CN102867652A - Titanium oxide film with ultraviolet light blocking and surface self-cleaning effects - Google Patents
Titanium oxide film with ultraviolet light blocking and surface self-cleaning effects Download PDFInfo
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- CN102867652A CN102867652A CN2012103589729A CN201210358972A CN102867652A CN 102867652 A CN102867652 A CN 102867652A CN 2012103589729 A CN2012103589729 A CN 2012103589729A CN 201210358972 A CN201210358972 A CN 201210358972A CN 102867652 A CN102867652 A CN 102867652A
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- 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
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- 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
Abstract
The invention discloses a titanium oxide film with ultraviolet light blocking and surface self-cleaning effects, which is characterized in that: the light receiving surface of a dye-sensitized solar cell is coated with a titanium oxide (TiO2) film with ultraviolet light blocking, visible light anti-reflecting and surface self-cleaning effects. The titanium oxide film with ultraviolet light blocking and surface self-cleaning effects disclosed by the invention can filter ultraviolet light in sunlight, prevent photosensitive dye, electrolytes, sealing materials and the like in the cell from being damaged and prolong the service life of the cell; while filtering the ultraviolet light, the TiO2 film can enhance the scattering (anti-reflecting) effect to the visible light, and the photovoltaic conversion efficiency of the cell is improved. In addition, the TiO2 film has extremely high photocatalytic activity and super-hydrophilic property, so that the surface of the film-coated cell has a self-cleaning function.
Description
Technical field
The present invention relates to the application of thin film of titanium oxide in photoelectric conversion technique, particularly a kind of have ultraviolet ray and stop thin film of titanium oxide with the self-cleaning surface effect.
Background technology
DSSC (DSC) has the foundation structure that is similar to sandwich style, by light anode, photocathode (also claiming electrode) and the electrolyte ingredient that is filled in negative and positive two interpolars.The light anode is (usually to use nanometer porous titanium oxide, TiO by having deposited nanometer oxide semiconductor
2) film and the electrically conducting transparent substrate (such as electro-conductive glass, conducting polymer) of having adsorbed the monolayer light-sensitive coloring agent consist of; Very supported the conductive substrates (as support Pt electro-conductive glass) of catalyst time; Electrolyte has liquid state, solid-state and accurate solid-state dividing, and (oxidation-reduction pair commonly used is I wherein all to contain oxidation-reduction pair
–/ I
3 –).For the DSC battery that uses liquid electrolyte, adopt at last encapsulant with electrolyte sealability between light anode and photocathode.The operation principle of DSC battery is: sunlight is from light anode one side irradiation battery, dye molecule is subjected to behind the solar light irradiation by ground state transition to excitation state, the dye molecule that is in excitation state with electronic injection in semi-conductive conduction band, electronics flows in the external circuit after arriving conductive substrates by diffusion, and finally arrive photocathode, be in the dyestuff of oxidation state by the reduction of the reduction-state material in the electrolyte, regeneration, and the oxidation state material in the electrolyte is accepted to be reduced behind an electronics at photocathode, thereby finishes a circulation.Hence one can see that, is adsorbed on TiO
2The light-sensitive coloring agent on surface plays and absorbs sunlight and to TiO
2Conduction band injects the key effect of the energy antenna of electronics.Electrolyte has played the important function of carrier transport.
TiO
2It is a kind of semiconductor of broad stopband.Anatase crystalline form TiO
2Energy gap be 3.2 eV, be 385 nm to the cut-off absorption wavelength of sunlight, rutile crystal form TiO
2Energy gap be 3.0 eV, be 405 nm to the cut-off absorption wavelength of sunlight.Sunlight mainly is comprised of ultraviolet ray (λ＜400 nm), visible light (400 nm ~ 700 nm), infrared ray (λ〉700 nm) three parts.Therefore, TiO
2Can absorb the ultraviolet ray in the sunlight, and the electronics on its valence band can be excited and transit to conduction band, on conduction band and valence band, produce respectively corresponding light induced electron (e –) and photohole (h+).TiO
2Photohole has superpower oxidability, and its reaction can be 402.8 MJ/mol, is higher than all kinds of chemical bond energy in the organic compound, can cause most organic substance generation oxidation reactions, finally generates CO
2And H
2The inorganic molecules such as O.In DSSC, efficiently light-sensitive coloring agent only absorbs visible light and part Infrared usually, absorbing ultraviolet not, and the ultraviolet ray excited TiO that is not absorbed by light-sensitive coloring agent
2The photohole with superpower oxidability of rear generation can make to be adsorbed on TiO
2The light-sensitive coloring agent on surface decomposes, the effect of degradedness antenna.Simultaneously, TiO
2Be excited rear generation light induced electron can also with electrolyte in oxidation state material generation electron recombination reaction, reduced the ability of electrolyte transport charge carrier.In addition, up to the present, great majority are lower for the uvioresistant performance of the encapsulant of DSC, and under ultraviolet ray was shone for a long time, encapsulant also was degraded, destroys, and lose sealing property and finally cause the electrolyte leakage.More than each factor all will cause greatly reduce the useful life of DSC.
So, stop efficiently the ultraviolet ray in the sunlight, avoid semiconductor TiO
2Being excited, allowing as much as possible visible light and infrared ray by conductive substrates simultaneously, absorbed by light-sensitive coloring agent, is to guarantee the long-term key of using of DSC battery.On the other hand, the DSC battery in use, its surface has the automatically cleaning ability to the maintenance of battery efficiency and attractive in appearancely all is of great practical significance.
Summary of the invention
Goal of the invention: be to solve DSC battery some problems in actual applications, the invention provides and a kind ofly have ultraviolet ray and stop thin film of titanium oxide with the self-cleaning surface effect.Its objective is that the sensitive surface at the DSC battery prepares one deck TiO
2Film, this layer TiO
2The ultraviolet ray of film in both can the filtering sunlight, the light-sensitive coloring agent in the protection battery is not destroyed, and prolongs the useful life of battery; The scattering property of incident light be can improve again, thereby utilance and the battery efficiency of light improved; This TiO of while
2Film has high photocatalytic activity and Superhydrophilic, can make the battery surface of filming have self-cleaning function.
For achieving the above object, one of technical scheme that adopts provides a kind ofly to be had ultraviolet ray and stops and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: have at sensitive surface preparation one deck of DSSC that ultraviolet ray stops, visible light is anti-reflection and the TiO of self-cleaning surface effect
2Film.
Wherein, described TiO
2The thin film technology method is: physical vaporous deposition, chemical precipitation method, sol-gal process, electrodeposition process, film construction from part or spray pyrolysis; Described physical vaporous deposition comprises: evaporation, magnetic control radio frequency sputtering method or molecular beam epitaxy; Described chemical vapour deposition technique comprises: atmospheric pressure vapour deposition process, low pressure vapour deposition process; Described sol-gel process comprises: spin-coating method, dip coating, drop-coating, spraying process, get rid of embrane method, czochralski method; Described electrodeposition process comprises: anodic electrodeposition method, cathodic electrodeposition, electrophoresis; Described film construction from part comprises: LB membrane technology, soft lithography, self-assembling technique, static packaging technology, template group packing technique.
Wherein, described TiO
2The thickness of film is 10 nm ~ 800 nm.
Wherein, adopt described sol-gal process to prepare TiO
2During film, used titanium colloidal sol has mixed various ingredients, comprises titanium compound, stabilizing agentof sol and alcoholic solvent, and the volume ratio of three's component is: 1:1:3 ~ 1:1:5; Add therein complexing additive and oxidant, the volume ratio of complexing additive and titanium compound is 1% ~ 5%; The volume ratio of oxidant and titanium compound is 1 ~ 10.
Wherein, described titanium compound is one or more in titanium tetrachloride, butyl titanate, tetraethyl titanate, the isopropyl titanate.
Wherein, described stabilizing agentof sol is one or more in acetylacetone,2,4-pentanedione, ethylenediamine, citric acid, acetic acid, hydrochloric acid, nitric acid, the sulfuric acid.
Wherein, described alcoholic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, the tert-butyl alcohol.
Wherein, described complexing additive is one or more in boric acid, phosphoric acid, the wolframic acid.
Wherein, described oxidant is one or more in perchloric acid, hypochlorous acid, hydrogen peroxide, potassium hyperchlorate, the concentrated sulfuric acid, potassium permanganate, the nitric acid.
Wherein, adopt described chemical vapour deposition technique to prepare TiO
2During film, the heating-up temperature of Conducting Glass is 300～650 ° of C, and the reaction temperature in the reactor is 100 ~ 200 ° of C, and the operating rate of substrate is 5 ~ 200 mm/s.
Wherein, adopt described magnetic control RF sputtering method to prepare TiO
2Film, control TiO
2Film thickness is 10 nm ~ 800 nm.
Beneficial effect: the present invention is applied in the DSSC, the effectively ultraviolet ray in the filtering sunlight, and the light-sensitive coloring agent in the protection battery, electrolyte, encapsulant etc. are not destroyed, and prolong the useful life of battery; In the filtering ultraviolet line, this type of TiO
2Film has high photocatalytic activity and Superhydrophilic, can make the battery surface of filming have self-cleaning function.
Description of drawings
Fig. 1 is simple glass and has prepared TiO
2The light transmittance curve chart that the glass of film obtains respectively.
Fig. 2 is the structural representation that has prepared DSSC of the present invention.
The accompanying drawing sign: the light transmittance curve of 1-simple glass, 2-has prepared TiO
2The glass transmission curve of film, 3-thin film of titanium oxide, 4-electro-conductive glass, 5-be to electrode, 6-nano-titanium oxide, 7-light-sensitive coloring agent.
Embodiment
The present invention is that the sensitive surface at the DSC battery prepares one deck TiO
2Film reaches shielding of ultraviolet, protects light-sensitive coloring agent, strengthens visible light transmissivity, makes battery surface have the automatically cleaning ability.By adjusting TiO
2Crystalline form and film thickness, filtering ultraviolet line effectively, and visible light and ultrared transmitance are substantially unaffected.Sunlight is before seeing through the conductive substrates of light anode, and ultraviolet ray at first is applied to the TiO of light entrance face
2Film absorption, can effectively the degrade microbe such as organic greasy dirt, kill bacteria of glass surface of produced simultaneously photohole, make dirt be difficult for being attached to its surface, even adhere to also be and outer moisture film combination, externally wind-force, water drench under the effects such as impulse force, self gravitation, can be automatically from nano-TiO
2Surfacial spalling is got off.Ultraviolet ray in the natural daylight is enough to keep nano-TiO
2Sterilization, the water-wet behavior on surface, thus make it have long-term self-cleaning decontamination effect.Meanwhile, the Nano semiconductor TiO of inside battery
2Avoid by ultraviolet ray excited, thereby effectively protected the not oxidized degraded of light-sensitive coloring agent.
Preparation technology of the present invention is simple to operation: various ingredients is mixed, and preparation forms specific titanium colloidal sol through sol-gel process, with high-pressure spray gun, whirler or film balance colloidal sol is coated in the sensitive surface of DSC battery, through Overheating Treatment acquisition TiO
2Film.The colloidal sol of this scheme preparation can at room temperature be deposited a week, deposits for 2 ~ 3 weeks under the low temperature.
Except direct sensitive surface at the DSC battery prepares TiO
2Outside the film, the present invention has also adopted physical vaporous deposition and chemical vapour deposition technique with TiO
2Film prepares first on the nonconductive surface of electro-conductive glass, then this is prepared with TiO
2The electro-conductive glass of film is used for the assembling of DSC battery.
The present invention is described in detail below in conjunction with drawings and Examples.
Embodiment 1
Butyl titanate (5 ml), acetylacetone,2,4-pentanedione (5 ml) are dissolved in the ethanol (40 ml), after mixing 15 –, 30 min, add the wolframic acid, acetylacetone,2,4-pentanedione (1 ml) and the hydrochloric acid (0.3 ml) that are equivalent to butyl titanate quality 2 mol%, form mixed solution, form colloid after fully stirring, and under 5 ° of C, reacting 8 h, 60 ° of C of normal pressure heat 1 h after taking out, and namely get titanium colloidal sol.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 2
Butyl titanate (5 ml), acetylacetone,2,4-pentanedione (5 ml) are dissolved in ethanol (40 ml), mix 15 –, 30 min after, add phosphoric acid and the acetic acid (0.3 ml) be equivalent to butyl titanate quality 2 mol%, stirring at room 8 h obtain colloidal sol.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 3
Metatitanic acid isopropyl ester (5 ml), citric acid (4 ml) are dissolved in methyl alcohol (50 ml), after mixing 15 –, 30 min, add the phosphoric acid, the citric acid (0.3 ml) that are equivalent to metatitanic acid isopropyl ester quality 2 mol%, after fully stirring, form colloid, and under room temperature, reacting 8 h, 65 ° of C of normal pressure heat 2 h after taking out, and namely get titanium colloidal sol.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 4
Titanium tetrachloride (5 ml), nitric acid (1ml) are dissolved in propyl alcohol (50 ml), after mixing 15 –, 30 min, add the wolframic acid, citric acid (0.3 ml) and the nitric acid (0.3 ml) that are equivalent to metatitanic acid isopropyl ester quality 2 mol%, form mixed solution, after fully stirring, form colloid, and under room temperature, react 10 h, 70 ° of C of normal pressure heat 3 h after taking out, and namely get titanium colloidal sol.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 5
Behind metatitanic acid isopropyl ester (5 ml), acetic acid (1 ml) mix and blend 15 – 30 min, mixture is joined (200 ml) hydrolysis in the deionized water, stir 1 h, then add nitric acid (4 ml) acid.Heating mixed liquor to 80 ° C pours solution in the autoclave into reaction 8 h under 240 ° of C after reacting 60 min.Centrifugation mixed liquor after reaction finishes removes ionized water, adds ethanol and ultrasonic dispersion, just obtains TiO
2Colloidal solution.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 6
At first butyl titanate (25 ml) is mixed with acetylacetone,2,4-pentanedione (4 ml).In addition nitric acid (1 ml) is joined in the deionized water (70 ml).Mixed liquor with butyl titanate and acetylacetone,2,4-pentanedione under the room temperature slowly joins in the aqueous solution of nitric acid, heats this mixed solution to 80 ° C, and vigorous stirring 90 min get colloidal sol after the cooling.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 7
Butyl titanate (13 ml) is slowly joined in the mixed solution of nitric acid (1 ml) and deionized water (70 ml).Heat this mixed solution to 80 ° C, vigorous stirring 30 min get colloidal sol after the cooling.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 8
Titanium tetrachloride (5 ml) slowly is added drop-wise in the deionized water (40 ml), dropwises rear continuation and stir 10 min.Add ammoniacal liquor in mentioned solution, regulating the pH value is 7 o'clock, continues to stir 10 min, produces a large amount of white solid precipitations.Filtering and washing repeatedly after, filter cake is dissolved in the deionized water, then to wherein adding 10 ml hydrogen peroxide, dissolution of solid, solution becomes orange-yellow, continues to stir 1 h.Stirring after complete is 3 to wherein adding hydrogen peroxide to pH value again, stirs behind 12 h and this mixed liquor to be heated to 100 ° of C, 4 h that reflux.Get colloidal sol after the cooling.Impregnated in the DSC battery of surface cleaning in the above-mentioned colloidal solution or colloidal solution is dropped on the sensitive surface of DSC battery, form uniform colloid film with czochralski method or spin-coating method at sensitive surface.Perhaps use spray gun spray paste liquid solution, at the uniform colloid film of sensitive surface formation of DSC battery.Dry film 1 ~ 30 min obtains water white TiO under the condition of room temperature ~ 50 ° C
2Film.
Embodiment 9
Adopt the magnetic control RF sputtering method to prepare TiO
2Film.With TiO
2Ceramic target places the coating machine negative electrode, heats under the vacuum degree of 10-3 Pa, removes the residual air in the cavity, again argon gas (Ar) is introduced vacuum chamber as the sputter working gas through mass flow controller.Open radio-frequency power supply, produce aura and put, make working gas ionization, the Ar+ ion accelerates to fly to negative electrode under electric field action, and the bombardment target surface makes TiO
2The atom of target surface splashes out, is deposited on nonconductive surface one side on the Conducting Glass, forms TiO
2Film, control TiO
2Film thickness be 200 nm.This depositing Ti O
2The electro-conductive glass of film can be directly used in the preparation of DSC battery.
Embodiment 10
Adopt chemical vapour deposition technique to prepare TiO
2Film.The temperature of Conducting Glass is 300～650 ° of C.Use isopropyl titanate as reactant, nitrogen is as carrier gas, and oxygen and steam are as catalysts.Mode by bubbling is brought the reactant isopropyl titanate into reactor with carrier gas, and the reaction temperature in the reactor is 100 ~ 200 ° of C.Oxygen and steam begin to mix in reactor with reactant, and are deposited on the nonconductive surface of electro-conductive glass.In the film preparation process, the operating rate of substrate is 5 ~ 200 mm/s.This depositing Ti O
2The electro-conductive glass of film can be directly used in the preparation of DSSC.
With reference to Fig. 1, by the TiO of above-described embodiment preparation
2Film can all absorb the ultraviolet ray below 380 nm; reach more than 85% at visible-range 400 ~ 700 nm light transmittances; the filter ultraviolet film of this as a result sufficient proof the present invention preparation is absorbing ultraviolet effectively; and do not affect the transmitance of visible light; be applied to effectively to protect dyestuff not destroyed by ultraviolet ray in the DSC battery, strengthen the stability of DSC battery.
Above content is the further description of the present invention being done in conjunction with optimal technical scheme, can not assert that the implementation of invention only limits to these explanations.Concerning the general technical staff of the technical field of the invention, under the prerequisite that does not break away from design of the present invention, can also make simple deduction and replacement, all should be considered as protection scope of the present invention.
Claims (11)
1. one kind has ultraviolet ray and stops and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: have at sensitive surface preparation one deck of DSSC that ultraviolet ray stops, visible light is anti-reflection and the TiO of self-cleaning surface effect
2Film.
2. described according to claim 1 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: described TiO
2The thin film technology method is: physical vaporous deposition, chemical precipitation method, sol-gal process, electrodeposition process, film construction from part or spray pyrolysis; Described physical vaporous deposition comprises: evaporation, magnetic control radio frequency sputtering method or molecular beam epitaxy; Described chemical vapour deposition technique comprises: atmospheric pressure vapour deposition process, low pressure vapour deposition process; Described sol-gel process comprises: spin-coating method, dip coating, drop-coating, spraying process, get rid of embrane method, czochralski method; Described electrodeposition process comprises: anodic electrodeposition method, cathodic electrodeposition, electrophoresis; Described film construction from part comprises: LB membrane technology, soft lithography, self-assembling technique, static packaging technology, template group packing technique.
3. described according to claim 1 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: described TiO
2The thickness of film is 10 nm ~ 800 nm.
4. described according to claim 2 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: adopt described sol-gal process to prepare TiO
2During film, used titanium colloidal sol has mixed various ingredients, comprises titanium compound, stabilizing agentof sol and alcoholic solvent, and the volume ratio of three's component is: 1:1:3 ~ 1:1:5; Add therein complexing additive and oxidant, the volume ratio of complexing additive and titanium compound is 1% ~ 5%; The volume ratio of oxidant and titanium compound is 1 ~ 10.
5. described according to claim 4 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect that it is characterized in that: described titanium compound is one or more in titanium tetrachloride, butyl titanate, tetraethyl titanate, the isopropyl titanate.
6. described according to claim 4 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect that it is characterized in that: described stabilizing agentof sol is one or more in acetylacetone,2,4-pentanedione, ethylenediamine, citric acid, acetic acid, hydrochloric acid, nitric acid, the sulfuric acid.
7. described according to claim 4 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect that it is characterized in that: described alcoholic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, the tert-butyl alcohol.
8. described according to claim 4 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect that it is characterized in that: described complexing additive is one or more in boric acid, phosphoric acid, the wolframic acid.
9. described according to claim 4 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect that it is characterized in that: described oxidant is one or more in perchloric acid, hypochlorous acid, hydrogen peroxide, potassium hyperchlorate, the concentrated sulfuric acid, potassium permanganate, the nitric acid.
10. described according to claim 2 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: adopt described chemical vapour deposition technique to prepare TiO
2During film, the heating-up temperature of Conducting Glass is 300～650 ° of C, and the reaction temperature in the reactor is 100 ~ 200 ° of C, and the operating rate of substrate is 5 ~ 200 mm/s.
11. described according to claim 2 a kind ofly have ultraviolet ray and stop and the thin film of titanium oxide of self-cleaning surface effect, it is characterized in that: adopt described magnetic control RF sputtering method to prepare TiO
2Film, control TiO
2Film thickness is 10 nm ~ 800 nm.
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| CN108987581A (en) * | 2018-07-25 | 2018-12-11 | 中节能万润股份有限公司 | A kind of automatically cleaning perovskite solar battery and preparation method thereof |
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