CN102290254A - Light anode of dye sensitized solar cell and preparation method thereof - Google Patents
Light anode of dye sensitized solar cell and preparation method thereof Download PDFInfo
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- CN102290254A CN102290254A CN 201110147436 CN201110147436A CN102290254A CN 102290254 A CN102290254 A CN 102290254A CN 201110147436 CN201110147436 CN 201110147436 CN 201110147436 A CN201110147436 A CN 201110147436A CN 102290254 A CN102290254 A CN 102290254A
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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 discloses a light anode of a dye sensitized solar cell and a preparation method thereof. The method comprises the following steps: mixing hollow titanium dioxide nano particles with a solvent, a bonding agent and a dispersing agent uniformly, and dispersing the mixture fully; then evaporating out the dispersing agent and the solvent, thus obtaining a coating slurry; coating the coated slurry on the surface of electrically conducting glass, thus forming a required titanium coating layer; and carrying out multi-gradient constant-temperature sintering and dipping and sensitization of dye, thus obtaining the light anode provided by the invention. According to the invention, the titanium dioxide nano particles of hollow structures (the diameter is about 100-300nm, and the wall thickness is 20-50nm) are applied to the light anode of the dye sensitized solar cell, the hollow titanium dioxide nano particles are prepared into the dispersed slurry and the slurry is applied to the light anode, so that the photoelectric conversion efficiency and stability of the dye sensitized solar cell are improved, and the purpose of improving the photoelectric performance of the dye sensitized solar cell is achieved finally.
Description
Technical field
The invention belongs to new material technology and technical field of new energies, more particularly, relate to material of a kind of DSSC and preparation method thereof.
Background technology
In the last few years, DSSC (DSSCs) is as a kind of novel solar battery, because of its cost of manufacture low, technology is simple, the electricity conversion height, stable performance, and advantage such as environmental sound, be subjected to all circles and paid close attention to widely and a large amount of research, had good application prospect and practical value.In order further to improve the efficient and the stability of DSSC, people are to its each part: titanium dioxide photo anode, electrolyte, sensitizer and electrode all done the further investigation and the exploration of system, and obtained interim achievement and breakthrough.Wherein, the nano titanium oxide photo-anode film with loose structure and good crystalline shape has played very crucial effect to the raising of its electricity conversion, becomes a new focus of dye-sensitized solar cells research field.The nano-crystalline titanium dioxide of multiple different-shape, as nano particle, nanotube, nano wire, nanofiber and hollow sphere etc., all be applied in the middle of the research preparation of light anode perforated membrane, and obtained good effect and progress, improved the transformation efficiency and the performance of DSSC.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, (diameter is about 100-300nm with the titanium dioxide nano-particle of hollow structure, wall thickness 20-50nm) is applied to the light anode of DSSC, the hollow titanium dioxide nano-particle is made dispersed paste to be applied on the light anode, be intended to improve the photoelectric conversion efficiency and the stability of DSSC, finally reach the purpose of improving the DSSC photoelectric properties.
Purpose of the present invention is achieved by following technical proposals:
A kind of dye-sensitized solar cell anode, disperse, hollow titanium dioxide nano-particle therein.
A kind of method for preparing dye-sensitized solar cell anode, carry out according to following step: with hollow titanium dioxide nano-particle and solvent, binding agent, dispersant evenly after, fully disperse, evaporate dispersant and solvent again, obtain to apply slurry; To apply slurry and be coated in conductive glass surface, form needed coating of titanium dioxide, after the immersion sensitization of too much gradient constant temperature sintering and dyestuff, promptly obtain smooth anode of the present invention again.
In technical scheme of the present invention, the hollow titanium dioxide nano-particle can be put down in writing [J.H.Park by document, S.Y.Jung, J.Power Sources 194 (2009) 574-579] following method be prepared: adopt method of emulsion polymerization to make polystyrene sphere, and with it as template, method by titanium tetrachloride hydrolysis forms the titanium dioxide nano-sphere body with nucleocapsid structure, final through high temperature sintering formation diameter 100-300nm, wall thickness 20-50nm hollow titanium dioxide nano-sphere (but because the instability of itself structure, can have the titania nanoparticles of a certain amount of fragmentation).
In the method for preparing the light anode, at first need hollow titanium dioxide nano-particle and solvent, binding agent and dispersant and fully dispersion with preparation, represent that according to mass parts wherein the hollow titanium dioxide nano-particle is that 0.5-2 part, dispersant are that 2-8 part, binding agent are that 0.2-1 part, solvent are 40-80 part.
Described dispersant is one or more in terpinol, n-butanol, the isopropyl alcohol.
Described binding agent is one or both in polyoxyethylene groups octylphenol ether, the ethyl cellulose.
Described solvent is one or more in ethanol, carrene, the acetone.
Secondly after mixing, reach the purpose of abundant dispersion by methods such as sonic oscillation, ball mill ball milling, hand lappings, steam dispersant, solvent again, make the coating slurry of suitable concentration, wherein the solid content of titanium dioxide is 10-25%, and promptly the quality of titanium dioxide accounts for the percentage of final coating coating slurry quality.
The titania slurry that makes the most at last is coated in FTO (tin ash of doped with fluorine) or ITO (tin indium oxide) conductive glass surface, form the coating of titanium dioxide (coating layer thickness is generally at 5-20 μ m) of desired thickness, this how empty photo-anode film after the immersion sensitization of too much gradient constant temperature sintering and dyestuff, obtains smooth anode of the present invention again.
Described dye photoactivation agent is normal Bipyridine metal complexes series, phenol cyanines series, porphyrin series, the pure organic dyestuff series of using in the solar cell field, as the bipyridyl ruthenium complex compound, and N3, N719, Z907, Black dye.
Technical scheme of the present invention, the hollow titanium dioxide nano-particle is made dispersed paste to be applied on the light anode, and this light anode helps the application of full-bodied electrolyte in DSSC, improve the photoelectric conversion efficiency and the stability of DSSC, finally reach the purpose of improving the DSSC photoelectric properties.
Description of drawings
Fig. 1 is the light anode SEM figure of hollow titanium dioxide-coated of the present invention.
Fig. 2 is the photoelectric properties test curve of the DSSC of carrying out among the technical scheme embodiment of the present invention, wherein curve 1 is for being made the I-V curve of DSSC by the hollow titanium dioxide nano-particle slurry of 100wt% content, curve 2 is for being made the I-V curve of DSSC by the hollow titanium dioxide nano-particle slurry of 50wt% content, curve 3 is for being made the I-V curve of DSSC by the hollow titanium dioxide nano-particle slurry of 5wt% content.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
At first, according to document record [J.H.Park, S.Y.Jung, J.Power Sources 194 (2009) 574-579] method be prepared the hollow titanium dioxide nano-particle: adopt method of emulsion polymerization to make polystyrene sphere, and with it as template, method by titanium tetrachloride hydrolysis forms the titanium dioxide nano-sphere body with nucleocapsid structure, final through high temperature sintering formation diameter 100-300nm, wall thickness 20-50nm hollow titanium dioxide nano-sphere carries out the preparation of following optoelectronic pole.
Get laboratory homemade hollow titanium dioxide nano-particle 1g (hollow titanium dioxide nano-particle content is 100%), ethyl cellulose 0.5g, terpinol 4g, be dissolved in the 75ml absolute ethyl alcohol, sonic oscillation 30min under 30 ℃, 80 hertz pours solution in the agate jar into then, ball milling 10-24h on ball mill, the 300r/min that wherein revolves round the sun, rotation 150r/min.After treating that the solution dispersing and mixing is evenly, the outstanding ethanol, 35 ℃ of temperature, rotating speed 105r/min, time 1-2h of steaming.Then slurry is transferred in the agate mortar, hand lapping 1h, control suitable concn and viscosity (the TiO2 solid content is 10-25%) store for future use it.
Get laboratory homemade hollow titanium dioxide nano-particle 0.05g, commercialization nano titanium oxide (P25 of German goldschmidt chemical corporation) 0.95g (hollow titanium dioxide nano-particle content is 5%), ethyl cellulose 0.5g, terpinol 4g is dissolved in the 75ml carrene, sonic oscillation 30min under 30 ℃, 80 hertz, then solution is poured in the agate jar, ball milling 10-24h on ball mill, the 300r/min that wherein revolves round the sun, rotation 150r/min.After treating that the solution dispersing and mixing is evenly, the outstanding carrene, 35 ℃ of temperature, rotating speed 105r/min, time 1-2h of steaming.Then slurry is transferred in the agate mortar, hand lapping 1h, control suitable concn and viscosity (the TiO2 solid content is 10-25%) store for future use it.
Get laboratory homemade hollow titanium dioxide nano-particle 0.5g, commercialization nano titanium oxide (P25 of German goldschmidt chemical corporation) 0.5g (hollow titanium dioxide nano-particle content is 50%), ethyl cellulose 0.5g, terpinol 4g is dissolved in 75ml acetone, sonic oscillation 30min under 30 ℃, 80 hertz, then solution is poured in the agate jar, ball milling 10-24h on ball mill, the 300r/min that wherein revolves round the sun, rotation 150r/min.After treating that the solution dispersing and mixing is evenly, the outstanding acetone, 35 ℃ of temperature, rotating speed 105r/min, time 1-2h of steaming.Then slurry is transferred in the agate mortar, hand lapping 1h, control suitable concn and viscosity (the TiO2 solid content is 10-25%) store for future use it.
With scotch adhesive tape control thickness, titania slurry is coated on the FTO electro-conductive glass through silk screen printing (preferably can before coating, uses 30-50mmol/L TiCL
4Handle electro-conductive glass, at 70 ℃ of constant temperature 40min), leave standstill 5min, put into 80-125 ℃ of baking oven constant temperature 3-5min, repeat aforesaid operations more once.Sintering: 325 ℃, constant temperature 10-30min; 375 ℃, constant temperature 10-25min; 450 ℃, constant temperature 10-30min; 500 ℃, constant temperature 10-25min.Preferred sintering schedule is: 325 ℃, and constant temperature 30min; 375 ℃, constant temperature 20min; 450 ℃, constant temperature 20min; 500 ℃, constant temperature 25min.Treat that the temperature cooling is again through going over TiCL
4Handle electro-conductive glass, at last at 500 ℃ of sintering 10-30min.At last with TiO
2The light anode is immersed in the 20-50mmol/L N719 solution under (wherein the tert-butyl alcohol: the volume ratio of acetonitrile is 1: 1) room temperature and keeps 10-24h, uses alcohol flushing then, and oven dry is to be measured.
Above-mentioned membrane electrode and the FTO electro-conductive glass that plates Pt are assembled into DSSC, and wherein electrolyte is 0.5mol/L LiI, 0.05mol/L I
2, 0.6mol/L 1, the mixed solution of the acetonitrile of 2-dimethyl-3-propyl group iodate imidazole salts (DMPII), 0.4mol/L tetra-tert pyridine (TBP), 0.1mol/L guanidine thiocyanate and valeronitrile (volume ratio 1: 1).(illumination is 100mW/cm under standard solar simulator (CHF-XM500 of company xenon source/500W xenon lamp is freely opened up in Beijing)
2), (German IMe6) tests the photoelectric properties of this DSSC with electrochemical workstation, and wherein the electrode effective area is 0.2826cm
2, the electric potential scanning interval is-0.8-0V that sweep speed is 10mV/s.In addition, by field emission scan tunnel microscope (SEM) photo-anode film that makes is carried out check and analysis, as shown in Figure 1, this photo-anode film is made up of a large amount of porous hollow ball, and the spheroid suitable size is evenly distributed, loose porous, have bigger specific area (40-90m
2/ g), help the light anode carries out scattering absorption and sensitizer dyestuff to incident light absorption, and void content is bigger, help the infiltration and the transmission of electrolyte (especially high viscosity, big molecule electrolyte), positive effect is arranged for the raising of the electricity conversion of DSSC.
Curve 1 is for being made the I-V curve of DSSC by the hollow titanium dioxide nano-particle slurry of 100% content, its short-circuit current density is 13.4mA/cm
2, open circuit voltage is 0.712V, total photoelectric conversion efficiency is 6.22%; Curve 2 is for being made the I-V curve of DSSC by the hollow titanium dioxide nano-particle slurry of 50% content, its short-circuit current density is 13.0mA/cm
2, open circuit voltage is 0.696V, total photoelectric conversion efficiency is 5.42%; Curve 3 is for being made the I-V curve of DSSC by the hollow titanium dioxide nano-particle slurry of 5% content, its short-circuit current density is 11.5mA/cm
2, open circuit voltage is 0.704V, total photoelectric conversion efficiency is 4.36%.Therefore the hollow titanium dioxide nano-particle is applied to the light anode of DSSC, density is low because it has, specific area is big, the good optical characteristic, makes the electricity conversion of DSSC improve a lot than ordinary titanium dioxide (P25 of German goldschmidt chemical corporation).
More than the present invention has been done exemplary description; should be noted that; under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (9)
1. a dye-sensitized solar cell anode is characterized in that, therein the disperse, hollow titanium dioxide nano-particle.
2. method for preparing dye-sensitized solar cell anode, it is characterized in that, carry out according to following step: with hollow titanium dioxide nano-particle and solvent, binding agent, dispersant evenly after, fully disperse, evaporate dispersant and solvent again, obtain to apply slurry; To apply slurry and be coated in conductive glass surface, form needed coating of titanium dioxide, after the immersion sensitization of too much gradient constant temperature sintering and dyestuff, promptly obtain smooth anode of the present invention again.
3. a kind of method for preparing dye-sensitized solar cell anode according to claim 2 is characterized in that, described hollow titanium dioxide nano-particle is that 0.5-2 part, dispersant are that 2-8 part, binding agent are that 0.2-1 part, solvent are 40-80 part.
4. a kind of method for preparing dye-sensitized solar cell anode according to claim 2 is characterized in that described dispersant is one or more in terpinol, n-butanol, the isopropyl alcohol.
5. a kind of method for preparing dye-sensitized solar cell anode according to claim 2 is characterized in that described binding agent is one or both in polyoxyethylene groups octylphenol ether, the ethyl cellulose.
6. a kind of method for preparing dye-sensitized solar cell anode according to claim 2 is characterized in that described solvent is one or more in ethanol, carrene, the acetone.
7. a kind of method for preparing dye-sensitized solar cell anode according to claim 2 is characterized in that, in the described coating slurry, the solid content of titanium dioxide is 10-25%.
8. a kind of method for preparing dye-sensitized solar cell anode according to claim 2, it is characterized in that, described dyestuff is normal Bipyridine metal complexes series, phenol cyanines series, porphyrin series, the pure organic dyestuff series of using in the solar cell field, as the bipyridyl ruthenium complex compound, N3, N719, Z907, Black dye.
9. the application of hollow titanium dioxide nano-particle in the preparation dye-sensitized solar cell anode.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623195A (en) * | 2012-04-27 | 2012-08-01 | 湖北大学 | Method for preparing solar cell through quantum dot and dye synergistic sensitization of TiO2 nanorod array |
| CN103871748A (en) * | 2014-02-25 | 2014-06-18 | 天津大学 | Compound photo-anode applied to dye-sensitized solar cell and preparation method of compound photo-anode |
| CN105632772A (en) * | 2016-03-17 | 2016-06-01 | 东华大学 | Preparation method for titanium dioxide photoanode of titanium-based flexible dye-sensitized solar cell |
| CN105895804A (en) * | 2016-04-08 | 2016-08-24 | 武汉理工大学 | Low-cost perovskite solar cell and preparation method thereof |
| CN106601486A (en) * | 2017-01-05 | 2017-04-26 | 浙江师范大学 | Erbium europium rare earth doped dye-sensitized solar cell and preparation method thereof |
| CN112853540A (en) * | 2020-12-31 | 2021-05-28 | 厦门大学 | Titanium-based pore-forming agent and application thereof in fuel cell |
| CN113035574A (en) * | 2021-03-05 | 2021-06-25 | 安徽元琛环保科技股份有限公司 | Preparation method and application of waste SCR denitration catalyst for dye-sensitized solar cell |
| CN114999831A (en) * | 2022-07-06 | 2022-09-02 | 复旦大学 | Fiber photo-anode, preparation method thereof and application thereof in solar cell |
-
2011
- 2011-06-02 CN CN 201110147436 patent/CN102290254A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of power sources》 20090418 Jong Hyuk Park et al. Nanostructured photoelectrode consisting of TiO2 hollow spheres for non-volatile electrolyte-based dye-sensitized solar cells 第194卷, 第1期 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623195A (en) * | 2012-04-27 | 2012-08-01 | 湖北大学 | Method for preparing solar cell through quantum dot and dye synergistic sensitization of TiO2 nanorod array |
| CN103871748A (en) * | 2014-02-25 | 2014-06-18 | 天津大学 | Compound photo-anode applied to dye-sensitized solar cell and preparation method of compound photo-anode |
| CN103871748B (en) * | 2014-02-25 | 2016-08-24 | 天津大学 | A kind of composite light anode for dye-sensitized solar cell and preparation method |
| CN105632772A (en) * | 2016-03-17 | 2016-06-01 | 东华大学 | Preparation method for titanium dioxide photoanode of titanium-based flexible dye-sensitized solar cell |
| CN105632772B (en) * | 2016-03-17 | 2018-10-23 | 东华大学 | A kind of preparation method of titanium-based flexible dye-sensitized solar battery titanium dioxide photo anode |
| CN105895804A (en) * | 2016-04-08 | 2016-08-24 | 武汉理工大学 | Low-cost perovskite solar cell and preparation method thereof |
| CN106601486A (en) * | 2017-01-05 | 2017-04-26 | 浙江师范大学 | Erbium europium rare earth doped dye-sensitized solar cell and preparation method thereof |
| CN112853540A (en) * | 2020-12-31 | 2021-05-28 | 厦门大学 | Titanium-based pore-forming agent and application thereof in fuel cell |
| CN113035574A (en) * | 2021-03-05 | 2021-06-25 | 安徽元琛环保科技股份有限公司 | Preparation method and application of waste SCR denitration catalyst for dye-sensitized solar cell |
| CN114999831A (en) * | 2022-07-06 | 2022-09-02 | 复旦大学 | Fiber photo-anode, preparation method thereof and application thereof in solar cell |
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Application publication date: 20111221 |