CN101894688B - Method for preparing dye sensitization solar battery electrode at low temperature - Google Patents
Method for preparing dye sensitization solar battery electrode at low temperature Download PDFInfo
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- CN101894688B CN101894688B CN 201010214195 CN201010214195A CN101894688B CN 101894688 B CN101894688 B CN 101894688B CN 201010214195 CN201010214195 CN 201010214195 CN 201010214195 A CN201010214195 A CN 201010214195A CN 101894688 B CN101894688 B CN 101894688B
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- titanium dioxide
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- solar battery
- sensitization solar
- dye sensitization
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention relates to a method for preparing a dye sensitization solar battery electrode at low temperature, which is on the basis of the advantages of anode material P25 type titanium dioxide particles that can be widely applied at present. Titanium dioxide sol which is specially made is added for improving the sizing agent preparation process, so that the defects of preparing the sizing agent by the P25 type titanium dioxide particles can be made up, the bridge connection action among the P25 particles can be enhanced, the transmission resistance of photoelectron in a film is reduced, a long-time high-temperature hydro-thermal reaction which wastes time and energy is avoided, and the light current of a battery is improved.
Description
Technical field:
The invention belongs to field of energy source materials, particularly a kind of method of preparing dye sensitization solar battery electrode at low temperature.
Background technology:
Since nineteen nineties, DSSC is subjected to the extensive concern of various circles of society, and its main feature is environmental friendliness, and is with low cost, and preparation equipment is simple etc.Yet, one of low principal element that is still its suitability for industrialized production of restriction of electricity conversion, and titanium dioxide film materials is the central factor that influences the DSSC photoelectric properties, thereby can prepare high performance anode material becomes current research focus in the industry.
Many research groups all over the world are in the technology of preparing of being devoted to research and develop the Novel Titanium dioxide slurry, for example the present used method of Michael Gratzel group is high-temperature water heat treatment behind the preparation colloidal sol, the slurry electricity conversion of this method preparation can reach 11.7%, is current tidemark.But the long pyroreaction of this arts demand, energy consumption is big, and is dangerous high.Simultaneously, the P25 type titania powder that Degussa company produces also is the anode preparation material of present extensive use, and the P25 particle size distribution is even, and favorable dispersibility is cheap, has realized producing in batches.Be a kind of anode material that more easily obtains, yet the anode photoelectric properties of P25 preparation but are not the photoelectric properties optimum, can reach about 8% at present.
Summary of the invention:
The object of the present invention is to provide a kind of method of preparing dye sensitization solar battery electrode at low temperature, P25 type titanium dioxide based on easy acquisition, to wherein adding TiO 2 sol, improve the titania slurry performance, avoid the bridge defects between the P25 titanium dioxide granule, avoid long-time high-temperature water thermal response, strengthened the photoelectron conductibility of anode film, thereby improved the efficient of battery.
The objective of the invention is to be achieved by the following technical programs, a kind of method of preparing dye sensitization solar battery electrode at low temperature may further comprise the steps:
1) preparation of titanium dioxide anode slurry
Count isopropyl titanate: ethylene glycol: glacial acetic acid=1: (3-10): 20 in molar ratio; At first ethylene glycol evenly is heated to 60 ℃, dropwise adds isopropyl titanate in the whipping process, be added dropwise to complete back insulated and stirred 15min, add glacial acetic acid then, progressively be warming up to 90 ℃, stir more than 10 hours to being transparence colloidal sol;
With above-mentioned colloidal sol and P25 titanium dioxide granule by mass ratio (1-10): 1 mixes, and high-energy ball milling grinds 4h, makes used by dye sensitization solar battery titanium dioxide anode slurry;
2) preparation of film
Get the titanium dioxide anode slurry that step 1) makes, coating filmform, the work area of film is 1cm
2, thickness is 8-10 μ m, after the air dry, is warming up to 200 ℃ of insulation 15min successively, 250 ℃ of insulation 15min, 540 ℃ of insulation 30min; When being cooled to 80 ℃ the titanium dioxide electrodes film is taken out, immerse in the ethanol solution of N3 dyestuff of 0.5mM, take out after leaving standstill 24h, use alcohol flushing, flush away is adsorbed on surperficial dyestuff, obtains titanium dioxide membrane electrode provided;
3) packaging and testing
With thickness be the surlyn film of 80um with titanium dioxide membrane electrode provided and Pt to electrode package, inject electrolyte in the aperture of reserving from the Pt electrode, behind the sealing of hole under the standard sunlight its photoelectric properties of test.
Described N3 dyestuff is that suitable-two thiocyanates-two (4,4 '-dicarboxylic acids-2,2 '-bipyridine) close ruthenium dye.
The inventive method is based on the advantage of the anode material P25 type titanium dioxide granule of present extensive use, to wherein adding TiO 2 sol, the pulp preparation process is improved, remedied the deficiency of the slurry of p25 type titanium dioxide granule preparation, strengthened the bridge joint effect between the P25 particle, reduce the transport resistance of photoelectron in film, avoided the long-time high-temperature water thermal response of time consumption and energy consumption, improved the photoelectric current of battery.
Description of drawings
Figure 1 shows that the film surface appearance of low-temperature pulp coating;
Figure 2 shows that the film light electric current contrast of low-temperature pulp and P25 type preparation of granules;
(a) the membrane electrode current curve of cryosol pulp preparation of the present invention;
(b) the membrane electrode current curve of P25 type preparation of granules;
Figure 3 shows that the thin film power contrast of low-temperature pulp and P25 type preparation of granules;
(a) the membrane electrode power curve of cryosol pulp preparation of the present invention;
(b) the membrane electrode power curve of P25 type preparation of granules.
The film electrode photoelectric performance comparison of table 1 cryosol slurry of the present invention and P25 type preparation of granules
| Sample | Jsc/(mA) | Voc/(V) | Pm | FF | η |
| P25 type titanium dioxide granule | 9.39 | 0.73 | 2.55 | 0.37 | 2.55 |
| Cryosol slurry of the present invention | 9.60 | 0.74 | 3.15 | 0.44 | 3.15 |
Embodiment
Embodiment one:
(1) preparation of slurry
Isopropyl titanate: ethylene glycol: the mol ratio of glacial acetic acid is 1: 3: 20, ethylene glycol is placed in the round mouth flask, evenly be heated to 60 ℃, under vigorous stirring, dropwise add isopropyl titanate, drip the back and keep this temperature to stir 15min, add glacial acetic acid then, progressively be warming up to 90 ℃, stirred 12 hours, this moment, sol solution was transparence.
The above-mentioned sol solution that obtains is mixed by mass ratio with the P25 titanium dioxide granule at 1: 1, grind 4h, make titania slurry through high energy ball mill.
(2) preparation of film
Get an amount of above-mentioned slurry, coating filmform, the work area of film is 1cm
2, thickness is at 8-10 μ m.After the air dry, put into Muffle furnace, be warming up to 200 ℃ of insulation 15min, 250 ℃ of insulation 15min, 540 ℃ of insulation 30min.The field emission scanning electron microscope picture of gained titanium dioxide membrane electrode provided when cooling to the titanium deoxid film after the roasting with the furnace 80 ℃ takes out the titanium dioxide electrodes film as shown in Figure 1, in the ethanol solution of the N3 dyestuff of immersion 0.5mM, leaves standstill 24h.Titanium dioxide electrodes is taken out from dye solution, use alcohol flushing, flush away is adsorbed on the dyestuff on surface, obtains titanium dioxide membrane electrode provided.
(3) packaging and testing
The surlyn film that with thickness is 80um is with titanium deoxid film and Pt electrode package, in the aperture of Pt electrode reservation, inject an electrolyte, test its photoelectric properties behind the sealing of hole under the standard sunlight, the photoelectric properties data of gained titanium dioxide membrane electrode provided are as shown in table 1
Embodiment two:
Embodiment two is identical with embodiment one step, and difference is: during the preparation sol solution, and isopropyl titanate: ethylene glycol: glacial acetic acid 1: 10: 20 in molar ratio; When being mixed with slurry with P25 type titanium dioxide granule, the mass ratio of sol solution and P25 type titanium dioxide is 3: 1.
Embodiment three:
Embodiment three is identical with embodiment one step, and difference is: during the preparation sol solution, and isopropyl titanate: ethylene glycol: glacial acetic acid 1: 20: 20 in molar ratio; When being mixed with slurry with P25 type titanium dioxide granule, the mass ratio of sol solution and P25 type titanium dioxide is 10: 1.
Claims (2)
1. the method for a preparing dye sensitization solar battery electrode at low temperature is characterized in that, may further comprise the steps:
1) preparation of titanium dioxide anode slurry
Count isopropyl titanate: ethylene glycol: glacial acetic acid=1: (3-10): 20 in molar ratio; At first ethylene glycol evenly is heated to 60 ℃, dropwise adds isopropyl titanate in the whipping process, be added dropwise to complete back insulated and stirred 15min, add glacial acetic acid then, be warming up to 90 ℃, stir more than 10 hours to being transparence colloidal sol;
With above-mentioned colloidal sol and P25 titanium dioxide granule by mass ratio (1-10): 1 mixes, and high energy ball mill grinds 4h, makes used by dye sensitization solar battery titanium dioxide anode slurry;
2) preparation of film
Get the titanium dioxide anode slurry that step 1) makes, coating filmform, the work area of film is 1cm
2, thickness is 8-10 μ m, after the air dry, is warming up to 200 ℃ of insulation 15min successively, 250 ℃ of insulation 15min, 540 ℃ of insulation 30min; When being cooled to 80 ℃ the titanium dioxide electrodes film is taken out, immerse in the ethanol solution of N3 dyestuff of 0.5mM, take out after leaving standstill 24h, use alcohol flushing, flush away is adsorbed on surperficial dyestuff, obtains titanium dioxide membrane electrode provided;
3) packaging and testing
With thickness be the surlyn film of 80um with titanium dioxide membrane electrode provided and Pt to electrode package, inject electrolyte in the aperture of reserving from the Pt electrode, behind the sealing of hole under the standard sunlight its photoelectric properties of test.
2. according to the method for the described a kind of preparing dye sensitization solar battery electrode at low temperature of claim 1, it is characterized in that described N3 dyestuff is that suitable-two thiocyanates-two (4,4 '-dicarboxylic acids-2,2 '-bipyridine) close ruthenium dye.
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| CN 201010214195 CN101894688B (en) | 2010-06-30 | 2010-06-30 | Method for preparing dye sensitization solar battery electrode at low temperature |
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| CN 201010214195 CN101894688B (en) | 2010-06-30 | 2010-06-30 | Method for preparing dye sensitization solar battery electrode at low temperature |
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| CN102260898A (en) * | 2011-06-30 | 2011-11-30 | 襄樊学院 | Preparation technology of P25 coated titanium dioxide nanotube array electrode material |
| CN102723213B (en) * | 2012-06-23 | 2015-11-11 | 三峡大学 | A kind of preparation method of dye-sensitized solar cell anode |
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| JP4585212B2 (en) * | 2004-03-19 | 2010-11-24 | Ｊｘ日鉱日石エネルギー株式会社 | Titania having a nanotube shape and method for producing the same |
| WO2008007448A1 (en) * | 2006-07-13 | 2008-01-17 | Teijin Dupont Films Japan Limited | Dye-sensitized solar cell, and electrode and laminated film therefor |
| CN101471397B (en) * | 2007-12-28 | 2010-09-01 | 清华大学 | Method for preparing polymer emulsion of optical anode of dye sensitization battery |
| CN101339851A (en) * | 2008-08-18 | 2009-01-07 | 中国科学院上海技术物理研究所 | Dye-sensitized solar cell anode preparing method |
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