CN102074374B - Doping dye sensitized solar cell photo anode, preparation method and application thereof - Google Patents

Doping dye sensitized solar cell photo anode, preparation method and application thereof Download PDF

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CN102074374B
CN102074374B CN 201110037120 CN201110037120A CN102074374B CN 102074374 B CN102074374 B CN 102074374B CN 201110037120 CN201110037120 CN 201110037120 CN 201110037120 A CN201110037120 A CN 201110037120A CN 102074374 B CN102074374 B CN 102074374B
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laminated film
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CN102074374A (en
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徐进章
牛海红
万磊
张守伟
刘玲
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Hefei University of Technology
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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
    • 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 doping dye sensitized solar cell photo anode, preparation method and application thereof, wherein the doping dye sensitized solar cell photo anode is divided into three layers in structure; the first layer is a common glass; the second layer is a SnO2 transparent conductive film doped with F; the third layer is a nanocrystalline porous composite film formed by doping the nano particle with mesoporous semiconductor at wide band with nanocrystalline semiconductor particles, wherein dyes are attached on the nanocrystalline porous composite film. The doping dye sensitized solar cell photo anode is used in doping dye sensitized solar cells. The doping dye sensitized solar cell photo anode of the invention can improve the photoelectric conversion performance of cells and increase the photoelectric conversion efficiency of solar cells well, and has the advantages of simple preparing technology, good repeatability and low cost; the doping dye sensitized solar cell photo anode not only can be used in dye sensitized solar cell materials, but also can be used in the fields of photocatalysis, gas sensitive material and the like.

Description

Dopant dye sensitization solar battery photoanode, its preparation method and application thereof
One, technical field
The present invention relates to a kind of mesoporous semiconductor doping nanocrystalline titanium dioxide photo anode, its preparation method and application thereof, the solar battery photoanode of dopant dye sensitization specifically, its preparation method and application thereof belong to technical field of solar batteries.
Two, background technology
Solar energy is a kind of inexhaustible, nexhaustible, cleaning renewable resource, has special advantages and huge development and use potentiality, is the following tool new forms of energy of development prospect.Sensu lato solar energy is the source of many energy on the earth, like potential energy of wind energy, chemical energy, water etc.The solar energy of narrow sense then is limited to photo-thermal, photoelectricity and photochemical direct conversion of solar radiation.Make full use of the coordinated development that solar energy helps keeping getting along amiably and peacefully of man and nature and energy and environment.
Solar cell is to one of approach of effective utilization of solar photoelectric utilization.At present; The application of solar cell gets into departments such as industry, commerce, agricultural, communication, household electrical appliance and public utility from military field, space industry; Especially can be dispersedly in the outlying district, high mountain, desert, island and rural area use, to save the very high transmission line of cost.In the long run; Invention along with the improvement of solar cell manufacturing technology and new light-electrical switching device; Various countries are to the protection of environment with to the great demand of regeneration clean energy resource; Solar cell will be to utilize the more practicable method of solar radiant energy, can be to utilize solar energy to open vast vistas on a large scale human future.
For the semiconductor p-n junction solar cell of traditional high cost of manufacture, by Institute of Technology (EP-FL) such as Lausanne, SUI height
Figure BDA0000046721740000011
Deng teach in 1991 on " nature " magazine the report with nanocrystalline TiO 2Film is novel solar cell-dye-sensitized solar cells (Dye-Sensitized Solar Cell on basis; Hereinafter to be referred as DSSC) be easy to get (semi-conducting material that thin-film material such as titanium dioxide is a kind of aboundresources, safety non-toxic, chemical property is stable) with its raw material, (be merely monocrystaline silicon solar cell 1/10) cheap for manufacturing cost, preparation technology's characteristic of simple become photovoltaic hot research fields and emphasis rapidly.People recognize that gradually DSSC has the large-scale application prospect, are new selections of solar cell at a low price.Research to it will help alleviating current energy crisis and environmental pollution problems, have very important reality and far-reaching significance, and then open up a brand-new road for the universalness of solar cell, civil nature.
Nano-crystalline titanium dioxide film plays important effect in the DSSC device: support and absorbing dye, as the carrier that transmits electronics.Parameters such as the specific area of nano-titanium dioxide film, aperture, voidage, thickness, crystal formation; Directly influence the adsorbance of dyestuff in the DSSC, the right effective transmission of OR electricity hull and the electrolyte of electronics from dyestuff excitation state to electro-conductive glass.Thereby the performance of nano thin-film also is the problem that the DSSC field can not be ignored to the excellent very crucial influence of the performance of DSSC to its research.At present; The research of nano thin-film is focused mostly on different condition in a certain preparation method to the cell photoelectric Effect on Performance; Or synthetic, seek new semiconductor/compound semiconductor materials, so that it is electrolytical compound with dyestuff to the light induced electron that the utilization and the minimizing of sunlight is injected into the semiconductor conduction to improve semiconductor optical anode.
Electrolytical compound with dyestuff to the light induced electron that the utilization and the minimizing of sunlight is injected into the semiconductor conduction band in order to improve semiconductor optical anode, reported method mainly contains methods such as surface chemical modification, compound other sulls of semiconductor and pattern design at present.But existent method can not reach gratifying degree on the complexity of technology and properties of product.
Three, summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point; The opto-electronic conversion performance that a kind of technology is simple, can more effectively improve battery is provided, improves dopant dye sensitization solar battery photoanode, its preparation method and the application thereof of the photoelectric conversion efficiency of solar cell.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of dopant dye sensitization solar battery photoanode of the present invention are: structurally be divided into three layers, ground floor wherein is a simple glass; The second layer is the SnO that mixes F 2Nesa coating; The 3rd layer of nanocrystalline porous laminated film that forms for the mesoporous semi-conductive nano-particle doped nano crystal semiconductor particle in broad stopband; On said nanocrystalline porous laminated film, be adsorbed with dyestuff.
The characteristics of dopant dye sensitization solar battery photoanode of the present invention also are: the mesoporous semi-conductive nano particle in said broad stopband is SiO 2Nano particle.
The characteristics of dopant dye sensitization solar battery photoanode of the present invention also are: said nano crystal semiconductor particle is TiO 2Nano particle.
The characteristics of dopant dye sensitization solar battery photoanode of the present invention also are: said nanocrystalline porous laminated film is SiO 2And TiO 2Laminated film.
The characteristics of dopant dye sensitization solar battery photoanode of the present invention also are: described dyestuff is the N719 dyestuff.
The preparation method's of dopant dye sensitization solar battery photoanode of the present invention characteristics are to carry out as follows:
A, preparation doping SiO 2TiO 2Slurry:
With particle size is the SiO of 2-50nm 2Powder and particle size are that the P25 powder of 15-50nm mixes, and add respectively that analytically pure acetic acid, deionized water, absolute ethyl alcohol, terpinol, ethyl cellulose grind, magnetic agitation, ultrasonic dispersion and rotary distillation, obtain the SiO that mixes 2TiO 2Slurry;
B, preparation doping SiO 2TiO 2Nanocrystalline porous laminated film:
Cover the SnO that mixes F in said surface of ordinary glass 2Nesa coating forms electro-conductive glass, and said electro-conductive glass is carried out TiCl 4After the preliminary treatment, the doping SiO that adopts silk screen printing that step a is made 2TiO 2Slurry is printed on the electro-conductive glass and leaves standstill, drying, repeat print, leave standstill and dry after carry out TiCl again through sintering 4Reprocessing; Sintering obtains the SiO that mixes once more subsequently 2TiO 2Nanocrystalline porous laminated film;
C, preparation doping SiO 2TiO 2Nanocrystalline complex light anode:
The doping SiO that will make through step b 2TiO 2Nanocrystalline porous laminated film put into and take out after Muffle furnace is warming up to design temperature, in the ethanol solution of N719 dyestuff, soak, take out the dyestuff of back with absolute ethyl alcohol flush away remained on surface, promptly get the SiO that mixes after drying up 2TiO 2Nanocrystalline complex light anode.
The preparation method's of dopant dye sensitization solar battery photoanode of the present invention characteristics also are preparation doping SiO among the said step a 2TiO 2The process of slurry is:
Get P25 powder 5g, with SiO 2With TiO 2Mix said SiO 2Quality be TiO 2The 2.5-15% of quality; Add 1-2mL acetic acid successively respectively, divide 5 times with each 1mL and add the 5ml deionized water altogether, divide 15 times with each 1mL and add the 15mL absolute ethyl alcohol altogether; Divide with each 2.5mL to add 15mL absolute ethyl alcohol altogether for 6 times, whenever added liquid agitation 3 minutes; Add the 100mL absolute ethyl alcohol again and get slurry; With said slurry magnetic agitation 10 minutes, mixing speed was 200-400 rev/min; Again through ultrasonic dispersion 60 minutes; Add the 20g terpinol subsequently, repeat magnetic agitation and ultrasonic dispersion; Add 3g ethyl cellulose and 30g absolute ethyl alcohol again and repeat magnetic agitation and ultrasonic dispersion; Last in Rotary Evaporators 30-70 ℃ of slurry that obtained can be used for silk screen printing in following rotary distillation 2-8 hour.
The preparation method's of dopant dye sensitization solar battery photoanode of the present invention characteristics also are preparation doping SiO among the said step b 2TiO 2The process of nanocrystalline porous laminated film be:
It is that 20-300mM, temperature are 70 ℃ TiCl that electro-conductive glass is placed concentration 4Submergence was handled 30 minutes in the aqueous solution, took out the TiCl with deionized water flush away conductive glass surface 4The aqueous solution dries up for use; Adopt silk screen printing, the doping SiO that step a is made with 100-400 purpose silk screen 2TiO 2Slurry is printed on the electro-conductive glass, leaves standstill 3 minutes, and 125 ℃ of dried 8 minutes are repeated print, left standstill and dry according to the thickness of desired nanocrystalline porous laminated film; Naturally cool to room temperature after at least 15 minutes with 500 ℃ of sintering then, placing concentration again is that 20-300 mM, temperature are 70 ℃ TiCl 4Submergence was handled after 30 minutes in the aqueous solution, took out the TiCl with deionized water flush away conductive glass surface 4The aqueous solution dries up and is placed in the Muffle furnace with 500 ℃ of sintering at least 15 minutes, obtains the SiO that mixes 2TiO 2Nanocrystalline porous laminated film.
The preparation method's of dopant dye sensitization solar battery photoanode of the present invention characteristics also are preparation doping SiO among the said step c 2TiO 2The process of nanocrystalline complex light anode be:
The doping SiO that step b is prepared gained 2TiO 2Nanocrystalline porous laminated film place Muffle furnace with 500 ℃ of sintering 30 minutes; Take out when cooling to 70-150 ℃ then; The ethanol solution of putting into concentration immediately and be the N719 dyestuff of 10-70mM soaked 10-30 hour; Take out the dyestuff of back, dry up and promptly obtain the SiO that mixes with absolute ethyl alcohol flush away remained on surface 2TiO 2Nanocrystalline complex light anode.
The characteristics of the purposes of dopant dye sensitization solar battery photoanode of the present invention are in dye-sensitized solar cells, to use.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the present invention uses that the photo-anode film of mesoporous silicon oxide dopen Nano crystal titanium dioxide semiconductor fabrication contacts with electro-conductive glass well, face is smooth; Solved the problem that nano-porous film is peeled off easily; Through changing the mesoporous semi-conductive doping in broad stopband, realize photoelectron effectively being transmitted in the titanium dioxide grid to effectively control such as titania nanoparticles size, specific surface area size and voidage; Obviously suppress the generation of dark current; Significantly improve current density, the Fermi level of titanium dioxide is improved, open circuit voltage has part to promote; Can well improve the opto-electronic conversion performance of battery, improve the photoelectric conversion efficiency of solar cell.
2, preparation technology of the present invention is simple, and repeatability is good, and is with low cost, not only can be applied to the DSSC material, and use in field such as photocatalysis, gas sensitive material again.
Four, description of drawings
Fig. 1 is the SiO of variable concentrations 2/ TiO 2The XRD figure of slurry.
Fig. 2 is the TEM figure of the nanocrystalline porous laminated film of embodiment 3 preparations.
Fig. 3 is the HR-TEM figure of the nanocrystalline porous laminated film of embodiment 3 preparations.
Fig. 4 is the surperficial FESEM figure of the nanocrystalline porous laminated film (four layers) of the present invention's preparation, SiO 2Addition be TiO 27.5% of quality.
Fig. 5 is the section FESEM figure of the nanocrystalline porous laminated film (four layers) of the present invention's preparation, SiO 2Addition be TiO 27.5% of quality.
The I-V figure of the DSSC (Cell 3) that the nanocrystalline porous complex light anode that Fig. 6 prepares for the present invention is assembled into.
Five, embodiment
Embodiment 1:
A, preparation doping SiO 2TiO 2Slurry:
Get P25 powder 5g, with SiO 2With TiO 2Mix SiO 2Quality be TiO 22.5% of quality adds 1mL acetic acid successively respectively, divides 5 times with each 1mL and adds the 5ml deionized water altogether, divides 15 times with each 1mL and adds the 15mL absolute ethyl alcohol altogether, divides with each 2.5mL to add 15mL absolute ethyl alcohol altogether for 6 times, whenever adds liquid agitation 3 minutes; Add the 100mL absolute ethyl alcohol again and get slurry; With said slurry magnetic agitation 10 minutes, mixing speed was 300 rev/mins; Again through ultrasonic dispersion 60 minutes; Add the 20g terpinol subsequently, repeat magnetic agitation and ultrasonic dispersion; Add 3g ethyl cellulose and 30g absolute ethyl alcohol again and repeat magnetic agitation and ultrasonic dispersion; Last in Rotary Evaporators 40 ℃ of following rotary distillations obtained can be used for the slurry of silk screen printing in 6 hours, be designated as slurry B.
B, preparation doping SiO 2TiO 2Nanocrystalline porous laminated film:
The FTO electro-conductive glass was used liquid detergent, alcohol, acetone ultrasonic cleaning 20 minutes successively, rinse well, dry up, place aqueous isopropanol to soak 5 days with deionized water.
Clean conductive glass is taken out, dry up.Being placed on concentration is that 100mM, temperature are 70 ℃ TiCl 4Submergence was handled 30 minutes in the aqueous solution, took out the TiCl with deionized water flush away conductive glass surface 4The aqueous solution dries up for use; Adopt screen printing technique, slurry B is printed on the electro-conductive glass, left standstill 3 minutes, 125 ℃ of dried 8 minutes with 200 purpose silk screens.Repeat print, leave standstill, dry step 4 time; Then 150 ℃ 10 minutes; 325 ℃ 5 minutes, 375 ℃ 5 minutes, 450 ℃ 15 minutes, 500 ℃ naturally cooled to room temperature after 30 minutes, placing concentration again is that 125mM, temperature are 70 ℃ TiCl 4Submergence was handled after 30 minutes in the aqueous solution, took out the TiCl with deionized water flush away conductive glass surface 4The aqueous solution, dry up be placed in the Muffle furnace 150 ℃ 10 minutes; 325 ℃ 5 minutes, 375 ℃ 5 minutes, 450 ℃ 15 minutes, 500 ℃ 30 minutes, the mass ratio that obtains mixing is 2.5% SiO 2With TiO 2Nanocrystalline porous laminated film.
C, preparation doping SiO 2TiO 2Nanocrystalline complex light anode:
With SiO 2With TiO 2Nanocrystalline porous laminated film naturally cool to about 120 ℃ and to take out, the ethanol solution of putting into 50mM N719 immediately soaks 30h.Take out the dyestuff of back with absolute ethyl alcohol flush away remained on surface, dry up, promptly get nanocrystalline complex light anode, it is to be packaged to keep in Dark Place.
Embodiment 2:
The preparation method of present embodiment is with embodiment 1, and that different is SiO 2Addition be TiO 25% of quality, the slurry that can be used for silk screen printing that obtains among the step a is designated as slurry C.
Embodiment 3:
The preparation method of present embodiment is with embodiment 1, and that different is SiO 2Addition be TiO 27.5% of quality, the slurry that can be used for silk screen printing that obtains among the step a is designated as slurry D.
Surface and section to this laminated film carry out four layers of SiO of printing that scanning electron microscopy (FE-SEM) analysis obtains 2/ TiO 2Slurry, the thickness behind the sintering are about 17.9 μ m.By Fig. 4,5 can know that laminated film shows that smooth, nano particle is evenly distributed, and form network-like structure connected to one another, (are TiO at bigger particle 2) around be distributed with smaller (for SiO 2) particle, this granule has not only increased TiO 2Effective connection between the particle also makes TiO simultaneously 2More firm with combining between the electro-conductive glass.
Embodiment 4:
The preparation method of present embodiment is with embodiment 1, and that different is SiO 2Addition be TiO 210% of quality, the slurry that can be used for silk screen printing that obtains among the step a is designated as slurry E.
Embodiment 5:
The preparation method of present embodiment is with embodiment 1, and that different is SiO 2Addition be TiO 212.5% of quality, the slurry that can be used for silk screen printing that obtains among the step a is designated as slurry F.
Embodiment 6:
The preparation method of present embodiment is with embodiment 1, and that different is SiO 2Addition be TiO 215% of quality, the slurry that can be used for silk screen printing that obtains among the step a is designated as slurry G.
Embodiment 7:
The preparation method of present embodiment is with embodiment 1, and different is not add SiO 2, the slurry that can be used for silk screen printing that obtains among the step a is designated as slurry A.
With slurry A-G successively in 150 ℃ 10 minutes, 325 ℃ 5 minutes, 375 ℃ 5 minutes, 450 ℃ 15 minutes, 500 ℃ were carried out sintering in 30 minutes, the powder that obtains carries out XRD, BJH and BET respectively and analyzes.The XRD analysis of Fig. 1 shows and contains SiO 2For the 2.5-15% slurry all is anatase structured, SiO 2Adding do not change TiO 2Crystalline phase, only reduced TiO 2Crystallite dimension.The TiO that this and scanning electron microscopy (FE-SEM) analysis obtain 2It is consistent that the diameter of particle is about 15-40nm; Slurry D is analyzed on scanning projection electron microscope (TEM), and by Fig. 2,3 can know at the reasonable anatase TiO of crystallization 2Particle around be attached with cotton-shaped SiO 2Particle, this makes light induced electron effectively in the titanium dioxide grid, to transmit, and obviously suppresses the generation of dark current, significantly improves current density, has improved the efficient of battery on the very big then degree.
With the dopant dye sensitization solar battery photoanode encapsulation preparation dye-sensitized solar cells of embodiment 1-7 preparation, concrete steps are following:
Cleaned up on the FTO electro-conductive glass after drying up printing one deck platinum slurry beating an aperture in advance, 410 ℃ of sintering 30 minutes in Muffle furnace, the hole that obtains and be printed with platinum is to electrode.The doping SiO that respectively embodiment 1-7 is prepared 2SiO 2/ TiO 2Nanocrystalline complex light anode is folded to electrode pair with the hole that is printed with platinum, inserts the thick three-back-shaped heat-sealing film of 60 μ m between two electrodes, and with 130 ℃ of packaging by hot pressing of heat sealing machine, hot pressing time is 20 seconds.Priming by vacuum electrolyte 1 (0.6M MPII, 0.1M I 2, 0.5MTBP, the 3-methoxypropionitrile solution of 0.1M LiI is as electrolyte), reusable heat envelope film and slide are sealed aperture, are assembled into battery, obtain SiO 2Addition is respectively 0%, 2.5%, and 5%, 7.5%, 10%, 12.5%, 15% dye-sensitized solar cells is designated as Cell 0 respectively, and Cell 1, and Cell 2, Cell3, Cell 4, and Cell 5, and Cell 6.
Dopant dye sensitization solar battery photoanode encapsulation preparation dye-sensitized solar cells with embodiment 3 preparations repeats above-mentioned encapsulation step, and electrolyte 1 is changed to electrolyte 2 (0.6M MPII, 0.1M I 2, 0.5M TBP, the acetonitrile solution of 0.1M LiI is as electrolyte) and the dye-sensitized solar cells that obtains, be designated as Cell 10.
Dopant dye sensitization solar battery photoanode encapsulation preparation dye-sensitized solar cells with embodiment 3 preparations repeats above-mentioned encapsulation step, and electrolyte 1 is changed to electrolyte 3 (0.60M BMII, 0.03M I 2, 0.10M guanidine thiocyanate, the V of 0.50M TBP Second is fine: V Valeronitrile=85: 15 solution is as electrolyte) dye-sensitized solar cells that obtains, be designated as Cell 11.
(the simulated light exposure intensity is 100W/m for the xenon lamp of light source 500W, AM=1.5 to adopt Keithley2400 digital source table and solar simulator 2) the I-V indicatrix of the different battery Cell1-11 that obtain of test, can obtain the open circuit voltage V of battery thus Oc, short-circuit current density J Sc, fill factor, curve factor FF, energy conversion efficiency η, its result sees table 2-4.
Table 1 shows that along with the increase of doping, open circuit voltage and fill factor, curve factor do not have obvious variation, and short-circuit current density reaches very big variation is arranged, and has directly caused the significant change of battery efficiency.When doping was 7.5%, short-circuit current density reached maximum 21.143mAcm -2, photoelectric conversion efficiency 8.4254.Table 2 shows that along with increasing of the printing number of plies, the open circuit voltage and the fill factor, curve factor of battery slightly descend, but current density but has very big lifting, has caused the lifting of battery efficiency.Table 3 shows, when using acetonitrile to replace the 3-methoxypropionitrile as the electrolyte of solvent as the electrolyte of solvent, the open circuit voltage variations of battery is little, and current density, fill factor, curve factor, battery efficiency increase.In electrolyte, remove LiI, add the thiocyanic acid guanidinesalt after, open circuit voltage obviously increases, short circuit current changes not quite with fill factor, curve factor, but battery efficiency increases with the increase of open circuit voltage.
Simple glass is meant Na among the embodiment 2SiO 3, CaSiO 3, SiO 2Or Na 2OCaO6SiO 2The N719 dyestuff is the ethanol solution that cis-two (different thiocyanate)-two (4-carboxylic acid, 4 '-carboxylic acid TBuA bipyridine) is closed ruthenium (II).
Table 1 uses the mesoporous silicon oxide dopen Nano crystal titanium dioxide semiconductor fabrication bright dipping composite thin film anode of different quality ratio, uses electrolyte 1 to be assembled into the photoelectric properties contrast of dye-sensitized cell
Figure BDA0000046721740000071
Table 2 mass ratio is that 7.5% mesoporous silicon oxide dopen Nano crystal titanium dioxide semiconductor different layers numeral system is equipped with the bright dipping composite thin film anode, is assembled into the photoelectric properties contrast of dye-sensitized cell
Cell 7 (1 layer) 0.817611 5.6 0.682359253 3.124264816
Cell 8 (2 layers) 0.7821538 11.44 0.627879615 5.618166
Cell 9 (3 layers) 0.7437143 14.24 0.592863665 6.27871768
Cell 3 (4 layers) 0.71789 21.143 0.55509 8.4254
Table 3 mass ratio is 7.5% mesoporous silicon oxide dopen Nano crystal titanium dioxide semiconductor (3 layers) preparation bright dipping composite thin film anode, uses different electrolyte to be assembled into the photoelectric properties contrast of dye-sensitized cell
Cell 9 (electrolyte 1) 0.7437143 14.24 0.592863665 6.27871768
Cell10 (electrolyte 2) 0.739117 16 0.602158758 7.1210524
Cell 11 (electrolyte 3) 0.8091938 14.32 0.608631046 7.05260672

Claims (4)

1. dopant dye sensitization solar battery photoanode, it is characterized in that: structurally be divided into three layers, ground floor wherein is a simple glass; The second layer is the SnO that mixes F 2Nesa coating; The 3rd layer of nanocrystalline porous laminated film that forms for the mesoporous semi-conductive nano-particle doped nano crystal semiconductor particle in broad stopband; On said nanocrystalline porous laminated film, be adsorbed with dyestuff;
The mesoporous semi-conductive nano particle in said broad stopband is SiO 2Nano particle;
Said nano crystal semiconductor particle is TiO 2Nano particle;
Said nanocrystalline porous laminated film is SiO 2And TiO 2Laminated film;
Said SiO 2Quality be TiO 2The 2.5-15% of quality;
Described dyestuff is the N719 dyestuff.
2. preparation method who prepares the said dopant dye sensitization of claim 1 solar battery photoanode is characterized in that carrying out as follows:
A, preparation doping SiO 2TiO 2Slurry:
Getting P25 powder 5g, is the SiO of 2-50nm with particle size 2With particle size be the TiO of 15-50nm 2Mix said SiO 2Quality be TiO 2The 2.5-15% of quality; Add 1-2mL acetic acid successively respectively, divide 5 times with each 1mL and add the 5ml deionized water altogether, divide 15 times with each 1mL and add the 15mL absolute ethyl alcohol altogether; Divide with each 2.5mL to add 15mL absolute ethyl alcohol altogether for 6 times, whenever added liquid agitation 3 minutes; Add the 100mL absolute ethyl alcohol again and get slurry; With said slurry magnetic agitation 10 minutes, mixing speed was 200-400 rev/min; Again through ultrasonic dispersion 60 minutes; Add the 20g terpinol subsequently, repeat magnetic agitation and ultrasonic dispersion; Add 3g ethyl cellulose and 30g absolute ethyl alcohol again and repeat magnetic agitation and ultrasonic dispersion; Last in Rotary Evaporators 30-70 ℃ of doping SiO that obtained can be used for silk screen printing in following rotary distillation 2-8 hour 2TiO 2Slurry;
B, preparation doping SiO 2TiO 2Nanocrystalline porous laminated film:
Cover the SnO that mixes F in said surface of ordinary glass 2Nesa coating forms electro-conductive glass, and said electro-conductive glass is carried out TiCl 4After the preliminary treatment, the doping SiO that adopts silk screen printing that step a is made 2TiO 2Slurry is printed on the electro-conductive glass and leaves standstill, drying, repeat print, leave standstill and dry after carry out TiCl again through sintering 4Reprocessing; Sintering obtains the SiO that mixes once more subsequently 2TiO 2Nanocrystalline porous laminated film;
C, preparation doping SiO 2TiO 2Nanocrystalline complex light anode:
The doping SiO that will make through step b 2TiO 2Nanocrystalline porous laminated film put into and take out after Muffle furnace is warming up to design temperature, in the ethanol solution of N719 dyestuff, soak, take out the dyestuff of back with absolute ethyl alcohol flush away remained on surface, promptly get the SiO that mixes after drying up 2TiO 2Nanocrystalline complex light anode.
3. preparation method according to claim 2 is characterized in that preparation doping SiO among the said step b 2TiO 2The process of nanocrystalline porous laminated film be:
It is that 20-300mM, temperature are 70 ℃ TiCl that electro-conductive glass is placed concentration 4Submergence was handled 30 minutes in the aqueous solution, took out the TiCl with deionized water flush away conductive glass surface 4The aqueous solution dries up for use; Adopt silk screen printing, the doping SiO that step a is made with 100-400 purpose silk screen 2TiO 2Slurry is printed on the electro-conductive glass, leaves standstill 3 minutes, and 125 ℃ of dried 8 minutes are repeated print, left standstill and dry according to the thickness of desired nanocrystalline porous laminated film; Naturally cool to room temperature after at least 15 minutes with 500 ℃ of sintering then, placing concentration again is that 20-300 mM, temperature are 70 ℃ TiCl 4Submergence was handled after 30 minutes in the aqueous solution, took out the TiCl with deionized water flush away conductive glass surface 4The aqueous solution dries up and is placed in the Muffle furnace with 500 ℃ of sintering at least 15 minutes, obtains the SiO that mixes 2TiO 2Nanocrystalline porous laminated film.
4. preparation method according to claim 2 is characterized in that preparation doping SiO among the said step c 2TiO 2The process of nanocrystalline complex light anode be:
The doping SiO that step b is prepared gained 2TiO 2Nanocrystalline porous laminated film place Muffle furnace with 500 ℃ of sintering 30 minutes; Take out when cooling to 70-150 ℃ then; The ethanol solution of putting into concentration immediately and be the N719 dyestuff of 10-70mM soaked 10-30 hour; Take out the dyestuff of back, dry up and promptly obtain the SiO that mixes with absolute ethyl alcohol flush away remained on surface 2TiO 2Nanocrystalline complex light anode.
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