CN101814377B - Preparation method of TiO2 film of dye-sensitized solar battery with high conversion efficiency under low light intensity - Google Patents
Preparation method of TiO2 film of dye-sensitized solar battery with high conversion efficiency under low light intensity Download PDFInfo
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- CN101814377B CN101814377B CN2010101811087A CN201010181108A CN101814377B CN 101814377 B CN101814377 B CN 101814377B CN 2010101811087 A CN2010101811087 A CN 2010101811087A CN 201010181108 A CN201010181108 A CN 201010181108A CN 101814377 B CN101814377 B CN 101814377B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000084 colloidal system Substances 0.000 claims abstract description 29
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 31
- 239000000975 dye Substances 0.000 claims description 11
- 239000002390 adhesive tape Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012327 Ruthenium complex Substances 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 13
- 238000005286 illumination Methods 0.000 abstract description 2
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 abstract 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical class OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- -1 titanate ester compound Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a preparation method of a TiO2 film of a dye-sensitized solar battery with high conversion efficiency under low light intensity. The preparation method mainly comprises the following steps of: preparing colloid by using the raw materials of isopropyl titanate, citric acid and glycol, then spreading the colloid on FTO evenly and afterwards strickling a colloid film on the FTO; then, drying for 25 to 30min at the temperature of 100 DEG C in a drying oven, then putting into a heat treatment furnace, annealing for 50 to 70min at the temperature of 450 DEG C and cooling naturally to the temperature of 80 to 100 DEG C so as to obtain a first layer of film; operating on the obtained first layer of film repeatedly so as to obtain two layers of colloid films; and afterwards, putting the two obtained layers of films into an ethanol solution of the N719 dye of a ruthenium coordination compound so as to obtain the light anode of the TiO2 film sensitized by the dye. The solar battery prepared by the film prepared by using the method has very high conversion efficiency under low light intensity, and the conversion efficiency can reach 11.83 percent under the illumination of 5mW/cm2.
Description
Technical field
The present invention relates to a kind of dye-sensitized solar battery with high conversion efficiency under low light intensity TiO
2The preparation method of film.
Background technology
M. in 1991
The laboratory has proposed a kind of novel with dye sensitization TiO first
2Nano-crystal film is the dye sensitized nano crystal thin-film solar cells (Dye-sensitized solar cells) of light anode, and the photoelectric conversion efficiency of battery reaches 7.1% under sunlight, thereby has opened the research boom of DSSC.DSSC TiO
2Film is because lower cost of manufacture, high theoretical conversion efficient and nontoxic pollution-free, and has good application prospects.
Traditional preparation process nano dye sensitization TiO
2The method of film is to adopt sol-gel process and cladding process: with titanate ester compound etc. be that TiO is prepared in presoma slow hydrolysis in acidic aqueous solution
2Colloidal sol is through autoclave heat treatment, evaporate, add surfactant and grind preparation TiO
2Slurry is then through method depositing Ti O on conductive substrates such as silk screen printing, blade blade coating, spin coatings
2Perhaps directly use cladding process, with the nano-TiO of business level
2Powder adds surfactant and an amount of organic solvent grinds preparation TiO
2Slurry is filmed then, after annealing preparation about 450 ℃.Except above-mentioned two kinds of methods commonly used, also have liquid phase deposition, chemical vapour deposition technique, magnetron sputtering deposition method, electrodeposition process, plasma spraying method etc.
But the DSSC TiO that above existing method makes
2Though film can obtain higher photoelectric conversion efficiency, its preparation technology is too complicated, and cost is too high, and photoelectric conversion efficiency is low under low electricity is strong, can't use in area at low sunshine.
Summary of the invention
The object of the invention just provides a kind of dye-sensitized solar battery with high conversion efficiency under low light intensity TiO
2The preparation method of film, the film that this kind method makes has very high conversion efficiency as the solar cell of light anode preparation under low light intensity, and use in the area that is particularly useful for low sunshine.
The present invention realizes that the technical scheme that its goal of the invention adopts is, a kind of dye-sensitized solar battery with high conversion efficiency under low light intensity TiO
2The preparation method of film, its concrete practice is:
A, preparation TiO
2Colloid
Take by weighing the raw material isopropyl titanate respectively by 1: 5: 20 molar ratio, citric acid and ethylene glycol, ethylene glycol is heated to 60-70 ℃, then when stirring, isopropyl titanate is added in the ethylene glycol, at last citric acid is added and be warming up to 85-95 ℃, constant temperature stirs until the solution clarification, obtains colloidal sol; Then, according to isopropyl titanate: the TiO of commodity P25 by name
2=1: 7 molar ratio mixes the colloidal sol that makes and P25 and stirred 1-2 hour in mortar, obtain uniform TiO
2Colloid;
B, preparation TiO
2Film
Cling the FTO (SnO of doped with fluorine with the transparent adhesive tape covering
2Electro-conductive glass) around, drips TiO at the position that does not cover transparent adhesive tape
2Colloid spreads over colloid on the FTO more uniformly, and the colloidal film on the FTO is wipeed off; 100 ℃ of dry 25-30min in drying box put into 450 ℃ of annealing of heat-treatment furnace 50-70min more then, naturally cool to 80-100 ℃ and obtain first tunic;
Colloid drops with a step adds on first tunic again, repeats then above to sprawl, wipes off, dry, annealing and cooling down operation, obtains two-layer colloidal film; Put into concentration immediately and be in the middle of the ethanolic solution of ruthenium complex N719 dyestuff of 0.4-0.6mmol/L, soak 24-30h; Take out the back and use absolute ethyl alcohol drip washing, dry naturally, promptly.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention produces polyester by citric acid in the solution and the reaction of ethylene glycol generation polymerization esterification, Ti-O key in organic alkoxide disperses uniformly and is fixed in the polyester network, polyester decomposes a large amount of extremely small pores of generation when annealing, thereby has formed the structure that particle diameter is little, specific area is big.Simultaneously because P
25TiO
2Powder can not fully evenly distribute in polyester, therefore, irregular nano particle occurred in the annealing rear surface and has piled up the duct that convexes to form; And by double-deck thin film-forming method, making its distribution of particles more even, connectivity is better, thereby shows bigger fill factor, curve factor and opto-electronic conversion preferably.Have very high conversion efficiency with its solar cell that makes under low light intensity, the photoelectric properties experimental result shows, the solar cell that makes with gained film of the present invention is at 5mW/cm
2The low light level according to down, electricity conversion is particluarly suitable for the low area of intensity of sunshine and uses up to 11.83%.
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is the TiO of the embodiment of the invention one preparation
2The X-ray diffractogram of film (XRD).
Fig. 2 is the TiO of the embodiment of the invention one preparation
2The surface of film and cross section ESEM (SEM) figure.
Fig. 3 is the TiO of the embodiment of the invention one preparation
2The volt-ampere of the solar cell of film preparation (V-I) curve.
Embodiment
Embodiment one
A kind of embodiment of the present invention is a kind of dye-sensitized solar battery with high conversion efficiency under low light intensity TiO
2The preparation method of film, its concrete practice is:
A, preparation TiO
2Colloid
Take by weighing the raw material isopropyl titanate respectively by 1: 5: 20 molar ratio, citric acid and ethylene glycol, ethylene glycol is heated to 60 ℃, then when stirring, isopropyl titanate is added in the ethylene glycol, at last citric acid is added and be warming up to 90 ℃, constant temperature stirs until the solution clarification, obtains colloidal sol; Then, according to isopropyl titanate: the TiO of commodity P25 by name
2=1: 7 molar ratio mixes the colloidal sol that makes and P25 and stirred 1 hour in mortar, obtain uniform TiO
2Colloid;
B, preparation TiO
2Film
Cling the FTO (SnO of doped with fluorine with the transparent adhesive tape covering
2Electro-conductive glass) around, drips TiO at the position that does not cover transparent adhesive tape
2Colloid spreads over colloid on the FTO more uniformly, and the colloidal film on the FTO is wipeed off; Then in drying box 100 ℃ of dry 30min (minute), put into 450 ℃ of annealing of heat-treatment furnace 60min again, naturally cool to 80 ℃ and obtain first tunic;
Colloid drops with a step adds on first tunic again, repeats then above to sprawl, wipes off, dry, annealing and cooling down operation, obtains two-layer colloidal film; Put into concentration immediately and be in the middle of the ethanolic solution of ruthenium complex N719 dyestuff of 0.5mmol/L, soak 24h; Take out the back and use absolute ethyl alcohol drip washing, dry naturally, promptly.
Embodiment two
The concrete practice of this example is:
A, preparation TiO
2Colloid
Take by weighing the raw material isopropyl titanate respectively by 1: 5: 20 molar ratio, citric acid and ethylene glycol, ethylene glycol is heated to 65 ℃, then when stirring, isopropyl titanate is added in the ethylene glycol, at last citric acid is added and be warming up to 95 ℃, constant temperature stirs until the solution clarification, obtains colloidal sol; Then, according to isopropyl titanate: the TiO of commodity P25 by name
2=1: 7 molar ratio mixes the colloidal sol that makes and P25 and stirred 2 hours in mortar, obtain uniform TiO
2Colloid;
B, preparation TiO
2Film
Cling the FTO (SnO of doped with fluorine with the transparent adhesive tape covering
2Electro-conductive glass) around, drips TiO at the position that does not cover transparent adhesive tape
2Colloid spreads over colloid on the FTO more uniformly, and the colloidal film on the FTO is wipeed off; 100 ℃ of dry 25min in drying box put into 450 ℃ of annealing of heat-treatment furnace 50min more then, naturally cool to 90 ℃ and obtain first tunic;
Colloid drops with a step adds on first tunic again, repeats then above to sprawl, wipes off, dry, annealing and cooling down operation, obtains two-layer colloidal film; Put into concentration immediately and be in the middle of the ethanolic solution of ruthenium complex N719 dyestuff of 0.4mmol/L, soak 28h; Take out the back and use absolute ethyl alcohol drip washing, dry naturally, promptly.
Embodiment three
The concrete practice of this example is:
A, preparation TiO
2Colloid
Take by weighing the raw material isopropyl titanate respectively by 1: 5: 20 molar ratio, citric acid and ethylene glycol, ethylene glycol is heated to 70 ℃, then when stirring, isopropyl titanate is added in the ethylene glycol, at last citric acid is added and be warming up to 85 ℃, constant temperature stirs until the solution clarification, obtains colloidal sol; Then, according to isopropyl titanate: the TiO of commodity P25 by name
2=1: 7 molar ratio mixes the colloidal sol that makes and P25 and stirred 1.5 hours in mortar, obtain uniform TiO
2Colloid;
B, preparation TiO
2Film
Cling the FTO (SnO of doped with fluorine with the transparent adhesive tape covering
2Electro-conductive glass) around, drips TiO at the position that does not cover transparent adhesive tape
2Colloid spreads over colloid on the FTO more uniformly, and the colloidal film on the FTO is wipeed off; 100 ℃ of dry 28min in drying box put into 450 ℃ of annealing of heat-treatment furnace 70min more then, naturally cool to 100 ℃ and obtain first tunic;
Colloid drops with a step adds on first tunic again, repeats then above to sprawl, wipes off, dry, annealing and cooling down operation, obtains two-layer colloidal film; Put into concentration immediately and be in the middle of the ethanolic solution of ruthenium complex N719 dyestuff of 0.6mmol/L, soak 30h; Take out the back and use absolute ethyl alcohol drip washing, dry naturally, promptly.
Fig. 1 is the TiO of embodiment one preparation
2The X-ray diffractogram of film (XRD).As can be seen from Figure 1, except that the peak of substrate FTO, six main peak positions lay respectively at 25.4 °, 37.8 °, 48.1 °, 54.0,55.1 ° and 62.7 ° among the figure, contrast TiO
2Standard P DF card, that they are corresponding respectively as can be known is anatase phase TiO
2101,004,200,105,211 and 204 crystal faces.2 θ angles are two small peaks to have occurred on 27.4 and 36.1 ° the position in the drawings, and that corresponding then is rutile phase TiO
2110 crystal faces, so the TiO of this method preparation
2The main crystal formation that exists is an anatase, wherein contains very a spot of rutile.The XRD diffraction maximum peak width of film is less, as can be known TiO
2The well-crystallized.
Fig. 2, Fig. 3 are respectively the TiO of embodiment one preparation
2The surface of film and section S EM figure.
By Fig. 2, Fig. 3 as seen, the TiO for preparing
2Film surface is loose porous, and particle diameter is even, and particle diameter is about 25nm.Little TiO
2Particle diameter has guaranteed the specific area that film is big, has guaranteed the adsorbance of dyestuff.It is duct about 200nm that the surface of film all has some to pile up the aperture convex to form by nano particle, and the pore passage structure of these perforations has not only increased specific area but also provides valid approach for the absorption of dye molecule, the diffusion of electrolyte.
Fig. 4 is the V-I curve of solar cell under different illumination intensity of embodiment one preparation.As seen from Figure 4, at 5mW/cm
2Low light be 1.95mA/cm according to the short-circuit current density under the strength simulation standard solar irradiation
2More than, photoelectric conversion efficiency is 11.83%.
The TiO2 of commodity used in the present invention P25 by name can be from directly buying on the market.
The TiO2 of commodity P25 by name obtains by titanium tetrachloride hydrogen flame combustion, and reactive mode is as follows:
TiCl4+2H2+O2→TiO2+4HCl
The TiO2 of commodity P25 by name is a nano titanium oxide, is a kind of very thin white powder, and the surface has the hydrogen-oxygen group to make its possess hydrophilic property, and this product is without any the pigment feature.The average grain diameter of basic granules is approximately 21nm, and the size of particle and the density of 4g/cm3 make it have 50m
2The special surface of/g.P25 belongs to mixed crystal type, and the weight ratio of anatase and rutile is approximately 80/20; Because two kinds of mixing up of structure have increased TiO
2Intracell defect concentration has increased the concentration of charge carrier, and electronics, number of cavities are increased, and makes it have the stronger TiO that is captured in
2The ability of solution component (water, oxygen, organic substance) on surface is engaged in showing bigger fill factor, curve factor and opto-electronic conversion preferably thereby make.
Ruthenium complex N719 dyestuff used in the present invention is general trade name, and its chemical name is: two (TBuA) cis-two (isothiocyanos) two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) ruthenium (II).
Claims (1)
1. dye-sensitized solar battery with high conversion efficiency under low light intensity TiO
2The preparation method of film, its concrete practice is:
A, preparation TiO
2Colloid
Take by weighing the raw material isopropyl titanate respectively by 1: 5: 20 molar ratio, citric acid and ethylene glycol, ethylene glycol is heated to 60-70 ℃, then when stirring, isopropyl titanate is added in the ethylene glycol, at last citric acid is added and be warming up to 85-95 ℃, constant temperature stirs until the solution clarification, obtains colloidal sol; Then, according to isopropyl titanate: the TiO of commodity P25 by name
2=1: 7 molar ratio mixes the colloidal sol that makes and P25 and stirred 1-2 hour in mortar, obtain uniform TiO
2Colloid;
B, preparation TiO
2Film
Cling the FTO (SnO of doped with fluorine with the transparent adhesive tape covering
2Electro-conductive glass) around, drips TiO at the position that does not cover transparent adhesive tape
2Colloid spreads over colloid on the FTO more uniformly, and the colloidal film on the FTO is wipeed off; 100 ℃ of dry 25-30min in drying box put into 450 ℃ of annealing of heat-treatment furnace 50-70min more then, naturally cool to 80-100 ℃ and obtain first tunic;
Colloid drops with a step adds on first tunic again, repeats then above to sprawl, wipes off, dry, annealing and cooling down operation, obtains two-layer colloidal film; Put into concentration immediately and be in the middle of the ethanolic solution of ruthenium complex N719 dyestuff of 0.4-0.6mmol/L, soak 24-30h; Take out the back and use absolute ethyl alcohol drip washing, dry naturally, promptly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101811087A CN101814377B (en) | 2010-05-24 | 2010-05-24 | Preparation method of TiO2 film of dye-sensitized solar battery with high conversion efficiency under low light intensity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101811087A CN101814377B (en) | 2010-05-24 | 2010-05-24 | Preparation method of TiO2 film of dye-sensitized solar battery with high conversion efficiency under low light intensity |
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| Publication Number | Publication Date |
|---|---|
| CN101814377A CN101814377A (en) | 2010-08-25 |
| CN101814377B true CN101814377B (en) | 2011-09-14 |
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| CN1857769A (en) * | 2006-04-20 | 2006-11-08 | 华中师范大学 | Low temperature process of preparing carbon-doped mesoporous TiO2 visible light catalyst |
| CN101232049A (en) * | 2007-01-26 | 2008-07-30 | 中国科学院物理研究所 | Nanometer oxide porous membrane electrode and preparing method and application thereof |
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