CN101866753B - Photoanode surface treatment method of dye sensitization solar batteries - Google Patents
Photoanode surface treatment method of dye sensitization solar batteries Download PDFInfo
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- CN101866753B CN101866753B CN 200910082432 CN200910082432A CN101866753B CN 101866753 B CN101866753 B CN 101866753B CN 200910082432 CN200910082432 CN 200910082432 CN 200910082432 A CN200910082432 A CN 200910082432A CN 101866753 B CN101866753 B CN 101866753B
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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 treating titanium dioxide photoanode film surfaces of dye sensitization solar batteries. The method comprises the following steps: soaking the titanium dioxide photoanode film surfaces of the sensitization solar batteries into liquid, wherein the liquid is selected from one kind or a plurality of kinds of materials in purified water, diluted acid and oxyful and mixed liquid of the liquid and organic solvents thereof, the diluted acid is selected from hydrochloric acid, nitric acid, acetic acid, sulfuric acid and/or oxalic acid with the concentration smaller than 1M, the organic solvents are selected from methanol, ethanol, glycol, propanetriol and a mixture thereof, and preferably, the liquid is hydrochloric acid with the concentration smaller 1M; and using gas with strong oxidizers-gases for treating the titanium dioxide photoanode film surfaces of the dye sensitization solar batteries, wherein the oxidizing gas is selected from one kind or a plurality of kinds of gas in oxygen gas, ozone and chlorine gas, preferably the ozone. The photoanode electron recombination process of the dye sensitization solar batteries treated by the method is effectively restrained, the photoelectric converting efficiency is obviously improved, and in addition, the invention has the advantages of simple implementation process, economy and environment protection, and is suitable for large-scale application.
Description
Technical field
The present invention relates to DSSC and make the field, relate in particular to a kind of processing method of photoanode surface of DSSC.
Background technology
The human entering since 21st century; The energy problem that faces is severe day by day; All actively seeking redress hardy in the world wide; Therefore regenerative resource has also received the attention of national governments, and wherein solar energy receives much concern with inexhaustible, nexhaustible advantage especially, thereby solar cell also becomes the focus in the new forms of energy research field.DSSC (DSC) is as a kind of novel solar battery of following nanosecond science and technology to grow up in recent years, with its good performance with economical, the preparation method has caused the research boom in the global range easily.DSSC is mainly by TiO
2The light anode, redox electrolytes liquid and electrode three parts are formed, and the light anode is as wherein important part has been brought into play the important function that absorbing dye transports electronics.After
professor of engineering college of Swiss Confederation in 1991 introduces the light anode with loose structure; Improved the charge-exchange area of dyestuff adsorbance and electrolyte widely; Battery efficiency is issued to 7.1% in the exposure intensity of AM1.5; Progressively rise to more than 11% again subsequently, brought the prospect of practicability.
According to the operation principle of DSC, electronics injects TiO from the dye molecule of excitation state
2Conduction band in, arrive transparency electrode through random walk transmittance process in film then, again via external circuit be transported to after the electrode with the I in the electrolyte
3 -Be reduced to I
-, finally by I
-With the excitation state reducing dyes is ground state, constitutes a closed-loop path.In the process of this series charge transmission, the topmost step that the restriction battery efficiency improves is to occur in TiO
2The electronics at/dyestuff/electrolyte interface place injects and transmission course.Electronics is at TiO
2When transmitting in the perforated membrane and the compound a large amount of losses that caused electronics of electrolyte.This compound generally acknowledged microscopic origin is at present: extensively be present in TiO
2The surperficial oxygen defect of brilliant particle (particle diameter 20-40nm) of receiving causes the coordination of surperficial Ti atom not enough, thereby has formed the complex centre of electronics.Simultaneously; Because there is the surface oxygen defective inevitably in the brilliant particle of receiving in the P25 powder of large-scale production at present (for the nanometer powder (mass ratio 20%: 80%) of rutile and anatase mixing); Therefore; Pointedly TiO2 light anode is carried out surface modification and modification, reduce the oxygen defect of particle surface, the surface recombination that suppresses electronics will become the critical path of further lifting battery efficiency.
Existing photoanode surface processing method mainly can be divided three classes: (1) is coated on TiO with the metal compound layer of non-Ti
2The surface forms the barrier layer and suppresses compound; TiO is handled through the Ti salt or Ti alkoxide (the main at present titanium tetrachloride that the uses) aqueous solution that adopt low concentration in [Chem.Mater.2002,14,2930-2935] (2)
2Film makes the titanium ion in the solution repair a part of defective after the defect state place hydrolysis of brilliant particle receiving, and reduces electron recombination, improves photoelectric current.[J.Phys.Chem.B 2006,110,19191-19197] (3) adopt the method for UV-irradiation to raise the efficiency.[Adv.Funct.Mater.2006,16,1228-1234] yet, in the above-mentioned first method, new metal compound layer is because lattice coefficient mismatch, reasons such as energy level difference itself also can cause new defect state, so very limited to the effect of battery efficiency lifting; As for second method; Though can obtain effect preferably; But because distribute numerous defective bit on the complexity of hydrolytic process and the inner huge specific area of titanium dioxide photo anode, make that the film after this method optimization does not reach optimum state, have the further space of lifting.And operating process more complicated; The salting liquid of preparation must be hydrolyzed under the condition that is higher than room temperature (60-90 ℃); To reach the effect that repair on the surface; And also need increase later the step of high temperature sintering in hydrolysis, and consumed lot of energy, increased production cost of cells, energy resource consumption and manufacturing cycle.In addition, the solution after the hydrolysis can pollute as entering environment as waste water to a certain extent.In the third method, thereby the main effect of ultraviolet light is to rely on the light radiation of shortwave that residual organic is decomposed to reach the purpose of removing residue, and the method only belongs to a kind of processing means of purifying in essence, is of limited application.
Defective to above existing method; The present invention proposes a kind of simple efficient; Have simultaneously the surface treatment method of dye-sensitized solar cells of the reparation surface oxygen defective of universality again, can suppress electron recombination effectively, improve short-circuit photocurrent and battery efficiency.
Summary of the invention
Term used herein only if point out in addition, is to understand according to its conventional sense.
" P25 " of use described herein is meant a kind of TiO of open transaction in the market
2Nanometer powder, its composition are the TiO of rutile and two kinds of crystal formations of anatase (mass ratio 20%: 80%)
2The mixing nanometer powder, average grain diameter is 21nm.
The object of the present invention is to provide a kind of method of titanium dioxide photo anode film surface of new processing DSSC, to realize optimizing the light anode performance of DSSC.
The invention provides a kind of method of handling the titanium dioxide photo anode film surface of DSSC, said method comprises:
1) the titanium dioxide photo anode film surface with DSSC soaks in liquid, said liquid be selected from pure water, diluted acid and the hydrogen peroxide solution one or more with and with the mixed liquor of organic solvent; Said diluted acid is hydrochloric acid, nitric acid, acetic acid, sulfuric acid and/or the oxalic acid of concentration less than 1M; Said organic solvent is selected from methyl alcohol, ethanol, ethylene glycol, glycerine, and composition thereof; Preferably, said liquid is the hydrochloric acid of concentration less than 1M;
2) use oxidizing gas to handle the titanium dioxide photo anode film surface of DSSC, said oxidizing gas is selected from one or more in oxygen, ozone and the chlorine, is preferably ozone;
Simultaneously, said method is not used the titanium dioxide photo anode film surface of UV treatment DSSC.
Preferably, the concentration of said ozone is greater than 0.01mg/m
3, be preferably 0.01～200mg/m
3And the preparation method of said ozone is selected from the following method one or more: with method, uviol lamp method, electrolysis and the nuclear radiation method of ozone generator through electrion oxidation air or oxygen.
Preferably, said method also comprises the titanium dioxide photo anode film surface that the using gases drying is soaked into, and said gas is selected from air, nitrogen and mist thereof.
Preferably, said method is at room temperature carried out.
Preferably, the used time of said method is 5-60 minute.
Preferably, the thickness of said titanium dioxide photo anode film is 0.1-20 μ m.
Preferably, the preparation method of said titanium dioxide photo anode film is selected from following one or more:
A. be that the synthetic nanometer powder of presoma or the mixing nanometer powder of rutile and anatase are the feedstock production slurry with titanium salt, titanium alkoxide; And process the titanium dioxide photo anode film after it is filmed; Wherein said titanium salt is titanium tetrachloride and/or titanium sulfate, and said titanium alkoxide is butyl titanate and/or tetraisopropyl titanate;
B. the titanium dioxide photo anode film that adopts the titanium dioxide nanostructure of electrochemistry anodic oxidation, hydro thermal method or template preparation to form, described titanium dioxide nanostructure are selected from a kind of in nanotube, nanometer rods, nano-tube array and the nanometer stick array;
C. be the slurry of feedstock production and the titanium dioxide photo anode film that makes after the titanium dioxide nanostructure described in the method b mixes with the mixing nanometer powder of the titanium salt described in the method a, titanium alkoxide or rutile and anatase; With
D. utilize the titanium dioxide photo anode film of solution-treated with method for preparing, the titanium dioxide photo anode film of fired formation again, wherein said solution are the titanium salt aqueous solution and/or titanium alcohol saline solution.
Preferably, the coating method among the said method a be selected from knife coating, silk screen print method, get rid of the method for being coated with, in czochralski method and the natural evaporation method one or more.
Preferably; Titanium dioxide nanostructure among said method b and the method c is of a size of 1-100nm; And also mixed the nanostructure of other metal oxide in the said titanium dioxide nanostructure; Said other metal oxide is selected from one or more in zinc oxide, magnesia, tin oxide, alundum (Al, calcium oxide, vanadic oxide, nickel oxide and the chrome green; The molal quantity of the metal oxide that wherein mixes is no more than the molal quantity of titanium dioxide nanostructure, and said other metal oxide nanostructure is of a size of 1-300nm.
Preferably, the solution among the said method d is the aqueous solution or the organic solution of the aqueous solution or the organic solution or the titanium alkoxide of titanium salt, and wherein said titanium salt is titanium tetrachloride and/or titanium sulfate, and said titanium alkoxide is butyl titanate and/or tetraisopropyl titanate; Organic solvent in the said organic solution is selected from one or more in methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, cyclohexanone, pentane, hexane, octane, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, acetone, espeleton, methylisobutylketone, acetonitrile, pyridine, phenol, benzene, toluene and the xylenes.
Compared with prior art; Advantage of the present invention is: through using the method for diluted acid combined with ozone gas treatment dye-sensitized solar cell anode; Repaired in a large amount of oxygen vacancy defects that exist of titanium dioxide surface through the oxidation of strong oxidizer at micro-scale, the complex centre of having reduced charge carrier has effectively suppressed the recombination process of electronics; The short-circuit photocurrent and the electricity conversion of battery have been improved; Simultaneously, this method implementation process is simple, economy, environmental protection, be fit to extensive the use, can be used as the optimization technology in preparation of industrialization dye-sensitized solar cell anode flow process and the flexible substrate DSSC.Efficiency of dye-sensitized solar battery after the processing is average to improve about 9% relatively, reaches as high as 15%.
Embodiment
The concrete embodiment of following reference explains the present invention.It will be appreciated by those skilled in the art that these embodiment only are used to explain the object of the invention, the scope that it does not limit the present invention in any way.
Embodiment 1: the preparation of titanium dioxide photo anode film reaches the efficiency test by its battery that makes
A. will use precursor pulp blade coating that commodity P25 powder (available from Degussa) makes on the transparent conducting glass of wash clean; Annealing is 30 minutes in 80 high temperature of degree oven dry back 450, obtains titanium dioxide photo anode film sample 1, sample 2, the sample 3 of about 15 micron thickness;
B. after with 0.5M watery hydrochloric acid titanium dioxide photo anode sample 2 and sample 3 being soaked into, wait the titanium deoxid film surface fully behind the adsorbed water molecule, film is dried up to no macroscopic water droplet with air or nitrogen.Being placed on humidity then is lower than in 30% the environment and uses 0.05mg/m respectively
3Ozone treatment 20 and 40 minutes.Ozone is produced by ozone generator;
C. the sample of handling well 2 and sample 3 and untreated sample 1 are put into simultaneously the commodity N3 dyestuff absorbing dye 12 hours of 0.03mol/L;
Sample 1, sample 2, the sample 3 that d. will fully adsorb dyestuff are assembled into battery, testing efficiency, and the battery efficiency after sample 2 samples 3 are handled obviously is superior to untreated sample 1.
The result is shown in following table 1:
Table 1
| Short-circuit photocurrent density (mA cm -2) | Open circuit voltage (mV) | Fill factor, curve factor | Efficient (%) | |
| Sample 1 | 11.58 | 692 | 0.732 | 5.86 |
| Sample 2 | 11.87 | 695 | 0.741 | 6.11 |
| Sample 3 | 12.12 | 695 | 0.736 | 6.19 |
Drawn by table 1 among the embodiment 1: this method can make that battery efficiency is average to be improved approximately 5% relatively, and as a kind of low cost, low energy consumption, the simple surface treatment method of enforcement, this result is illustrated in that battery efficiency is improved significantly in the practical application.
Embodiment 2: the preparation of titanium dioxide photo anode film reaches the efficiency test by its battery that makes
A. in 230 ℃ autoclave will with HNO
3The synthetic TiO 2 precursor slurry of the metatitanic acid four isopropyl ester hydrolysis of peptization mixed the back blade coating on the transparent conducting glass of wash clean with titania nanotube by weight 4: 1; Annealing is 30 minutes in 80 high temperature of degree oven dry back 450, obtains the titanium dioxide photo anode film sample 4-7 of about 15 micron thickness;
B. after with 0.5M watery hydrochloric acid titanium dioxide photo anode sample 5-7 being soaked into, wait titanium deoxid film surface fully behind the adsorbed water molecule, film is dried up to no macroscopic water droplet with air or nitrogen.Being placed on humidity then is lower than in 30% the environment and uses 0.1mg/m respectively
3Ozone treatment 5,10 and 20 minutes.Ozone is produced by ozone generator;
C. with the sample 5-7 that handles well with put into the commodity N3 dyestuff absorbing dye 12 hours of 0.03mol/L simultaneously for the sample 4 of reason not;
The sample 4-7 that d. will fully adsorb dyestuff is assembled into battery, testing efficiency, and the battery efficiency after sample 5-7 handles obviously is superior to untreated sample 4.
The result is shown in following table 2:
Table 2
| Short-circuit photocurrent density (mA cm -2) | Open circuit voltage (mV) | Fill factor, curve factor | Efficient (%) | |
| Sample 4 | 11.27 | 718 | 0.729 | 5.89 |
| Sample 5 | 12.33 | 727 | 0.728 | 6.53 |
| Sample 6 | 12.33 | 745 | 0.732 | 6.72 |
| Sample 7 | 12.53 | 747 | 0.72 | 6.74 |
Drawn by table 2 among the embodiment 2: this method can make the average raising about 13% relatively of battery efficiency; Be up to 15%; As a kind of low cost, low energy consumption, the simple surface treatment method of enforcement, this result is illustrated in that battery efficiency is improved significantly in the practical application.
Embodiment 3: the preparation of titanium dioxide photo anode film reaches the efficiency test by its battery that makes
A. will use precursor pulp blade coating that commodity P25 powder (available from Degussa) makes on the transparent conducting glass of wash clean, annealing is 30 minutes in 80 high temperature of degree oven dry back 450, obtains the titanium dioxide photo anode sample 9-15 of about 15 micron thickness;
B. after with 0.5M watery hydrochloric acid titanium dioxide photo anode sample 10-15 being soaked into, wait titanium deoxid film surface fully behind the adsorbed water molecule, film is dried up to no macroscopic water droplet with air or nitrogen.Placing humidity to be lower than 30% environment sample 10-12 then handled 5,10 and 20 minutes with the ultra violet lamp of 150W respectively; Sample 13-15 places the position of equal value with sample 10-12; But can not receive the direct irradiation of uviol lamp, can only touch the ozone that produces in the environment.Ozone produces concentration 0.2mg/m by the airborne oxygen of the short-wave ultraviolet light irradiation of uviol lamp
3
C. with sample 10-15 that handles well and the commodity N3 dyestuff absorbing dye 12 hours of putting into 0.03mol/L for untreated sample 9 simultaneously;
The sample 9-15 that d. will fully adsorb dyestuff is assembled into battery, testing efficiency, and the battery efficiency after sample 10-15 handles obviously is superior to untreated sample 9.
The result is shown in following table 3:
Table 3
| Short-circuit photocurrent density (mA cm -2) | Open circuit voltage (mV) | Fill factor, curve factor | Efficient (%) | |
| Sample 9 | 12.19 | 694 | 0.7 | 5.92 |
| Sample 10 | 13.19 | 704 | 0.69 | 6.42 |
| Sample 11 | 13.27 | 719 | 0.674 | 6.43 |
| Sample 12 | 13.54 | 696 | 0.689 | 6.5 |
| Sample 13 | 12.62 | 722 | 0.701 | 6.39 |
| Sample 14 | 13.2 | 706 | 0.695 | 6.48 |
| Sample 15 | 13.37 | 701 | 0.697 | 6.53 |
Drawn by table 3 among the embodiment 3: this method can make that battery efficiency is average to be improved approximately 10% relatively, and as a kind of low cost, low energy consumption, the simple surface treatment method of enforcement, this result is illustrated in that battery efficiency is improved significantly in the practical application.
Embodiment 4: the preparation of titanium dioxide photo anode film reaches the efficiency test by its battery that makes
A. will use precursor pulp blade coating that commodity P25 powder (available from Degussa) makes on the transparent conducting glass of wash clean, annealing is 30 minutes in 80 high temperature of degree oven dry back 450, obtains the titanium dioxide photo anode sample 16-20 of about 15 micron thickness;
B. sample 16-20 is immersed in the aqueous solution of titanium tetrachloride of 0.05mol/L, take out the back oven dry of water flushing surface after in the baking oven of 80 degree, leaving standstill 30 minutes.Through annealing in 450 the high temperature 30 minutes, obtain the light anode of modifying through titanium tetrachloride again;
C. after will passing through titanium dioxide photo anode sample 17-20 that titanium tetrachloride modifies and soak into 0.5M watery hydrochloric acid, wait the titanium deoxid film surface fully behind the adsorbed water molecule, film is dried up to no macroscopic water droplet with air or nitrogen.Be placed on humidity then and be lower than the uviol lamp direct irradiation not of using 150W in 30% the environment respectively; Can only touch the ozone that produces in the environment; Handled 10,20,30 and 40 minutes, ozone produces concentration 0.2mg/m by the airborne oxygen of the short-wave ultraviolet light irradiation of uviol lamp
3
D. the sample 17-20 that handles well and untreated sample 16 are put into simultaneously the commodity N3 dyestuff absorbing dye 12 hours of 0.03mol/L;
The sample 16-20 that e. will fully adsorb dyestuff is assembled into battery, testing efficiency, and the battery efficiency after sample 17-20 handles obviously is superior to untreated sample 16.The result is as shown in table 4:
Table 4
| Short-circuit photocurrent density (mA cm -2) | Open circuit voltage (mV) | Fill factor, curve factor | Efficient (%) | |
| Sample 16 | 14.73 | 675 | 0.679 | 6.75 |
| Sample 17 | 14.63 | 677 | 0.692 | 6.85 |
| Sample 18 | 14.61 | 677 | 0.71 | 7.02 |
| Sample 19 | 15 | 678 | 0.703 | 7.16 |
| Sample 20 | 14.71 | 691 | 0.7 | 7.12 |
Drawn by table 4 among the embodiment 4: this method can make that battery efficiency is average to be improved approximately 5% relatively, and as a kind of low cost, low energy consumption, the simple surface treatment method of enforcement, this result is illustrated in that battery efficiency is improved significantly in the practical application.
In sum; Method of the present invention is as a kind of low cost, low energy consumption, the simple surface treatment method of enforcement; Can make that battery efficiency is stably average relatively to be improved approximately 9%, be up to 15%, it is considered to battery efficiency and has obtained remarkable increase in practical application.Simultaneously; Surface treatment method is the means that a kind of back is modified; Its effect is can be stably with the performance boost 10% of original smooth anode, believe the titanium dioxide photo anode film that is applied to high-quality DSSC after, can push battery performance to a new height.
Claims (12)
1. method of handling the titanium dioxide photo anode film surface of DSSC is characterized in that said method comprises:
1) the titanium dioxide photo anode film surface with DSSC soaks in liquid, said liquid be selected from pure water, diluted acid and the hydrogen peroxide solution one or more with and with the mixed liquor of organic solvent; Said diluted acid is a concentration less than in hydrochloric acid, nitric acid, acetic acid, sulfuric acid or the oxalic acid of 1M one or more; Said organic solvent is selected from one or more of methyl alcohol, ethanol, ethylene glycol, glycerine;
2) use oxidizing gas to handle the titanium dioxide photo anode film surface of DSSC, said oxidizing gas is selected from one or more in oxygen, ozone and the chlorine;
Simultaneously, said method is not used the titanium dioxide photo anode film surface of UV treatment DSSC.
2. method according to claim 1 is characterized in that, the liquid described in the step 1) of said method is the hydrochloric acid of concentration less than 1M, and step 2) described in oxidizing gas be ozone.
3. method according to claim 1 is characterized in that the concentration of said ozone is greater than 0.01mg/m
3And the preparation method of said ozone is selected from the following method one or more: with method, uviol lamp method, electrolysis and the nuclear radiation method of ozone generator through electrion oxidation air or oxygen.
4. method according to claim 3 is characterized in that, the concentration of said ozone is 200mg/m
3Below.
5. method according to claim 1 and 2 is characterized in that, said method also comprises the titanium dioxide photo anode film surface that the using gases drying is soaked into, and said gas is selected from air, nitrogen and mist thereof.
6. method according to claim 1 and 2 is characterized in that said method is at room temperature carried out.
7. method according to claim 1 and 2 is characterized in that, the used time of said method is 5-60 minute.
8. method according to claim 1 and 2 is characterized in that, the thickness of said titanium dioxide photo anode film is 0.1-20 μ m.
9. method according to claim 1 and 2 is characterized in that, the preparation method of said titanium dioxide photo anode film is selected from following one or more:
A. be that the synthetic nanometer powder of presoma or the mixing nanometer powder of rutile and anatase are the feedstock production slurry with titanium salt, titanium alkoxide; And process the titanium dioxide photo anode film after it is filmed; Wherein said titanium salt is titanium tetrachloride and/or titanium sulfate, and said titanium alkoxide is butyl titanate and/or tetraisopropyl titanate;
B. the titanium dioxide photo anode film that adopts the titanium dioxide nanostructure of electrochemistry anodic oxidation, hydro thermal method or template preparation to form, described titanium dioxide nanostructure are selected from a kind of in nanotube, nanometer rods, nano-tube array and the nanometer stick array;
C. be the slurry of feedstock production and the titanium dioxide photo anode film that makes after the titanium dioxide nanostructure described in the method b mixes with the mixing nanometer powder of the titanium salt described in the method a, titanium alkoxide or rutile and anatase; With
D. utilize the titanium dioxide photo anode film of solution-treated with method for preparing, the titanium dioxide photo anode film of fired formation again, wherein said solution are the titanium salt aqueous solution or organic solution and/or titanium alcohol saline solution or organic solution.
10. method according to claim 9 is characterized in that, the coating method among the said method a is selected from knife coating, silk screen print method, gets rid of the method for being coated with, in czochralski method and the natural evaporation method one or more.
11. method according to claim 9; It is characterized in that; Titanium dioxide nanostructure among said method b and the method c is of a size of 1-100nm; And also mixed the nanostructure of other metal oxide in the said titanium dioxide nanostructure; Said other metal oxide is selected from one or more in zinc oxide, magnesia, tin oxide, alundum (Al, calcium oxide, vanadic oxide, nickel oxide and the chrome green, and the molal quantity of the metal oxide that wherein mixes is no more than the molal quantity of titanium dioxide nanostructure, and said other metal oxide nanostructure is of a size of 1-300nm.
12. method according to claim 9; It is characterized in that; Solution among the said method d is the aqueous solution or the organic solution of the aqueous solution or the organic solution or the titanium alkoxide of titanium salt; Wherein said titanium salt is titanium tetrachloride and/or titanium sulfate, and said titanium alkoxide is butyl titanate and/or tetraisopropyl titanate; Organic solvent in the said organic solution is selected from one or more in methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, cyclohexanone, pentane, hexane, octane, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, acetone, espeleton, methylisobutylketone, acetonitrile, pyridine, phenol, benzene, toluene and the xylenes.
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| CN102254701B (en) * | 2011-05-17 | 2012-07-04 | 武汉理工大学 | Anodizing method capable of improving performance of titanium dioxide based dye sensitized solar cell |
| CN102723204B (en) * | 2012-06-19 | 2015-10-14 | 大连理工大学 | The titanium foil sheet preparation method of dye-sensitized solar cells light anode |
| CN103903816B (en) * | 2012-12-28 | 2018-01-12 | 中国科学院上海硅酸盐研究所 | The fast preparation method of used as dye-sensitized solar cell photo-anode screen printing sizing agent |
| CN105321721B (en) * | 2015-12-02 | 2018-02-09 | 常州大学 | A kind of preparation method of dye-sensitized solar cell anode material |
| CN105489378A (en) * | 2015-12-30 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Preparation method of light cathode for dye-sensitized solar cell |
| CN110828182A (en) * | 2019-11-29 | 2020-02-21 | 南昌航空大学 | Preparation method of magnesium-doped tin dioxide photo-anode |
| CN111243867A (en) * | 2020-01-20 | 2020-06-05 | 南昌航空大学 | Preparation method of acid-treated dye-sensitized solar cell photo-anode |
| CN114447446A (en) * | 2022-01-07 | 2022-05-06 | 齐鲁工业大学 | Aqueous zinc ion battery additive, electrolyte prepared from same and application of electrolyte |
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| CN101354968A (en) * | 2008-09-16 | 2009-01-28 | 彩虹集团公司 | Light anode for dye sensitization solar battery and preparation method thereof |
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