CN101937777A - Method for manufacturing dye sensitized solar cell - Google Patents
Method for manufacturing dye sensitized solar cell Download PDFInfo
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- CN101937777A CN101937777A CN 201010231193 CN201010231193A CN101937777A CN 101937777 A CN101937777 A CN 101937777A CN 201010231193 CN201010231193 CN 201010231193 CN 201010231193 A CN201010231193 A CN 201010231193A CN 101937777 A CN101937777 A CN 101937777A
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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
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Abstract
The invention provides a method for manufacturing a dye sensitized solar cell. The method is characterized by comprising the following specific steps of: immersing conductive glass into titanium containing solution and drying the conductive glass to obtain a conductive transparent substrate; dissolving a hydrophobic polymer in a solvent, adding titanium dioxide nanoparticles or hydrolysable titanium salt into the solvent and forming a fiber membrane through electrostatic spinning; thermally pressing and calcining the fiber membrane to remove organic ingredients in the fiber membrane; immersing the fiber membrane into sensitization dye solution and drying the fiber membrane; and packaging the obtained solar cell. The method has the advantages of higher photoelectricity conversion efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of DSSC, belong to the new textile material application.
Background technology
Along with the countries in the world industrial expansion, human increasing to the environmental demand of resource, shortage of resources is restricting human development just day by day.Solar energy resources is a kind of inexhaustible precious resources.The human utilization of always being devoted to solar energy.The appearance of solar cell is for the mankind's development provides enormous motivation.DSSC (dye-sensitized solar cell, DSSC) also claim "
Cell " because outstanding advantages such as low cost, high efficiency, long-life are subjected to scientific worker's generally attention, more and more demonstrate powerful competitiveness.
Common DSSC is to adopt fine and close titanium dioxide semiconductor film, titania nanoparticles or the titanium dioxide nano-rod absorption carrier as dyestuff.Adopt the titanium dioxide semiconductor film as the DSSC of the absorption carrier of dyestuff because can only be from absorption monolayer dyestuff on the film surface, and the dyestuff of individual layer can only absorb the sunlight less than 1%, the multilayer dyestuff has hindered the transmission of electronics again, has the low shortcoming of optoelectronic transformation efficiency.Adopt titania nanoparticles or the titanium dioxide nano-rod DSSC as the absorption carrier of dyestuff, continuity is relatively poor, in use, easily causes dyestuff to be revealed.
Summary of the invention
It is simple and have a preparation method of the DSSC of higher optoelectronic transformation efficiency to the purpose of this invention is to provide a kind of technology.
In order to achieve the above object, technical scheme of the present invention provides a kind of preparation method of DSSC, it is characterized in that, concrete steps are:
The first step, electro-conductive glass is immersed in the titaniferous solution, drying obtains the conductive, transparent substrate;
Second step, hydrophobic polymer is dissolved in the solvent, adds titania nanoparticles or hydrolyzable titanium salt, gained solution is carried out electrostatic spinning, the fiber that is spinned is directly deposited in the conductive, transparent substrate that the first step obtains form tunica fibrosa;
The 3rd step, with second tunica fibrosa that obtain of step together with the conductive, transparent substrate under 1-10MPa pressure, 90-120 ℃, through 15-60 minute hot-pressing processing, carry out 400-500 ℃ of calcining subsequently, to remove the organic principle in the tunica fibrosa;
The 4th step, the tunica fibrosa that the 3rd step was obtained immerse in the sensitizing dyestuff solution drying together with the conductive, transparent substrate;
The 5th goes on foot, injects electrolyte solution in tunica fibrosa, adopting the platinum electrode of lining polyimide film or PETG film is counterelectrode, the encapsulation solar cell.
Electro-conductive glass in the described first step is fluorine doping stannic oxide electro-conductive glass, stibium doping stannic oxide electro-conductive glass or indium tin oxide-coated glass.
Titaniferous solution in the described first step is a titanium tetrafluoride solution.
Hydrophobic polymer in described second step is ethyl cellulose, acetyl cellulose, polyacrylonitrile, polystyrene, zein, polymethyl methacrylate, Merlon, polyvinyl acetate, PLA, polyvinyl chloride, poly-own lactones, poly butylene succinate, poly-succinic acid-butanediol-be total to-mutual-phenenyl two acid bromide two alcohol ester, poly-hydroxyl valerate or polyamide.
Solvent in described second step is N, dinethylformamide, N, N-dimethylacetylamide, oxolane, carrene, dichloroethanes, chloroform, monochloro methane, acetone, formic acid, one or both mixtures of toluene and cyclohexane.
Described hydrolyzable titanium salt is a tetraisopropoxy titanium.
The thickness of the tunica fibrosa after described the 3rd step calcining is the 1-20 micron.
Sensitizing dyestuff in described the 4th step is bipyridyl ruthenium series, many pyridines of carboxylic acid phthalocyanine series, organic molecule dyestuff or high molecular dye.Preferably suitable-two thiocyanates-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II), suitable-two chloro-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II), suitable-two bromo-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) and close ruthenium (II), suitable-two iodo-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II) (cis-X
2Bis (2,2 '-bipyridyl-4,4 '-dicarboxylate) ruthenium (II), wherein X=Cl
-, Br
-, I
-Or NCS
-), porphyrin, phthalocyanine, oxidation anthracene or poly-phthalocyanine.
The present invention compares with the Optical Electro-Chemistry solar cell of routine, is significantly improved on semi-conducting electrode and dyestuff.Nano porous titanium dioxide fiber in the inorganic nano poriferous titanium dioxide fiber DSSC is just as a sponge, has superhigh specific surface area, can absorb more dyestuff monolayer, so promptly overcome the shortcoming that to adsorb monolayer in the original battery and absorb a small amount of sunlight, can make sunlight repeatedly reflection in the nano porous titanium dioxide fiber again, sunlight is absorbed repeatedly, can produce bigger photoelectric current, thereby improve optoelectronic transformation efficiency greatly.The present invention has utilized that inorganic nano poriferous titanium dioxide fiber continuity is good, specific area is high, thereby the absorbing dye amount improves greatly and electronics is good along machine direction transmission continuity, thereby has obtained to have the inorganic nano poriferous titanium dioxide fiber DSSC of higher optoelectronic transformation efficiency.
Embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1
The first step, the tin ash electro-conductive glass that fluorine is mixed immerses in the titanium tetrafluoride solution (0.04M), handles 12 hours down at 60 ℃, as the electrically conducting transparent base material of DSSC.
Second step was dissolved in polyvinyl acetate (Mn 500000) in the dimethyl formamide solution, was mixed with concentration and is 11.5% solution (calculating with mass percent); Then 1 gram tetraisopropoxy titanium and 0.5 gram acetate are added in the 5 polyvinyl acetate ester solutions that prepare in advance of gram, stir and form uniform solution.The solution for preparing is at room temperature carried out electrostatic spinning, the spinning condition that is adopted is that voltage is 17 kilovolts, the fiber receiving range is 16 centimetres, injection of solution speed is 1.5 milliliters/hour, and the prepared fiber of electrostatic spinning directly deposits in the preprepared conductive, transparent substrate of the first step and forms tunica fibrosa.
In the 3rd step, the tunica fibrosa that second step was obtained is heated to 90 ℃ together with the conductive, transparent substrate, and keeps 60 minutes, applies the pressure of 1MPa then; Then the tunica fibrosa for preparing was calcined one hour down at 400 ℃, the thickness of calcining back tunica fibrosa is 1 micron.
The 4th step, go on foot the tunica fibrosa that obtains is immersed in 0.3mM together with the conductive, transparent substrate suitable-two thiocyanates-two (2 with the 3rd, 2 '-bipyridine-4,4 '-dicarboxylic acids) closes in ruthenium (II) ethanol solution, kept 20 hours under the room temperature, and then be immersed in the absolute ethyl alcohol, take out dry subsequently.
The 5th step, in inorganic nano poriferous titanium dioxide fiber film, inject electrolyte solution in the packaged battery process, counterelectrode adopts platinum electrode lining polyimide film, used electrolyte solution is to contain 1-propyl group 2,3-methylimidazole iodide (0.6M), tetrabutyl pyridine (0.5M), the acetonitrile solution (0.05M) of lithium iodide (0.1M) and iodine.Can arrive 10% through the prepared inorganic nano poriferous titanium dioxide fiber DSSC conversion ratio of test.
Embodiment 2
The first step immerses the stibium doping stannic oxide electro-conductive glass in the titanium tetrafluoride solution (0.04M), handles 12 hours down at 60 ℃, as the electrically conducting transparent base material of DSSC.
Second step was dissolved in polyacrylonitrile (Mn 80000) in the dimethyl formamide solution, was mixed with concentration and is 15% solution (calculating with mass percent); Then 1 gram tetraisopropoxy titanium and 0.5 gram acetate are added in 5 polyacrylonitrile solution that prepare in advance of gram, stir and form uniform solution.The solution for preparing is at room temperature carried out electrostatic spinning, the spinning condition that is adopted is that voltage is 20 kilovolts, the fiber receiving range is 15 centimetres, injection of solution speed is 1 milliliter/hour, and the prepared fiber of electrostatic spinning directly deposits in the preprepared conductive, transparent substrate of the first step and forms tunica fibrosa.
In the 3rd step, the tunica fibrosa that second step was obtained is heated to 120 ℃ together with the conductive, transparent substrate, and keeps 15 minutes, applies the pressure of 10MPa then; Then the tunica fibrosa for preparing was calcined one hour down at 500 ℃, the thickness of calcining back tunica fibrosa is 20 microns.
The 4th step, go on foot the tunica fibrosa that obtains is immersed in 0.3mM together with the conductive, transparent substrate suitable-two thiocyanates-two (2 with the 3rd, 2 '-bipyridine-4,4 '-dicarboxylic acids) closes in ruthenium (II) ethanol solution, kept 20 hours under the room temperature, and then be immersed in the absolute ethyl alcohol, take out dry subsequently.
The 5th step, packaged battery.In inorganic nano poriferous titanium dioxide fiber film, inject electrolyte solution in the packaged battery process, counterelectrode adopts platinum electrode lining polyimide film, used electrolyte solution is to contain 1-propyl group 2,3-methylimidazole iodide (0.6M), tetrabutyl pyridine (0.5M), the acetonitrile solution (0.05M) of lithium iodide (0.1M) and iodine.Can arrive 9% through the prepared inorganic nano poriferous titanium dioxide fiber DSSC conversion ratio of test.
Embodiment 3
The first step immerses indium tin oxide-coated glass in the titanium tetrafluoride solution (0.04M), handles 12 hours down at 60 ℃, as the electrically conducting transparent base material of DSSC.
Second step, poly butylene succinate (Mn 20000) is separated in carrene/chloroform (weight ratio 3/1) solution, be mixed with concentration and be 13% solution (calculating) with mass percent; Add 4 gram titania nanoparticles (Aladdin net commercial form is bought, particle diameter 10-100 nanometer) to 20 then and restrain in the poly-butyric acid butanediol ester solution for preparing in advance, stir and form uniform solution.The solution for preparing is at room temperature carried out electrostatic spinning, the spinning condition that is adopted is that voltage is 20 kilovolts, the fiber receiving range is 15 centimetres, and injection of solution speed is 1 milliliter/hour, and the prepared fiber of electrostatic spinning directly deposits in the preprepared conductive, transparent substrate of the first step.
In the 3rd step, the tunica fibrosa that second step was obtained is heated to 120 ℃ together with the conductive, transparent substrate, and keeps 15 minutes, applies the pressure of 10MPa then; Then the tunica fibrosa for preparing was calcined one hour down at 500 ℃, the thickness of calcining back tunica fibrosa is 10 microns.
The 4th step, go on foot the tunica fibrosa that obtains is immersed in 0.3mM together with the conductive, transparent substrate suitable-two thiocyanates-two (2 with the 3rd, 2 '-bipyridine-4,4 '-dicarboxylic acids) closes in ruthenium (II) ethanol solution, kept 20 hours under the room temperature, and then be immersed in the absolute ethyl alcohol, take out dry subsequently.
The 5th step, in inorganic nano poriferous titanium dioxide fiber film, inject electrolyte solution in the packaged battery process, counterelectrode adopts platinum electrode lining polyimide film, used electrolyte solution is to contain 1-propyl group 2,3-methylimidazole iodide (0.6M), tetrabutyl pyridine (0.5M), the acetonitrile solution (0.05M) of lithium iodide (0.1M) and iodine.Can arrive 8.5% through the prepared inorganic nano poriferous titanium dioxide fiber DSSC conversion ratio of test.
Other embodiment, difference be to prepare in the inorganic nano poriferous titanium dioxide fiber film the dyestuff difference of the different and absorption of the polymer that uses.
Embodiment 4
The first step immerses indium tin oxide-coated glass in the titanium tetrafluoride solution (0.04M), handles 12 hours down at 60 ℃, as the electrically conducting transparent base material of DSSC.
Second step, will gather own lactones (113kDa) and separate in chloroform soln, be mixed with concentration and be 13% solution (calculating) with mass percent; That then 4 gram titania nanoparticles (Aladdin net commercial form buy, particle diameter 10-100 nanometer) are added to 20 grams prepare in advance is poly-in oneself in the lipoprotein solution, stirs and forms uniform solution.The solution for preparing is at room temperature carried out electrostatic spinning, the spinning condition that is adopted is that voltage is 15 kilovolts, the fiber receiving range is 10 centimetres, and injection of solution speed is 1 milliliter/hour, and the prepared fiber of electrostatic spinning directly deposits in the preprepared conductive, transparent substrate of the first step.
In the 3rd step, the tunica fibrosa that second step was obtained is heated to 150 ℃ together with the conductive, transparent substrate, and keeps 15 minutes, applies the pressure of 10MPa then; Then the tunica fibrosa for preparing was calcined one hour down at 500 ℃, the thickness of calcining back tunica fibrosa is 10 microns.
The 4th step, go on foot the tunica fibrosa that obtains is immersed in 0.3mM together with the conductive, transparent substrate suitable-two thiocyanates-two (2 with the 3rd, 2 '-bipyridine-4,4 '-dicarboxylic acids) closes in ruthenium (II) ethanol solution, kept 20 hours under the room temperature, and then be immersed in the absolute ethyl alcohol, take out dry subsequently.
The 5th step, in inorganic nano poriferous titanium dioxide fiber film, inject electrolyte solution in the packaged battery process, counterelectrode adopts platinum electrode lining polyimide film, used electrolyte solution is to contain 1-propyl group 2,3-methylimidazole iodide (0.6M), tetrabutyl pyridine (0.5M), the acetonitrile solution (0.05M) of lithium iodide (0.1M) and iodine.Can arrive 8.5% through the prepared inorganic nano poriferous titanium dioxide fiber DSSC conversion ratio of test.
Other embodiment, difference be to prepare in the inorganic nano poriferous titanium dioxide fiber film the dyestuff difference of the different and absorption of the polymer that uses.
Claims (8)
1. the preparation method of a DSSC is characterized in that, concrete steps are:
The first step, electro-conductive glass is immersed in the titaniferous solution, drying obtains the conductive, transparent substrate;
Second step, hydrophobic polymer is dissolved in the solvent, adds titania nanoparticles or hydrolyzable titanium salt, gained solution is carried out electrostatic spinning, the fiber that is spinned is directly deposited in the conductive, transparent substrate that the first step obtains form tunica fibrosa;
The 3rd step, with second tunica fibrosa that obtain of step together with the conductive, transparent substrate under 1-10MPa pressure, 90-120 ℃, through 15-60 minute hot-pressing processing, carry out 400-500 ℃ of calcining subsequently, to remove the organic principle in the tunica fibrosa;
The 4th step, the tunica fibrosa that the 3rd step was obtained immerse in the sensitizing dyestuff solution drying together with the conductive, transparent substrate;
The 5th goes on foot, injects electrolyte solution in tunica fibrosa, adopting the platinum electrode of lining polyimide film or PETG film is counterelectrode, the encapsulation solar cell.
2. the preparation method of DSSC as claimed in claim 1 is characterized in that, the electro-conductive glass in the described first step is fluorine doping stannic oxide electro-conductive glass, stibium doping stannic oxide electro-conductive glass or indium tin oxide-coated glass.
3. the preparation method of DSSC as claimed in claim 1 is characterized in that, the titaniferous solution in the described first step is a titanium tetrafluoride solution.
4. the preparation method of DSSC as claimed in claim 1, it is characterized in that the hydrophobic polymer in described second step is ethyl cellulose, acetyl cellulose, polyacrylonitrile, polystyrene, zein, polymethyl methacrylate, Merlon, polyvinyl acetate, PLA, polyvinyl chloride, poly-own lactones, poly butylene succinate, poly-succinic acid-butanediol-be total to-mutual-phenenyl two acid bromide two alcohol ester, poly-hydroxyl valerate or polyamide.
5. the preparation method of DSSC as claimed in claim 1 is characterized in that, the solvent in described second step is N, dinethylformamide, N, N-dimethylacetylamide, oxolane, carrene, dichloroethanes, chloroform, monochloro methane, acetone, formic acid, one or both mixtures of toluene and cyclohexane.
6. the preparation method of DSSC as claimed in claim 1 is characterized in that, described hydrolyzable titanium salt is a tetraisopropoxy titanium.
7. the preparation method of DSSC as claimed in claim 1 is characterized in that, the thickness of the tunica fibrosa after described the 3rd step calcining is the 1-20 micron.
8. the preparation method of DSSC as claimed in claim 1, it is characterized in that, sensitizing dyestuff in described the 4th step is suitable-two thiocyanates-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II), suitable-two chloro-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II), suitable-two bromo-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II), suitable-two iodo-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II), porphyrin, phthalocyanine, oxidation anthracene or poly-phthalocyanine.
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Cited By (7)
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| CN102169910A (en) * | 2011-01-14 | 2011-08-31 | 南开大学 | Thin film solar cell based on sulfur compound nanocrystalline |
| CN102274017A (en) * | 2011-05-20 | 2011-12-14 | 吉林大学 | Wireless dynamic electrocardiogram monitoring device and monitoring method based on pure silver nano fibrous membrane |
| CN105369475A (en) * | 2015-08-27 | 2016-03-02 | 新疆大学 | SnSb/carbon nanofiber active material and manufacturing method thereof |
| CN105624820A (en) * | 2016-01-30 | 2016-06-01 | 南京邮电大学 | Polystyrene/porphyrin derivative composite nano-fiber, method for preparing same and application of polystyrene/porphyrin derivative composite nano-fiber |
| CN105742070A (en) * | 2016-03-07 | 2016-07-06 | 深圳大学 | High-catalytic-activity counter electrode material of solar cell and preparation method therefor |
| CN106283212A (en) * | 2015-06-24 | 2017-01-04 | 湖南人文科技学院 | A kind of method of electrostatic spinning prepares the method for hybrid inorganic-organic perovskite fiber membrane |
| CN111312525A (en) * | 2020-01-20 | 2020-06-19 | 南昌航空大学 | Preparation method of quantum dot sensitized solar cell with ultrathin PMMA passivation layer |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169910A (en) * | 2011-01-14 | 2011-08-31 | 南开大学 | Thin film solar cell based on sulfur compound nanocrystalline |
| CN102169910B (en) * | 2011-01-14 | 2013-06-05 | 南开大学 | Thin film solar cell based on sulfur compound nanocrystalline |
| CN102274017A (en) * | 2011-05-20 | 2011-12-14 | 吉林大学 | Wireless dynamic electrocardiogram monitoring device and monitoring method based on pure silver nano fibrous membrane |
| CN106283212A (en) * | 2015-06-24 | 2017-01-04 | 湖南人文科技学院 | A kind of method of electrostatic spinning prepares the method for hybrid inorganic-organic perovskite fiber membrane |
| CN105369475A (en) * | 2015-08-27 | 2016-03-02 | 新疆大学 | SnSb/carbon nanofiber active material and manufacturing method thereof |
| CN105369475B (en) * | 2015-08-27 | 2017-10-20 | 新疆大学 | Tin antimony and carbon nano-fiber active material and preparation method thereof |
| CN105624820A (en) * | 2016-01-30 | 2016-06-01 | 南京邮电大学 | Polystyrene/porphyrin derivative composite nano-fiber, method for preparing same and application of polystyrene/porphyrin derivative composite nano-fiber |
| CN105624820B (en) * | 2016-01-30 | 2018-05-11 | 南京邮电大学 | Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application |
| CN105742070A (en) * | 2016-03-07 | 2016-07-06 | 深圳大学 | High-catalytic-activity counter electrode material of solar cell and preparation method therefor |
| CN105742070B (en) * | 2016-03-07 | 2017-12-05 | 深圳大学 | A kind of high catalytic activity solar cell is to electrode material and preparation method thereof |
| CN111312525A (en) * | 2020-01-20 | 2020-06-19 | 南昌航空大学 | Preparation method of quantum dot sensitized solar cell with ultrathin PMMA passivation layer |
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Application publication date: 20110105 |