JP3480002B2 - Electrochromic dimming window - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic (hereinafter referred to as E
(Referred to as C) regarding the light control window.

[0002]

2. Description of the Related Art A dimming window using the EC phenomenon has been conventionally known, and generally has a structure shown in FIG. 4, 1,7 a transparent substrate made of material such as glass,
2 and 6 SnO _2, Zn-doped Ga O of which the transparent conductive film doped with In ₂ O _3, F-doped Sn,
3 the oxide back to the original transparent when colored to be electrochemically reduced in the reduction coloring type EC film Ru is oxidized (WO _3, Ti
Film made of O _2, etc.), 5 consists of an oxide back to the original transparent when colored to be electrochemically oxidized by the oxidation coloring type EC film Ru is reduced (NiO, IrO _2, or the like) film also 4 is a liquid or semi-solid organic lithium electrolyte or proton electrolyte.

Reference numeral 8 is a sealing material made of epoxy resin , butyl rubber or the like and having low gas permeability, and 9 is a power source for supplying a current for energizing the light control window. As a result of studying such a conventional EC dimming window , reduction emission of WO ₃ etc.
Although the durability of the color EC film is at a practical level, the driving durability of the oxidation color EC film such as NiO is not sufficient. Therefore, the EC dimming window immediately after manufacturing has a visible light transmittance of 70%.
Between 20% and 20% , 40 after thousands of cycles
Changes only between % and 20% , between 30% and 10%
To go be decreased decolorization transmittance gradually rather, NiO when the drive voltage is too high it was found that the prone plaques uneven EC dimming window dissolved.

[0004] Visible light transmittance variation were small cycle (
Visible light transmittance varies between 60% and 30%
The cycle has a driving life of 100,000 times or more, but when the visible light transmittance change width becomes large, the EC light control window may be deteriorated in appearance. This is a reduction coloring such as WO ₃
The type EC film is stable to the coloring / discoloring cycle in the organic electrolyte, whereas the oxidative coloring type EC film such as NiO becomes unstable in the coloring / discoloring cycle in the organic electrolyte, and depending on the case. It is considered that the cause is that the change in characteristics occurs only by contact with the organic electrolyte .

[0005]

The object of the present invention is to solve the above-mentioned drawbacks of the prior art, that is, the oxidative coloring type E C.
It is intended to solve the problem that the characteristics such as stability of the color fading and decoloring characteristics and durability are deteriorated by the contact of the film with the organic electrolyte.

[0006]

Means for Solving the Problems The present invention has been made to solve the above problems, a first substrate having a first transparent conductive film and the reduction coloring electrochromic layer were sequentially formed , the second transparent conductive film with oxidized color type electrochromic electrolyte gap can be Mick film and are relatively and the second substrate are sequentially formed a filled, the first and second
In the electrochromic dimming window in which the periphery of the substrate is sealed, a protective film having ion conductivity and for avoiding direct contact with the electrolyte is formed by using the reduction coloring electrochromic film or the oxidation coloring electrochromic film. providing an electrochromic light control window, characterized in that formed on the at least one membrane.

[0007] The first and second substrate is preferably a glass transparent substrate, said first and second transparent conductive film is Sn
Doped In ₂ O ₃ , F-doped SnO ₂ , Ga
ZnO and the like can be preferably used.

[0008] or wherein the reduction coloring type EC film Ru is colored to be electrochemically reduced oxidation back to the original transparent oxide
Rana is, can be preferably used WO _3, TiO _2, etc. as oxide.

[0009] or wherein the oxidative coloring type EC film Ru is colored to be electrochemically redox back to the original transparent oxide
Rana is, as the oxide NiO, IrO _2, or the like can be preferably used.

[0010] The protective layer, proton conductivity, the lithium conductivity and proton - selected from lithium mixed conducting
That either have an ionic conductivity, Ta ₂ O ₅ less likely to be electrochemically _{corroded, Sb 2 O 5, LiNbO 3} , Ce
It is preferably composed of any oxide selected from O ₂ , Y ₂ O ₃ and La ₂ O ₅ .

The electrolyte is prepared by adding LiCl to an organic solvent of γ-butyrolactone or propylene carbonate.
A solution electrolyte in which a supporting electrolyte such as O ₄ , LiBF ₄ , LiCF ₃ SO ₃ or the like is dissolved is preferable.

[0012] Alternatively, the electrolyte is a poly oxy ethylene emissions
A film-like electrolyte composed by supporting the supporting electrolyte, those ion conductivity is 1 [mu] S / cm or more.

[0013] Figure 1-3 is a sectional view of a basic configuration of the present invention, parts and components shown in the figure 1-9, the description will be the same as the Figure 4 the conventional example Omit it.
In FIG. 1, the protective film 10 is laminated on the reduction coloring type EC film 3.
ing. In FIG. 2, the protective film 11 is formed on the oxidation coloring type EC film 5.
It is stacked. Figure 3 protective film 10 on the reduction coloring type EC film 3, is, and the protective film 11 on the oxide color forming EC film 5 are laminated.

[0014] In FIG. 1, a glass, on a transparent substrate 1, 7, such as plastic, I n ₂ O ₃ which is Sn-doped,
A transparent conductive film 2 and 6, such as F-doped SnO _2, Ga-doped ZnO is formed. 3 is a reductive coloring type EC film, colored and is electrochemically reduced Ru is oxidized
Oxide back to the original transparent (WO _3, TiO _2, etc.)
A film, 5 is the oxidation coloring type EC film, the coloring to be electrochemically oxidized Ru is reduced oxide back to the original transparent (N
iO, film made of IrO _2, etc.), also 4 electrolyte der
It is a liquid or semi-solid organic lithium electrolyte or proton electrolyte. 8 is epoxy resin , butyl rubber, etc.
A sealing material having low gas permeability, and 9 is a power supply for supplying a current for energizing this light control window.

[0015] The have been exposed transparent conductive film at the edge of the substrate 1, 7, a low resistance in this portion (e.g., 1Ω Not
Mitsuru) forming a metal bus bar, connecting to a power supply lead. Although not shown in FIG. 1, in order to keep the distance between the substrates 1 and 7 constant, spacers such as fine transparent particles such as glass spheres may be dispersed between them.

The transparent conductive film 2 and 6 doped with Sn an In
₂ O ₃ ( ITO), F-doped SnO ₂ , Ga
A Zn O of any mixed oxide film-loop, it is preferable that a sheet resistance of 1~10Ω / □, a sputtering method, may be deposited at an electron beam method or other appropriate means.

[0017] From the reduction coloring type EC film 3 is an oxide back to the original transparent when colored to be electrochemically reduced Ru is oxidized
It may be Re Do, 1000 to 1000 and WO _3, TiO _2, etc.
It is preferably formed as a thickness of 0 Å. Oxidized color forming EC film 5 Ru is colored to be electrochemically redox
If Re Tona oxide back to the original transparent and well, NiO, I
The and rO _2, etc. 1000 to 10000 <br/> Rukoto be formed by the thickness of Å is preferred.

Reduction coloring type EC film 3 and oxidation coloring type EC film 5
The film thickness ratio of the normal 1: is a 1, EC dimming window after fabrication
To measure changes in transmittance of the Chakushoiro, it may be selected as appropriate film thickness ratio as with no color remaining on during discoloring.

The reduction coloring type EC film 3 on the protective film 10 is, proton conductivity, the lithium conductivity, proton - have an ionic conductivity such as lithium mixed conducting, electrochemically corroded hard oxides, e.g. Ta ₂ O ₅ , Sb ₂ O ₅ , Li
It is preferably composed of a hydrated oxide such as NbO ₃ , CeO ₂ , Y ₂ O ₃ and La ₂ O ₅ . When using a hydrated oxide of Ta ₂ O ₅ , a film thickness of 500 to 500
Film is formed so as to be 5000 Å, and it is 3500c by infrared spectroscopy
It is preferable that the near-dated m ^-1 for a film having an absorption of OH group.

Further, the film quality of the protective film (film thickness, compactness, etc.) determined optimum value of details on how, after ized EC dimming window, the response time of the transmittance change was measured, with the dimming window 10cm square 5 If it takes more than a minute, it may be thinned or made porous , and then cycle driving may be performed to increase the film thickness or densify it when the oxidation coloring type EC film 5 is dissolved.

The electrolyte 4 is an organic lithium electrolyte liquid or semi-solid, proton electrolyte and lithium - either a proton mixed conducting electrolyte. Examples of the liquid electrolyte include organic solvents such as γ-butyrolactone and propylene carbonate, LiClO ₄ , LiBF ₄ , and LiCF _3.
A supporting electrolyte such as SO ₃ is dissolved in 0.01 to 1M, and water is added.
Like the concentration is those prepared to 100~5000ppm
Good The spacing between the substrates 1 and 7 about 10~300μm are preferred.

[0022] As the organic electrolyte semisolid, film-like electrolyte or the like which can be supported a supporting electrolyte of the foregoing to those based on polyoxyethylated ethylene emissions and the like are preferable. If the ionic conductivity is 1 μS / cm or more,
What is called a so-called organic solid electrolyte can be used in principle. For example, polyoxyethylene, A chestnut <br/> rate, and mixing the light-curable prepolymer and a liquid electrolyte such as urethane, a photopolymerization initiator acetophenone 0.0
It is also possible to fill the space between the two substrates 1 and 7 with the addition of about 1 to 0.1% and cure by irradiation with ultraviolet rays from a mercury lamp or the like.

[0023]

[Function] Conventionally, NiO is used as the oxidation coloring type EC film,
For EC dimming window using WO ₃ as a reduction coloring type EC film
There are, for example, colored (+ 1.5V, 20sec), decolorization (-1.5V, 40 sec) repeated cycles thousands of times performing the visible size of the black spots of a and color erasing impossible partial black dots It happened, but those black spots and blackening are WO
It was found that Ni was generated on the above ₃ and the main component was Ni. Further, since Ni was also detected in the electrolytic solution, it is presumed that Ni was eluted from the oxidative coloring type NiO into the electrolytic solution by the driving for coloration / decoloration, and was electrolytically deposited on WO ₃ .

As a countermeasure against this, the concentration of water in the electrolytic solution should be 2
By setting the amount to be 0 to 300 ppm, the black and white color and the coloring / decoloring cycle until blackening are extended to 1 to 20,000 times, and the size of the black dot is
Although the number decreased, the black spots remained unerasable.

The protective film on the oxidative coloring type EC film (NiO) of the present invention is a selective permeable film which can pass (proton hopping) OH ⁻ necessary for the EC effect of NiO, but cannot pass nickel ions. it is conceivable that. The protective film of the electrolyte anion (ClO ₄ ^-, etc.), cationic (L
Regarding whether or not it is better to allow i ⁺ ) to pass through, it is preferable to pass them through, at least from the viewpoint of the conductivity of the protective film. It can be inferred that the protective film prevents direct contact between the EC substance and the electrolyte, and also has an effect of suppressing decomposition and foaming of the electrolyte component on the EC electrode.

The protective film on the reduction coloring type EC film (WO ₃ ) is composed of cations or protons necessary for WO ₃ coloration and decoloration.
It passes lithium and sodium, but not nickel ions. Further, due to the electronic insulating property, it is possible to prevent the eluted nickel ions from receiving a charge on WO ₃ and depositing.

The hydrated ion diameter in an aqueous solution is H ⁺ (9
^{Å), Li + (6 Å} ), OH - (3.5 Å), ClO 4 -
It is (3.5 Å ), Ni ²⁺ (6 Å ), and it is not clear whether it is the same even in the organic electrolyte, but if the pore size is about 4 Å , the selective permeability of OH ⁻ and Ni ²⁺ can be explained. It seems to be. In addition, the state is in the WO ₃ Li ⁺ is not the name in the hydration products
It is highly possible that such Li ⁺ will enter 1.2
Since the diameter is Å or less, there is a good possibility that hydrated Ni ²⁺ can be blocked on WO ₃ .

[0028]

EXAMPLES The present invention will be described in more detail below with reference to specific examples of the present invention with reference to FIGS. In Figure 1-3, the parts and components indicated by reference numeral 1-9 is common to FIG. 4 of the prior art, a description thereof will be omitted.

Example 1 As shown in FIG. 1, Sn doping with a sheet resistance of 10 Ω / □ was performed.
Was an In ₂ O ₃ WO ₃ (reduction coloring type EC film 3) on the (first and second transparent conductive films 2, 6) a glass substrate (substrate 1, 7 of the first and second) and NiO (oxidation Coloring type EC film 5)
Each film was formed to a thickness of 5000 Å . Further, Ta ₂ O ₅ (protective film 10) was formed into a film having a thickness of 1000 Å only on WO ₃ to prepare two substrates 1 and 7. The periphery of the two substrates 1 and 7 was sealed with an epoxy resin (sealing material 8) so that the distance between them was 50 μm, and 1M LiC was filled in the gap.
An EC dimming window was prepared by injecting and sealing γ-butyrolactone (electrolyte 4) containing 10 ppm of 10 ₄ and H ₂ O. As a result, an EC light control window having a color life of 100,000 times or more was obtained.

[0030] (Example 2) As shown in FIG. 2, shea over sheet resistance 10 [Omega / □ of Sn-doped
Was an In ₂ O ₃ WO ₃ (reduction coloring type EC film 3) on the (first and second transparent conductive films 2, 6) a glass substrate (substrate 1, 7 of the first and second) and NiO (oxidation Coloring type EC film 5)
Each film was formed to a thickness of 5000 Å . Further, Ta ₂ O ₅ (protective film 11) was formed into a film having a thickness of 1000 Å only on NiO to prepare two substrates 1 and 7. The periphery was sealed with an epoxy resin (sealing material 8) so that the distance between the two substrates 1 and 7 was 50 μm, and 1M LiClO was filled in the gap.
₄ , γ-butyrolactone (electrolyte 4) containing 1000 ppm of H ₂ O was injected to prepare an EC dimming window sealed. Similar to Example 1, an EC dimming window having a coloring / discoloring cycle life of 100,000 times or more was obtained.

Example 3 As shown in FIG. 3, Sn doping with a sheet resistance of 10 Ω / □ was performed.
Was an In ₂ O ₃ WO ₃ (reduction coloring type EC film 3) on the (first and second transparent conductive films 2, 6) a glass substrate (substrate 1, 7 of the first and second) and NiO (oxidation Coloring type EC film 5)
Each film was formed to a thickness of 5000 Å . Furthermore it Ta ₂ O ₅ (protective film 10, 11) on the WO ₃ Oyo <br/> beauty NiO
It was produced two substrates 1,7 was deposited to a thickness of respectively 1000 Å. The periphery is sealed with an epoxy resin (sealing material 8) so that the distance between the two substrates 1 and 7 is 50 μm,
Γ-Butyrolactone (electrolyte 4) containing 1M LiClO ₄ and H ₂ O 1000 ppm was injected into the void to form a sealed EC dimming window . Similar to Example 1, an EC dimming window having a coloring / discoloring cycle life of 100,000 times or more was obtained.

(Embodiment 4) With the same structure as in Embodiments 1 to 3, the oxidation coloring type EC film 5 is formed.
Similar characteristics were obtained when CoO was used.

(Example 5) With the same structure as in Examples 1 to 3, the same characteristics were obtained when the solvent of the electrolyte 4 was propylene carbonate, dimethyl sulfoxide, or a nitrile-based solvent.

(Embodiment 6) With the same configuration as in Embodiment 2, the protective film 11 is formed of Ta ₂ O _5.
Instead of Sb ₂ O ₅ with a thickness of 150 or 1500 Å
Similar characteristics were obtained even when in the film formation. The protective film Sb ₂ O ₅ of 5000 Å is formed by sputtering or EB evaporation.
When the film was formed to a thickness , black spots and blackening did not occur even after 50,000 times of coloration / decoloration cycles.

[0035] In a similar configuration as Example 7 Examples 1-3, the protective film 10 and 1
1 instead of Ta ₂ O ₅ , LiNbO ₃ , B ₂ O ₃ , C
Similar characteristics were obtained when any of hydrated oxides such as eO ₂ , ZrO ₂ , Y ₂ O ₃ and La ₂ O ₅ was used. Especially when B ₂ O ₃ is laminated on NiO, the electric capacity is NiO.
Ing to more than twice that of the only. Similar excellent characteristics were obtained with a mixed oxide such as B-Zr-O.

(Embodiment 8) With the same structure as in Embodiments 1 to 3, the supporting electrolyte is LiC.
Similar characteristics were obtained when any of supporting electrolytes such as LiBF ₄ and LiCF ₃ SO ₃ was used instead of 10 ₄ .

[0037] In a similar configuration as Example 9 Example 1-3, the electrolyte 4 poly Oki
Shi ethylene emissions, and acrylate, and a mixture of either a liquid electrolyte photocurable prepolymers of urethane,
Addition of a photopolymerization initiator such as acetophenone to 0.01 to
Similar characteristics were obtained even when about 0.1% was added between the two substrates 1 and 7 and cured by irradiation with ultraviolet rays from a mercury lamp or the like.

(Embodiment 10) With the same structure as in Embodiments 1 to 3, the oxidation coloring type EC film 5 is formed.
Similar characteristics were also obtained when was a P-type semiconductor Ni-La-O composite oxide.

[0039]

INDUSTRIAL APPLICABILITY The present invention is an EC which is electrochemically decolorized.
In EC dimming window using a substance, the EC layer as an active material, by providing a protective film having ionic conductivity and corrosion resistance, durable and prevents the electrolytic electrolyte direct contact of the active material the EC dimming window that Re work. Further, with the stability of the wear decoloration in wearing decoloring cycle test or the like by optimizing the characteristics of the protective film was excellent cormorants have the improved characteristics such as durability effect.

[Brief description of drawings]

FIG. 1 is a sectional view of a basic configuration of an EC dimming window according to a first embodiment of the present invention.

FIG. 2 is a sectional view of a basic configuration of an EC dimming window according to a second embodiment of the present invention.

FIG. 3 is a sectional view of a basic configuration of an EC dimming window according to a third embodiment of the present invention.

FIG. 4 is a cross-sectional view of the basic configuration of a conventional EC dimming window.

[Explanation of symbols]

1: The first substrate 2: first transparent conductive film 3: reduction coloring type EC film 4: electrolyte 5: oxidation color type EC film 6: a second transparent conductive film 7: second substrate 8: sealing material 9 : Power supply 10: protective film 11: protective film

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G02F 1/15

Claims (2)

(57) [Claims] 1. A first substrate on which a first transparent conductive film and a reduction coloring electrochromic film are sequentially formed, and a second substrate on which a second transparent conductive film and an oxidation coloring electrochromic film are sequentially formed. electrolyte gap can be by relative a substrate is filled in said first and second electrochromic dimming window substrate peripheral is sealed, the protective layer to avoid direct contact with the previous SL electrolyte , at least formed of on either one of the reduction coloring electrochromic film or oxidative coloring type electrochromic layer
The protective film has a proton conductivity, a lithium conductivity and
Any one selected from proton-lithium mixed conductivity
Having ion conductivity, Ta ₂ O ₅ , Sb ₂ O ₅ , LiN
selected from _{bO 3, CeO 2, Y 2} O 3 and _La 2 _{O 5}
An electrochromic dimming window characterized by being made of one of the oxides described above . 2.First transparent conductive film and reduction coloring type electro
A first substrate on which a chromic film is sequentially formed and a second transparent substrate.
Bright conductive film and oxidative coloring electrochromic film
The electrolyte is placed in the gap formed by facing the formed second substrate.
Is filled, and the periphery of the first and second substrates is sealed.
The electrochromic dimming window
The protective film to avoid direct contact with the quality
Formed on the electrochromic film The protective film is OH ⁻ Through Ni ²⁺ Through
Characterized by a non-selective permeable membrane Electro black
Mick dimming window.