CN100533786C - Flexible dye sensitized solar energy cell photoanode preparation method and apparatus - Google Patents
Flexible dye sensitized solar energy cell photoanode preparation method and apparatus Download PDFInfo
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- CN100533786C CN100533786C CNB2007101339893A CN200710133989A CN100533786C CN 100533786 C CN100533786 C CN 100533786C CN B2007101339893 A CNB2007101339893 A CN B2007101339893A CN 200710133989 A CN200710133989 A CN 200710133989A CN 100533786 C CN100533786 C CN 100533786C
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- 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
- Y02E10/549—Organic PV cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a method and equipment of preparing flexible photo-anodes for dye-sensitized solar cells, and ensures an obtained semiconductor film free of cracks and superior in good uniformity and controllable thickness. The invention solves the problems of the prior art, such as long preparation time, poor repeatability, random distribution of local surface density of the semiconductor film, and high cracking risk. The flexible photo-anode is obtained by spray-coating of a conductive substrate by using a high-voltage electrostatic method and has good surface uniformity, and the surface semiconductor film doesn't produce cracks after random bending, thereby substantially realizing the flexibility. The preparation method is performed at normal temperature and pressure, without needing sinter process, thereby saving production energy and making it possible for nano-sized semiconductor materials with poor heat resistance to be applied in the field. The invention provides a new approach to improve the quality of the dye-sensitized solar cells.
Description
One, technical field
The invention belongs to a kind of technology for preparing dye-sensitized solar cell anode, relate in particular to a kind of preparation method and equipment of flexible dye sensitized solar energy cell photoanode.
Two, background technology
Prior art: as the focus that solves energy crisis and environmental pollution, solar energy is a kind of pollution-free and inexhaustible energy, more and more is subjected to the attention of national governments in recent years.Countries such as the U.S., Japan, Germany have all issued corresponding laws and regulations, encourage to use regenerative resources such as solar energy.Along with the raising of conversion efficiency of solar cell, the reduction of cost, do not go out 20 years, solar energy just can be competed with other electric power energy.
China is the fastest-rising country of energy-consuming in the world, also is SO
2, NO
x, CO
2Discharging big country, the pressure of environmental pollution is more and more big.And energy resource structure of China and energy resources layout are not ideal, the per capita resources poorness.The Chinese government actively encourages the development and use of solar energy, and " the regenerative resource method " of new promulgation implemented on January 1st, 2006.But at present present Research has bigger gap with technical merit and developed country, develops solar energy and be one of urgent research topic that China scientific worker faces.
At present, many countries such as Switzerland, the U.S., Australia, Japan have all dropped into a large amount of resources and have carried out dye-sensitized solar cells (Dye-sensitized Solar Cell, research and development DSC).In China's 973 projects " basic research of long-lived novel photovoltaic cell at a low price, ", the dye sensitized nano crystal thin film solar cell is listed in primary study, and domestic a lot of scientific research institutions carry out the research work at the various aspects of DSSC just energetically.
DSCs mainly by surface adsorption Nano semiconductor light anode, electrolyte, the Pt of dye sensitizing agent electrode is formed.Traditional DSCs is an electrode basement with the clear glass that is coated with FTO or ITO metal conductive oxide layer all.In recent years, with the plastics of flexible, lightweight or metal forming be electrode basement prepare flexible DSCs battery in light weight, flexible, with low cost because of it, outstanding advantage such as be widely used and caused the great attention of Chinese scholars and research institution.With the DSCs light weight that flexible substrates makes, flexible, not only be beneficial to the continuously manufacturing of battery and mechanization, drum-type production, thereby reduction manufacturing cost, and expanded the range of application of this class battery greatly, as embedding the notebook computer tank wall, under illumination condition, computer is charged; Being contained in the electric automobile vehicle body is the motor power supply; Cover the roof supply electric consumption on lighting in house etc.; Even can be widely used on the daily living articles such as umbrella, clothing, development potentiality is very big.
DSC realizes flexibility, and key technology is the preparation of light anode.Compare with substrate of glass, the preparation technology of flexible substrates light anode is completely different.The former traditional preparation process method is: with nano-TiO
2Pressed powder adds solvent, certain dispersant, stabilizer etc., through grind, sonicated, under the effect of high speed shear power, it is separated into uniform sol liquid, adopt knife coating or silk screen print method on electro-conductive glass, prepares nothing and split TiO
2The trace coating is carried out high temperature sintering again, thereby obtains the light anode.The latter can not adopt traditional handicraft to its high temperature sintering because substrate is the electrically conducting transparent macromolecular material of non-refractory.The main at present ITO/PET that adopts (PETG of plating tin indium oxide) film, its heat resisting temperature is lower than 150 ℃, and temperature is too high, and the PET substrate is easily broken, is out of shape.Therefore, the low-temperature fabrication of soft-light anode becomes key.
The main method of the flexible DSCs of preparation is mechanical pressed film method at present.At first with TiO
2Nanometer powder is dispersed in the solvent, is coated in subsequently on the flexible substrates, dries the back naturally film is applied instantaneous high pressure realization mechanical compaction, impels TiO
2The formation that neck connects between the nano particle improves TiO
2The film specific area reduces average pore size.Though the efficient of mechanical pressed film method is higher relatively, the light anode TiO of preparation
2The film particle only limits to physical bond, and the neck of formation connects imperfect, and bond strength is lower, and high pressure can not flatten film surface smoothly fully, and local surfaces density is random distribution still.Mechanical compaction finishes back TiO
2Film can remain on the pressing plate, causes the part of film to come off, even when electrode bending, TiO
2Be full of cracks will appear in film.
The low-temperature sintering method.This method is at TiO
2Do not use any organic substance in the preparation process of film, only under cryogenic conditions, carry out sintering processes, but the battery efficiency of length consuming time, acquisition is low.
Hydro thermal method.This method is made solvent with water, by heating airtight water heating kettle, forms the reaction environment of low temperature, high pressure, to adhering to TiO
2The ITO/PET of presoma carries out 12 hours low-temperature hydrothermal sintering.Adopt this method can obtain stable mechanical performance, the homogeneity light anode of defectives such as nothing is curled, cracking.But meeting residual fraction organic substance in the electrode, TiO
2Particle aggregation is incomplete, and this in addition method manufacturing cycle is long, efficient is lower, is difficult for realizing suitability for industrialized production.
Spin-coating method.This method is the TiO that the ITO/PET flexible substrates is immersed in Detitanium-ore-type
2In rare nitric acid colloidal solution of nano particle, prepare TiO with the speed spin coating of 800~3000r/min
2Film is at last at 100 ℃ of sintering 24h.By concentration and the spin coating rate controlled thickness of controlling initial colloidal solution.Work as TiO
2Concentration surpasses 20%, the gained uneven film thickness, and central thickness is greater than the edge.When spin coating speed is lower than 700r/min, also will obtain similar thickness distribution and produce macroscopic crack.This method can only obtain even, the free from flaw TiO that thickness is no more than 1 μ m
2Film.
Though the research of flexible DSCs has certain progress, its key problem still concentrates on the low-temperature fabrication aspect of light anode.
Three, summary of the invention
Technical problem: the present invention is directed to above-mentioned technical problem, provide that a kind of cost is low, manufacturing process simply prepares flexible dye sensitized solar energy cell photoanode fast, method and equipment thereof easily, can realize the semiconductive thin film flawless that obtains, homogeneity is good, controllable thickness solves such electrode fabrication length consuming time at present, poor reproducibility, semiconductive thin film local surfaces density random distribution, shortcoming easy to crack.
Technical scheme: the present invention adopts high-pressure electrostatic method spraying coating conductive substrates, obtains soft-light anode.The emulsion that forms with semiconductor nano and volatile organic solvent is slurry, adopts the substrate of soft light conductive film, by precise injection pump Digital Control slurry sample introduction speed, applies the constant voltage high-pressure electrostatic at outlet, makes emulsion charged.Utilize the mutual exclusion principle of like charges, the volatile characteristic of solvent, obtain finely dispersed charged semiconductor grain spraying.Under high voltage electrostatic field, charged particle is done directed movement, arrives the conductive film substrate and gathers film forming, obtains the light anode.
Manufacture method is:
A. be light anode electrode base material with the compliant conductive macromolecule membrane, substrate thickness is 0.1cm~1cm, and visible light transmissivity is greater than 50%, and surperficial square resistance is 10 Ω/~300 Ω/;
B. after the base material cleaning, the zone that does not need in the substrate to spray is sealed with insulating material;
C. prepare semiconductor slurry: semiconductor nano powder and volatile organic solvent are mixed, and wherein nanometer powder and organic solvent mass ratio are 1:100~20:100;
D. the Nano semiconductor slurry is injected syringe pump, regulating syringe pump outlet and substrate conducting surface distance is 1cm~50cm, it is 0.1ml/h~50ml/h that the syringe pump spraying rate is set, prepare out sample, opening high voltage source simultaneously, at the syringe pump outlet slurry to be applied electrostatic pressure be 1kV~50kV, the control spray time is 1min~300min, substrate conducting surface ground connection;
E. Luo Lu substrate conducting surface receives charged semiconductor spraying, and piles up the homogeneous film that formation has micron order thickness gradually, stops to throw off insulating material after the spraying, gets soft-light anode;
F. absorbing dye, above-mentioned soft-light anode directly immerses in the dye solution behind 80 ℃~150 ℃ heating 5min~30min, takes out behind soaking at room temperature 20h~24h, with the absolute ethyl alcohol flushing, dries, must dye sensitized flexible light anode.
Volatile organic solvent is ethanol, acetone or isopropyl alcohol.The compound method of semiconductor slurry is at room temperature magnetic agitation 0.5h~5h, and ultrasonic dispersion 10min~60min filters with 200~450 mesh standard sieves.
Semiconductor slurry is being with like charges under the high-pressure electrostatic effect, under the precise injection pump promoted, the slurry trace went out sample.Owing to repel mutually between like charges, emulsion is separated into spraying leaving outlet passage moment, and basad conducting surface is done directed movement under the electrostatic field that forms between outlet and conductive substrates.In the motion process, organic solvent volatilizees rapidly, and semiconductor grain arrives conducting surface and also gathers film forming, and the conducting film of substrate surface, release are given in the electrically charged conduction of institute.
A kind of preparation method's of flexible dye sensitized solar energy cell photoanode equipment, comprise syringe pump, high voltage source, bracing frame, flexible substrates and horizontal objective table, syringe pump is located on the bracing frame, syringe pump is provided with the outlet of vertical, the scalable adjusting of outlet, high voltage source is electrically connected with outlet, and horizontal objective table is located under the outlet, flexible substrates is located on the horizontal objective table, flexible substrates ground connection.Beneficial effect:
1, adopt high-pressure electrostatic method spraying coating conductive substrates, obtain soft-light anode, the photoanode surface homogeneity is good, and after curling arbitrarily, surperficial semiconductive thin film does not have obvious crackle, has realized flexible truly;
2, by adjusting insulating material shape, the size that substrate surface covers, requirement according to application places is fabricated to desired shapes with electrode, even on the on-plane surface conductive substrates, produce irregularly shaped or curved surface (as sphere) light anode, improved the universality of this type of solar cell;
3, adopt precise injection pump Digital Control slurry to go out sample speed, apply the constant voltage high-pressure electrostatic at outlet, make emulsion charged, utilize the mutual exclusion principle of like charges, the volatile characteristic of solvent, obtain finely dispersed charged semiconductor grain spraying, under high voltage electrostatic field, charged particle is done directed movement, arrive the conductive film substrate and gather film forming and obtain the light anode, pump parameters such as sample speed, spray time, voltage by control slurry concentration, injection, can accurately control thickness of semiconductor film;
4, the emulsion that forms with semiconductor nano and volatile organic solvent is slurry, filters with 200 orders~450 mesh standard sieves, effectively removes the obviously nanocluster of reunion, makes the homogeneity of photoanode surface of slurry and preparation thereof better;
5, manufacturing process is carried out at normal temperatures and pressures, no sintering process, save energy consumption, make of the application of the not good nano semiconductor material of some thermal endurances become possible (material destroyed as nanostructure in sintering, that crystal transfer etc. takes place) simultaneously in this field, for the raising of this type of battery performance provide new may;
6, method rapid and convenient, easy to learn, favorable reproducibility, and low cost of manufacture, technology is simple, can realize automation, digital control, and the efficient height is beneficial to continuous, flowing water suitability for industrialized production;
7, the DSCs that makes based on soft light anode can curl, shear, in light weight, easily combine with construction material, the glass that can be used for wearable mobile phone and palmtop PC and automobile industry, even can make necklace, utilize sunlight to be powering portable devices, widened the range of application of solar cell.
Four, description of drawings
Fig. 1 is high-pressure electrostatic spraying schematic diagram.1, the outlet 5 of syringe pump 2, high voltage source 3, bracing frame 4, syringe pump, charged spray 6, substrate conducting surface 7, flexible substrates 8, insulating material 9, ground connection 10, horizontal objective table
Fig. 2 is the DSC photoelectricity test curve (output current of DSC and photovoltage curve, i.e. I-V curve) based on this flexible optoelectronic utmost point.
In the I-V curve, the intercept of curve on ordinate is that short-circuit current density (Jsc) is the current density of circuit when being in short circuit (external resistance be zero), equals the short circuit current of battery and the ratio of battery effective area.
The intercept of curve on abscissa is open circuit voltage (Voc), the voltage when promptly circuit is in open circuit (external resistance infinity).
Five, embodiment
Embodiment 1:a, be the light anode electrode material with compliant conductive macromolecule membrane ITO/PET, substrate thickness is 100um, and visible light transmissivity 75%, surperficial square resistance are 14 Ω/.
B, substrate is cleaned.In deionized water, splash into several liquid detergents, with substrate rinsing therein a few minutes, with in KOH isopropyl alcohol saturated solution, soaking 2 hours again behind the deionized water rinsing, behind deionized water rinsing, sonic oscillation cleaned 10 minutes in deionized water, absolute ethyl alcohol successively, and absolute ethyl alcohol flushing back dries up with nitrogen.
C, according to actual needs, seal with insulating tape in the place that does not need in the substrate to spray, and seal the geometry, the shape of size Control light anode in zone by adjustment, produce the light anode that adapts to the different places demand, even on the on-plane surface conductive substrates, produce and have light anode irregularly shaped or curved surface (as the sphere film).
D, with nano-TiO
2Slurry injects syringe pump, regulates outlet and substrate conducting surface distance, spraying rate is set prepares out sample, opens high voltage source simultaneously and at outlet slurry is applied high-pressure electrostatic.
E, exposed ITO conducting surface receive charged TiO
2Spraying, and build up and become to have certain thickness homogeneous film, stop to throw off insulating tape after the spraying, obtain soft-light anode.
F, absorbing dye.Above-mentioned electrode directly immerses the ethanolic solution of N3 dyestuff (Australian DYESOL company buy) behind 80 ℃ of heating 30min (N3 concentration is 3 * 10
-4Mol/L) in, take out behind the soaking at room temperature 20h,, dry with the absolute ethyl alcohol flushing.
TiO wherein
2Slurry is TiO
2Nanometer powder (P25, Degussa company buys) is that 1:100 mixes with ethanol by mass ratio, room temperature magnetic agitation 0.5h, and ultrasonic dispersion 10min filters with 200 mesh standard sieves.During the spraying substrate, accurately controlling the slurry spraying rate with syringe pump is 0.1ml/h, and it is 5kV that outlet applies electrostatic high-pressure, and outlet and substrate conducting surface distance are 3cm, and spray time is 300min.The substrate conducting surface needs ground connection.Spraying process is finished in the clean room.Substrate is at horizontal plane, and outlet is vertical with it.
Embodiment 2:a, be the light anode electrode material with compliant conductive macromolecule membrane ITO/PET, substrate thickness is 125um, and visible light transmissivity 80%, surperficial square resistance are 100 Ω/.
B, substrate is cleaned.In deionized water, splash into several liquid detergents, with substrate rinsing therein a few minutes, with in KOH isopropyl alcohol saturated solution, soaking 2 hours again behind the deionized water rinsing, behind deionized water rinsing, sonic oscillation cleaned 10 minutes in deionized water, absolute ethyl alcohol successively, and absolute ethyl alcohol flushing back dries up with nitrogen.
C, according to actual needs, seal with insulating tape in the place that does not need in the substrate to spray, and seal the geometry, the shape of size Control light anode in zone by adjustment, produce the light anode that adapts to the different places demand, even on the on-plane surface conductive substrates, produce and have light anode irregularly shaped or curved surface (as the sphere film).
D, the nano-ZnO slurry is injected syringe pump, regulate outlet and substrate conducting surface distance, spraying rate is set prepares out sample, open high voltage source simultaneously and slurry is applied high-pressure electrostatic at outlet.
E, exposed ITO conducting surface receive charged ZnO spraying, and build up and become to have certain thickness homogeneous film, stop to throw off insulating tape after the spraying, obtain soft-light anode.
F, absorbing dye.Above-mentioned electrode directly immerses the ethanolic solution of N719 dyestuff (Australian DYESOL company buy) behind 100 ℃ of heating 20min (N719 concentration is 3 * 10
-4Mol/L) in, soaking at room temperature was taken out after 20 hours, with the absolute ethyl alcohol flushing, dried.
Wherein the ZnO slurry is that ZnO nanometer powder (HTZn-01, Haitai Nano Material Co., Ltd., Nanjing buys) is that 5:100 mixes with acetone by mass ratio, room temperature magnetic agitation 1h, and ultrasonic dispersion 20min filters with 250 mesh standard sieves.During the spraying substrate, accurately controlling the slurry spraying rate with syringe pump is 5ml/h, and it is 15kV that outlet applies electrostatic high-pressure, and outlet and substrate conducting surface distance are 10cm, and spray time is 20min.The substrate conducting surface needs ground connection.Spraying process is finished in the clean room.Substrate is at horizontal plane, and outlet is vertical with it.
Embodiment 3:a, be the light anode electrode material with compliant conductive macromolecule membrane ITO/PET, substrate thickness is 200um, and visible light transmissivity 85%, surperficial square resistance are 14 Ω/.
B, substrate is cleaned.In deionized water, splash into several liquid detergents, with substrate rinsing therein a few minutes, with in KOH isopropyl alcohol saturated solution, soaking 2 hours again behind the deionized water rinsing, behind deionized water rinsing, sonic oscillation cleaned 10 minutes in deionized water, absolute ethyl alcohol successively, and absolute ethyl alcohol flushing back dries up with nitrogen.
C, according to actual needs, seal with insulating tape in the place that does not need in the substrate to spray, and seal the geometry, the shape of size Control light anode in zone by adjustment, produce the light anode that adapts to the different places demand, even on the on-plane surface conductive substrates, produce and have light anode irregularly shaped or curved surface (as the sphere film).
D, with nanometer ZrO
2Slurry injects syringe pump, regulates outlet and substrate conducting surface distance, spraying rate is set prepares out sample, opens high voltage source simultaneously and at outlet slurry is applied high-pressure electrostatic.
E, exposed ITO conducting surface receive charged ZrO
2Spraying, and build up and become to have certain thickness homogeneous film, stop to throw off insulating tape after the spraying, obtain soft-light anode.
F, absorbing dye.Above-mentioned electrode directly immerses the ethanolic solution of N3 dyestuff (Australian DYESOL company buy) behind 150 ℃ of heating 5min (N3 concentration is 3 * 10
-4Mol/L) in, take out behind the soaking at room temperature 20h,, dry with the absolute ethyl alcohol flushing.
ZrO wherein
2Slurry is ZrO
2Nanometer powder (HTZr-01, Haitai Nano Material Co., Ltd., Nanjing buys) is that 10:100 mixes with isopropyl alcohol by mass ratio, room temperature magnetic agitation 1.5h, and ultrasonic dispersion 30min filters with 350 mesh standard sieves.During the spraying substrate, accurately controlling the slurry spraying rate with syringe pump is 15ml/h, and it is 25kV that outlet applies electrostatic high-pressure, and outlet and substrate conducting surface distance are 30cm, and spray time is 20min.The substrate conducting surface needs ground connection.Spraying process is finished in the clean room.Substrate is at horizontal plane, and outlet is vertical with it.
Embodiment 4:a, be the light anode electrode material with compliant conductive macromolecule membrane ITO/PET, substrate thickness is 125um, and visible light transmissivity 75%, surperficial square resistance are 14 Ω/.
B, substrate is cleaned.In deionized water, splash into several liquid detergents, with substrate rinsing therein a few minutes, with in KOH isopropyl alcohol saturated solution, soaking 2 hours again behind the deionized water rinsing, behind deionized water rinsing, sonic oscillation cleaned 10 minutes in deionized water, absolute ethyl alcohol successively, and absolute ethyl alcohol flushing back dries up with nitrogen.
C, according to actual needs, seal with insulating tape in the place that does not need in the substrate to spray, and seal the geometry, the shape of size Control light anode in zone by adjustment, produce the light anode that adapts to the different places demand, even on the on-plane surface conductive substrates, produce and have light anode irregularly shaped or curved surface (as the sphere film).
D, with nanometer Al
2O
3Slurry injects syringe pump, regulates outlet and substrate conducting surface distance, spraying rate is set prepares out sample, opens high voltage source simultaneously and at outlet slurry is applied high-pressure electrostatic.
E, exposed ITO conducting surface receive charged Al
2O
3Spraying, and build up and become to have certain thickness homogeneous film, stop to throw off insulating tape after the spraying, obtain soft-light anode.
F, absorbing dye.Above-mentioned electrode directly immerses the ethanolic solution of N3 dyestuff (Australian DYESOL company buy) 100 ℃ of heating after 3 minutes (N3 concentration is 3 * 10
-4Mol/L) in, soaking at room temperature was taken out after 20 hours, with the absolute ethyl alcohol flushing, dried.
Al wherein
2O
3Slurry is Al
2O
3Nanometer powder (HTAL-01, Haitai Nano Material Co., Ltd., Nanjing buys) is that 15:100 mixes with ethanol by mass ratio, room temperature magnetic agitation 3h, and ultrasonic dispersion 30min filters with 450 mesh standard sieves.During the spraying substrate, accurately controlling the slurry spraying rate with syringe pump is 1ml/h~15ml/h, and it is 20kV that outlet applies electrostatic high-pressure, and outlet and substrate conducting surface distance are 40cm, and spray time is 1min~120min.The substrate conducting surface needs ground connection.Spraying process is finished in the clean room.Substrate is at horizontal plane, and outlet is vertical with it.
Embodiment 5:a, be the light anode electrode material with compliant conductive macromolecule membrane ITO/PET, substrate thickness is 500um, and visible light transmissivity 75%, surperficial square resistance are 14 Ω/.
B, substrate is cleaned.In deionized water, splash into several liquid detergents, with substrate rinsing therein a few minutes, with in KOH isopropyl alcohol saturated solution, soaking 2 hours again behind the deionized water rinsing, behind deionized water rinsing, sonic oscillation cleaned 10 minutes in deionized water, absolute ethyl alcohol successively, and absolute ethyl alcohol flushing back dries up with nitrogen.
C, according to actual needs, seal with insulating tape in the place that does not need in the substrate to spray, and seal the geometry, the shape of size Control light anode in zone by adjustment, produce the light anode that adapts to the different places demand, even on the on-plane surface conductive substrates, produce and have light anode irregularly shaped or curved surface (as the sphere film).
D, the nano-MgO slurry is injected syringe pump, regulate outlet and substrate conducting surface distance, spraying rate is set prepares out sample, open high voltage source simultaneously and slurry is applied high-pressure electrostatic at outlet.
E, exposed ITO conducting surface receive charged MgO spraying, and build up and become to have certain thickness homogeneous film, stop to throw off insulating tape after the spraying, obtain soft-light anode.
F, absorbing dye.Above-mentioned electrode directly immerses the ethanolic solution of N3 dyestuff (Australian DYESOL company buy) behind 80 ℃ of heating 30min (N3 concentration is 3 * 10
-4Mol/L) in, take out behind the soaking at room temperature 20h,, dry with the absolute ethyl alcohol flushing.
Wherein the MgO slurry is that MgO nanometer powder (P25, Degussa company buys) is that 20:100 mixes with ethanol by mass ratio, room temperature magnetic agitation 5h, and ultrasonic dispersion 60min filters with 450 mesh standard sieves at last.During the spraying substrate, accurately controlling the slurry spraying rate with syringe pump is 1ml/h, and it is 25kV that outlet applies electrostatic high-pressure, and outlet and substrate conducting surface distance are 50cm, and spray time is 120min.The substrate conducting surface needs ground connection.Spraying process is finished in the clean room.Substrate is at horizontal plane, and outlet is vertical with it.
Embodiment 6: a kind of preparation method's of flexible dye sensitized solar energy cell photoanode equipment, comprise syringe pump 1, high voltage source 2, bracing frame 3, flexible substrates 7 and horizontal objective table 10, syringe pump 1 is located on the bracing frame 3, syringe pump 1 is provided with the outlet 4 of vertical, outlet 4 scalable adjustings, high voltage source 2 is electrically connected with outlet 4, and horizontal objective table 10 is located under the outlet 4, flexible substrates 7 is located on the horizontal objective table 10, flexible substrates 7 ground connection.
Claims (4)
1. the preparation method of a flexible dye sensitized solar energy cell photoanode is characterized in that preparation process is:
A. be light anode electrode base material with the compliant conductive macromolecule membrane, substrate thickness is 0.1cm~1cm, and visible light transmissivity is greater than 50%, and surperficial square resistance is 10 Ω/~300 Ω/;
B. after the base material cleaning, the zone that does not need in the substrate to spray is sealed with insulating material;
C. preparation of nano semiconductor slurry: semiconductor nano powder and volatile organic solvent are mixed, and described semiconductor nano powder is TiO
2, ZnO, ZrO
2, Al
2O
3Or MgO, wherein manocrystalline powders and organic solvent mass ratio are 1:100~20:100;
D. the Nano semiconductor slurry is injected syringe pump, regulating syringe pump outlet and substrate conducting surface distance is 1cm~50cm, it is 0.1ml/h~50ml/h that the syringe pump spraying rate is set, prepare out sample, opening high voltage source simultaneously, at the syringe pump outlet slurry to be applied electrostatic pressure be 1kV~50kV, the control spray time is 1min~300min, substrate conducting surface ground connection;
E. Luo Lu substrate conducting surface receives charged semiconductor spraying, and piles up the homogeneous film that formation has micron order thickness gradually, stops to throw off insulating material after the spraying, gets soft-light anode;
F. absorbing dye, above-mentioned soft-light anode directly immerses in the dye solution behind 80 ℃~150 ℃ heating 5min~30min, takes out behind soaking at room temperature 20h~24h, with the absolute ethyl alcohol flushing, dries, must dye sensitized flexible light anode.
2. the preparation method of a kind of flexible dye sensitized solar energy cell photoanode according to claim 1 is characterized in that described volatile organic solvent is ethanol, acetone or isopropyl alcohol.
3. the preparation method of a kind of flexible dye sensitized solar energy cell photoanode according to claim 1, the compound method that it is characterized in that semiconductor slurry is at room temperature magnetic agitation 0.5h~5h, ultrasonic dispersion 10min~60min filters with 200~450 mesh standard sieves.
4. the preparation method of a kind of flexible dye sensitized solar energy cell photoanode according to claim 1 is characterized in that substrate is a horizontal plane, and the syringe pump outlet is vertical with it.
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CN104637692B (en) * | 2015-01-22 | 2017-10-03 | 太原理工大学 | A kind of method that spraying process prepares dye-sensitized solar cell anode |
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