CN101894674B - Composite light anode for dye-sensitized solar cell and preparation method thereof - Google Patents
Composite light anode for dye-sensitized solar cell and preparation method thereof Download PDFInfo
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- CN101894674B CN101894674B CN 201010191326 CN201010191326A CN101894674B CN 101894674 B CN101894674 B CN 101894674B CN 201010191326 CN201010191326 CN 201010191326 CN 201010191326 A CN201010191326 A CN 201010191326A CN 101894674 B CN101894674 B CN 101894674B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a composite light anode for a dye-sensitized solar cell and a preparation method thereof. The composite light anode consists of common glass, an F-doped SnO2 transparent conductive film, a TiO2 compact film and a TiO2 nanoparticle/TiO2 nanowire composite film. The preparation method comprises the following steps of: preparing the compact TiO2 film with thickness of about 10 to 15nm on an FTO conductive glass substrate by magnetron sputtering technology; preparing TiO2 nanowires by hydrothermal synthesis technology; preparing the TiO2 nanoparticle/TiO2 nanowire composite film by a sol-gel method; and preparing the TiO2 nanoparticle/TiO2 nanowire composite light anode. The composite light anode has the advantages of improving the adsorption capacity of a photosensitive dye, ensuring that an electrode has high light capturing efficiency, improving the generation rate and transportation capability of a photon-generated carrier, and reducing the compounding process of the photon-generated carrier so as to improve the photoelectric conversion efficiency of the dye-sensitized solar cell.
Description
Technical field
The present invention relates to the development and utilization of new forms of energy, be specifically related to a kind of composite light anode for dye-sensitized solar cell and preparation method thereof.
Background technology
Got into since 20th century, in the process of economic development, be accompanied by huge energy-consuming, mineral resources such as coal, oil, natural gas are exhausted, and the energy crisis and the environmental pollution that cause have thus become the key issue that needs to be resolved hurrily.The method of head it off is the conventional industries energy-saving and emission-reduction on the one hand, is the reproducible clean energy resource of exploitation on the other hand.With the solar-photovoltaic technology is that the solar energy utilization of supporting brings revolutionary variation for human energy consumption structure.The main product of current solar cell is a silica-based solar cell, yet the electronics industry development has but aggravated the raw material supply anxiety of photovoltaic industry, and China's solar battery grade crystalline silicon production capacity is very low, restricts the bottleneck of China's photovoltaic industry development especially.Simultaneously, the silica-based solar cell cost approximately is 5～8 times of coal electricity cost, in order to compete mutually with traditional energy economically, also need increase substantially the efficient/cost ratio of solar cell, and this develops the task of third generation solar cell just.Compare with traditional silica-based solar cell; Dye-sensitized solar cells (Dye-Sensitized Solar Cell, be called for short DSSC) has cheap cost, rich in natural resources, stable performance, production process is simple, nontoxic, pollution-free and advantage such as suitable large-scale production.Relative other solar cells of DSSC have huge price advantage simultaneously, and according to estimates, the cost of DSSC is merely 1/5～1/10 of silicon solar cell, and DSSC will become a kind of competitive commercially produced product.
Dye-sensitized solar cells is a kind of photoelectrochemical solar cell, and it mainly constitutes by nano crystal semiconductor optical anode, dye sensitizing agent, electrolyte with to electrode four parts.Wherein the light anode is the core component of DSSC battery, and its structure and composition affect the photovoltaic performance, particularly conversion efficiency of battery strongly.The light anode of traditional DSSC generally adopts nano-TiO
2Porous membrane, TiO
2Though porous membrane is absorbing dye fully; But there are a large amount of crystal boundaries; Cause light induced electron in transmission course, to receive the influence that discharges with heat of capturing of particle surface defect state energy level; Make electron diffusion coefficient little, recombination rate increases, and has restricted the raising of DSSC photoelectric conversion efficiency.
Summary of the invention
The present invention provides a kind of composite light anode for dye-sensitized solar cell and preparation method thereof.
A kind of composite light anode for dye-sensitized solar cell provided by the invention, its structure by simple glass, mix the SnO of F
2Nesa coating (FTO), TiO
2Dense film and TiO
2Nano particle/TiO
2The nano wire laminated film is formed; The 1st layer is simple glass, and the 2nd layer for mixing the SnO of F
2Nesa coating (FTO), the 3rd layer is TiO
2Dense film, the 4th layer is TiO
2Nano particle/TiO
2The nano wire laminated film.
The preparation method of composite light anode for dye-sensitized solar cell provided by the invention, its preparation method may further comprise the steps:
1) adopt magnetron sputtering technique mixing the SnO of F
2Preparation one layer thickness is the TiO of 10～15nm on the nesa coating
2Dense film;
2) adopt the hydro-thermal synthetic technology to prepare TiO
2Nano wire;
3) adopt sol-gel technology preparing TiO
2Colloidal sol is TiO
2Nano wire adds in the colloidal sol, electromagnetic agitation, and ultrasonic dispersion forms the gel slurry;
4) adopt dip-coating method the gel slurry at fine and close TiO
2Form TiO on the film
2Nano particle/TiO
2The nano wire laminated film;
5) the TiO for preparing
2Nano particle/TiO
2The nano wire laminated film is put into the Muffle furnace sintering, and [structural formula is (n-2Bu at ruthenium complex N719 dyestuff then
4N)
2-cis-Ru (L
1)
2(NCS)
2] ethanol solution in soak 24h, take out the dyestuff of back flush away remained on surface, dry, just obtain composite light anode for dye-sensitized solar cell.
Above-mentioned steps 1) adopts magnetically controlled DC sputtering technology preparation TiO in
2The preparation process condition of dense film is: back of the body end vacuum 5 * 10
-4Pa, operating air pressure 2.5Pa, sputtering power are 100W, Ar and O
2Flow-rate ratio 5: 1, sputtering time 8～10min.
Above-mentioned steps 2) the hydro-thermal synthetic technology prepares TiO in
2The method of nano wire is: with 1g TiO
2Nano-powder and concentration behind the electromagnetic agitation 15min, obtain white suspension-turbid liquid after being the 30mL NaOH aqueous solution of 10mol/L, move in the autoclave that is put into 100mL, are put into 180 ℃ of insulation 24h in the insulating box to agitated reactor then; Reaction naturally cools to room temperature after finishing, and white depositions is cleaned with deionized water repeatedly; HCl pickling to pH value with 0.5mol/L equals 7 again, and then ultrasonic dispersion, at last with product 80 ℃ of oven dry; Through 450 ℃ of heat treatment 30min, the gained powder is TiO again
2Nano wire.
Above-mentioned steps 3) and 4) in TiO
2Nano particle/TiO
2The preparation method of nano wire laminated film: be that 1: 5: 13 mixed is made into A solution 89mL by volume with diethanol amine, Butyl Phthalate and absolute ethyl alcohol at first, magnetic agitation 2h is mixed into B solution 11mL with absolute ethyl alcohol and deionized water by 1: 10 volume ratio; Slowly splash into B solution in the A solution then; And use magnetic stirrer 30min, and then to add the 1g molecular weight be 2000 polyethylene glycol, magnetic agitation 30min;, stablized, even, faint yellow transparent colloidal sol; 12gTiO
2Nano wire adds in the colloidal sol, electromagnetic agitation 15min, and ultrasonic then dispersion 15min obtains the gel slurry; Being coated with TiO
2The FTO glass of dense film adopts dip-coating method to prepare laminated film as matrix, and wet film is repeating to lift behind 120 ℃ of dry 10min about 18 times, until reaching required thickness 10～12 μ m.
Above-mentioned steps 5) in the TiO for preparing
2Nano particle/TiO
2The nano wire laminated film is put into 450 ℃ of sintering 30min of Muffle furnace, cools to then about 80 ℃ to take out, and puts into 5.0 * 10 immediately
-4Soak 24h in the ruthenium complex N719 dyestuff ethanol solution of mol/L.Take out the dyestuff of back, dry, obtain complex light anode with ethanol flush away remained on surface.
The invention has the beneficial effects as follows:
Preparation TiO
2Nano particle/TiO
2The nano wire laminated film is as the light anode of DSSC, TiO
2The same TiO of the advantage of light utilization efficiency that nano wire is higher and good electron transfer characteristic
2Nano particle has the advantages of bigger specific area; Optimized the micro-structural of light anode; Complex light anode has not only improved the light-sensitive coloring agent adsorbance, has ensured that electrode has higher light capture rate, and has improved the generation rate and the transport capability of photo-generated carrier; Reduce the recombination process of photo-generated carrier, thereby improve the electricity conversion of DSSC.
Description of drawings
Fig. 1 is the structural representation of composite light anode for dye-sensitized solar cell.
Fig. 2 is the surface topography map of nano particle/nano wire laminated film.
In Fig. 1, the 1st layer is simple glass, and the 2nd layer for mixing the SnO of F
2Nesa coating (FTO), the 3rd layer is TiO
2Dense film, the 4th layer is TiO
2Nano particle/TiO
2The nano wire laminated film.
Fig. 2 is 100mL TiO
2Add 12g TiO in the colloidal sol
2The TiO of nano wire preparation
2Nano particle/TiO
2The scanning electron microscope diagram of nano wire laminated film can find out that nano wire forms network-like structure connected to one another.
Embodiment
1. adopt magnetron sputtering technique on FTO transparent conducting glass film, to prepare the fine and close TiO of one deck
2Film
Back of the body end vacuum 5 * 10
-4Pa, sputtering pressure 2.5Pa, Ar and O
2Flow-rate ratio 5: 1, sputtering power is 80W, sputtering time 8min, underlayer temperature are room temperature, TiO
2Thickness 10～the 15nm of dense film.
2. the hydro-thermal synthetic technology prepares TiO
2Nano wire
With 1g TiO
2Nano-powder and concentration behind the electromagnetic agitation 15min, obtain white suspension-turbid liquid after being the 30mL NaOH aqueous solution of 10mol/L, move in the autoclave that is put into 100mL, are put into 180 ℃ of insulation 24h in the insulating box to agitated reactor then.Reaction naturally cools to room temperature after finishing, and white depositions is cleaned with deionized water repeatedly; HCl pickling to pH value with 0.5mol/L equals 7 again, and then ultrasonic dispersion, at last with product 80 ℃ of oven dry; Through 450 ℃ of heat treatment 30min, the gained powder is TiO again
2Nano wire.XRD analysis shows this TiO
2Nano wire is anatase structured.Scanning electron microscope analysis obtains TiO
2About 50～the 200nm of nanowire diameter is about 4 μ m, has bigger draw ratio.
3. sol-gel process prepares TiO
2Nano particle/TiO
2The nano wire laminated film
At first diethanol amine, Butyl Phthalate and absolute ethyl alcohol are made into A solution by 1: 5: 13 mixed, magnetic agitation 2h becomes B solution with absolute ethyl alcohol and deionized water by 1: 10 mixed; Slowly splash into B solution in the A solution then; And use magnetic stirrer 30min, and then add 1g polyethylene glycol (molecular weight 2000), magnetic agitation 30min;, stablized, even, faint yellow transparent colloidal sol.Respectively 3,6,9 and 12g TiO
2Nano wire adds in the colloidal sol, electromagnetic agitation 15min, ultrasonic then dispersion 15min.Adopt and be coated with TiO
2The FTO glass of dense film is made matrix, adopts dip-coating method to prepare laminated film, and wet film repeats to lift behind 120 ℃ of dry 10min, until reaching required thickness 10～12 μ m.Film thickness is used Dektak
3The test of st step appearance.(SEM) observes laminated film smooth surface, TiO with electronic scanner microscope
2Nano wire is evenly distributed, and forms network-like structure connected to one another, along with TiO
2The increase of nano wire addition, network structure are more and more finer and close.
4.TiO
2Nano particle/TiO
2The assembling of nano wire complex light anode and battery
The TiO for preparing
2Nano particle/TiO
2The nano wire laminated film is put into 450 ℃ of sintering 30min of Muffle furnace, cools to then about 80 ℃ to take out, and puts into 5.0 * 10 immediately
-4Soak 24h in the mol/L N719 ethanol solution.Taking out the dyestuff of back with ethanol flush away remained on surface, dry, is exactly prepared composite light anode, keeps in Dark Place.Then with the FTO glass that is coated with the Pt film to electrode, KI/I
2Solution be electrolyte [0.5mol/L KI+0.05mol/L I
2Solvent: acetonitrile (volume integral 80)+isopropyl alcohol (volume fraction 20)], be assembled into battery.
5.TiO
2Nano particle/TiO
2The performance of nano wire complex light anode dye-sensitized cell
(optical power density is 100mW/cm for the xenon lamp of light source 500W, AM-1.5 to adopt Keithley2400 digital source table and solar simulator
2) the I-V characteristic curve of the different batteries 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 one.
The photoelectric properties of the dye-sensitized cell of the complex light anode assembling of table one heterogeneity ratio
Claims (1)
1. the preparation method of a composite light anode for dye-sensitized solar cell is characterized in that its preparation method may further comprise the steps:
1) adopt magnetron sputtering technique mixing the SnO of F
2Preparation one layer thickness is the TiO of 10～15nm on the nesa coating
2Dense film;
2) adopt the hydro-thermal synthetic technology to prepare TiO
2Nano wire;
3) adopt sol-gel technology preparing TiO
2Colloidal sol is TiO
2Nano wire adds in the colloidal sol, electromagnetic agitation, and ultrasonic dispersion forms the gel slurry;
4) adopt dip-coating method the gel slurry at fine and close TiO
2Form TiO on the film
2Nano particle/TiO
2The nano wire laminated film;
5) the TiO for preparing
2Nano particle/TiO
2The nano wire laminated film is put into the Muffle furnace sintering, in the ethanol solution of ruthenium complex N719 dyestuff, soaks 24h then, takes out the dyestuff of back flush away remained on surface, dries, and just obtains composite light anode for dye-sensitized solar cell;
Above-mentioned steps 1) adopts magnetically controlled DC sputtering technology preparation TiO in
2The preparation process condition of dense film is: back of the body end vacuum 5 * 10
-4Pa, operating air pressure 2.5Pa, sputtering power are 100W, Ar and O
2Flow-rate ratio 5: 1, sputtering time 8～10min;
Above-mentioned steps 2) the hydro-thermal synthetic technology prepares TiO in
2The method of nano wire is: with 1g TiO
2Nano-powder and concentration behind the electromagnetic agitation 15min, obtain white suspension-turbid liquid after being the 30mL NaOH aqueous solution of 10mol/L, move in the autoclave that is put into 100mL, are put into 180 ℃ of insulation 24h in the insulating box to agitated reactor then; Reaction naturally cools to room temperature after finishing, and white depositions is cleaned with deionized water repeatedly; HCl pickling to pH value with 0.5mol/L equals 7 again, and then ultrasonic dispersion, at last with product 80 ℃ of oven dry; Through 450 ℃ of heat treatment 30min, the gained powder is TiO again
2Nano wire;
Above-mentioned steps 3) and 4) in TiO
2Nano particle/TiO
2The preparation method of nano wire laminated film: be that 1: 5: 13 mixed is made into A solution 89mL by volume with diethanol amine, Butyl Phthalate and absolute ethyl alcohol at first, magnetic agitation 2h is mixed into B solution 11mL with absolute ethyl alcohol and deionized water by 1: 10 volume ratio; Slowly splash into B solution in the A solution then; And use magnetic stirrer 30min, and then to add the 1g molecular weight be 2000 polyethylene glycol, magnetic agitation 30min;, stablized, even, faint yellow transparent colloidal sol; 12gTiO
2Nano wire adds in the colloidal sol, electromagnetic agitation 15min, and ultrasonic then dispersion 15min obtains the gel slurry; Being coated with TiO
2The FTO glass of dense film adopts dip-coating method to prepare laminated film as matrix, and wet film repeats to lift 18 times behind 120 ℃ of dry 10min, until reaching required thickness 10～12 μ m;
Above-mentioned steps 5) in the TiO for preparing
2Nano particle/TiO
2The nano wire laminated film is put into 450 ℃ of sintering 30min of Muffle furnace, cools to 80 ℃ of taking-ups then, puts into 5.0 * 10 immediately
-4Soak 24h in the ruthenium complex N719 dyestuff ethanol solution of mol/L; Take out the dyestuff of back, dry, obtain complex light anode with ethanol flush away remained on surface.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557477A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Preparation method of in-situ vertically grown titanium dioxide nanosheet film |
| CN102157264A (en) * | 2011-01-26 | 2011-08-17 | 浙江大学 | Preparation method of composite membrane for dye sensitized solar cells |
| CN102254692B (en) * | 2011-04-18 | 2012-07-04 | 陕西师范大学 | Preparation method of dye-sensitized solar cell photoanode with reflection film |
| CN102254693B (en) * | 2011-04-18 | 2012-08-22 | 陕西师范大学 | Method for preparing light anode of dye-sensitized solar cell |
| CN102324311B (en) * | 2011-07-04 | 2012-09-26 | 武汉大学 | Method for preparing bifunctional DSSC (dye-sensitized solar cell) photo-anode |
| CN102637532B (en) * | 2012-04-19 | 2014-07-09 | 陕西师范大学 | Nanocable-containing DSC (dye-sensitized solar cell) photo-anode and preparation method thereof |
| CN103065804B (en) * | 2012-12-25 | 2015-11-18 | 浙江大东南集团有限公司 | A kind of preparation method of solar battery light anode |
| CN108648918B (en) * | 2018-05-10 | 2020-02-14 | 西北工业大学 | TiO 22(B)NWs/TiO2NP dye sensitization solar battery photo-anode and preparation method thereof |
| CN110349753B (en) * | 2019-05-23 | 2021-11-19 | 广东工业大学 | Rare earth doped up-conversion titanium dioxide nanostructure composite photo-anode and preparation method and application thereof |
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| JP2004265767A (en) * | 2003-03-03 | 2004-09-24 | Ube Ind Ltd | Prediction process for physical properties of metal complex dyes |
| CN101075660A (en) * | 2006-05-18 | 2007-11-21 | 三星电子株式会社 | Semiconductor electrode containing phosphate and solar cell using the same |
| CN101232052A (en) * | 2008-02-01 | 2008-07-30 | 大连七色光太阳能科技开发有限公司 | Dye sensitization solar cell module |
| CN101381099A (en) * | 2008-10-13 | 2009-03-11 | 彩虹集团公司 | Nano TiO2 preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101702377B (en) * | 2009-10-29 | 2012-05-23 | 彩虹集团公司 | Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004265767A (en) * | 2003-03-03 | 2004-09-24 | Ube Ind Ltd | Prediction process for physical properties of metal complex dyes |
| CN101075660A (en) * | 2006-05-18 | 2007-11-21 | 三星电子株式会社 | Semiconductor electrode containing phosphate and solar cell using the same |
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| CN101381099A (en) * | 2008-10-13 | 2009-03-11 | 彩虹集团公司 | Nano TiO2 preparation method |
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