CN103871748B - A kind of composite light anode for dye-sensitized solar cell and preparation method - Google Patents
A kind of composite light anode for dye-sensitized solar cell and preparation method Download PDFInfo
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- CN103871748B CN103871748B CN201410064105.3A CN201410064105A CN103871748B CN 103871748 B CN103871748 B CN 103871748B CN 201410064105 A CN201410064105 A CN 201410064105A CN 103871748 B CN103871748 B CN 103871748B
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- light anode
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- polyethylene glycol
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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 kind of composite structure light anode for DSSC and preparation method；Using titanium dioxide, Graphene is electrode material, using the high viscosity hydrophilic liquid polymer polyethylene glycol of PEG200～PEG800 as dispersant, using polyethylene glycol PEG20000 as the curing agent of electrode.The method using the present invention, Graphene is stable being dispersed in PEG400 liquid of energy after ultrasonic disperse, the most scattered relatively good after seven days, does not reunite；The complex light anode of preparation, after soaking dyestuff, it can be seen that the electrode diaphragm of formation is dense, crack does not occur；The representational monomer DSSC working curve of the complex light anode that the present invention makes, illustrates that the battery performance obtained is stable, has good photoelectric transformation efficiency.
Description
Technical field
The present invention relates to field of renewable energy technology, in more detail, relate to a kind of DSSC
Complex light anode and preparation method thereof.
Background technology
Along with the continuous acceleration of oil crisis, energy demand is continuously increased by people, and solar energy takes as one
The most nexhaustible energy, enjoy people to pay close attention to.Solar cell can be directly by solar energy as one
Be converted to a kind of device of battery, the heat subject that always scientific circles are widely studied.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)Professor achieves breakthrough in this research field,
They are by the nanoporous TiO of high-specific surface area2Electrode replaces traditional plate electrode to be incorporated into dye sensitization too
In the research of sun energy battery, and achieve the photoelectric transformation efficiency of 7.1%.At present, this seminar is at low light level bar
Battery effect is broken through to 13.1% under part, under 1 sunlight conditions, already more than 12%, be a kind of
The solar cell of great development prospect.
TiO2The advantages such as it is little that nano particle has particle size, high-specific surface area, are on the one hand conducive to electric transmission,
On the other hand Dye Adsorption is conducive to.But, nano particle there is also defect, structural disorder, substantial amounts of catches
Collecting the factors such as point, long transfer distance, thus cause electrode charge recombination easily occur, battery conversion efficiency declines.
It is directed to TiO2The shortcoming of nano particle, conductive carbon material (Graphene or CNT etc.) etc. is drawn energetically
Enter in light anode and study, improve the transmitting procedure of electric charge.
But, the conductive carbon material such as Graphene is difficult to by common solvent (water, ethanol etc.) dispersed, and this leads
Cause it in application process, there is restriction greatly.It is difficult in usual vehicle dispersed for conductive carbon material
Shortcoming, the present invention uses the high viscosity hydrophilic liquid polymer conduct such as polyethylene glycol, polyvinylpyrrolidone
A kind of dispersant, simultaneously as the dispersant of slurry, so can reduce the introducing of other surfactants, right
The impact that the surface texture of electrode and activity produce, and it is compound to propose a kind of DSSC accordingly
Light anode and preparation method thereof.
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 formed by conductive carbon material and polycrystalline nanoparticle Material cladding.Employing high viscosity is hydrophilic
Property liquid polymers is as a kind of dispersant of conductive carbon material (Graphene or CNT etc.), second as poly-in liquid
Glycol (PEG200～PEG800), polyvinylpyrrolidone etc..
Technical scheme is as follows:
A kind of composite structure light anode for DSSC, employing titanium dioxide, Graphene are
Electrode material, using the high viscosity hydrophilic liquid polymer polyethylene glycol of PEG200～PEG800 as dispersion
Agent, using polyethylene glycol PEG20000 as the curing agent of electrode.
The present invention is for the preparation method of the composite structure light anode of DSSC, including walking as follows
Rapid:
1) by ultrasonic 0.5h in Graphene and hydrophilic liquid polymer PEG200～PEG800 polyethylene glycol～
24h so that material is fully dispersed, the concentration forming graphene dispersing solution is 0.01mg/ml～10mg/ml.
2) the polyethylene glycol PEG20000 using molecular weight to be 20000 is as the curing agent of electrode, adds water
As the solvent of PEG20000, water volume ratio v/v5%～50% in a liquid, stirring and dissolving；Then press
The amount removing step 1 of Graphene needed for electrode) in conductive carbon material dispersion liquid；Solid phase Graphene content is
0.010%～0.040%, liquid phase P EG20000 content is 5%～20%, is simultaneously introduced PEG200～PEG800
As the dispersant of slurry, making PEG toatl proportion in a liquid is 50%～95%, by a size of 10～200nm
TiO2Nano material is ultrasonic 0.5h～6h in above-mentioned mixing liquid, and then stirring 0.5h～24h is formed
The slurry of toughness, makes composite be homogeneously dispersed in slurry；
3) by step 2) material that obtains is coated in conductive substrates uniformly；
4) it is held on 10h～72h removal moisture content in air by scraping the pole piece coated so that electrode material is formed
A kind of gluey film；Carry out electrode sintering, it is thus achieved that complex light anode film；Be conducive to electrode film at sintering simultaneously
During be not susceptible to chap；
5) electrode film is formed after complex light anode film is soaked in dye solution immersion.
Described step 3) uses knife coating, suspension method, silk screen print method or spraying process coating.
Described step 4) electrode sintering, uses and sinters under air atmosphere, or uses sintering under protective atmosphere.
Solvent/concentration/time etc. that the different types of dyestuff of described step 5) needs is different from, it is difficult to complete
Portion summarizes.During with N719, N3 dyestuff, complex light anode film is soaked in 10-5～10-3mol/L N719、
The acetonitrile solution of N3 dyestuff or alcohol solution dipping 4h～72h form electrode film.
The method using the present invention, what Graphene can be stable after ultrasonic disperse is dispersed in PEG400 liquid
In, the most scattered relatively good after seven days, do not reunite, as shown in Figure 1；Use the embodiment of the present invention 2
The complex light anode of preparation, after soaking dyestuff, its design sketch is as shown in Figure 2, it can be seen that the diaphragm of formation
Dense, crack does not occur；Accompanying drawing 3 be use the present invention make complex light anode have representative
Property monomer DSSC working curve, illustrate that the battery performance that obtains is stable, there is good photoelectric transformation efficiency.
Accompanying drawing explanation
Fig. 1 Graphene is scattered picture in PEG400 liquid, picture be respectively a) dispersion before, b) ultrasonic
After 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 uses the J-V performance map of the complex light anode that the present invention makes.Battery performance is stable, has good
Good photoelectric transformation efficiency.
Detailed description of the invention
Embodiment 1:
1) PEG600 is used to hang as graphene dispersion agent, the PEG600-Graphene forming 0.01mg/ml
Supernatant liquid, ultrasonic agitation 0.5h, form slurry.
2) 0.005g PEG20000(solid masses ratio 5%) and deionized water (water volume ratio in a liquid
V/v5%), stirring and dissolving.It is subsequently adding the PEG600 dispersant as slurry, makes PEG in a liquid
Toatl proportion is 95%.Add 0.1g TiO2A length of 100～the nanotube of 200nm and step 1) Graphene divide
Dissipating liquid, solid phase Graphene content 0.011%, the mixing liquid ultrasonic 0.5h of formation, then stirring 24h is formed
The slurry of toughness.
3) make composite be homogeneously dispersed in slurry and will be subsequently formed slurry to be laid in 0.2826cm2's
In groove, scalpel knife coating is used to scratch.
4) moisture content during 10h removes pole piece during pole piece is held on air, ultimately forms a kind of gluey film.Subsequently
Use 500 DEG C of sintering 1.5h sintering in Muffle furnace, form certain thickness film.
5) film of acquisition is soaked in 10-3The alcohol solution dipping 4h of mol/L N719 dyestuff forms dyestuff
The electrode complex light anode of sensitization.This technique does not affect the structure of material, does not easily cause caving in of material structure.
Embodiment 2:
1) use PEG400 as graphene dispersion agent, ultrasonic 6h, form the PEG400-stone of 1mg/ml
Ink alkene suspension.Design sketch is shown in accompanying drawing 1 of the present invention, before picture is respectively a) dispersion, b) after ultrasonic disperse, c)
Place 24h and d) place the PEG400-graphene solution of 7 days.
2) 0.01g PEG20000(solid masses ratio 10%) and 0.1ml deionized water (water is in a liquid
Volume ratio v/v23%), stirring and dissolving.It is then respectively adding the PEG400 dispersant as slurry, makes PEG
Toatl proportion in a liquid is 75%, the TiO of 0.1g size 10nm2Nano particle and step 1) Graphene
Dispersion liquid, makes solid phase Graphene content 0.025%, the mixing liquid ultrasonic 2h of formation, and then stirring 5h is formed
The slurry of toughness.
3) formation slurry is laid in 0.2826cm2Groove in, shelve and use scalpel knife coating after 20min
Scratch.
4) moisture content during 24h removes pole piece during pole piece is held on air, ultimately forms a kind of electrode film.?
Muffle furnace sinters 400 DEG C of sintering 1h.
5) film of acquisition is soaked in 10-4The acetonitrile solution of mol/L N719 dyestuff soaks 24h and forms dyestuff
The electrode complex light anode electrode of sensitization.Design sketch is shown in accompanying drawing 2 of the present invention, the composite light anode table of formation
Face is regular, thickness is uniform, without obvious crackle.
6) the complex light anode J-V performance curve prepared according to above-mentioned steps is tested.Design sketch is shown in that the present invention is attached
Fig. 3, the photoelectric transformation efficiency using composite light anode to be reached is 5.02%, and ratio is added without Graphene
Light anode improves 18.0%.
Embodiment 3:
1) use PEG200 as graphene dispersion agent, ultrasonic 24h, form the PEG200-of 10mg/ml
Graphene suspension.
2) 0.005g PEG20000(solid masses ratio 5%) and 0.1ml deionized water (water is in a liquid
Volume ratio v/v5%), stirring and dissolving.It is then respectively adding the PEG200 dispersant as slurry, makes PEG
Toatl proportion in a liquid is 50%, the TiO of 0.1g100～200nm2Nanotube and step 1) Graphene divide
Dissipating liquid, make solid phase Graphene content 0.039%, the mixing liquid ultrasonic 0.5h of formation, then stirring 6h is formed
The slurry of toughness.
3) make composite be homogeneously dispersed in slurry and will be subsequently formed slurry to be laid in 0.2826cm2Groove
In, use scalpel knife coating to scratch.
4) moisture content during 72h removes pole piece during pole piece is held on air, ultimately forms a kind of gluey film.Subsequently
Use 450 DEG C of sintering 1h sintering in Muffle furnace, use TiCl4After post processing, again sinter 30min, shape
Become certain thickness film.
5) film of acquisition is soaked in 10-5It is quick that the acetonitrile solution of mol/L N3 dyestuff soaks 72h formation dyestuff
The electrode complex light anode changed.
Claims (3)
1. the preparation method for the composite structure light anode of DSSC, it is characterized in that composite structure light anode uses titanium dioxide, Graphene or other conductive carbon material to be electrode material, using the high viscosity hydrophilic liquid polymer polyethylene glycol of PEG200～PEG800 as dispersant, using polyethylene glycol PEG20000 as the curing agent of electrode；Comprise the steps:
1) by Graphene ultrasonic 0.5h～24h in hydrophilic liquid polymer PEG200～PEG800 polyethylene glycol so that material is fully dispersed, the concentration forming graphene dispersing solution is 0.01mg/ml～10mg/ml；
2) the polyethylene glycol PEG20000 using molecular weight to be 20000 is as the curing agent of electrode, adds the water solvent as PEG20000, water volume ratio 5%～50% in a liquid, stirring and dissolving；Then press the amount removing step 1 of Graphene needed for electrode) in graphene dispersing solution；Solid phase Graphene content is 0.010%～0.040%, and liquid phase P EG20000 content is 5%～20%, is simultaneously introduced PEG200～the PEG800 dispersant as slurry, forms mixing liquid, and making PEG200～PEG800 toatl proportion in a liquid is 50%～95%；By a size of 10～the TiO of 200nm2Nano material is ultrasonic 0.5h～6h in above-mentioned mixing liquid, and then stirring 0.5h～24h forms the slurry of toughness, makes composite be scattered in slurry；
3) by step 2) obtain slurry and be coated on uniformly in conductive substrates；
4) it is held on 10h～72h removal moisture content in air by scraping the pole piece coated so that electrode material forms a kind of gluey film；Carry out electrode sintering, it is thus achieved that complex light anode film；
5) the complex light anode film of dye sensitization is formed after complex light anode film being soaked in dye solution immersion.
2. the method for claim 1, is characterized in that described step 3) in use knife coating, suspension method, silk screen print method or spraying process coating.
3. the method for claim 1, is characterized in that described step 4) electrode sintering, use and sinter under air atmosphere, or use sintering under protective atmosphere.
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| CN201410064105.3A CN103871748B (en) | 2014-02-25 | 2014-02-25 | A kind of composite light anode for dye-sensitized solar cell and preparation method |
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| CN103871748B true CN103871748B (en) | 2016-08-24 |
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| 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 |
| 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 |
Citations (3)
| 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 |
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| 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 |
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