CN1237146C - Electrochromatic material and its prepn - Google Patents
Electrochromatic material and its prepn Download PDFInfo
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- CN1237146C CN1237146C CN 02155719 CN02155719A CN1237146C CN 1237146 C CN1237146 C CN 1237146C CN 02155719 CN02155719 CN 02155719 CN 02155719 A CN02155719 A CN 02155719A CN 1237146 C CN1237146 C CN 1237146C
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- transparent conductive
- film
- following group
- electrochromic material
- compound
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Abstract
The present invention relates to a method for preparing electrochromic material. The method comprises the following steps: a transparent conductive thin film is formed on transparent base material; an electroless plating technology is used for leading a metal thin film to be formed on the transparent conductive thin film; the metal thin film is oxidized so that a metal oxide thin film is formed on the transparent conductive thin film. When voltage is applied to the metal oxide thin film, the metal oxide thin film can generate the electrochromic characteristic.
Description
[technical field]
The present invention relates to a kind of electrochromism (electrochromic) material and preparation method thereof, particularly relate to a kind of electrochromic material, and a kind of use electroless plating method (electrolessplating technique) is made the method for this electrochromic material.
[background technology]
One electrochromic material comprises a transparent substrate, usually and is formed at a transparent conductive film on this base material and a metal oxide film that is formed on this conductive film.This metal oxide film, for example nickel oxide (nickel oxide) film can produce the electrochromism characteristic when being applied in a voltage.This metal oxide film be by earlier with a deposit metal films to this conductive film, then this metallic film is given oxidation and forms.This metallic film generally is by a wet process, for example electrochemical deposition method (electrochemical deposition), so-gel technology (sol-gel techniques) and rotary coating technology (spin-coating techniques), or one do process, and for example vacuum vapour deposition (vacuumevaporation), sputter technology (sputtering techniques) make with electrochemical plating (electrode deposition).This sputter technology, such as radio frequency one sputter (rf-sputtering) needs expensive an equipment and a sizable space with reactive direct solenoid sputter (reactive dc magnetronsputtering).This so-gel technology then may obtain the metallic film of inferior quality because of heating when removing solvent.Electroplate rule and be that reproducibility (cyclic ability) is relatively poor and aging (aging) speed of prepared metal oxide film is fast (only have an appointment 300 times look become the life-span).
[summary of the invention]
Main purpose of the present invention is to provide a kind of method of using electroless plating method to make an electrochromic material, and it can overcome the shortcoming of aforementioned conventional art; The present invention also provides a kind of electrochromic material, and a kind of electrochromism device.
Of the present invention a kind of in order to prepare the method for electrochromic material, comprise the following step: (a) on a transparent substrate, form a transparent conductive film, to make a transparent conductive substrate, (b) by electroless plating one metallic film is formed on the transparent conductive film of this transparent conductive substrate, (c) this metallic film is given oxidation, on this transparent conductive film, to form a metal oxide film, when applying a voltage to this metal oxide film, this metal oxide film can produce the electrochromism characteristic.
Electrochromic material of the present invention is made by aforesaid method.Electrochromism device of the present invention then comprise the space first and second electrode layer, be arranged on an auxiliary electrode layer and the electrochromism layer between this first and second electrode layer and be arranged on this auxiliary electrode layer and the electrochromism layer between the conductive polymer layer, this electrochromism layer comprises the electrochromic material of making according to aforesaid method.
[description of drawings]
The present invention is described in detail below in conjunction with drawings and Examples:
Fig. 1 is a functional diagram, and of the present invention one consecutive steps in order to the preferred embodiment for preparing an electrochromic material method is described.
Fig. 2 is a synoptic diagram, and the electrochromism device that has an electrochromism layer by method of the present invention formed is described.
Fig. 3 is a synoptic diagram, and how the transparence and the aging situation of the prepared electrochromic material of beasurement base the present invention are described.
Fig. 4 is a ultraviolet spectral analysis figure, illustrates according to the prepared electrochromic material of the present invention in visible region (300～820nm) transparence, the variation under the electrochromism reaction of carrying out different number of times.
Fig. 5 is one electric current-potential ph diagram ph (C.V.diagram), illustrates according to the electric current-potential variation of the prepared electrochromic material of the present invention under the electrochromism reaction of carrying out 1,100,500 and 1000 number (cycle).
[embodiment]
Fig. 1 is the functional diagram of consecutive steps of a preferred embodiment of an explanation the inventive method.This method comprises the following step: (a) form a transparent conductive film on a transparent substrate, to make a transparent conductive substrate, (b) by electroless plating one metallic film is formed on the transparent conductive film of this transparent conductive substrate, (c) this metallic film is given oxidation, on this transparent conductive film, to form a metal oxide film, when this film is applied in a voltage, can produce the electrochromism characteristic.
This metallic film is made of nickel.The electroless plating of the metallic film on this transparent conductive substrate is by using a plating bath (plating bath) with a constituent to carry out, this constituent comprises a water soluble nickel salt, a reductive agent, and optionally, a sequestrant (chelating agent) and a buffer reagent (buffer).This nickel salt is the compound that is selected from the following group: single nickel salt (nickel sulfate) and nickelous chloride (nickel chloride).This reductive agent is the compound that is selected from the following group: hypophosphite (hypophosphitesalt), diamine (hydrazine) and sodium borohydride (sodium borohydride).This sequestrant is the compound that is selected from the following group: (trisodiumcitrate dihydrate, molecular formula is Na to the Trisodium Citrate hydrate
3C
6O
7H
5H
2O), tartrate (tartaric acid), sodium tartrate, citric acid (citric acid) and ammonium chloride (ammonium chloride).This buffer reagent is the compound that is selected from the following group: boric acid (boric acid), toxilic acid (maleic acid) and methylene-succinic acid (itaconic acid).Preferably, this electroless operation is to carry out under the temperature between in 40 to 60 ℃.
Preferably, this water soluble nickel salt is a single nickel salt, and this reductive agent is a sodium hypophosphite, and this sequestrant is the Trisodium Citrate hydrate, and this buffer reagent is a boric acid.
Preferably, this transparent substrate is made by a material that is selected from the following group: glass, polyvinyl chloride (polyvinyl chloride), polyethylene (polyethylene), polycarbonate (polycarbonate), and polyethylene terephthalate (polyethyleneterephthalate).
Preferably, this transparent conductive film is made by a material that is selected from the following group: tin indium oxide (indium tin oxide, abbreviation ITO), antimony tin (antimony tinoxide, abbreviation ATO), fluorine oxide tin (fluorine-doped tin oxide, be called for short FTO), and iridium oxide tin (iridium tin oxide is called for short IRTO).Preferably, this transparent conductive film is made by ITO.
Preferably, this metal oxide film is by under the oxygen existence condition, and under in 150 to 450 ℃ the temperature, the metallic film of this transparent conductive film top is heated and makes.
Because this metallic film and the qualitative difference of conductive film in order to increase the bonding strength between this metallic film and the conductive film, preferably, before carrying out electroless plating, can be carried out surface treatment to this transparent conductive substrate.This surface treatment comprises the following step: (1) is with this transparent conductive substrate degrease (degreasing), (2) use a sensitizing solution that comprises a sensitizing agent (sensitizingagent) that this transparent conductive film is given sensitization, (3) by using an activated solution that comprises an activator, this transparent conductive film is activated.This sensitizing agent is the compound that is selected from the following group: tin chloride (tin chloride) and titanium chloride (titaniumchloride).This activator is the compound that is selected from the following group: Palladous chloride (palladium chloride) and platinum chloride (platinum chloride).Preferably, aforesaid sensitization and activation step are to carry out under the temperature between the room temperature to 50 ℃.For example when using tin chloride and Palladous chloride to be used as sensitizing agent and activator respectively, the tin ion (Sn in sensitization this sensitizing solution of operating period
2+) can infiltrate in the micropore on this conductive film surface, and this palladium ion can produce redox with tin ion during activation act, the palladium that is reduced can replace tin ion and implant in the micropore.
Preferably, this sensitizing agent is a tin chloride, and sensitizing solution is by tin chloride being dissolved in the hydrochloric acid soln and make.
Preferably, this activator is a Palladous chloride, and this activation solution is by Palladous chloride being dissolved in the hydrochloric acid soln and make.
Fig. 2 illustrates an electrochromism device (ECD), and it comprises the electrochromism layer 103 of an electrochromic material of making according to the inventive method.One conductive polymer layer 104, an auxiliary electrode layer (charge-balancing counter electrode layer) 105 and this electrochromism layer 103 are folded between first and second electrode layer 102, the 102a together, and electrically connect (electrical connected) to first and second electrode layer 102,102a.This first and second electrode layer 102,102a relatively are formed on first and second glass substrate 101, the 101a.When applying a voltage to first and second electrode layer 102,102a by current potential input 106, this electrochromism layer 103 can carry out electrochemical redox, and then cause the optical density of electromagnetic spectrum to change, produce painted (coloring) and decolouring (bleaching) characteristic whereby.
Each following embodiment will illustrate how the method according to this invention makes this electrochromic material.
＜embodiment 1 〉
Use glass baseplate and ITO conductive film to make transparent conductive substrate in the present embodiment.Utilize the ultrasound concussion in a cleaning soln, this transparent conductive substrate to be given degrease.This cleaning soln is to see through the interfacial agent of a predetermined amount to be dissolved in the deionized water (de-ionized water) of 50ml and to make.Then with this transparent conductive substrate of deionized water wash.Use one to comprise 0.5g tin chloride (SnCl
2), the sensitizing solution of the constituent of the hydrochloric acid of 0.5ml and 50ml deionized water, this washed transparent conductive substrate is carried out sensitization.This sensitization step is to carry out under room temperature 5 to 50 minutes.Then use one to comprise 0.025g Palladous chloride (PdCl
2), the activation solution of the constituent of 0.5ml hydrochloric acid and 50ml deionized water, this transparent conductive substrate is activated.This activation step is to carry out under room temperature 2 to 20 minutes.Afterwards, with this activatory transparent conductive substrate of deionized water wash, then this substrate immersion is gone into one and comprise 1.6g single nickel salt (NiSO
46H
2O), 3.61g Trisodium Citrate hydrate, 2.7g ammonium chloride (NH
4Cl) with 0.75g sodium hypophosphite (NaH
2PO
2H
2In the bath of constituent O), to carry out electroless plating.This electroless plating step is to carry out 0.5 to 20 minute under in 45 to 85 ℃ the temperature.Use deionized water wash this by electroless substrate, and then give drying.Use hydrochloric acid that metal (nickel) plated film of the nonconductive surface of this substrate one side is removed.Afterwards, by heating with this substrate in atmosphere under in 150 to 400 ℃ of temperature calcination (oxidation) last 30 to 120 minutes, and handle to make by annealing (annealing) and form the nickel protoxide film on this ITO conductive film.
＜embodiment 2 〉
The experimental procedure of present embodiment is similar to Example 1, and difference is: the constituent in this electroless plating bath comprises 3.0g single nickel salt, 6.0g Trisodium Citrate hydrate, 4.0g boric acid and 2.0g sodium hypophosphite.
＜electrochromism reaction test 〉
Use as shown in Figure 3 cyclic voltammetric meter (Cyclic Voltammeter) 301 and ultraviolet spectral analysis instrument (UV Spectrum Analyzer) 303, prepared electrochromic material among the embodiment 1 is carried out the electrochromism reaction test.Place a UV groove (cell) 302 to test the electrochromic material that makes.This UV groove 302 comprises a KOH electrolyte solution 4 bodies, and be immersed in a pair of comparative electrode 1 (counterelectrode) in this solution, a reference electrode 2 (platinum electrode) and a working electrode 3 (workingelectrode uses this electrochromic material).At test period, by apply+1.5V is to voltage square wave (square-wave) output and input volt of-1.5V, the electrochromic material of this working electrode 3 can carry out following reversible reaction:
(A)
(B)
The generation of NiOOH can cause the painted of this electrochromic material in the reaction (B), and Ni (OH)
2Generation then cause the decolouring of this electrochromic material.
As shown in Figure 4, this ultraviolet spectral analysis instrument uses the visible light that is distributed in 300 to 820nm wavelength to measure the transparence (transmittance) (using the KOH of solvent as 1M) of this electrochromic material.This electrochromic material is by Ni (OH)
2State is to the NiOOH state, or on the contrary by the NiOOH state to Ni (OH)
2The transparence change amount of state is represented the electrochromism characteristic of this electrochromic material.The result shows that this electrochromic material reacts (B) afterwards in the electrochromism of experiencing 1000 times, by NiOOH to Ni (OH)
2It is close with initial electrochromism reaction that the transparence of (decolouring) changes, this represents that this electrochromic material is behind decoloring reaction 1000 times, still can keep good electrochromism ability, there is no tangible catabiosis, and the transparence variation at visible region is quite obvious, has the potentiality as intelligent shading window material.
As shown in Figure 5, electric current, the current potential during this electrochromism reaction (B) of this cyclic voltammetric instrumentation amount changes.The result shows that this electrochromic material is after the electrochromism of experiencing 1000 times is reacted, and its redox potential skew is little, and representative catabiosis after reacting 1000 times is not obvious.
Take a broad view of above-mentionedly, compared to method in the past, the present invention uses electroless plating techniques to prepare the method for electrochromic material, is the simple and low cost method of process, and longer by the electrochromic material life-span that the inventive method makes.
Though the present invention is detailed in explaining by above-mentioned detailed description and preferred embodiment, the present invention should not be interpreted as limited by previous embodiment; Relatively, the equivalence variation of making from the technology contents of this case specification sheets announcement is contained in the present invention.Therefore, do not departing under the essential ideas of the present invention, the simple equivalent of doing according to claim of the present invention changes generally, all should belong in the scope that claim of the present invention contains.
Claims (17)
1, a kind of in order to prepare the method for electrochromic material, it is characterized in that comprising the following step:
(a) on a transparent substrate, form a transparent conductive film, to make a transparent conductive substrate; (b) by electroless plating one metallic film is formed on the transparent conductive film of this transparent conductive substrate; (c) this metallic film is given oxidation, to form a metal oxide film on this transparent conductive film, when applying a voltage to this metal oxide film, this metal oxide film can produce the electrochromism characteristic;
Wherein, this metallic film is made of nickel, and the electroless plating of the metallic film on this transparent conductive substrate is by using a plating bath with a constituent to carry out, and this constituent comprises a water soluble nickel salt, a reductive agent, and optionally, a sequestrant and a buffer reagent; This nickel salt is the compound that is selected from the following group: single nickel salt, nickelous chloride, and their combination; This reductive agent is the compound that is selected from the following group: hypophosphite, diamine, sodium borohydride, and their combination; This sequestrant is the compound that is selected from the following group: Trisodium Citrate hydrate, tartrate, sodium tartrate, citric acid, ammonium chloride, and their combination; This buffer reagent is the compound that is selected from the following group: boric acid, toxilic acid, methylene-succinic acid, and their combination;
Before carrying out electroless plating, further comprise following treatment step: (1) is with this transparent conductive substrate degrease; (2) use a sensitizing solution that comprises a sensitizing agent that this transparent conductive film is given sensitization; (3) by using an activated solution that comprises an activator, this transparent conductive film is activated; This sensitizing agent is the compound that is selected from the following group: tin chloride, titanium chloride, and their combination; This activator is the compound that is selected from the following group: Palladous chloride, platinum chloride, and their combination.
2, as claimed in claim 1 in order to prepare the method for electrochromic material, it is characterized in that: this water soluble nickel salt is a single nickel salt, and this reductive agent is a sodium hypophosphite, and this sequestrant is the Trisodium Citrate hydrate, and this buffer reagent is a boric acid.
3, as claimed in claim 1 in order to prepare the method for electrochromic material, it is characterized in that: this transparent substrate is made by a material that is selected from the following group: glass, polyvinyl chloride, polyethylene, polycarbonate, and polyethylene terephthalate.
4, as claimed in claim 3 in order to prepare the method for electrochromic material, it is characterized in that: this transparent conductive film is made by a material that is selected from the following group: tin indium oxide, antimony tin, fluorine oxide tin, and iridium oxide tin.
5, as claimed in claim 4 in order to prepare the method for an electrochromic material, it is characterized in that: this metal oxide film is by in the presence of oxygen, and under in 150 to 450 ℃ the temperature, the metallic film of this transparent conductive film top is heated and made.
6, as claimed in claim 1 in order to prepare the method for an electrochromic material, it is characterized in that: this sensitizing agent is a tin chloride, and sensitizing solution is by tin chloride being dissolved in the hydrochloric acid soln and make.
7, as claimed in claim 6 in order to prepare the method for an electrochromic material, it is characterized in that: this activator is a Palladous chloride, and this activation solution is by Palladous chloride being dissolved in the hydrochloric acid soln and make.
8, a kind of electrochromic material for preparing with the method for claim 1, comprise a transparent substrate, and be formed at the metal oxide film that transparent conductive film and on this transparent substrate is formed on this transparent conductive film and can produces the electrochromism characteristic when being applied in a voltage, wherein, this metal oxide film is by electroless plating one metallic film on this transparent conductive film, and then this metallic film is given oxidation and make.
9, electrochromic material as claimed in claim 8, it is characterized in that: this metallic film is made of nickel, and the electroless plating of the metallic film on this transparent conductive substrate is by using a plating bath with a constituent to carry out, this constituent comprises a water soluble nickel salt, a reductive agent, and optionally, a sequestrant and a buffer reagent; This nickel salt is the compound that is selected from the following group: single nickel salt, nickelous chloride, and their combination; This reductive agent is the compound that is selected from the following group: hypophosphite, diamine, sodium borohydride, and their combination; This sequestrant is the compound that is selected from the following group: Trisodium Citrate hydrate, tartrate, sodium tartrate, citric acid, ammonium chloride, and their combination; This buffer reagent is the compound that is selected from the following group: boric acid, toxilic acid, methylene-succinic acid, and their combination.
10, electrochromic material as claimed in claim 9 is characterized in that: this water soluble nickel salt is a single nickel salt, and this reductive agent is a sodium hypophosphite, and this sequestrant is the Trisodium Citrate hydrate, and this buffer reagent is a boric acid.
11, electrochromic material as claimed in claim 10 is characterized in that: this transparent substrate is made by a material that is selected from the following group: glass, polyvinyl chloride, polyethylene, polycarbonate, and polyethylene terephthalate.
12, electrochromic material as claimed in claim 11 is characterized in that: this transparent conductive film is made by a material that is selected from the following group: tin indium oxide, antimony tin, fluorine oxide tin, and iridium oxide tin.
13, electrochromic material as claimed in claim 12 is characterized in that: this metal oxide film is by in the presence of oxygen, and under in 150 to 450 ℃ the temperature, the metallic film of this transparent conductive film top is heated and makes.
14, a kind of electrochromism device, first and second electrode layer that comprises the space, be arranged on an auxiliary electrode layer and an electrochromism layer between this first and second electrode layer, and be arranged on conductive polymer layer between this auxiliary electrode layer and the electrochromism layer, this electrochromism layer comprises the electrochromic material with the method preparation of claim 1, comprising a transparent substrate, one is positioned at transparent conductive film and on this transparent substrate can produce the electrochromism characteristic when being applied in a voltage metal oxide film, this metal oxide film is by electroless plating one metallic film on this transparent conductive film, and then this metallic film is given oxidation and make.
15, electrochromism device as claimed in claim 14, it is characterized in that: this metallic film is made of nickel, and the electroless plating of the metallic film on this transparent conductive substrate is by using a plating bath with a constituent to carry out, this constituent comprises a water soluble nickel salt, a reductive agent, and optionally, a sequestrant and a buffer reagent; This nickel salt is the compound that is selected from the following group: single nickel salt, nickelous chloride, and their combination; This reductive agent is the compound that is selected from the following group: hypophosphite, diamine, sodium borohydride, and their combination; This sequestrant is the compound that is selected from the following group: Trisodium Citrate hydrate, tartrate, sodium tartrate, citric acid, ammonium chloride, and their combination; This buffer reagent is the compound that is selected from the following group: boric acid, toxilic acid, methylene-succinic acid, and their combination.
16, electrochromism device as claimed in claim 15, it is characterized in that: this water soluble nickel salt is a single nickel salt, this reductive agent is a sodium hypophosphite, and this sequestrant is the Trisodium Citrate hydrate, this buffer reagent is a boric acid.
17, electrochromism device as claimed in claim 16 is characterized in that: this metal oxide film is under the condition that exists at oxygen, and under in 150 to 450 ℃ the temperature, the metallic film of this transparent conductive film top is heated and makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155719 CN1237146C (en) | 2002-12-06 | 2002-12-06 | Electrochromatic material and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155719 CN1237146C (en) | 2002-12-06 | 2002-12-06 | Electrochromatic material and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1506437A CN1506437A (en) | 2004-06-23 |
| CN1237146C true CN1237146C (en) | 2006-01-18 |
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ID=34236045
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|---|---|---|---|
| CN 02155719 Expired - Fee Related CN1237146C (en) | 2002-12-06 | 2002-12-06 | Electrochromatic material and its prepn |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008049275A1 (en) * | 2006-10-25 | 2008-05-02 | Feng Chia University | Flexible electromic apparatus |
| CN101377599B (en) * | 2007-08-28 | 2010-09-29 | 逢甲大学 | Electrochromism reflecting device |
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2002
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Granted publication date: 20060118 Termination date: 20101206 |