CN103871748A - Compound photo-anode applied to dye-sensitized solar cell and preparation method of compound photo-anode - Google Patents

Compound photo-anode applied to dye-sensitized solar cell and preparation method of compound photo-anode Download PDF

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CN103871748A
CN103871748A CN201410064105.3A CN201410064105A CN103871748A CN 103871748 A CN103871748 A CN 103871748A CN 201410064105 A CN201410064105 A CN 201410064105A CN 103871748 A CN103871748 A CN 103871748A
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graphene
electrode
anode
light anode
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CN103871748B (en
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田建华
廖文明
单忠强
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Tianjin University
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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

Abstract

The invention provides a compound photo-anode applied to a dye-sensitized solar cell (DSSC) and a preparation method of the compound photo-anode. Titanium dioxide and graphene are taken as electrode materials, high-viscosity hydrophilic liquid polymer polyethylene glycol PEG 200-PEG 800 is taken as a dispersing agent, and polyethylene glycol PEG 20000 is taken as curing agents of electrodes. After the method provided by the invention is adopted, graphene can be stably dispersed into PEG 400 liquid after being ultrasonically dispersed, and can still be well dispersed after seven days without agglomeration; after the prepared compound photo-anode is soaked in a dye, formed electrode diaphragms are relatively compact, and no cracking phenomenon occurs; the compound photo-anode prepared through the preparation method provided by the invention has a representative monomer DSSC working curve, so that the obtained cell is stable in performance and good in photoelectric conversion efficiency.

Description

A kind of composite light anode for dye-sensitized solar cell and preparation method
Technical field
The present invention relates to field of renewable energy technology, in more detail, relate to a kind of composite light anode for dye-sensitized solar cell and preparation method thereof.
Background technology
Along with the continuous acceleration of oil crisis, the continuous increase of people to energy demand, solar energy, as a kind of inexhaustible energy, enjoys people to pay close attention to.Solar cell, as a kind of a kind of device that can directly solar energy be converted to battery, is the heat subject of scientific circles' broad research always.From silica-based solar cell efficient III-V compounds of group solar cell and copper-indium-galliun-selenium film solar cell finally, until 1991, Lausanne, SUI Gao Deng engineering institute (EPFL)
Figure BDA0000469551430000011
professor has obtained breakthrough in this research field, and they are by the nanoporous TiO of high-specific surface area 2electrode replaces traditional plate electrode to be incorporated in the research of DSSC, and has obtained 7.1% photoelectric conversion efficiency.At present, this seminar breaks through to 13.1% by battery effect under low light condition, under 1 sunlight conditions, has exceeded 12%, is a kind of solar cell that has development prospect.
TiO 2the advantages such as it is little that nano particle has particle size, high-specific surface area, are conducive to electric transmission on the one hand, are conducive on the other hand Dye Adsorption.But nano particle also exists defect, structural disorder, a large amount of trap sites, the factors such as long transfer distance, thus cause electrode to be prone to charge recombination, battery conversion efficiency declines.Be directed to TiO 2the shortcoming of nano particle, conductive carbon material (Graphene or carbon nano-tube etc.) etc. is introduced in light anode energetically to be studied, and improves the transmitting procedure of electric charge.
But the conductive carbon materials such as Graphene are difficult for dispersed by common solvent (water, ethanol etc.), this causes it in application process, to exist great restriction.Be difficult for homodisperse shortcoming in usual vehicle for conductive carbon material, the present invention adopts the high viscosity such as polyethylene glycol, polyvinylpyrrolidone hydrophilic liquid polymer as a kind of dispersant, while is as the dispersant of slurry, can reduce like this introducing of other surfactants, on the surface texture of electrode and the active impact producing, and a kind of composite light anode for dye-sensitized solar cell and preparation method thereof is proposed accordingly.
Summary of the invention
The invention provides a kind of composite structure light anode for DSSC and preparation method, this composite structure light anode is to be composited by conductive carbon material and polycrystalline Nano granular materials.Adopt a kind of dispersant of high viscosity hydrophilic liquid polymer as conductive carbon material (Graphene or carbon nano-tube etc.), as liquid macrogol (PEG200～PEG800), polyvinylpyrrolidone etc.
Technical scheme of the present invention is as follows:
A kind of composite structure light anode for DSSC, adopting titanium dioxide, Graphene is electrode material, using the high viscosity hydrophilic liquid polymer poly ethylene glycol of PEG200～PEG800 as dispersant, the curing agent using polyethylene glycol PEG20000 as electrode.
The present invention, for the preparation method of the composite structure light anode of DSSC, comprises the steps:
1) by ultrasonic 0.5h～24h in Graphene and hydrophilic liquid polymer P EG200～PEG800 polyethylene glycol, material is fully disperseed, the concentration that forms graphene dispersing solution is 0.01mg/ml～10mg/ml.
2) the polyethylene glycol PEG20000 that employing molecular weight is 20000, as the curing agent of electrode, adds the solvent of water as PEG20000, volume ratio v/v5%～50% of water in liquid, stirring and dissolving; Then press the amount removing step 1 of the required Graphene of electrode) in conductive carbon material dispersion liquid; Solid phase Graphene content is 0.010%～0.040%, and liquid phase P EG20000 content is 5%～20%, adds the dispersant of PEG200～PEG800 as slurry simultaneously, and making the toatl proportion of PEG in liquid is 50%～95%, will be of a size of the TiO of 10～200nm 2nano material is ultrasonic 0.5h～6h in above-mentioned mixing material, then stirs the slurry of 0.5h～24h formation toughness, and composite material is scattered in slurry equably;
3) by step 2) material that obtains is coated in conductive substrates uniformly;
4) be held on 10h in air～72h and remove moisture content scraping the pole piece coating, make electrode material form a kind of gluey film; Carry out electrode sintering, the complex light anode film of acquisition; Be conducive to electrode film is difficult for chapping simultaneously in sintering process;
5) complex light anode film is soaked in to the rear electrode film that forms of immersion in dye solution.
In described step 3), adopt knife coating, suspension method, silk screen print method or spraying process to apply.
Described step 4) electrode sintering, adopts sintering under air atmosphere, or adopts sintering under protective atmosphere.
Solvent/concentration/time that the dissimilar dyestuff of described step 5) needs etc. are not identical, are difficult to whole summaries.During with N719, N3 dyestuff, complex light anode film is soaked in to 10 -5～10 -3the acetonitrile solution of mol/L N719, N3 dyestuff or alcohol solution dipping 4h～72h form electrode film.
Adopt method of the present invention, Graphene is stable being dispersed in PEG400 liquid of energy after ultrasonic dispersion, and that after seven days, still disperses is relatively good, does not reunite, as shown in Figure 1; The complex light anode that adopts the embodiment of the present invention 2 to prepare, is soaking after dyestuff, and its design sketch as shown in Figure 2, can find out that the diaphragm of formation is dense, does not occur crack; Accompanying drawing 3 is the representational monomer DSSC working curves that adopt the complex light anode of the present invention's making, illustrates that the battery performance obtaining is stable, has good photoelectric conversion efficiency.
Accompanying drawing explanation
The picture that Fig. 1 Graphene disperses in PEG400 liquid, before picture is respectively a) and disperses, b) after ultrasonic dispersion, c) place 24h and d) place the experimental result of 7 days.
After Fig. 2 electrode sintering and soak the camera figure of dyestuff.
Fig. 3 adopts the J-V performance map of the complex light anode that the present invention makes.Battery performance is stable, has good photoelectric conversion efficiency.
Embodiment
Embodiment 1:
1) adopt PEG600 as Graphene dispersant, form the PEG600-graphene suspension of 0.01mg/ml, ultrasonic agitation 0.5h, forms slurry.
2) 0.005g PEG20000(solid masses is than 5%) and deionized water (the volume ratio v/v5% of water in liquid), stirring and dissolving.Then add the dispersant of PEG600 as slurry, making the toatl proportion of PEG in liquid is 95%.Add 0.1g TiO 2length is nanotube and the step 1) graphene dispersing solution of 100～200nm, solid phase Graphene content 0.011%, and the ultrasonic 0.5h of mixing material of formation, then stirs 24h and forms the slurry of toughness.
3) make composite material be scattered in equably in slurry and subsequently formation slurry is laid in to 0.2826cm 2groove in, adopt scalpel knife coating to carry out blade coating.
4) pole piece is held on 10h in air and removes the moisture content in pole piece, finally forms a kind of gluey film.Adopt subsequently 500 ℃ of sintering 1.5h sintering in Muffle furnace, form certain thickness film.
5) film of acquisition is soaked in to 10 -3the alcohol solution dipping 4h of mol/L N719 dyestuff forms the electrode complex light anode of dye sensitization.This technique does not affect the structure of material, is difficult for causing caving in of material structure.
Embodiment 2:
1) adopt PEG400 as Graphene dispersant, ultrasonic 6h, the PEG400-graphene suspension of formation 1mg/ml.Design sketch is shown in accompanying drawing 1 of the present invention, before picture is respectively a) and disperses, b) after ultrasonic dispersion, c) place 24h and d) place the PEG400-graphene solution of 7 days.
2) 0.01g PEG20000(solid masses is than 10%) and 0.1ml deionized water (the volume ratio v/v23% of water in liquid), stirring and dissolving.Then add respectively the dispersant of PEG400 as slurry, making the toatl proportion of PEG in liquid is the TiO of 75%, 0.1g size 10nm 2nano particle and step 1) graphene dispersing solution, make solid phase Graphene content 0.025%, and then the ultrasonic 2h of mixing material of formation stirs 5h and form the slurry of toughness.
3) formation slurry is laid in to 0.2826cm 2groove in, adopt scalpel knife coating to carry out blade coating after shelving 20min.
4) pole piece is held on 24h in air and removes the moisture content in pole piece, finally forms a kind of electrode film.400 ℃ of sintering 1h of sintering in Muffle furnace.
5) film of acquisition is soaked in to 10 -4the acetonitrile solution of mol/L N719 dyestuff soaks the electrode complex light anode electrode of 24h formation dye sensitization.Design sketch is shown in accompanying drawing 2 of the present invention, the composite material photoanode surface of formation is regular, even thickness, without obvious crackle.
6) the complex light anode J-V performance curve that test is prepared according to above-mentioned steps.Design sketch is shown in accompanying drawing 3 of the present invention, and the photoelectric conversion efficiency that adopts composite material light anode to reach is 5.02%, has improved 18.0% than the light anode that does not add Graphene.
Embodiment 3:
1) adopt PEG200 as Graphene dispersant, ultrasonic 24h, the PEG200-graphene suspension of formation 10mg/ml.
2) 0.005g PEG20000(solid masses is than 5%) and 0.1ml deionized water (the volume ratio v/v5% of water in liquid), stirring and dissolving.Then add respectively the dispersant of PEG200 as slurry, make the TiO that the toatl proportion of PEG in liquid is 50%, 0.1g100～200nm 2nanotube and step 1) graphene dispersing solution, make solid phase Graphene content 0.039%, and then the ultrasonic 0.5h of mixing material of formation stirs 6h and form the slurry of toughness.
3) make composite material be scattered in equably in slurry and subsequently formation slurry is laid in to 0.2826cm 2groove in, adopt scalpel knife coating to carry out blade coating.
4) pole piece is held on 72h in air and removes the moisture content in pole piece, finally forms a kind of gluey film.Adopt subsequently 450 ℃ of sintering 1h sintering in Muffle furnace, adopt TiCl 4after reprocessing, sintering 30min again, forms certain thickness film.
5) film of acquisition is soaked in to 10 -5the acetonitrile solution of mol/L N3 dyestuff soaks the electrode complex light anode of 72h formation dye sensitization.

Claims (4)

1. the composite structure light anode for DSSC, it is characterized in that it is electrode material that composite structure light anode adopts titanium dioxide, Graphene or other conductive carbon materials, using the high viscosity hydrophilic liquid polymer poly ethylene glycol of PEG200～PEG800 as dispersant, the curing agent using polyethylene glycol PEG20000 as electrode.
2. the preparation method of composite structure light anode as claimed in claim 1, is characterized in that, comprises the steps:
1) by ultrasonic 0.5h～24h in Graphene and hydrophilic liquid polymer P EG200～PEG800 polyethylene glycol, material is fully disperseed, the concentration that forms graphene dispersing solution is 0.01mg/ml～10mg/ml.
2) the polyethylene glycol PEG20000 that employing molecular weight is 20000, as the curing agent of electrode, adds the solvent of water as PEG20000, volume ratio v/v5%～50% of water in liquid, stirring and dissolving.Then press the amount removing step 1 of the required Graphene of electrode) in graphene dispersing solution.Solid phase Graphene content is 0.010%～0.040%, and liquid phase P EG20000 content is 5%～20%, adds the dispersant of PEG200～PEG800 as slurry simultaneously, and making the toatl proportion of PEG in liquid is 50%～95%, will be of a size of the TiO of 10～200nm 2nano material is ultrasonic 0.5h～6h in above-mentioned mixing material, then stirs the slurry of 0.5h～24h formation toughness, and composite material is scattered in slurry.
3) by step 2) obtain slurry and be coated on uniformly in conductive substrates;
4) be held on 10h in air～72h and remove moisture content scraping the pole piece coating, make electrode material form a kind of gluey film; Carry out electrode sintering, the complex light anode film of acquisition;
5) complex light anode film is soaked in to the rear electrode film that forms of immersion in dye solution.
3. method as claimed in claim 2, is characterized in that adopting knife coating, suspension method, silk screen print method or spraying process to apply in described step 3).
4. as profit requires the method as described in 2, it is characterized in that described step 4) electrode sintering, adopt sintering under air atmosphere, or adopt sintering under protective atmosphere.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106783185A (en) * 2016-12-15 2017-05-31 电子科技大学 A kind of novel environmental solar energy collector based on sensitizing dyestuff
CN106876143A (en) * 2015-12-11 2017-06-20 天津榛发科技有限责任公司 A kind of Graphene DSSC
CN108212118A (en) * 2017-11-30 2018-06-29 江苏新四态水膜科技有限公司 A kind of hydrophilic material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102290254A (en) * 2011-06-02 2011-12-21 天津大学 Light anode of dye sensitized solar cell and preparation method thereof
CN102874799A (en) * 2012-09-25 2013-01-16 南京工业大学 Method for preparing graphene and titanium dioxide composite material by vapor phase reduction method
CN102969169A (en) * 2012-11-26 2013-03-13 同济大学 Preparation method of working electrode of novel dye-sensitized solar cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102290254A (en) * 2011-06-02 2011-12-21 天津大学 Light anode of dye sensitized solar cell and preparation method thereof
CN102874799A (en) * 2012-09-25 2013-01-16 南京工业大学 Method for preparing graphene and titanium dioxide composite material by vapor phase reduction method
CN102969169A (en) * 2012-11-26 2013-03-13 同济大学 Preparation method of working electrode of novel dye-sensitized solar cell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106876143A (en) * 2015-12-11 2017-06-20 天津榛发科技有限责任公司 A kind of Graphene DSSC
CN106783185A (en) * 2016-12-15 2017-05-31 电子科技大学 A kind of novel environmental solar energy collector based on sensitizing dyestuff
CN106783185B (en) * 2016-12-15 2019-01-18 电子科技大学 A kind of novel environmental solar energy collector based on sensitizing dyestuff
CN108212118A (en) * 2017-11-30 2018-06-29 江苏新四态水膜科技有限公司 A kind of hydrophilic material

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