CN101770869B - Method for preparing titanium dioxide films for dye-sensitized solar battery - Google Patents
Method for preparing titanium dioxide films for dye-sensitized solar battery Download PDFInfo
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- CN101770869B CN101770869B CN 201010116694 CN201010116694A CN101770869B CN 101770869 B CN101770869 B CN 101770869B CN 201010116694 CN201010116694 CN 201010116694 CN 201010116694 A CN201010116694 A CN 201010116694A CN 101770869 B CN101770869 B CN 101770869B
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- solar battery
- deoxid film
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- titanium dioxide
- dye sensitization
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 40
- 229910052719 titanium Inorganic materials 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 40
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 38
- 206010070834 Sensitisation Diseases 0.000 claims description 21
- 230000008313 sensitization Effects 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 12
- 239000001856 Ethyl cellulose Substances 0.000 claims description 10
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 10
- 229920001249 ethyl cellulose Polymers 0.000 claims description 10
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 10
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 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 description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000005622 photoelectricity Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 18
- 239000000975 dye Substances 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- METIGIXCFPEQNM-UHFFFAOYSA-M amino-(2-bromoethyl)-dimethylazanium;bromide Chemical compound [Br-].C[N+](C)(N)CCBr METIGIXCFPEQNM-UHFFFAOYSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
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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 method for preparing titanium dioxide films for a dye-sensitized solar battery, comprising the following steps: (a) titanium dioxide sol with 1-10 wt percent of titanium dioxide, 5-10nm of grain size and 10-100mg/mL of concentration and titanium dioxide powder with 5-15 wt percent of titanium dioxide and 20-40nm of grain size are uniformly ground, 80-90 wt percent of pore-forming agent is added, and the obtained 100wt percent of mixture are grounded for 0.5-2 hours; (b) titanium dioxide slurry is coated on conductive glass and is dried for 5-15 minutes at 100-130 DEG C; and (c) the conductive glass coated with the titanium dioxide slurry is sintered for 0.5-2 hours at 450-500 DEG C; by adopting the method in the invention, the process is simple, the operation is easy, the preparation period is short, thereby being beneficial to industrialization; in addition, the photoelectricity conversion efficiency of the dye-sensitized solar battery assembled by the titanium dioxide films is high by adopting the method.
Description
Technical field
The present invention relates to a kind of method of DSSC (DSC) that be used to prepare with titanium deoxid film, the method for preparing the used by dye sensitization solar battery titanium deoxid film that can increase substantially battery efficiency in particular to a kind of easy to implement being used to.
Background technology
DSSC with its environmental protection, efficient, cheap, the life-span is long etc., and advantage has caused the extensive concern of countries in the world.At present, the highest electricity conversion of DSC has surpassed 11%, and near the level of present commercialization polysilicon solar cell, and its cost of manufacture only is the 1/5-1/10 of silicon solar cell, therefore becomes the third generation solar cell of very advantageous.
DSC is usually by the porous nano titanium dioxide (TiO of absorbing dye
2) film light anode, electrolyte solution and electrode is formed.When solar irradiation was mapped on the battery, dye molecule absorbed luminous energy and is excited, and excitation state electronics instability is injected into TiO fast
2In the conduction band, the TiO by porous again
2Film is transferred to the light anode, is transferred to electrode by load from external circuit, and the oxidation state dye molecule that loses electronics simultaneously is very fast by I
-Reduction has realized separation of charge; Oxidation-reduction pair (I in the electrolyte
3-/ I
-) hole transport is arrived electrode, with electron recombination, thereby finish a circulation.
Find out TiO by above-mentioned principle
2Film is one of important component part of DSC, and it is the TiO by nano-scale
2Particle is connected to each other the loose structure with three-dimensional network that forms, TiO
2The particle arrangement is reasonable, and connectivity is good, helps the conduction of electronics, thereby can improve the electricity conversion of DSSC greatly.
Chinese patent CN 1921153A discloses a kind of preparation method of nanocrystalline titanium dioxide film used by dye sensitization solar battery, described method with titanium salt as the titanium source, do template with high polymer, it is dissolved in the organic solvent to obtain initial slurry, print titanium dioxide film with screen printing technique at conductive glass surface, after high-temperature process, obtain nanocrystalline titanium dioxide film.Yet the photoelectric conversion efficiency of the DSC that the nanocrystalline titanium dioxide film that is obtained by this method is made is lower.
Chinese patent CN 101323504A discloses a kind of preparation method of macroporous-mesoporous nanocrystalline titania film.Mainly comprising TiO 2 precursor with czochralski method of described method prepares titanium deoxid film attached to adopting on the synthetic ordered big hole template of polystyrene microsphere emulsion by dry, sintering.This method complex process, film forming is thinner, takes time and effort.
Therefore, significant is a kind of method that is used to prepare the used by dye sensitization solar battery titanium deoxid film of exploitation, described method is easy to implement, and titanium deoxid film prepared therefrom can increase substantially the battery efficiency of DSSC.
Summary of the invention
The purpose of this invention is to provide a kind of method that is used to prepare the used by dye sensitization solar battery titanium deoxid film, described method is easy and simple to handle, easy to implement, and when being used for DSSC, can increase substantially dye-sensitized cell efficient by the titanium deoxid film of described method preparation.
In order to realize above purpose, the present inventor has carried out intensive research and has obtained unpredictable consequence.
The invention provides a kind of method that is used to prepare the used by dye sensitization solar battery titanium deoxid film, it is characterized in that, described method comprises the following steps:
(a) be that 5-10nm, concentration are that the particle diameter of the TiO 2 sol of 10-100mg/mL and 5-15 weight % is that the titania powder of 20-40nm evenly grinds with the titanium dioxide particle diameter of 1-10 weight %, the pore creating material that adds 80-90 weight %, the mixture of the 100 weight % that obtain was ground 0.5-2 hour, obtain titania slurry;
(b) described titania slurry is coated on the electro-conductive glass, and at 100-130 ℃ of dry 5-15 minute; With
(c) with the described electro-conductive glass that is coated with titania slurry at 450-500 ℃ of sintering 0.5-2 hour, obtain the used by dye sensitization solar battery titanium deoxid film.
Compare with the prior art in this area, the invention has the advantages that: the method according to this invention technology is simple, easy operating, and manufacturing cycle is short, helps industrialization, and by the TiO of this method preparation
2Film local continuity is good, helps the conduction of electronics, short texture, and specific area is big, has increased the adsorbance of dyestuff.In addition, by this TiO
2The electricity conversion height of the DSSC that film assembles.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) photo that shows titanium deoxid film prepared in the comparative example.
Fig. 2 is the SEM photo that shows titanium deoxid film prepared in the embodiments of the invention 3.
Fig. 3 is the SEM photo that shows titanium deoxid film prepared in the embodiments of the invention 5.
Embodiment
By prior art as can be known, titanium deoxid film is one of important component part of DSSC, by regulating the spatial arrangement of TiO 2 particles in the film, make it rational in infrastructure, connectivity is good, help the conduction of electronics, just might improve the electricity conversion of DSSC greatly.The inventor finds under study for action, the TiO 2 sol by will having specified particle diameter, specific concentrations with specified weight than with the titania powder mixed grinding and utilize in the titanium deoxid film that prior art is prepared from, film local continuity is good, help the conduction of electronics, short texture, specific area is big, has increased the adsorbance of dyestuff.In addition, the DSSC of being made by this titanium dioxide membrane electrode provided can show high electricity conversion.
Based on above content, the present invention proposes a kind of method that is used to prepare the used by dye sensitization solar battery titanium deoxid film, it is characterized in that, described method comprises the following steps:
(a) be that 5-10nm, concentration are that the particle diameter of the TiO 2 sol of 10-100mg/mL and 5-15 weight % is that the titania powder of 20-40nm evenly grinds with the titanium dioxide particle diameter of 1-10 weight %, the pore creating material that adds 80-90 weight %, the mixture of the 100 weight % that obtain was ground 0.5-2 hour, obtain titania slurry;
(b) described titania slurry is coated on the electro-conductive glass, and at 100-130 ℃ of dry 5-15 minute; With
(c) with the described electro-conductive glass that is coated with titania slurry at 450-500 ℃ of sintering 0.5-2 hour, obtain the used by dye sensitization solar battery titanium deoxid film.
According to some preferred embodiment of the present invention, the thickness of described used by dye sensitization solar battery titanium deoxid film is 10-20 μ m.
According to some preferred embodiment of the present invention, described pore creating material is that terpinol, concentration are ethanolic solution, polyethylene glycol or their combination of the ethyl cellulose of 5-15 weight %.
According to some preferred embodiment of the present invention, in step (b), described titania slurry is coated on the electro-conductive glass via silk screen printing or knife coating.
In said method, described TiO 2 sol can be according to prior art for preparing as known in the art.
According to certain embodiments of the present invention, prepare described TiO 2 sol by following method: under 50-70 ℃ stirring condition, the organic titanic compound of 1-15 weight % is dissolved in the organic solvent of 40-60 weight %, the plasticizer that adds 30-50 weight %, the mixture of the 100 weight % that obtain is heated to 70-90 ℃, stirred 0.5-1 hour, thereby obtain being dissolved in TiO 2 sol in the organic solvent.According to some preferred embodiment of the present invention, described organic titanic compound is isopropyl titanate or tetrabutyl titanate.Described organic solvent is ethylene glycol, isopropyl alcohol or their combination.Described plasticizer is citric acid, malic acid, tartaric acid, xylitol or their combination.
According to certain embodiments of the present invention, described TiO 2 sol is by the inorganic titanium salt preparation of hydrolysis.Described inorganic titanium salt is a titanium tetrachloride.
According to some preferred embodiment of the present invention, described titania powder has the particle diameter of 20-40nm, can be purchased or according to prior art for preparing as known in the art, it includes but not limited to that particle diameter is the titania powder (P25 powder, Degussa company (Degussa Company)) of 20nm.
Below in conjunction with embodiment the present invention is described in more detail.It may be noted that these are described and embodiment is in order to make the present invention be convenient to understanding, but not limitation of the present invention.Protection scope of the present invention is as the criterion with appending claims.
Embodiment 1
12g ethylene glycol is heated to 60 ℃, add 2g isopropyl titanate (A Faaisha chemistry Co., Ltd (Alfa Aesar Company)) while stirring, continue to add the 10g citric acid and temperature is risen to 90 ℃, this colloidal sol of continuation stirring became transparent in 0.5 hour until it, promptly obtain TiO
2Colloidal sol.(TECNAI-G2 FEI) measures this TiO through transmission electron microscope (TEM)
2The TiO of colloidal sol
2Particle diameter is 5-10nm.With this colloidal sol of 1g and 6g average grain diameter is titania powder (the P25 powder of 20nm, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution of ethyl cellulose that adds the 10 weight % of 19g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g.Continue to grind 1 hour, promptly obtain TiO
2Slurry.With TiO
2Slurry is printed on the electro-conductive glass (NSG FTO-14, Wuhan Ge Ao instrument company) with silk screen print method, and the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
(Mitutoyo, 293-340) thickness of the described titanium deoxid film of Ce Lianging is 20 microns with the high-precision spiral mircrometer gauge.
With this titanium dioxide electrodes concentration be 0.3 milli rub/liter the ethanolic solution of N719 dyestuff (seven-colour-light science and technology) in soaked 20 hours, drip electrolyte (0.6M BMII, 0.1MGuSCN, 0.5M TBP, 0.03M I2, solvent: acetonitrile/positive valeronitrile=85/15, seven-colour-light science and technology) assemble electrode with platinum plating the back, is assembled into battery with sandwich structure.Employing xenon source (PLS-SXE 300/300UV, Beijing pool Fei Lai Science and Technology Ltd.) and data source table (2400, the keithley) photoelectric properties of test battery, test condition is: AM:1.5,100mW/cm
2The test result of the photoelectric properties of battery is shown in the table 1.
Embodiment 2
12g ethylene glycol is heated to 60 ℃, add 2g isopropyl titanate (A Faaisha chemistry Co., Ltd (Alfa Aesar Company)) while stirring, continue to add the 10g citric acid and temperature is risen to 90 ℃, this colloidal sol of continuation stirring became transparent in 0.5 hour until it, promptly obtain TiO
2Colloidal sol.(TECNAI-G2 FEI) measures this TiO through transmission electron microscope (TEM)
2The TiO of colloidal sol
2Particle diameter is 5-10nm.With this colloidal sol of 2g and 6g average grain diameter is titania powder (the P25 powder of 20nm, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution of ethyl cellulose that adds the 10 weight % of 18g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g.Continue to grind 1 hour, promptly obtain TiO
2Slurry.With TiO
2Slurry is printed on the electro-conductive glass (NSG FTO-14, Wuhan Ge Ao instrument company) with silk screen print method, and the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.
Embodiment 3
12g ethylene glycol is heated to 60 ℃, add 2g isopropyl titanate (A Faaisha chemistry Co., Ltd (Alfa Aesar Company)) while stirring, continue to add the 10g citric acid and temperature is risen to 90 ℃, this colloidal sol of continuation stirring became transparent in 0.5 hour until it, promptly obtain TiO
2Colloidal sol.(TECNAI-G2 FEI) measures this TiO through transmission electron microscope (TEM)
2The TiO of colloidal sol
2Particle diameter is 5-10nm.With this colloidal sol of 3g and 6g average grain diameter is titania powder (the P25 powder of 20nm, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution of ethyl cellulose that adds the 10 weight % of 17g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g.Continue to grind 1 hour, promptly obtain TiO
2Slurry.With TiO
2On the electro-conductive glass that slurry is printed on silk screen print method (NSG FTO-14, Wuhan Ge Ao instrument company), the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.
Embodiment 4
In cold bath, 2.5 of 15ml is rubbed/liter titanium tetrachloride (analyze pure, East China, the Tianjin chemical reagent work) aqueous solution and 0.65 hydrochloric acid (analyze pure, East China, the Tianjin chemical reagent work) solution that rubs/rise of 53ml under agitation mix.Drip 12.5% ammoniacal liquor (analyze pure, East China, Tianjin chemical reagent work) again, the pH value is adjusted to 5.This mixed solution is centrifugal, use the deionized water cleaning and filtering, drip nitric acid (analyze pure, East China, Tianjin chemical reagent work) (TiO at last
2: HNO
3=5: 1 (mol ratio)).After Ultrasonic Pulverization, make TiO 2 sol.(TECNAI FEI) measures this TiO through transmission electron microscope (TEM)
2The TiO of colloidal sol
2Particle diameter is 5-10nm.
With this colloidal sol of 1g and 6g average grain diameter is titania powder (the P25 powder of 20nm, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution of ethyl cellulose that adds the 10 weight % of 19g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g.Continue to grind 1 hour, promptly obtain TiO
2Slurry.With TiO
2It is 0.2cm that slurry is printed on electro-conductive glass (NSG FTO-14, Wuhan Ge Ao instrument company) upper film effective area with silk screen print method
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.
Embodiment 5
Colloidal sol and 6g average grain diameter titania powder (the P25 powder that is 20nm with preparation among the 2g embodiment 4, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution of ethyl cellulose that adds the 10 weight % of 18g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g.Continue to grind 1 hour, promptly obtain TiO
2Slurry.With TiO
2Slurry is printed on the electro-conductive glass (NSGFTO-14, Wuhan Ge Ao instrument company) with silk screen print method, and the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 0.5 minute 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.
Embodiment 6
Colloidal sol and 6g average grain diameter titania powder (the P25 powder that is 20nm with preparation among the 3g embodiment 4, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution of ethyl cellulose that adds the 10 weight % of 17g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g.Continue to grind 1 hour, promptly obtain TiO
2Slurry.With TiO
2Slurry is printed on the electro-conductive glass (NSGFTO-14, Wuhan Ge Ao instrument company) with silk screen print method, and the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.
Embodiment 7
Colloidal sol and 6g average grain diameter titania powder (the P25 powder that is 20nm with preparation among the 5g embodiment 4, Degussa company (Degussa Company)) mixed grinding is even, the ethanolic solution that adds the ethyl cellulose of 15g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g 10 weight %.Continue to grind 1 hour, promptly obtain TiO
2Slurry is with TiO
2Slurry is printed on the electro-conductive glass (NSGFTO-14, Wuhan Ge Ao instrument company) with silk screen print method, and the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.Comparative example
Grinding the 6g average grain diameter is the titania powder (P25 powder, Degussa company (Degussa Company)) of 20nm, adds the ethanolic solution of ethyl cellulose of the 10 weight % of 20g terpinol (analyze pure, East China, Tianjin chemical reagent work) and 30g to it.Continue to grind 1 hour, promptly obtain TiO
2Slurry.(TECNAI FEI) measures this TiO through transmission electron microscope (TEM)
2Grain diameter is 20-40nm.With TiO
2Slurry is printed on the electro-conductive glass (NSG FTO-14, Wuhan Ge Ao instrument company) with silk screen print method, and the film effective area is 0.2cm
2Electro-conductive glass, is placed in the tube furnace (OTF-1200X, Hefei section crystalline substance) after 5 minutes 125 ℃ of dryings, in air atmosphere 500 ℃ of sintering 0.5 hour.With its room temperature cooling, take out and promptly get titanium dioxide membrane electrode provided subsequently.
By with embodiment 1 in identical method the titanium dioxide electrodes that obtains is characterized.The thickness of prepared titanium deoxid film is 20 microns.The test result of the photoelectric properties of battery is shown in the table 1.
The photoelectric properties of the dye-sensitized cell that table 1 is assembled by embodiment 1-7 and the prepared titanium dioxide membrane electrode provided of comparative example respectively relatively
| Short circuit current (Isc/mA) | Open circuit voltage (Voc/V) | Fill factor, curve factor (ff) | Transformation efficiency (η/%) | |
| Embodiment 1 | 3.93 | 0.77 | 0.60 | 9.08 |
| Embodiment 2 | 4.01 | 0.77 | 0.60 | 9.23 |
| Embodiment 3 | 3.96 | 0.75 | 0.61 | 8.96 |
| Embodiment 4 | 3.90 | 0.75 | 0.61 | 8.85 |
| Embodiment 5 | 4.39 | 0.76 | 0.61 | 10.05 |
| Embodiment 6 | 4.26 | 0.76 | 0.59 | 9.58 |
| Embodiment 7 | 4.05 | 0.76 | 0.59 | 9.25 |
| Comparative example | 3.22 | 0.76 | 0.62 | 7.60 |
The data of being compared with comparative example by embodiment 1-7 as can be known, by introduce particle diameter in the preparation process of titanium deoxid film is that 5-10nm, concentration are the TiO 2 sol of 10-100mg/mL, can significantly improve the battery performance of the DSC that is assembled by resulting titanium dioxide membrane electrode provided.For example, in embodiment 5, adopt the battery efficiency of the DSC of the inventive method preparation to improve greatly, reached 10.05% electricity conversion.This battery efficiency than the DSC that is assembled by the unmixed titanium dioxide membrane electrode provided that the pulp preparation of TiO 2 sol arranged has improved 32%.
Fig. 1, Fig. 2 and Fig. 3 have shown scanning electron microscopy (SEM) photo of titanium deoxid film prepared in comparative example and embodiment 3 and 5 respectively.As can be seen, do not add the film TiO of TiO 2 sol
2Crystal grain is arranged very fine and close, and granular size is about 20-40nm; TiO behind the interpolation TiO 2 sol
2The film grain size is distributed in 5-40nm, and local continuity is better, and structure is more loose, and specific area increases relatively, makes it can help the conduction of electronics on the one hand, can adsorb more dyestuff on the other hand, thereby improve the electricity conversion of battery.
Claims (9)
1. a method that is used to prepare the used by dye sensitization solar battery titanium deoxid film is characterized in that, described method comprises the following steps:
(a) be that 5-10nm, concentration are that the particle diameter of the TiO 2 sol of 10-100mg/mL and 5-15 weight % is that the titania powder of 20-40nm evenly grinds with the titanium dioxide particle diameter of 1-10 weight %, the pore creating material that adds 80-90 weight %, the mixture of the 100 weight % that obtain was ground 0.5-2 hour, obtain titania slurry, wherein said pore creating material is that terpinol, concentration are ethanolic solution, polyethylene glycol or their combination of the ethyl cellulose of 5-15 weight %;
(b) described titania slurry is coated on the electro-conductive glass, and at 100-130 ℃ of dry 5-15 minute; With
(c) with the described electro-conductive glass that is coated with titania slurry at 450-500 ℃ of sintering 0.5-2 hour, obtain the used by dye sensitization solar battery titanium deoxid film.
2. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 1 is characterized in that: the thickness of described used by dye sensitization solar battery titanium deoxid film is 10-20 μ m.
3. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 1 is characterized in that: in step (b), via silk screen printing or knife coating described titania slurry is coated on the electro-conductive glass.
4. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 1, it is characterized in that: described TiO 2 sol prepares by following method: under 50-70 ℃ stirring condition, the organic titanic compound of 1-15 weight % is dissolved in the organic solvent of 40-60 weight %, the plasticizer that adds 30-50 weight %, the mixture of the 100 weight % that obtain is heated to 70-90 ℃, stirred 0.5-1 hour.
5. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 4 is characterized in that: described organic titanic compound is isopropyl titanate or tetrabutyl titanate.
6. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 4 is characterized in that: described organic solvent is ethylene glycol, isopropyl alcohol or their combination.
7. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 4 is characterized in that: described plasticizer is citric acid, malic acid, tartaric acid, xylitol or their combination.
8. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 1 is characterized in that: described TiO 2 sol is by the inorganic titanium salt preparation of hydrolysis.
9. the method that is used to prepare the used by dye sensitization solar battery titanium deoxid film according to claim 8 is characterized in that: described inorganic titanium salt is a titanium tetrachloride.
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