KR20160127866A - Method for manufacturing electrochromic layer and electrochromic device - Google Patents
Method for manufacturing electrochromic layer and electrochromic device Download PDFInfo
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- KR20160127866A KR20160127866A KR1020150058765A KR20150058765A KR20160127866A KR 20160127866 A KR20160127866 A KR 20160127866A KR 1020150058765 A KR1020150058765 A KR 1020150058765A KR 20150058765 A KR20150058765 A KR 20150058765A KR 20160127866 A KR20160127866 A KR 20160127866A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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Abstract
A manufacturing method of an electrochromic layer and an electrochromic device including the same are disclosed. A process of synthesizing nickel oxide and cation-doped nickel oxide particles having various morphologies by using various kinds of nickel oxide precursors, and a process of synthesizing the nickel oxide-containing thin film electrochromic layer . An electrochromic layer and a electrochromic device including the electrochromic layer, which can improve easiness and productivity in a manufacturing process while having a performance exceeding a conventional electrochemical vapor deposition method in terms of thin film stability and color control ratio by a large area roll-to-roll coating method / RTI >
Description
BACKGROUND OF THE
The phenomenon of electrochromism is a phenomenon in which the color reversibly changes according to an oxidation-reduction reaction caused by an externally applied voltage. Such electrochromism phenomenon can be applied to window and automobile room mirror. Since visibility is secured and user can actively control the transmittance, various coloring changes are possible, and the prospect for future products is very bright.
The electrochromic materials can be divided into an oxidative colored form that shows a color when oxidized and a reduced colored form that shows a color when reduced when a redox reaction occurs. Examples of the reduced colored material include inorganic materials such as WO 3 , TiO 2 , and Nb 2 O 5 Metal oxides and organic high molecular materials such as polyaniline, polythiophene polybiorgen, and polypyrrole. Examples of the oxidation-coloring materials include prussian blue, IrO 2 , and NiO. The chemical formula of nickel oxide is NiO. When it is oxidized to Ni 3+ , it becomes brownish color. When it becomes Ni 2+ , it shows light yellow. When such oxidative discoloration type nickel oxide is doped with a cation such as Al 3+ or Li + , it has an advantage of increasing the transmittance and decreasing the response speed upon decolorization. Particularly, studies on lithium-nickel-doped lithium nickel oxide have been conducted. Generally, the lithium nickel oxide thin film is fabricated by electrochemical deposition, chemical bath deposition, sol-gel method and sputtering. However, And has a limitation in terms of durability and electrochromic characteristics. In order to produce a thin film by electrochemical deposition, cyclic voltammetry, amperometric and potentiometric methods can be used. When lithium ions are used instead of strong bases as electrolytes, the discoloration efficiency The thickness of the electrode must be increased. Increasing the electrodeposition time to increase the thickness increases the peeling phenomenon because of the weak adhesion between the conductive glass surface and the nickel oxide, and the Ni (OH) 2 precipitate is formed in the solution during the deposition, The larger the size of the counter electrode, the more difficult it is in the process. In addition, since the nickel oxide thin film thus deposited has no crystallinity, a peak-to-peak occurs during the oxidation-reduction reaction and the electrochromic characteristics are not excellent. Chemical solution deposition also has the disadvantage that it is difficult to deposit uniformly on the surface of the electrode contained in the solution because the precipitation occurs immediately upon addition of the reactant, and the durability is weak. Currently, the most common method for preparing nickel oxide thin films is the sputtering method, which has a disadvantage in that the production cost is high and residual coloration occurs at the time of decolorization.
Although a wet coating method using a coating solution has been attempted to overcome the disadvantages of attempts to manufacture nickel oxide thin films as described above, there has been no report on a method for producing a uniform thin film without haze.
The present invention has been made in view of the problems of the prior art, and provides a method of manufacturing an electrochromic layer for an electrochromic device formed using a wet coating method.
The present invention provides an electrochromic device comprising the above-described improved electrochromic layer.
The present invention provides a method for preparing a electrochromic layer comprising the steps of: (a) preparing nickel oxide particles or nickel-doped nickel oxide particles; (b) preparing a coating solution comprising the nickel oxide particles or the cation-doped nickel oxide particles; And (c) applying the coating solution onto the coating object.
The preparation of the coating solution of step (b) comprises the steps of: dispersing the nickel oxide particles or the nickel ion particles doped with the cation into a solvent to produce a dispersion solution in which nickel oxide particles are dispersed; And adding a component for binding to the dispersion solution.
The process of forming the dispersion solution includes injecting an inorganic binder which is not hydrolyzed into the nickel oxide particles or a solvent containing the cation-doped nickel oxide particles.
The component for the binding is a hydrolyzed inorganic binder.
The thickness of the coating layer applied to the coating object may be 100 nm to 10 탆.
The cation is a lithium cation.
The present invention also provides an electrochromic device comprising: a light-transmitting substrate; A transparent electrically conductive first electrode; A second electrode disposed opposite to the first electrode; An electrochromic layer coated on the first electrode between the first electrode and the second electrode; And an electrolyte disposed between the first electrode and the second electrode, wherein the electrochromic layer is manufactured by any one of the above-described methods for producing an electrochromic layer.
The second electrode is activated by irradiating UV light by applying WO 3 .
According to the present invention, as compared with the conventional electrochemical method in which the continuous production process is not possible and the thin film stability is also inferior, a wet coating method capable of a continuous roll-to-roll type process such as micro gravure coating A method of making a layer is provided. Therefore, it is possible to manufacture a uniform and large-area electrochromic electrode in a short period of time, regardless of the type of substrate, by lowering the production cost. Such a manufacturing method of the present invention provides an electrochromic thin film which is simple in the process of forming a coating liquid and is excellent in film stability and durability, thereby making it possible to manufacture various kinds of electrochromic devices.
1 is a cross-sectional view schematically showing a part of an electrochromic device including an electrochromic layer containing nickel oxide according to the present invention.
FIG. 2 is a graph showing XRD patterns of various kinds of modified nickel oxide precursors synthesized in Examples I to III and Comparative Examples. FIG.
3 is a graph showing XRD patterns of nickel oxides obtained by heat treatment of various kinds of modified nickel oxide precursors synthesized in Examples I to III and Comparative Examples.
4 is a graph showing an XRD pattern according to the Li content of lithium-doped nickel oxide (Li-NiO) synthesized in Example I-4.
5 is FE-SEM photographs of nickel oxide synthesized in Examples I to 3 and Comparative Examples.
6 is FE-SEM photographs of various contents of lithium-doped nickel oxide (Li-NiO) synthesized in Example I-4.
7 is an FE-SEM photograph of various types of nickel oxide thin film electrochromic layers applied to a substrate by the method of Example II-1. here,
(A) applied the method of Example II-1 using a comparative example,
(B) applied the method of Example II-1 using Example I-2,
(C) was applied to Example II-1 using Example I-4.
8 is a graph showing the relationship between the light transmittance measured at a wavelength of 550 nm and the light transmittance measured at a wavelength of 550 nm when a switching step potential of -0.7 V and + 1.5 V (vs Ag) is applied to the thin film electrochromic layer of FIG. It is a graph showing the change with time.
FIG. 9 is a graph showing a change with time of the oxidation-reduction current under the conditions shown in FIG.
10 is a graph showing a change in light transmittance measured at a wavelength of 550 nm when a cycle is repeated up to 30 times under the same conditions as in FIG.
FIG. 11 is an FE-SEM photograph of various contents of lithium-doped nickel oxide thin film electrochromic layers applied on a substrate through Example II-1,
(A) applied Example II-1 to Example I-4 (
(B) was applied to Example I-4 (
(C) was applied to Example I-4 (
12 is an FE-SEM photograph of the Li-NiO (10%) thin film electrochromic layer prepared in Example II-1.
FIG. 13 is a graph showing a change in transmittance measured at a wavelength of 660 nm according to cyclic voltammogram and potential change in the non-aqueous electrolyte solution of the structure of FIG. 12; FIG.
FIG. 14 is a graph showing the relationship between the wavelength of 660 nm and the wavelength of 660 nm when the switching step potential (vs Ag) is applied to the Li-NiO (15%) thin film electrochromic layer prepared by the method of Example II-2 for 30 seconds at -0.7 V and +12 V, FIG. 3 is a graph showing a change with time of the light transmittance measured in FIG.
FIG. 15 is a graph showing changes in light transmittance measured at a wavelength of 660 nm with time when various kinds of switching step potentials are applied to the electrochromic device manufactured in Example III for 30 seconds each.
FIG. 16 is a graph showing a change in light transmittance measured at a wavelength of 660 nm when the cycle is repeated up to 46 times under the condition shown in FIG. 15. FIG.
17 is a graph showing a change with time in the light transmittance measured at a wavelength of 660 nm when the switching step potential (vs Ag) of ± 1.2 V is applied for 30 seconds to the electrochromic device manufactured in Example III to be.
18 is a graph of coloration and decolorization transmittance due to oxidation-reduction at the 2nd and 29, 000th cycles when the cycle is repeated under the same conditions as in Fig.
19 is a graph and a photograph showing a change in light transmittance measured at a wavelength of 660 nm when a cycle is repeated up to 29,000 times under the same conditions as in Fig.
FIG. 20 is a graph showing a change in transmittance in a visible light region after irradiating the electrochromic device prepared in Example III with light before and after the electrolyte injection for one hour. FIG.
FIG. 21 is a graph showing the relationship between the oxidation-reduction (UV) and the oxidation-reduction (UV) of the electrochromic device fabricated by Example III when the UV lamp was irradiated for 1 hour and the case Of the light transmittance.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the embodiments of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
First of all, the present invention provides a method for manufacturing an electrochromic layer which can be applied to a large-area electrochromic device using a wet coating method capable of mass production at low cost, and an electrochromic device including the same. Here, the process includes synthesizing a cation-doped nickel oxide having excellent solvent dispersibility by controlling the particle shape using various kinds of nickel oxide precursors. Nickel oxide or cation-doped nickel oxide nano-powder is dispersed in a solvent, and then a silicone-based inorganic binder is mixed to prepare a coating solution. Where an inorganic binder can be applied as a binding element. The coating solution thus prepared is applied by a large area roll-to-roll coating such as a microgravure coating. Accordingly, an electrochromic layer for an electrochromic device, which has a performance exceeding a conventional electrochemical vapor deposition method in terms of thin film stability, color contrast ratio, etc., and which can increase productivity and productivity in a manufacturing process, can be provided.
The present invention will be described in detail with reference to the drawings.
1 is a cross-sectional view schematically showing a part of an electrochromic device including an electrochromic layer containing nickel oxide according to the present invention.
The
When a flexible plastic substrate is applied to the
The structure of FIG. 1 in which the
The coating liquid for forming the
If the amount of the electrochromic material is more than the proper amount, the durability of the electrode is deteriorated because the film adhesion of the thin film is lowered. If the amount is less than the proper amount, the film adhesion is good but the electrochromic material content is small. Less. Therefore, a proper ratio of M-NiO, an inorganic binder and a solvent is a very important factor in order to have a proper response time, a change in transmittance upon discoloration and coloring, and excellent durability.
The thickness of the coating layer may be 100 nm to 10 mu m. When the thickness of the coating layer is lower than 100 nm, the response time is fast but the change of the transmittance is small. When the thickness of the coating layer is 10 μm or more, cracks are generated in the coating layer or ions and electrons are difficult to move, Loses.
The M-NiO particles used in the present invention may have various shapes of aggregated particles depending on the kind, time, and order of synthesis of the precursor, and the flower-like particle shape rather than the spherical shape has better solvent dispersibility. In the synthesis of M-NiO particles, lithium ions are generally doped, but doping of cations such as Al 3+ , Zr 4+ , Co 2+ , Cu 2+ and the like is also possible. In the present invention, no separate dispersing agent is used in the preparation of the coating liquid as described in detail below.
In the present invention, the binder (binder) used for forming the coating solution is prepared by using a silane compound as a precursor and synthesizing a silicon oxide sol formed by hydrolysis in a polar solvent containing water at an appropriate viscosity. The silane compound used in this case may be selected from the group consisting of tetraethoxy silane, tetramethoxy silane, trimethoxymethyl silane, triethoxyethyl silane, triethoxy methyl silane, triethoxymethyl silane, trimethoxyoctyl silane, triethoxyoctyl silane, trimethoxypropyl silane, 3-2-aminoethylaminopropyltrimethoxysilane (3- 2-aminoheptylamine propyl trimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, and the like can be used. For reference, hydrolysis of the alkoxysilane is possible in both acid and base.
The entire process of the coating solution used in the present invention will be briefly described. First, the synthesized M-NiO is put in ethanol, mixed with an alkoxysilane and an alkylalkoxysilane mixed solution, and mixed for a predetermined period of time. The hydrolyzed alkoxysilane And an alkylalkoxysilane mixed binder solution are added and mixed again for a certain period of time. In this case, the mixing time after the addition of the hydrolyzed mixed binder solution requires the optimum time. If the mixing time is short, the uniformity and adhesion of the coated thin film are poor. If the mixing time is too long, It becomes impossible. The stability of the coating solution may be stable for several days depending on the mixing ratio between the M-NiO dispersion solution and the hydrolyzed binder solution.
In the structure of Fig. 1 described above, the coating liquid thus obtained is applied on the transparent electrically
After drying, the film adhesion can be increased by the heat treatment, and the heat treatment temperature can be up to 400 ° C depending on the type of the
Hereinafter, examples and comparative examples of the present invention will be described in detail. For reference, Examples 1 to 4 of Example I are examples of a process of forming a nickel oxide, Examples 1 and 2 of Examples II are examples of a coating solution and a coating process thereof, Example III is a process of manufacturing an electrochromic device .
Ⅰ. Synthesis of various kinds of nickel oxides
<Example I-1>
Al-doped < RTI ID = 0.0 > a-Ni (OH) 2 From Al-NiO synthesis
0.080 mol (23.2739 g) of nickel nitrate (Ni (NO 3 ) 2 .6H 2 O) and 0.008 mol (3.0087 g) of aluminum nitrate (Al (NO 3 ) 3 .9H 2 O) are completely dissolved in 100 ml of distilled water . 100 ml of 2M sodium hydroxide (NaCl) is slowly dropped into the solution at 50 ° C for 1 hour, and then reacted at 60 ° C for 19 hours. As the reaction proceeded, a pale green precipitate was formed. The precipitate was centrifuged at 15,000 rpm for 20 minutes (three times repeatedly), washed and vacuum dried to obtain Al-doped α-Ni (OH) 2 , the precursor was heat-treated at 500 ° C. for 3 hours to obtain Al-NiO like XRD shown in FIG.
≪ Example I-2 >
NiO synthesis from γ-NiOOH
250 ml of 1 M nickel sulfate (NiSO 4 .6H 2 O) and 62.5 ml of ammonia (NH 3 , 25-28%) were mixed and 250 ml of 0.25 M potassium persulfate (K 2 S 2 O 8 ) The resulting precipitate was centrifuged at 4,000 rpm for 10 minutes (three times repeatedly), and then dried at 130 ° C. for one day to obtain γ-NiOOH as shown in FIG. 2 , And this precursor was heat-treated at 400 ° C. for 3 hours to obtain NiO like XRD shown in FIG.
≪ Example I-3 >
α-4Ni (OH) 2 Synthesis of NiO from -γ-NiOOH
To 250 ml of 1 M nickel sulfate (NiSO 4 .6H 2 O) was added 250 ml of 0.25 M potassium persulfate (K 2 S 2 O 8 ) and 62.5 ml of ammonia (NH 3 , 25-28%) was slowly dropped for 20 minutes The reaction mixture was reacted at room temperature for 3 days, and the resulting precipitate was centrifuged at 4,000 rpm for 10 minutes (repeated 3 times) and then dried at 130 ° C for one day to obtain α-4Ni (OH) 2 After obtaining NiOOH, the precursor was heat-treated at 400 ° C for 3 hours to obtain NiO as shown in XRD in FIG.
≪ Example I-4 >
Li-doped a-4Ni (OH) 2 Li-NiO synthesis from -γ-NiOOH
100 ml of 1 M nickel sulfate (NiSO 4 .6H 2 O), 100 ml of 0.25 M potassium persulfate (K 2 S 2 O 8 ) and 5 ml to 15 ml of a 1M lithium acetate (CH 3 COOLi.2H 2 O) , 62.5 ml of ammonia (NH 3 , 25-28%) was slowly added dropwise for 20 minutes, and the reaction was allowed to proceed at room temperature for 3 days. The resulting precipitate was dissolved in 4,000 (OH) 2 -NiOOH was obtained by drying at 130 ° C. for 3 hours at 400 ° C. to obtain Li-NiO , And the XRD patterns of Li-NiO particles of 5%, 10% and 15% of them are shown in FIG.
<Comparative Example>
NiO synthesis from? -Ni (OH) 2
After dissolving 0.15 mol (30.8562 g) of nickel acetate (Ni (CH 3 COO) 2 .4H 2 O) in 200 mL of 2- (dimethylamino) ethanol and adding 200 mL of distilled water, a pale green precipitate is formed. The precipitate was centrifuged at 15,000 rpm for 20 minutes (three times repeated) and dried at 60 ° C. to obtain β-Ni (OH) 2 as in XRD shown in FIG. 2, Heat treatment was performed to obtain NiO as in XRD shown in Fig.
As can be seen from the FE-SEM photographs shown in FIGS. 5 and 6, the nickel oxide particles of various kinds produced by the above methods have different morphology of particles depending on the synthesis reagent, the content of doped metal ions, In Example I-1 and Comparative Example, spherical particles are shown, but particles synthesized by the method of Examples I to 2 to 4 have a flower-like particle shape. However, as shown in the XRD of FIGS. 3 and 4, regardless of the type of the nickel oxide precursor, when the precursors are heat-treated at 400 ° C. or higher, they exhibit the same XRD pattern.
Ⅱ. Fabrication of electrochromic layers of various kinds of nickel oxide thin films
<Example II-1>
Preparation of NiO Coating Solution Prepared from Various Nickel Precursors and Preparation of Thin Film Electrochromic Layer
1.8 g of the three kinds of NiO synthesized from Example I-2, Example I-4, and Comparative Example and 10 ml of ethanol were dispersed in a 20 ml vial, dispersed by ultrasonication, and mixed for 3 days. 2.18 ml of tetraethoxysilane mixed binder solution hydrolyzed in this solution was added and mixed at room temperature for 2 to 3 days to prepare a coating solution. The nickel oxide coating solution thus prepared was coated on a PEN substrate coated with ITO (60 Ω / sq) having an area of 10 × 25
≪ Example II-2 >
Preparation of Coating Solution with Variable Binder Composition and Preparation of Thin Film Electrochromic Layer
1.8 g of Li-NiO (15%) particles (Example I-4) and 10 ml of ethanol were added to vials and dispersed by ultrasonic wave for 30 minutes. Then, tetraethoxysilane mixed solution was added and mixed for 3 to 5 days , Hydrolyzed tetraethoxysilane mixed solution was added and mixed again for 2 to 3 days to prepare a coating solution having the composition shown in Table 1. The thus-prepared nickel oxide coating solution was bar-coated 10 times on a PEN substrate coated with ITO (60 Ω / sq) having an area of 10 × 25
Table 1 below shows the compositions of various coating solutions prepared using Li-doped nickel oxide prepared in Example I-4 according to the present invention.
Kinds
Tetraethoxysilane mixed solution
Fig. 7 is a graph showing the results of a comparison between the precursor β-Ni (OH) 2 , γ-NiOOH (Example I-2) and Li-α-Ni (OH) 2- γ- NiOOH (10% ) Is an FE-SEM image of a thin film electrochromic layer prepared by the method of Example II-1 (substrate: PEN / ITO, No. 6 bar).
The solvent dispersibility of the synthesized nickel oxide precursor largely varies depending on the particle shape of the synthesized nickel oxide precursor. In the comparative example (a) of FIG. 7, the spherical particles are non-uniformly distributed. However, It can be confirmed that they are uniformly distributed.
FIG. 8 shows the change in transmittance upon discoloration and coloring in the wavelength region of 550 nm when a voltage of -0.7 V and an applied voltage of +0.8 V are applied to the thin film electrochromic layer of FIG. 7 for 30 seconds, respectively. It can be seen that the electrochromic layer of (c) has the largest transmittance change. This seems to be due to the faster electron transfer rate as lithium ions are doped.
FIG. 9 shows the change of oxidation-reduction current with time under the condition of FIG. In order to use the electrode (first electrode) coated with the NiO electrochromic layer as a counter electrode to the WO 3 electrode (second electrode), the charge amount of the electrode coated with the WO 3 electrode and the NiO electrochromic layer during the oxidation- As shown in FIG. 9, when the oxidation and reduction reactions occur, the structure of (C) has the largest amount of charge. The results of the experiments of FIGS. 8 and 9 are summarized in Table 2.
Table 2 below shows the response time, the transmittance change and the charge density at 660 nm wavelength depending on the coloration and discoloration of the electrochromic layer of structures (a) to (c) in Fig.
time
(second)
(%)
time
(second)
(%)
(Decolorization / coloring)
10 shows the stability of the structure coated with NiO by repeating application of voltages of -0.7 V and +0.8 V for 30 seconds each for 30 seconds. There was almost no decrease in transmittance when it was repeated 30 times.
11 is an FE-SEM image of a thin film electrochromic layer prepared by the method of Example II-1 (substrate: PEN / ITO, No. 8 bar) obtained in Example I-4. Was increased from 5% to 15%, no change was observed on the surface of the thin film, and it was confirmed that a porous thin film was formed.
FIG. 12 is an FE-SEM image of a Li-NiO (10%) electrochromic layer prepared by coating on a conductive glass substrate, which is similar to FIG. It can be confirmed that a porous thin film is formed similarly to that formed on a plastic substrate.
13 shows changes in transmittance according to cyclic voltammogram and dislocation changes in the non-aqueous solution of the electrochromic layer-coated structure of FIG. 12, which is lower than that of the conductive plastic substrate. - The peak-to-peak during the reduction reaction was narrow, and the transmittance varied between about 45% and 85% depending on the electrode potential.
FIG. 14 is a graph showing the results of a comparison of the structure of a thin film electrochromic layer coated with the method of Example II-2 (substrate: Glass / ITO, No. 8 bar) using Li-NiO (15%) obtained in Example I- When the application voltage of 0.7V and + 0.8V is repeatedly applied for 30 seconds each, the change of the transmittance in the wavelength region of 660 nm is examined. In particular, the transmittance change during coloring and decolorization of the C3-E structure was 37.3%, and the response speed was also excellent, 3.7 and 2.5 seconds, respectively. The haze and thickness of the electrode decreased as the amount of the hydrolyzed mixed binder solution was increased. The electrochromic characteristics of the electrode coated with the thin film electrochromic layers were summarized in Table 3.
Table 3 below shows the electrochromic characteristics of the structures coated with the thin film electrochromic layers prepared according to various coating solution compositions.
Kinds
(Nm)
(%)
time
(second)
(%)
time
(second)
In order to disperse the synthesized nickel oxide into a solvent, it is very important to select an appropriate solvent. When water is used as a main solvent, the pH of the solution becomes high as NiO changes to Ni (OH) 2 As the precipitate starts to form, aggregation occurs and the thin film coating property is deteriorated due to the surface tension of water. In addition, since the silicon-based binder used as the binder is poor in stability under the base condition, a thin film excellent in durability can not be produced. When the alcohol is used as the main solvent, the solution dispersibility is improved. However, since the stability of the solution is drastically lowered by adding the hydrolyzed binder in order to improve the durability of the thin film, optimization of the dispersion period of the coating solution and the addition timing of the hydrolyzed binder . The use of an organic polymeric dispersant may increase the dispersibility of the coating solution, but it may be an obstacle to the oxidation-reduction reaction of the produced thin film. Therefore, an excellent thin film can be produced by mixing the silicon-based inorganic binder with a binder without a separate organic dispersant.
Ⅲ. Fabrication of complementary electrochromic devices
<Example III>
(Substrate: Glass / ITO, 600 nm) coated with Li-NiO (15%) prepared in Example II-1 and WO 3 (600 nm) produced by a wet coating method by the methods of Japanese Patent No. 10-1158425 and 10-1175607 A thin film electrode (substrate: Glass / ITO, 340 nm) was assembled into a sandwich type to prepare an electrochromic device. A 50 탆 thermocompression film was used as the spacer. After to the electrolyte injection drilled two holes in the diagonal corner of the WO 3 electrodes after membrane the injection port into the liquid lithium electrolyte (4M HQ115 / (g-BL + NMO + H 2 O) for injection, and the cover glass UV-epoxy For 30 minutes to 1 hour by UV lamp, or by silicone adhesive.
15 shows the response time change in the wavelength region of 660 nm when the applied voltage is changed to the electrochromic device fabricated by Example III. This is summarized in Table 4. The applied voltage at which the reduction reaction (decolorization) takes place with the electrode coated with the Li-NiO electrochromic layer in the two electrode portions of the electrochromic device as the working electrode was fixed at -1.2 V, Increasing the applied voltage for the reaction (coloring) from + 0.8V to 1.2V showed no significant difference in transmittance and response time during decolorization, but increased response time and decreased transmittance in coloring. In addition, when the difference between the applied and decolored voltages was fixed at 2.4 V and the coloring applied voltage was increased from 1.2 V to 1.6 V in order to lower the colored transmittance, the coloring transmittance was reduced from 49.3% to 41.9%, and the response time and charge density . Therefore, it is possible to fabricate an electrochromic device exhibiting an appropriate response speed and transmittance change by optimizing the applied voltage.
Table 4 below shows changes in the transmittance and charge density of the electrochromic device fabricated according to Example III of the present invention depending on the applied voltage.
(%)
(%)
(second)
+ 0.8V, 30s
+ 1.0V, 30s
+ 1.2V, 30s
+ 1.4V, 30s
+ 1.6V, 30s
16 shows changes in decoloring and coloring transmittance up to 46 times when the applied voltage is changed to the electrochromic device shown in Fig. The coloring and decolorizing transmittance were decreased by repeating cycles only when the applied voltage was -0.8 V at the decoloring time and the applied voltage was +1.6 V at the time of coloring but the transmittance change at the time of coloring and decoloring was not observed under the other conditions .
17 is a graph showing changes in transmittance of the second and 29,000th cycles in the 660 nm wavelength region when the electrochromic device manufactured in Example III is repeatedly applied for 30 seconds at an applied voltage of 1.2 V. FIG. As shown in Table 5, when the second cycle is compared with the 29,000th magnitude, the transmittance at decolorization decreased from 72.1% to 68.6%, and the transmittance at coloration slightly increased from 29.9% to 35.7%. Also, the response time of decolorization decreased from 2.1 sec to 1.6 sec in response time, and the response time increased slightly from 2.5 sec to 3.6 sec. The charge density also decreased as the cycle number increased.
Table 5 below shows the electrochromic characteristics of the electrochromic device according to the number of cycles.
(%)
(%)
(second)
FIG. 18 shows the transmittance change in the visible light region during coloring and discoloration at the second and 29,000th cycles under the same conditions as in FIG. 17. The transmittance in the visible light region was slightly reduced in the decolorizing step as the cycle was repeated, But slightly increased in transmittance at the time of coloring.
FIG. 19 shows the change in transmittance in the wavelength region of 660 nm according to the number of cycles of the electrochromic device shown in FIG. 17, which shows that the electrochromic device exhibits excellent durability due to no rapid change in transmittance even when the number of cycles is repeated have.
FIG. 20 shows the transmittance change after forming the electrochromic device according to Example III, and after irradiating the light before and after the injection of the electrolyte for one hour in the UV region. When the liquid electrolyte was filled, the transmittance of the electrochromic device in the visible light region was increased due to the refractive index match, and after one hour irradiation of the UV region, the color of the electrochromic device changed from brown to dark blue. This is because the WO 3 electrode constituting the electrochromic device is photo-discolored. When WO 3 is photoexited by light in the UV region, an electron-hole pair is generated and the resulting electron reduces the surrounding WO 3 , The holes are moved through the liquid electrolyte to the Li-NiO coated electrode to oxidize the nickel, thereby functioning to initialize the electrochromic device even if no external voltage is applied.
21 is a graph showing the results when the electrochromic device fabricated according to Example III was subjected to a voltage of 1.2 V for 30 seconds in the case of irradiating the electrochromic device with light in the UV region for 1 hour and in the case where the electrochromic device was not irradiated with light And the transmittance in the visible light region. Comparing the reduction-coloring transmittance difference in the 660 nm wavelength region, ΔT (%) of the device not irradiated with UV light was 6.7%, and ΔT (%) of the device irradiated with UV light was 20.6%. Since the Li-NiO electrode and the WO 3 thin film electrochromic layer used in the electrochromic device are all manufactured in the oxidative type, in order to drive the electrochromic device, a constant voltage is applied to the device for several tens of minutes or more, The initialization process must be done. However, if the initialization is performed by irradiating the electrochromic device with only light in the UV region as described above, it is possible to prevent the side reaction of the electrode caused by applying the voltage for a long time, and to perform the initialization by a very simple method. By appropriately adjusting the UV irradiation time according to the thickness of the electrode, a device having a stable transmittance difference from the beginning like the developed color fading device of FIG. 17 can be manufactured.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.
Claims (7)
(a) preparing nickel oxide particles or cation-doped nickel oxide particles;
(b) preparing a coating solution comprising the nickel oxide particles or the cation-doped nickel oxide particles; And
(c) applying the coating solution onto the coating object.
A step of dispersing the nickel oxide particles or the nickel oxide particles doped with the cation in a solvent to produce a dispersion solution in which nickel oxide particles are dispersed; And
And adding a component for binding to the dispersion solution.
Wherein the component for binding is a hydrolyzed inorganic binder.
Wherein the cation is a lithium cation.
A light transmitting substrate;
A transparent electrically conductive first electrode;
A second electrode disposed opposite to the first electrode;
An electrochromic layer coated on the first electrode between the first electrode and the second electrode; And
And an electrolyte disposed between the first electrode and the second electrode,
Wherein the electrochromic layer is formed by the method according to any one of claims 1 to 5.
A, electrochromic element and the second electrode is to be activated by irradiation with UV light by applying a WO 3.
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| KR1020150058765A KR20160127866A (en) | 2015-04-27 | 2015-04-27 | Method for manufacturing electrochromic layer and electrochromic device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019054720A1 (en) * | 2017-09-18 | 2019-03-21 | 주식회사 엘지화학 | Method for manufacturing electrochromic device |
| US10490763B2 (en) | 2017-10-26 | 2019-11-26 | Electronics And Telecommunications Research Institute | Display device and manufacturing method thereof |
| KR102136286B1 (en) * | 2019-11-28 | 2020-07-21 | 애드크로 주식회사 | Method of Manufacturing Anodic Electrochromic Ink Layer for Electrochromic Device and Electrochromic Device of the Same |
| KR20210140934A (en) * | 2020-05-14 | 2021-11-23 | (주)오리온엔이에스 | Electrochromic device having improved discoloring performance and driving method for thereof |
| CN113777845A (en) * | 2020-06-10 | 2021-12-10 | Skc株式会社 | Electrochromic device |
| KR20220048833A (en) * | 2020-10-13 | 2022-04-20 | 서울시립대학교 산학협력단 | High-performance and reliable electrochromic device and method for preparing the same |
| KR20230034034A (en) | 2021-09-02 | 2023-03-09 | 한국전기연구원 | Method for manufacturing an organic-inorganic hybrid binder for a photoelectrochromic layer of a photoelectrochromic device, organic-inorganic hybrid binder produced by this, and a photoelectrochromic device comprising the same |
| US11680309B2 (en) | 2017-09-18 | 2023-06-20 | Lg Chem, Ltd. | Method for preparing an electrochromic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090078046A (en) | 2008-01-14 | 2009-07-17 | 주식회사 하이닉스반도체 | Test apparatus of semiconductor integrated circuit and method using the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090078046A (en) | 2008-01-14 | 2009-07-17 | 주식회사 하이닉스반도체 | Test apparatus of semiconductor integrated circuit and method using the same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019054720A1 (en) * | 2017-09-18 | 2019-03-21 | 주식회사 엘지화학 | Method for manufacturing electrochromic device |
| US11680309B2 (en) | 2017-09-18 | 2023-06-20 | Lg Chem, Ltd. | Method for preparing an electrochromic device |
| US10490763B2 (en) | 2017-10-26 | 2019-11-26 | Electronics And Telecommunications Research Institute | Display device and manufacturing method thereof |
| KR102136286B1 (en) * | 2019-11-28 | 2020-07-21 | 애드크로 주식회사 | Method of Manufacturing Anodic Electrochromic Ink Layer for Electrochromic Device and Electrochromic Device of the Same |
| KR20210140934A (en) * | 2020-05-14 | 2021-11-23 | (주)오리온엔이에스 | Electrochromic device having improved discoloring performance and driving method for thereof |
| CN113777845A (en) * | 2020-06-10 | 2021-12-10 | Skc株式会社 | Electrochromic device |
| CN113777845B (en) * | 2020-06-10 | 2024-05-07 | Skc株式会社 | Electrochromic device |
| KR20220048833A (en) * | 2020-10-13 | 2022-04-20 | 서울시립대학교 산학협력단 | High-performance and reliable electrochromic device and method for preparing the same |
| KR20230034034A (en) | 2021-09-02 | 2023-03-09 | 한국전기연구원 | Method for manufacturing an organic-inorganic hybrid binder for a photoelectrochromic layer of a photoelectrochromic device, organic-inorganic hybrid binder produced by this, and a photoelectrochromic device comprising the same |
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