CN102183863B - Photoelectrochromic device and preparation method thereof - Google Patents
Photoelectrochromic device and preparation method thereof Download PDFInfo
- Publication number
- CN102183863B CN102183863B CN2011100850074A CN201110085007A CN102183863B CN 102183863 B CN102183863 B CN 102183863B CN 2011100850074 A CN2011100850074 A CN 2011100850074A CN 201110085007 A CN201110085007 A CN 201110085007A CN 102183863 B CN102183863 B CN 102183863B
- Authority
- CN
- China
- Prior art keywords
- electrode
- transparent substrate
- electrically conducting
- conducting transparent
- electrochomeric films
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Hybrid Cells (AREA)
Abstract
The invention provides a photoelectrochromic device and a preparation method thereof. The photoelectrochromic device comprises a dye-sensitized electrode, an electrochromic electrode and electrolyte containing a redox couple, wherein the electrolyte is positioned between the dye-sensitized electrode and the electrochromic electrode; the dye-sensitized electrode comprises a first transparent conductive substrate, a porous semiconductor film arranged on the surface of the first transparent conductive substrate, and a dye adsorbed on the surface of the porous semiconductor film; the dye is contacted with the electrolyte; the electrochromic electrode comprises an organic porous electrochromic film, a platinum catalyst layer and a second transparent conductive substrate arranged in turn; and the organic porous electrochromic film is contacted with the electrolyte. The photoelectrochromic device has the advantages of stable cycle performance and short color switching time.
Description
Technical field
The present invention relates to the electrochromic device field, particularly a kind of Photoelectrochromic device and preparation method thereof.
Background technology
The heat of sun in summer radiation is mainly through in the window inlet chamber, and people also need in certain sunlight inlet chamber to satisfy the needs of vision simultaneously.Therefore in order to keep indoor preference temperature and to satisfy the indoor light requirement, people need consume a large amount of electric energy and be used to cool off the solar radiation heat energy by in the window inlet chamber.Stable, reversible change color can take place in electrochromic under the effect of extra electric field, and power consumption is lower, can not have the sunshine of the regulation and control of machinery through window according to energy-conservation and comfortable requirement.Because it is low attractive in appearance with color changeable effect that electrochromic has power consumption, is expected to become decorative energy-saving material important in the future architecture.
Electrochromic device is the vitals of electrochromic performance colour change function, and existing electrochromic device is generally five-layer structure, and it comprises successively: first leads transparent electric glassy layer (TCO
1), be deposited on electrochromic layer (EC), the second transparent electric glassy layer (TCO of the first transparent conductive film laminar surface
2), be deposited on the ion storage layer (IS) of the second transparent conductive film laminar surface and place electrochromic layer and ion storage layer between ion-conducting membrane or electrolytic solution (IC).The electrochromism layer material is mainly transition metal oxide, and that the most frequently used is amorphous state WO
3, to use WO
3Material is an example as electrochromic layer, and the variable color mechanism of electrochromic device is following: WO
3Film is transparent in the attitude of fading, and extra electric field is added in TCO
1And TCO
2Electrode on, under electric field action, through TCO
1And TCO
2The electronics that provides injects WO through IC with fast ionic means transmission jointly jointly with the kation that is stored among the IS
3, under the electrochemical reduction effect, tungsten is reduced to positive pentavalent by positive sexavalence, generates blue tungsten bronze, and device is painted; When extra electric field is reverse, then result from above-mentioned opposite process, promptly electronics and ion are extracted out in painted electrochromic layer, and tungsten is oxidized to positive sexavalence by positive pentavalent, and electrochromic layer fades, and accomplishes a painted-process of fading thus.
Though electrochromic has above-mentioned advantage, but it needs additional power source, use the electric wire of large amount of complex to connect between electrochromic and the central source of power, make that thus the cost of electrochromic is higher, install also comparatively complicated.
Because DSSC has environmental protection, cost is low and characteristic of simple is installed; Prior art has DSSC and electrochromic device combined processes photic electrochromic device, so further cut down the consumption of energy, cost and simplification install.Report a kind of Photoelectrochromic device like Bechinger etc. at Nature, it is the nanocrystalline porous TiO of plating one deck on the TCO electro-conductive glass
2Film, dyestuff is adsorbed on TiO
2In the space of film, the WO of nanoporous
3Electrochromic layer is plated on the another side electro-conductive glass as to electrode, and the centre is filled with electrolytic solution, and electrolytic solution adopts the carbonic allyl ester that contains LiI usually.When solar radiation, dye molecule S absorbs the photon of incident, and to excited state S*, the dye molecule S* that is in excited state is injected into TiO rapidly with electronics by ground state transition
2On the conduction band, electronics is diffused on the TCO conductive glass electrode through network structure, gets into the WO to the nanoporous of electrode through external circuit again
3In, generating tungsten bronze, device is painted.When unglazed, because the electric capacity effect, can produce with photovoltage and equate but voltage in the opposite direction, impel electronics to turn back to TiO
2In, the Li ion turns back in the electrolyte, WO
3Fade.
Although photic electrochromic device need not additional power source, the electric wire that has saved many complicacies connects, and existing photic electrochromic device color is longer switching time, and cyclicity is also relatively poor, has limited its range of application.
Summary of the invention
The technical matters that the present invention solves is to provide a kind of Photoelectrochromic device, and this Photoelectrochromic device is short switching time, and has better cycle performance.
In view of this, the present invention provides a kind of Photoelectrochromic device, comprising: dye sensitized electrode, electrochromism electrode and contain the electrolytic solution of oxidation-reduction pair, and said electrolytic solution is between said dye sensitized electrode and electrochromism electrode;
Said dye sensitized electrode comprises: the first electrically conducting transparent substrate, and place the semiconductor porous film of the said first electrically conducting transparent substrate surface and be adsorbed in the surperficial dyestuff of said semiconductor porous film, said dyestuff contacts with electrolytic solution;
The electrochromism electrode, comprise setting gradually: organic porous electrochomeric films, platinum catalyst layer and the second electrically conducting transparent substrate, said organic porous electrochomeric films contacts with electrolytic solution.
Preferably, said organic porous electrochomeric films is 3, and 4-(2; 2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films, 3; 4 (2-methyl, 2-propyl group-propylene dioxy base) thiophen polymer fiber electrochomeric films, 3,4-ethene dioxythiophene polymer fiber electrochomeric films or 3; 4-(2,2-diethyl propenyl dioxy base) pyrroles's polymer fiber electrochomeric films.
Preferably, said semiconductor porous film is a nano-titanium dioxide film.
Preferably, the said first electrically conducting transparent substrate is fluorine-doped tin oxide electropane or tin-antiomony oxide electropane.
Preferably, the said second electrically conducting transparent substrate is indium tin oxide conductive film glass or zinc oxide aluminum electropane.
Preferably, said electrolytic solution is the carbonic allyl ester solution of lithium iodide and elemental iodine.
Preferably, the concentration of lithium iodide is 0.08～0.12mol/L in the said electrolytic solution, and the concentration of elemental iodine is 0.0008～0.0012mol/L.
Accordingly, the present invention also provides a kind of above-mentioned Photoelectrochromic preparation of devices method, comprising:
After the first electrically conducting transparent substrate surface applies semiconductor porous film, heat-treat, at said semiconductor porous film surface adsorption dyestuff, obtain dye sensitized electrode then;
After the second electrically conducting transparent substrate surface applies the platinum catalyst gel, heat-treat, indium tin oxide surfaces forms the platinum catalyst layer; At the organic porous electrochomeric films of said platinum catalyst laminar surface electropolymerization, obtain the electrochromism electrode;
Said electrochromism electrode, electrolytic solution and dye sensitized electrode are assembled, obtained the Photoelectrochromic device.
Preferably, said semiconductor porous film is a nano-titanium dioxide film.
Preferably, applying semiconductor porous film at the first electrically conducting transparent substrate surface is specially: employing is scraped the skill in using a kitchen knife in cookery and behind the first electrically conducting transparent substrate surface coated with nano titania slurry, is carried out drying.
It is preferably, said that after the first electrically conducting transparent substrate surface applies semiconductor porous film, to carry out heat treated temperature be 400 ℃～500 ℃.
It is preferably, said that after the second electrically conducting transparent substrate surface applies the platinum catalyst gel, to carry out heat treated temperature be 120～150 ℃.
Preferably, said organic porous electrochomeric films is 3,4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films.
Preferably, be specially at the organic porous electrochomeric films of said platinum catalyst laminar surface electropolymerization: dissolving Lithium perchlorate anhydrous and 3 in acetonitrile, 4-(2; 2-dimethyl allene dioxy base) thiophene; Obtain monomer solution after stirring, the concentration of lithium perchlorate is 0.06～0.14mol/L in the said monomer solution, 3; The concentration of 4-(2,2-dimethyl allene dioxy base) thiophene is 0.006～0.014mol/L;
Adopt chronoamperometry; The second electrically conducting transparent substrate to be covered with the platinum layer is a working electrode, is contrast electrode with the filamentary silver, and the conduct of platinum sheet is to electrode; All immerse with said working electrode, contrast electrode with to electrode and to carry out plated film in the monomer solution, plated film voltage is made as 1.3V～2V.
Preferably, the process of said assembling is specially: with tackifier and diameter is to be coated in the electrochromism electrode edge after 80～120 microns beaded glass mixes, and reserves injection port; Dye sensitized electrode is placed on behind the electrochromism electrode surface dye sensitized electrode and electrochromism electrode are clamped, treat that tackifier solidifies the back and in injection port, injects electrolytic solution, the injection back that finishes uses tackifier that injection port is sealed.
The present invention provides a kind of Photoelectrochromic device, and this Photoelectrochromic device comprises dye sensitized electrode, electrochromism electrode and the electrolytic solution between dye sensitized electrode and electrochromism electrode.Wherein dye sensitized electrode comprises: the first electrically conducting transparent substrate places the semiconductor porous film of the said first electrically conducting transparent substrate surface and is adsorbed in the surperficial dyestuff of said semiconductor porous film; The electrochromism electrode comprises and setting gradually: organic porous electrochomeric films, platinum catalyst layer and the second electrically conducting transparent substrate.Dye sensitized electrode is equivalent to the working electrode of dye-sensitized cell in the above-mentioned Photoelectrochromic device, the Pt catalyst layer in the electrochromic device and second conductive substrates be equivalent to again simultaneously dye-sensitized cell to electrode, the effect of Pt catalyst layer is to make reaction X
3 -+ 2e
-→ 3X
-More be prone to carry out, guarantee X in the electrolytic solution
-Be in higher concentration, so that dye-sensitized cell has better cycle performance, and then assurance improves the cycle performance of Photoelectrochromic device.
The present invention cooperates the organic electrochromic film that adopts porous structure as electrochomeric films simultaneously, and it is not merely electrolytic solution and has created chance with contacting of platinum catalyst layer, and platinum catalyst can be realized X
3 N-+ 2ne
-→ 3X
N-The catalytic effect of this reaction, it further shortens the color switching time of Photoelectrochromic device again in the characteristic that takes off attitude and coloured state weak point switching time simultaneously.Experiment showed, that Photoelectrochromic device provided by the invention has stable cycle performance, color is short switching time; In addition, this Photoelectrochromic device also has transmittance difference and photoelectric conversion rate preferably, is especially suitable for use as the dimming glass of electrochromic.
Description of drawings
Fig. 1 is the structural representation of Photoelectrochromic device provided by the invention;
Fig. 2 is an electrochromism electrode gluing synoptic diagram;
Fig. 3 is the Photoelectrochromic device of the present invention preparation cyclic curve in 637nm wavelength transmittance and time;
Fig. 4 is the i-v curve of the Photoelectrochromic device of the present invention's preparation.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The invention provides a kind of Photoelectrochromic device; Referring to shown in Figure 1 be the structural representation of Photoelectrochromic device provided by the invention; It comprises: dye sensitized electrode 1, electrolytic solution 2 and electrochromism electrode 3; Electrolytic solution 2 contains oxidation-reduction pair X in the electrolytic solution between dye sensitized electrode 1 and electrochromism electrode 3
N-And X
3 N-
In the Photoelectrochromic device of said structure; Dye sensitized electrode 1 comprises: the first electrically conducting transparent substrate 101; Place the semiconductor porous film 102 on the first electrically conducting transparent substrate, 101 surfaces; With the dyestuff 103 that is adsorbed in porous, electrically conductive semiconductive thin film 102 surfaces, wherein, dyestuff 103 contacts with electrolytic solution 2.
During use the first electrically conducting transparent substrate is connected with the lead that has switch with the second electrically conducting transparent substrate, above-mentioned Photoelectrochromic device realizes that the principle of self energizing variable color is following:
When solar irradiation was mapped on the dye molecule, dye molecule absorbed photon and becomes excited state, in semi-conductive conduction band, injects electronics, and dyestuff loses electronics and becomes Ionized dye molecule.Under the situation that external circuit breaks off, the electronics of generation accumulates at dye sensitized electrode.Ionized dye molecule can be by the X in the electrolytic solution
N-Reduction, X
n-generating polynomial (I) reaction: 3X
N-→ X
3 N-+ 2n
E-(I), Ionized dye molecule becomes the dye molecule that can excite again.Along with the carrying out of formula (I) reaction, the X in the electrolytic solution
3 -Content increases.Because the electrochomeric films that the present invention uses is porous structure, so can seeing through the porous electrochomeric films, electrolytic solution contacts with the Pt catalyst layer, the Pt of electrochromism electrode can catalysis type (II) reaction: X
3 N-+ 2ne
-→ 3X
N-(II), shorten the time of reaction (II) on the one hand, make this reaction more be prone to carry out simultaneously, Pt extracts the electronics in organic porous electrochomeric films 301 out in catalytic reaction, transfers to X
-And X
3 -In the oxidation-reduction pair, this moment, organic porous electrochomeric films was oxidized, and the color of Photoelectrochromic device transfers coloured state to by the attitude of fading.
In case external circuit is in short-circuit condition, the electronics that accumulates in the dye sensitized electrode will flow into organic porous electrochomeric films through external circuit, and with organic porous electrochomeric films reduction, this moment, the Photoelectrochromic device transferred the attitude of fading to by coloured state.
Therefore, above-mentioned Photoelectrochromic device is under the situation of solar light irradiation, and when telegraph circuit was in open circuit, the Photoelectrochromic device was in the attitude of fading, and when two electrodes were in short-circuit condition, the Photoelectrochromic device had been in coloured state.
Dye sensitized electrode is equivalent to the working electrode of dye-sensitized cell in the above-mentioned Photoelectrochromic device; Pt catalyst layer in the electrochromic device and second conductive substrates be equivalent to again simultaneously dye-sensitized cell to electrode; Therefore, dye sensitized electrode, surface are covered with second conductive substrates and the electrolytic solution formation dye-sensitized cell of Pt catalyst layer.Semiconductor porous film provides the space of absorption and the conduction band of electric transmission for dyestuff on the one hand; Complex dye is realized photoelectric converting function; On the other hand as ion storage layer; Cooperate electrochomeric films to realize the electrochromism function, therefore, ground floor conductive substrates, semiconductor porous film, electrochomeric films, electrolytic solution and second conductive substrates constitute electrochromic device.
Dye-sensitized cell converts the sun power that absorbs into electric energy, for electrochromic device provides driving voltage, makes electrochromic device need not impressed voltage and just can realize colour change function.The effect of Pt catalyst layer is to make reaction (II) more be prone to carry out, and guarantees X in the electrolytic solution
N-Be in higher concentration, so that dye-sensitized cell has better cycle performance, and then the cycle performance of assurance raising Photoelectrochromic device, pass through simultaneously to shorten the time of reacting (II), and then the color switching time of shortening Photoelectrochromic device.
Above-mentioned electrically conducting transparent substrate is preferably TCO glass, and TCO glass is meant at surface of plate glass and plates the assembly that the conductive oxide film (Transparent Conductive Oxide) of layer of transparent forms uniformly through physics or chemical plating method.The second electrically conducting transparent substrate that the electrochromism electrode uses in the above-mentioned Photoelectrochromic device preferably uses tin indium oxide (ITO) electro-conductive glass or zinc oxide aluminum (AZO) electro-conductive glass; Ito glass is on the basis of sodium calcium base or silicon boryl substrate glass, utilizes the method for magnetron sputtering to plate indium oxide layer tin film.AZO glass is through the vacuum magnetic control reactive sputtering process zinc oxide aluminum thin-film-coating to be made on glass substrate.Ito glass and AZO glass all have thin thickness, the characteristics that resistance is low.The second electrically conducting transparent substrate more preferably adopts thickness less, and the lower ito glass of resistance per square improves electrochromic property in order to reduce the thickness of Photoelectrochromic device.
The main effect of the organic porous electrochomeric films in the electrochromism electrode is the transmittance that changes entire device through redox reaction.With respect to the inorganic electrochromic film; It is in attitude and coloured state two states section switching time of fading; Need not impressed voltage and keep its fade attitude or coloured state, therefore adopt organic porous electrochomeric films can realize the switching of color in the short period of time, and color switching back is in stable condition.But the thermotolerance of organic porous electrochomeric films is relatively poor; And the Pt catalyst layer need be heat-treated and just had catalytic activity; The present invention places the Pt catalyst layer surface after the thermal treatment with organic porous electrochomeric films, and electrochomeric films is not destroyed when guaranteeing that Pt has catalytic activity.In addition, the present invention selects for use the reason of organic porous electrochomeric films to be that also the structure of porous is that electrolytic solution provides condition with contacting of Pt, makes Pt can bring into play its catalysis.
Organic porous electrochomeric films is preferably polythiofuran derivative electrochomeric films, polypyrrole derivant electrochomeric films.The polythiofuran derivative electrochomeric films is preferably 3,4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films, 3; 4 (2-methyl; 2-propyl group-propylene dioxy base) thiophen polymer fiber electrochomeric films, 3,4-ethene dioxythiophene polymer fiber electrochomeric films, polypyrrole derivant electrochomeric films is preferably 3; 4-(2,2-diethyl propenyl dioxy base) pyrroles's polymer fiber electrochomeric films.The present invention most preferably adopts 3,4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films, and it has electrochromic property preferably, and this polymer fiber film is transparent in oxidation state, is reduced the back and is mazarine.Select 3 for use; 4-(2; 2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films is as the electrochromic device of electrochromic layer assembling; Fade and colored state between switching time shorter, and the printing opacity rate variance under two states is bigger, can reach more than 65% in the 580nm wavelength.Voltage required during this external conversion is low, and a joint AAA battery is enough to be allowed to condition at switching under the two states fully.
The effect of electrolytic solution is a conveying electronic, and oxidation-reduction pair is provided simultaneously, and complex dye sensitization electrode is realized its performance.The present invention preferably selects the carbonic allyl ester solution of lithium iodide and elemental iodine as electrolytic solution.Because elemental iodine self has color; Therefore the concentration of the also preferred control elemental iodine of the present invention is in a lower scope; To improve the transparency under the glass transparent state; Electrolytic solution elemental iodine concentration is preferably 0.0008～0.0012mol/L, and the concentration of corresponding control lithium iodide is preferably 0.08～0.12mol/L.
The function of dyestuff is to convert sun power into electric energy in the dye sensitized electrode, and dyestuff can be type well known to those skilled in the art, preferably adopts the ruthenium complex dyestuff.Semiconductor porous film preferably adopts nano-titanium dioxide film.The first electrically conducting transparent substrate more preferably adopts fluorine-doped tin oxide conducting film (FTO) glass or tin-antiomony oxide conducting film (ATO) glass.For the ease of electric transmission, the semiconductor porous film of dye sensitized electrode need be heat-treated at higher temperature, and the semiconductor crystal formation is changed, and then guarantees semiconductive thin film realization electric transmission function.With the nano titanium oxide is example; Its need with nano-titanium dioxide film heat-treat make nano titanium oxide crystal transfer for becoming Detitanium-ore-type; And FTO glass and ATO glass heat resistance are good; Thermal stability is high, so the present invention selects for use FTO glass and ATO glass as the first electrically conducting transparent substrate.More preferably adopt the excellent more FTO glass of heat resistance, give the Photoelectrochromic device with stable electrochromic property.
Accordingly, the invention also discloses a kind of above-mentioned Photoelectrochromic preparation of devices method, comprise the steps:
After the first electrically conducting transparent substrate surface applies semiconductor porous film, heat-treat, receiving semiconductor porous film surface adsorption dyestuff, obtain dye sensitized electrode then;
After the second electrically conducting transparent substrate surface applies the platinum catalyst gel, heat-treat, indium tin oxide surfaces forms the platinum catalyst layer; At the organic porous electrochomeric films of said platinum catalyst laminar surface electropolymerization, obtain the electrochromism electrode;
Said electrochromism electrode, electrolytic solution and dye sensitized electrode are assembled, comprised the Photoelectrochromic device of electrochromism electrode, electrolytic solution and dye sensitized electrode successively.
Can know that by said method the present invention at first prepares electrochromism electrode and dye sensitized electrode, and then assembles.Wherein the preparation of electrochromism electrode is at first to prepare the platinum catalyst layer at the second electrically conducting transparent substrate surface, then at the organic porous electrochomeric films of platinum catalyst laminar surface electropolymerization.Be specially at the second electrically conducting transparent substrate preparation platinum catalyst layer: at first apply the platinum catalyst gel, heat-treat then, the Pt generation catalytic activity that is activated in heat treatment process at the second electrically conducting transparent substrate surface.In this step heat treatment step, heat treatment temperature is preferably 120～150 ℃, and the time is preferably 15～20min, and the second electrically conducting transparent substrate surface just forms the Pt catalyst layer after the thermal treatment.
Form the Pt catalyst layer need be on its surface the organic porous electrochomeric films of electropolymerization again.Because 3; 4-(2; 2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films has good electrochromic property, fade and colored state between switching time shorter, so the present invention preferably selects 3 for use; The preparation of 4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films.The present invention preferably according to following mode at Pt catalyst layer surface electropolymerization 3,4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films:
Dissolving Lithium perchlorate anhydrous and 3 in acetonitrile, 4-(2,2-dimethyl allene dioxy base) thiophene obtains monomer solution after stirring; Adopting chronoamperometry, is working electrode with the second electrically conducting transparent substrate that is covered with the platinum layer, is contrast electrode with the filamentary silver, and the platinum sheet is as to electrode, with said working electrode, and contrast electrode and electrode immersed jointly carry out plated film in the monomer solution.In order to guarantee the homogeneity of plated film, the concentration that the present invention more preferably controls lithium perchlorate in the monomer solution is 0.06～0.14mol/L, 3, and the concentration of 4-(2,2-dimethyl allene dioxy base) thiophene is 0.006～0.014mol/L, plated film voltage is made as 1.3V～2V.After finishing, plated film just obtains the electrochromism electrode.
The preparation process of dye sensitized electrode is: at first at the first electrically conducting transparent substrate surface semiconductor porous film; Heat-treat then; Obtain the first electrically conducting transparent substrate that the surface is covered with how empty semiconductive thin film after the thermal treatment; At semiconductor porous film surface adsorption dyestuff, obtain dye sensitized electrode thus then.The present invention preferably adopts nano-titanium dioxide film as how empty semiconductive thin film.It preferably prepares according to following mode:
Employing is scraped the skill in using a kitchen knife in cookery at the first electrically conducting transparent substrate surface coated with nano titanium deoxid film; Be specially to adopt and scrape the skill in using a kitchen knife in cookery and behind the first electrically conducting transparent substrate surface titanium dioxide coated nano pulp, carry out drying; Baking temperature is preferably 90～110 ℃, is preferably 5～15min drying time.
Behind the first electrically conducting transparent substrate surface coated with nano titanium dioxide film, need heat-treat, make titanium dioxide crystal form change into Detitanium-ore-type into, and then realize the electric transmission function it.The temperature of this step Technology for Heating Processing is preferably 400 ℃～500 ℃, and the time is preferably 15～25min.
Just can carry out the absorbing dye operation behind the heat treatment step; The absorbing dye operation can adopt technology well known to those skilled in the art; Concrete as: adsorb immersing in the dye solution behind the first electrically conducting transparent substrate cool to room temperature after the thermal treatment; Dye solution preferably uses methyl alcohol as solvent, and adsorption time is preferably 18～36 hours, reaches maximal value to guarantee absorption.
Electrolytic solution preferably adopts the carbonic allyl ester solution of lithium iodide and elemental iodine, and this kind electrolytic solution prepares according to following method: dissolving lithium iodide and elemental iodine in carbonic allyl ester, and utilize magnetic stirrer not exist to there being particle, obtain electrolytic solution.
Just can carry out assembling procedure after preparing electrochromism electrode, dye sensitized electrode and electrolytic solution according to the method described above, the present invention preferably assembles according to following mode:
It is that 80～120 microns beaded glass mixes the back electrochromism electrode is applied that tackifier is used diameter; Referring to shown in Figure 2 for electrochromism electrode gluing synoptic diagram; Tackifier 4 is coated in organic porous electrochomeric films 301 edges of the electrochromism utmost point, and reserves injection port 5;
Dye sensitized electrode is placed on the electrochromism electrode surface; And make organic porous electrochomeric films of semiconductor porous film and electrochromism electrode of dye sensitized electrode relative; Then dye sensitized electrode and electrochromism electrode are clamped; Treat that tackifier solidifies the back and in injection port, injects electrolytic solution, use tackifier that injection port is sealed after injection finishes.Owing to contain diameter in the tackifier and be 80～120 microns beaded glass; Therefore with after dye sensitized electrode and the clamping of electrochromism electrode; The beaded glass diameter is the thickness in two spaces between the electrode; Control the injection rate IR of electrolytic solution thus, avoid the very few electronics that influences of electrolytic solution injection rate IR to transmit, perhaps electrolytic solution injects the lengthening of the wastage of material that too much causes and color switching time.According to just obtaining the Photoelectrochromic device after the aforesaid way assembling.With just obtaining Photoelectrochromic window, display and rearview mirror etc. after Photoelectrochromic device and other component-assembled.
In order further to understand the present invention, Photoelectrochromic device provided by the invention is described below in conjunction with embodiment.Protection scope of the present invention is not limited by the following examples.
In following examples 3,4-(2,2-dimethyl allene dioxy base) thiophene (ProDOT-Me
2), lithium iodide, elemental iodine and carbonic allyl ester provide by Sigma-Aldrich company.Dyestuff, platinum catalyst gel and titania nanoparticles provide by Switzerland Solaronix company; The model of dyestuff is Ruthenium 535-4TBA; The model of platinum catalyst gel is Pt-Catalyst T/SP, and the model of titania nanoparticles is Ti-Nanoxide HT.Bi-component glue is provided by U.S. Henkel Loctite company, and model is 9460.
The preparation of preparation electrolytic solution: dissolving lithium iodide and elemental iodine in carbonic allyl ester, utilize magnetic stirrer not exist to there being particle, obtain electrolytic solution, the concentration of lithium iodide is 0.1mol/L in the electrolytic solution, the concentration of elemental iodine is 0.001mol/L.
Preparation electrochromism electrode: at first prepare monomer solution, dissolving Lithium perchlorate anhydrous and PProDOT-Me in acetonitrile
2, concentration is respectively 0.1mol/L and 0.01mol/L.Utilize magnetic stirrer to dissolving fully, stand for standby use; On ito glass, brush one deck platinum catalyst gel, heated 10 minutes down at 130 ℃; After being cooled to room temperature, utilize electrochemical workstation, be specially: adopt chronoamperometry at the platinum layer polymerization macromolecule electrochomeric films that powers on; As working electrode, filamentary silver is as contrast electrode with the ito glass that covers the platinum layer, and the conduct of platinum sheet is to electrode; Together immerse in the monomer solution, the platinum catalyst layer is over against the platinum sheet, and plated film voltage is set at 1.65V; The plated film time is 4 seconds, obtains the electrochromism electrode after plated film finishes.
The preparation dye sensitized electrode: be equipped with the layer of titanium dioxide nanometer particle film in the FTO scraper legal system of utilizing on glass, then with this FTO glass 100 ℃ dry 10 minutes down, again 450 ℃ of bakings 20 minutes down.FTO glass cools after the thermal treatment immersed in the dye solution later on to room temperature adsorb, dye solution is 10 milligrams of dye solids to be dissolved in 25 ml methanol fully process, and whole adsorption process continues 24 hours.
Assembling Photoelectrochromic device: be that 100 microns beaded glass mixes with two component glue with diameter earlier; Be coated in 3 of electrochromism electrode then; 4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films edge, and stay next injection port; Dye sensitized electrode is covered on the electrochromism electrode, make dye sensitized electrode nano titanium dioxide film and electrochromism electrode 3,4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films is relative, uses clamp two plate electrodes.After treating that two component gellings are solid, take off anchor clamps, utilize 1 milliliter of syringe that electrolytic solution is injected between two plate electrodes through the injection port that stays in advance, with two component glue injection port is sealed again after filling with.Obtain the Photoelectrochromic device after the assembled.
The electrochromic property of the Photoelectrochromic device of test present embodiment preparation; Referring to the cyclic curve of the Photoelectrochromic device for the present invention preparation shown in Figure 3 in 637nm wavelength transmittance and time; Can know that by figure this Photoelectrochromic device has stable cycle performance, this Photoelectrochromic device is transformed into pellucidity by coloured state and can within the 4s clock, accomplishes; Being transformed into colored state by pellucidity can accomplish within 1s, and color is shorter switching time.In addition, transmitance changes also greatly, and in the 637nm wavelength, transmittance can change to 47% from 9%, and transmittance changes and reaches 38%.
The opto-electronic conversion performance of the Photoelectrochromic device of test present embodiment preparation, referring to the i-v curve of the Photoelectrochromic device for the present invention's preparation shown in Figure 4, the short-circuit current density of this Photoelectrochromic device of test result demonstration is 2.92mA/cm
2, open circuit voltage is 0.66V, the photoelectricity transfer efficient is 1.12%.
Can be known that by The above results Photoelectrochromic device provided by the invention has stable cycle performance, color is short switching time; In addition, this Photoelectrochromic device also has transmittance difference and photoelectric conversion rate preferably, is especially suitable for use as the dimming glass of electrochromic.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (15)
1. a Photoelectrochromic device is characterized in that, comprising: dye sensitized electrode, electrochromism electrode and contain the electrolytic solution of oxidation-reduction pair, and said electrolytic solution is between said dye sensitized electrode and electrochromism electrode;
Said dye sensitized electrode comprises: the first electrically conducting transparent substrate, and place the semiconductor porous film of the said first electrically conducting transparent substrate surface and be adsorbed in the surperficial dyestuff of said semiconductor porous film, said dyestuff contacts with electrolytic solution;
The electrochromism electrode, comprise setting gradually: organic porous electrochomeric films, platinum catalyst layer and the second electrically conducting transparent substrate, said organic porous electrochomeric films contacts with electrolytic solution.
2. Photoelectrochromic device according to claim 1 is characterized in that, said organic porous electrochomeric films is 3; 4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films, 3,4 (2-methyl; 2-propyl group-propylene dioxy base) thiophen polymer fiber electrochomeric films, 3; 4-ethene dioxythiophene polymer fiber electrochomeric films or 3,4-(2,2-diethyl propenyl dioxy base) pyrroles's polymer fiber electrochomeric films.
3. Photoelectrochromic device according to claim 1 is characterized in that, said semiconductor porous film is a nano-titanium dioxide film.
4. Photoelectrochromic device according to claim 1 is characterized in that, the said first electrically conducting transparent substrate is fluorine-doped tin oxide electropane or tin-antiomony oxide electropane.
5. Photoelectrochromic device according to claim 1 is characterized in that, the said second electrically conducting transparent substrate is indium tin oxide conductive film glass or zinc oxide aluminum electropane.
6. Photoelectrochromic device according to claim 1 is characterized in that, said electrolytic solution is the carbonic allyl ester solution of lithium iodide and elemental iodine.
7. Photoelectrochromic device according to claim 6 is characterized in that, the concentration of lithium iodide is 0.08～0.12mol/L in the said electrolytic solution, and the concentration of elemental iodine is 0.0008～0.0012mol/L.
8. the said Photoelectrochromic preparation of devices of claim 1 method is characterized in that, comprising:
After the first electrically conducting transparent substrate surface applies semiconductor porous film, heat-treat, at said semiconductor porous film surface adsorption dyestuff, obtain dye sensitized electrode then;
The second electrically conducting transparent substrate is an indium tin oxide-coated glass, after the said second electrically conducting transparent substrate surface applies the platinum catalyst gel, heat-treats, and indium tin oxide surfaces forms the platinum catalyst layer; At the organic porous electrochomeric films of said platinum catalyst laminar surface electropolymerization, obtain the electrochromism electrode;
Said electrochromism electrode, electrolytic solution and dye sensitized electrode are assembled, obtained the Photoelectrochromic device.
9. preparation method according to claim 8 is characterized in that, said semiconductor porous film is a nano-titanium dioxide film.
10. preparation method according to claim 9 is characterized in that, apply semiconductor porous film at the first electrically conducting transparent substrate surface and be specially: employing is scraped the skill in using a kitchen knife in cookery and behind the first electrically conducting transparent substrate surface coated with nano titania slurry, carried out drying.
11. preparation method according to claim 9 is characterized in that, said after the first electrically conducting transparent substrate surface applies semiconductor porous film, to carry out heat treated temperature be 400 ℃～500 ℃.
12. preparation method according to claim 8 is characterized in that, said after the second electrically conducting transparent substrate surface applies the platinum catalyst gel, to carry out heat treated temperature be 120～150 ℃.
13. preparation method according to claim 8 is characterized in that, said organic porous electrochomeric films is 3,4-(2,2-dimethyl allene dioxy base) thiophen polymer fiber electrochomeric films.
14. preparation method according to claim 13 is characterized in that, is specially at the organic porous electrochomeric films of said platinum catalyst laminar surface electropolymerization: dissolving Lithium perchlorate anhydrous and 3 in acetonitrile; 4-(2,2-dimethyl allene dioxy base) thiophene obtains monomer solution after stirring; The concentration of lithium perchlorate is 0.06～0.14mol/L in the said monomer solution; 3, the concentration of 4-(2,2-dimethyl allene dioxy base) thiophene is 0.006～0.014mol/L;
Adopt chronoamperometry; The second electrically conducting transparent substrate to be covered with the platinum layer is a working electrode, is contrast electrode with the filamentary silver, and the conduct of platinum sheet is to electrode; All immerse with said working electrode, contrast electrode with to electrode and to carry out plated film in the monomer solution, plated film voltage is made as 1.3V～2V.
15. preparation method according to claim 8 is characterized in that, the process of said assembling is specially: with tackifier and diameter is to be coated in the electrochromism electrode edge after 80～120 microns beaded glass mixes, and reserves injection port; Dye sensitized electrode is placed on behind the electrochromism electrode surface dye sensitized electrode and electrochromism electrode are clamped, treat that tackifier solidifies the back and in injection port, injects electrolytic solution, the injection back that finishes uses tackifier that injection port is sealed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100850074A CN102183863B (en) | 2011-04-06 | 2011-04-06 | Photoelectrochromic device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100850074A CN102183863B (en) | 2011-04-06 | 2011-04-06 | Photoelectrochromic device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102183863A CN102183863A (en) | 2011-09-14 |
| CN102183863B true CN102183863B (en) | 2012-11-28 |
Family
ID=44570054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100850074A Expired - Fee Related CN102183863B (en) | 2011-04-06 | 2011-04-06 | Photoelectrochromic device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102183863B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI596789B (en) * | 2012-11-19 | 2017-08-21 | 國立雲林科技大學 | Photoelectrochromic cell device and method for forming the same |
| CN103898592B (en) * | 2014-02-26 | 2016-05-04 | 东华大学 | A kind of preparation method of electrochromic intelligent fiber |
| CN104317129B (en) * | 2014-10-28 | 2017-08-11 | 电子科技大学 | Electrochromic device of high flux screening electrochromic material and preparation method thereof |
| CN106048710A (en) * | 2016-05-20 | 2016-10-26 | 浙江工业大学 | Erbium-doped titanium-oxygen cluster compound and preparation method and application thereof |
| JP7141077B2 (en) * | 2017-11-28 | 2022-09-22 | 国立大学法人千葉大学 | display element |
| CN108983527A (en) * | 2018-08-28 | 2018-12-11 | 上海幂方电子科技有限公司 | A kind of self-powered type electrochromic device and preparation process |
| CN109346209A (en) * | 2018-08-29 | 2019-02-15 | 浙江工业大学 | A kind of needle-shaped nano-structure conducting polymer thin film i-PEDOT and the preparation method and application thereof |
| CN109283766A (en) * | 2018-10-08 | 2019-01-29 | 浙江工业大学 | A kind of optical drive electrochromism energy storage device and preparation method thereof |
| CN109901340A (en) * | 2019-02-28 | 2019-06-18 | 中国科学技术大学 | A kind of self energizing electrochomeric films and its preparation method and application |
| CN109752894A (en) * | 2019-03-11 | 2019-05-14 | 南京工业大学 | Intelligent window of adjusting luminance |
| CN111142301B (en) * | 2020-02-14 | 2022-10-14 | 辽宁大学 | High-performance electrochromic device and preparation method thereof |
| CN111752013B (en) * | 2020-06-29 | 2022-08-09 | 绍兴迪飞新材料有限公司 | Porous polymer optical thin film device and preparation method thereof |
| CN114351482B (en) * | 2021-12-14 | 2022-10-25 | 华南理工大学 | Electrochromic artistic garment fabric and preparation method and application thereof |
| CN114488642A (en) * | 2022-02-11 | 2022-05-13 | 中国科学技术大学 | Electro-dimming device and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1736323A1 (en) * | 2005-06-22 | 2006-12-27 | European Central Bank | Security document comprising an electrical power supply means controlling a security means |
| JP2007149666A (en) * | 2005-11-25 | 2007-06-14 | Seiko Epson Corp | Electrochemical cell structure and its manufacturing method |
| CN101726956A (en) * | 2009-11-18 | 2010-06-09 | 华东师范大学 | Novel unit module for solar-powered self-driven electronic paper apparatus and method for preparing same |
-
2011
- 2011-04-06 CN CN2011100850074A patent/CN102183863B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1736323A1 (en) * | 2005-06-22 | 2006-12-27 | European Central Bank | Security document comprising an electrical power supply means controlling a security means |
| JP2007149666A (en) * | 2005-11-25 | 2007-06-14 | Seiko Epson Corp | Electrochemical cell structure and its manufacturing method |
| CN101726956A (en) * | 2009-11-18 | 2010-06-09 | 华东师范大学 | Novel unit module for solar-powered self-driven electronic paper apparatus and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| 光电致变色器件的研究进展;刘勇等;《材料导报》;20060415(第04期);15-17 * |
| 刘勇等.光电致变色器件的研究进展.《材料导报》.2006,(第04期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102183863A (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102183863B (en) | Photoelectrochromic device and preparation method thereof | |
| Tong et al. | Recent advances in multifunctional electrochromic energy storage devices and photoelectrochromic devices | |
| CN101840795B (en) | Flexible dye-sensitized solar cell | |
| JP2008130553A (en) | Dye-sensitized solar battery and manufacturing method of dye-sensitized solar battery | |
| US20230104362A1 (en) | Dye sensitized photovoltaic cells | |
| Wu et al. | Highly optical performance photoelectrochromic device based on Br−/Br3− electrolyte | |
| Chen et al. | New fabrication process of long-life dye-sensitized solar cells by in situ gelation of quasi-solid polymer electrolytes | |
| CA2878406A1 (en) | Photoelectrically convertible composition comprising an anionic polymer, a laminate, and processes therefor | |
| CN102483998A (en) | Low temperature platinisation for dye-sensitised solar cells | |
| US10270050B2 (en) | Photoelectric conversion layer composition and photoelectric conversion element | |
| WO2010089263A2 (en) | Dye-sensitised solar cells | |
| CN105511192A (en) | High-stability and adjustable-light-transmittance environment monitoring window | |
| JP4050535B2 (en) | Method for producing dye-sensitized solar cell | |
| Santa-Nokki et al. | A dye-sensitized solar cell driven electrochromic device | |
| Wu et al. | Photoelectrochromic devices based on cobalt complex electrolytes | |
| KR20090066455A (en) | Hybrid dye-sensitized photovoltaic/thermal solar system | |
| JP2004063758A (en) | Dye sensitized solar cell and manufacturing method therefor | |
| JP2004214063A (en) | Photoelectric conversion element and photoelectric conversion module | |
| CN105549291A (en) | High-voltage switch cabinet with transparency capable of being freely adjusted | |
| KR100499271B1 (en) | Flexible dye-sensitized solar cells and method for manufacturing the same | |
| AU2011263761A1 (en) | Solar cells with multiple dyes. | |
| JP5191631B2 (en) | Method for manufacturing counter electrode and method for manufacturing photoelectric conversion element | |
| CN105470829A (en) | Anti-thunder power distribution cabinet allowing transparency to be adjusted freely | |
| TW202431658A (en) | Dye-sensitized photovoltaic cells | |
| Su | All-solid-state photoelectrochromic window with PMMA gel electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121128 Termination date: 20150406 |
|
| EXPY | Termination of patent right or utility model |