cross-sectional view of the fifth conductive clip. FIG. 7 is a plan view showing an example of the substrate. FIG. 8 is a plan view showing an example of the substrate. No. 90 is a schematic cross-sectional view showing an example of the 0ECD of the present invention expressed in a dimension ratio closer to the actual size than No. 111ffi. FIG. 1O is a sectional view of another example of the l-type clip. FIG. 11 is an explanatory diagram showing how the sealing material has entered the gap between the substrate and the tetraelectric clip. FIG. 12 is a sectional view of yet another example of the l-type clip. (Explanation of symbols of main parts) S ----・-1-l & Tentan A -----1 Upper electrode B -・-----1 - Lower electrode B+ ""-""'- Lower electrode Take-out part E -・-1----- Reduction coloring EC layer or W○3 layer F -
m-----Top electrode extraction part H-1---------
- Conductive clip C-----1 Sealing glass plate R-...-1-- Sealing material

Claims (1)

[Claims] 1. In an electrochromic element comprising at least an upper electrode, an electrochromic layer, and a lower electrode, conductive clips are attached to the lead-out portions of the upper electrode and the lower electrode, respectively, and external wiring is connected through these. An electrochromic element characterized by: 2. The electrochromic device according to claim 1, wherein the conductive clip is made of a substantially gutter-shaped metal having a U-shaped cross section. 3. The electrochromic device according to claim 2, wherein the metal is made of a metal having spring properties. 4. The electrochromic device according to claim 3, wherein the metal is phosphor bronze. 5. The electrochromic device according to claim 1, wherein the sealing glass plate is positioned by a conductive clip attached to the extraction portion. 6. The electrochromic device according to claim 1, wherein the conductive clip also serves as a shielding material for the periphery of the electrochromic device. 7. The electrochromic device according to claim 1, wherein the conductive clip also serves as a decorative material for the periphery of the electrochromic device.