CN103956269A - Method for preparing dye-sensitized solar cell through in-situ growth of TiO2 nano-particles/nanotubes - Google Patents

Method for preparing dye-sensitized solar cell through in-situ growth of TiO2 nano-particles/nanotubes Download PDF

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CN103956269A
CN103956269A CN201410142450.4A CN201410142450A CN103956269A CN 103956269 A CN103956269 A CN 103956269A CN 201410142450 A CN201410142450 A CN 201410142450A CN 103956269 A CN103956269 A CN 103956269A
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tio
nanotube
nano particle
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solution
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CN103956269B (en
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王浩
李思倩
张军
李全同
汪宝元
丁浩
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Hubei University
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention discloses a method for preparing a dye-sensitized solar cell through in-situ growth of TiO2 nano-particles/nanotubes. A titanium sheet is placed in an anodic oxidation solution to be subjected to two times of anodic oxidation reactions so as to obtain TiO2 nano-particles based on a titanium substrate; then, the titanium substrate is peeled off to obtain a TiO2 nano-particle film, the TiO2 nano-particle film is pasted on conductive glass, the conductive glass with the TiO2 nano-particle film is placed in a solution containing water to be subjected to a water treatment reaction, and a TiO2 nano-particle/nanotube composite structure is obtained; finally, the obtained composite structure is processed through annealing crystallization, and is soaked in a dye solution, and the dye-sensitized solar cell is assembled. According to the method, no externally added Ti sources are needed, the requirement for reaction conditions is low, the effect is remarkable, and the problems that in the prior art, experiment conditions cannot be easily controlled, operation is tedious, and the obtained TiO2 nano-particles easily bunch up are well solved.

Description

Growth in situ TiO 2the preparation method of the DSSC of nano particle/nanotube
Technical field
The present invention relates to semiconductor nano material technology and DSSC technical field, especially relate to a kind of growth in situ TiO 2the preparation method of the DSSC of nano particle/nanotube.
Background technology
In recent years, wide bandgap semiconductor nano-functional material TiO 2due to its unique physical structure and good photoelectric properties, the various fields such as transducer, photoelectron material, photocatalysis, battery electrode material and biomedical material have been widely used in.Nano-TiO 2material not only has stable chemical property, and there is excellent photocatalytic activity, can play the effect of the biofoulings such as bacterium for degrading, the more important thing is that it shows the compatibility good with organism in vivo, this haves laid a good foundation at biomedical aspect for it.TiO 2a kind of broad stopband (E g=3.2eV) N-shaped semi-conducting material, has superior electronic transmission performance, especially as a kind of semiconductor light-catalyst, is widely used in the aspects such as the depollution of environment, water decomposition and solar energy conversion.
Good photocatalytic and photoelectrochemical property require its TiO 2the specific area of material is large, and more reaction attachment point, stable crystal phase structure and separation and the transmission performance of light induced electron preferably can be provided.Anodised TiO 2be generally impalpable structure, after high-temperature annealing process, form the Anatase structure that has more catalytic activity.Although the TiO of Anatase 2nanotube can show higher electric transmission efficiency and collection efficiency, but under equal conditions, its specific area ratio nano particle is little, this just causes it when being made into DSSC, Dye Adsorption amount is less, thereby light is captured also thereupon less, photovoltaic energy conversion efficiency only has 4% left and right.Comparatively speaking, TiO 2nano particle capture the specific area that provides larger for light, still, electronics transmission path between the nano particle of lack of alignment is tortuous, causes compound increasing the weight of.Comprehensive above-mentioned reason, has proposed the TiO2NPs(nano particle by Anatase) and the TiO of Anatase 2nTAs(nanotube) TiO forming 2nPs/NTAs composite construction, this structure combines NPs compared with the characteristic of bigger serface and the more excellent electron transport property of NTAs, and its PhotoelectrocatalytiPerformance Performance is stronger.
At present, bibliographical information is about TiO 2the preparation method of NPs/NTAs composite construction mainly contains: (1) TiCl 4physical modification; (2) TiO 2nPs fills NTAs; (3) TiO 2nTAs surface-coated TiO 2powder; (4) electrochemical deposition TiO 2nPs.Said method all needs complicated experiment flow and strict experiment condition conventionally, and, the TiO of preparation 2nPs/NTAs composite construction, wherein TiO 2nPs is often not singly dispersed in the surface of nanotube, very easily occurs agglomeration, stops up nanotube bore, and then affects photoelectric properties.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of growth in situ TiO 2the preparation method of the DSSC of nano particle/nanotube, by adopting simple water treatment TiO 2the method of nanotube, directly on the amorphous nanotube of moulding, original position generates TiO 2nano particle, whole preparation process is simple to operate, safe and reliable, simultaneously environmentally safe.And without additional Ti source, test the TiO that shows that original position water treatment generates 2nano particle is evenly distributed in nanotube walls, has successfully realized TiO 2nPs/NTAs(nano particle/nanotube) preparation of composite construction nano-array and DSSC thereof.
The invention provides a kind of growth in situ TiO 2the preparation method of the DSSC of nano particle/nanotube, described preparation method is specially:
Titanium sheet is placed in to anodic oxidation solution and carries out anodic oxidation reactions twice, obtain the TiO based on titanium substrate 2nanotube, and titanium substrate is peeled off and obtain TiO 2nano-tube film, then by TiO 2the film of nanotube is pasted on electro-conductive glass and reacts in rearmounted aqueous solution, obtains TiO 2nano particle/nanotube composite construction, finally carries out annealing crystallization by the composite construction obtaining, and after soaking in dye solution, is assembled into DSSC.
The purity of described titanium sheet is more than 99.4%, and titanium sheet needed to carry out preliminary treatment before carrying out two step anodic oxidation reactionses, was specially, and titanium sheet is cut out to formation pectinate texture, then carries out drying up after ultrasonic cleaning standby.
Described two step anodic oxidation reactionses specifically comprise:
A, once oxidation reaction: pretreated titanium sheet and inert electrode are put into anodic oxidation solution, and external connection constant voltage power supply reacts;
B, go once oxidation reaction: the titanium sheet reacting completely is taken out, clean the ultrasonic oxide layer that makes separated with titanium substrate, take out titanium sheet, clean and dry up standbyly, obtain the clean titanium sheet that removes once oxidation of surface clean;
C, secondary oxidation reaction: the titanium sheet that removes once oxidation is put into remaining anodic oxidation solution after steps A reaction, externally carry out secondary oxidation with once oxidation reacting phase with constant voltage source and react, after reacting completely, taking-up, obtains the TiO based on titanium substrate 2nanotube.
Described anodic oxidation solution be the organic solvent of fluoride ion, by being that 0.2wt%-0.25wt% joins in anhydrous organic solvent and stirs and obtain by the chemical substance that contains fluoride ion according to mass percent.
The chemical substance of described fluoride ion is NaF, HF or NH 4f; Described anhydrous organic solvent is anhydrous ethylene glycol, dimethyl sulfoxide (DMSO) or glycerol.
The described detailed process that titanium substrate is peeled off is:
By the TiO based on titanium substrate 2nanotube is placed in H 2o 2in solution, soak, and slowly rinse with deionized water, make TiO 2nanotube is separated with titanium substrate, has obtained TiO 2nano-tube film, and adhered on the conducting surface of electro-conductive glass.
The detailed process of described treatment reaction is:
Stick to the TiO of the conducting surface of electro-conductive glass 2nano-tube film is put into the alcoholic solution below analytically pure alcohol or moisture mass fraction 40wt% after toasting under the high temperature of 150 ℃-300 ℃, after heating in water bath for reaction, obtain TiO 2nano particle/nanotube composite construction.
Described annealing crystallization is specially at 500 ℃ of-600 ℃ of temperature and toasts more than 3 hours; Described dye solution is N719 dye solution, and the TiO after annealing crystallization 2nano particle/nanotube composite construction soaks and within 24 hours, carries out above electrode assembling again in dyestuff.
The concentration of described N719 dye solution is 3 * 10 -4mol/L, solvent is that volume ratio is the acetonitrile of 1:1 and the mixed solution of the tert-butyl alcohol.
The advantage that the present invention has is:
(1) the present invention adopts traditional electrochemistry anodic oxidation, by regulating the concentration of reaction solution, successfully on business titanium sheet, prepares that pore size is consistent, the TiO of high-sequential 2nano-tube film, the method preparation process is simple, and cost of manufacture is low, and experimental period is short, and feasibility is high;
(2) generated in-situ TiO 2in nano particle/nanotube composite construction, the existence of nano particle can provide larger specific area for adhering to of dyestuff, and nanotube can make up the light induced electron conduction that the disordered state of nano particle causes and is obstructed and then compound defect occurs, improve Dye Adsorption amount, and then effectively promoted opto-electronic conversion performance.
(3) than traditional TiO for preparing heterostructure 2the method of nano particle/nanotube composite construction, the present invention adopts water treatment, experimentation is simple, does not need strict experiment condition in operation, product to environment without any pollution, and the TiO preparing 2nano particle/nano tube structure is clear, neat and orderly, and the dye sensitization battery light electric energy conversion efficiency that assembling obtains is significantly promoted to 7.25% than pure nano-tube array, has a extensive future.
Accompanying drawing explanation
Fig. 1 is TiO of the present invention 2the schematic diagram of nano particle/nanotube water treatment.
Fig. 2 is TiO of the present invention 2xRD figure after nano particle/nanotube water treatment certain hour.
In figure, there is TiO 2the phase of Anatase structure and FTO substrate.Illustrating in water treatment procedure has Anatase to occur.
Fig. 3 is TiO of the present invention 2the SEM figure of nano particle/nanotube.
Fig. 4 is the TiO of growth in situ of the present invention 2the I-V performance diagram of nano particle/nanotube composite Nano array electrode DSSC.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, can be implemented, but illustrated embodiment is not as a limitation of the invention so that those skilled in the art can better understand the present invention also.
The invention provides a kind of growth in situ TiO 2the preparation method of the DSSC of nano particle/nanotube, this preparation method has solved experiment condition in traditional treatment method and cannot accurately control, the composite construction difficult problem that is shaped.Its operating procedure is simple, and experimental cost is cheap, tests byproduct environmentally safe simultaneously; In addition, prepared TiO 2the overall structure of nano particle/nanotube composite construction is clear, and evenly, nanotube aperture thickness is controlled for nano particle size, can effectively be applied to curb environmental pollution, light degradation water, solar cell, the aspects such as biological coating, and can not cause burden to environment, have a good application prospect.
The present invention adopts titanium sheet as substrate, by two-step electrochemical anode oxidation method, controls the reaction time, generates TiO 2nanotube (TiO 2nTAs), based on preparation-obtained TiO 2nTAs, adopts deionized water to process, and successfully obtains the TiO of clear in structure 2nano particle/nanotube (TiO 2nPs/NTAs) composite construction, utilizes the TiO of growth in situ 2the assembling of NPs/NTAs composite construction obtains DSSC.
Concrete preparation flow of the present invention and technique are as follows:
(1) preliminary treatment of titanium sheet: the titanium sheet that is 0.2-0.3mm by thickness is cut into a certain size pectinate texture.Adopt successively deionized water, acetone (traditional Chinese medicines are analyzed pure), alcohol (traditional Chinese medicines are analyzed pure), deionized water to carry out ultrasonic cleaning, the time that each step is cleaned ultrasonic cleaning is generally more than 10-15 minute, the impurity of titanium plate surface is cleaned up, then in air, with hair-dryer, dry up standby.Described titanium sheet is commercial titanium foil sheet, and Ti content is more than 99.4%-99.6%, can certainly select purity at more than 99.6% titanium sheet, and the thickness of titanium sheet is about 1.0-1.5mm, is preferably 1.2mm.
(2) preparation of anodic oxidation solution: using the compound of fluoride ion as solute, this compound is joined in anhydrous organic solvent (traditional Chinese medicines are analyzed pure) according to certain mass percent (0.2wt%-0.25wt%) (mass percent that is compound is herein calculated), add magnetic stir bar, be placed on magnetic stirring apparatus, under room temperature, stir standby.
The chemical substance of described fluoride ion has NaF, HF or NH 4f.Described anhydrous organic solvent comprises ethylene glycol, dimethyl sulfoxide (DMSO) or glycerol.
TiO is prepared in (3) two step anodic oxidations 2nanotube, idiographic flow and process conditions are as follows:
A, once oxidation: pretreated titanium sheet and inert electrode are put into the anodic oxidation solution of above-mentioned preparation, external connection constant voltage power supply, supply voltage is 20-60V, under room temperature condition, reacts, and control reacts completely, and the time, at 2-8 hour, is generally 4 hours.Described inert electrode has stereotype or graphite electrode (graphite cake), is of a size of 0.5cm thick, and size is 3cm * 3.5cm.
B, remove once oxidation: the titanium sheet reacting completely is taken out, after rinsing well with deionized water, put into acidity or ultrasonic a period of time of strong oxidizing property solution as more than 5-10 minute, make oxide layer fully separated with titanium substrate, take out titanium sheet, with obtaining ganoid titanium sheet after deionized water rinsing, then under room temperature, with hair-dryer, dry up standby.Described strong oxidizing property solution is preferably hydrogen peroxide solution, and mass percent is 30wt%-50wt% or lower than 30wt%.
C, secondary oxidation: remaining anodic oxidation solution after reaction for once oxidation before the sample that removes once oxidation in step B is put into, and control the reaction time under the same terms of once oxidation, be oxidized for the second time.After certain hour (12-48 hour), take out, with deionized water rinsing remained on surface organic substance, obtain the TiO based on titanium substrate 2nTAs(nanotube).
(4) TiO 2nTAs peels off, shifts
The sample obtaining in above-mentioned steps (3) is placed in to the H that mass percent is 30wt% 2o 2in solution, after certain hour (5-10 minute), take out, specifically depending on film, come off the time, with the slow flushing of deionized water, can make it separated with titanium substrate, obtain complete TiO 2nTAs film.Adopt TiO 2colloid is by TiO 2nTAs film (the TiO preparing that faces up 2nTAs film is simultaneously positive, at ESEM, can see thering is nozzle structure, and another side is reverse side, also referred to as the back side, for being close to the one side of titanium sheet, it can't see the structure of pipe, the mouth of pipe seals, and is called barrier layer, and the thickness on barrier layer is relevant with factors such as anodised voltages), adhere to the conducting surface of cleaned FTO electro-conductive glass, because colloid clings TiO 2nano-tube film and being attached on FTO electro-conductive glass, by the colloid wiped clean of overflowing, keeps whole FTO conductive glass surface neatly standby, obtains the TiO based on FTO substrate 2nano-tube film.
(5) water treatment TiO 2nano-tube film
By the TiO based on FTO substrate preparing in step (4) 2nano-tube film is (150-300 ℃) baking certain hour (3-5 hour) at high temperature, to strengthen its TiO 2the adhesiveness on NTAs film and FTO surface.After taking-up sample, put into alcoholic solution or the analytically pure alcohol of moisture (mass fraction of water is less than 40wt%), the lower heating water bath certain hour (30 minutes-5 hours) of high temperature (60-200 ℃), obtains described TiO 2nano particle/nanotube composite construction.Water treatment procedure as shown in Figure 1, its reaction equation is:
TiO x+4H 20+(1-x/2)O 2——Ti(OH) 6 2-+2H +(1≤x≤2)
Ti(OH) 6 2-+2H +——TiO 2+4H 20
Wherein 1 is amorphous state TiO 2nanotube; 2 is water; 3 is FTO electro-conductive glass; 4 is Anatase TiO 2nano particle.
(6) assembling obtains the TiO of growth in situ 2the DSSC of nano particle/nanotube composite construction
By the TiO preparing in step (5) 2annealing crystallization under 500-600 ℃ of condition of nano particle/nanotube compound structure film high temperature, annealing crystallization mode can be for toasting more than 3 hours, and in dye solution, soak more than 24h with the Pt of magnetron sputtering deposition electrode assembling, be assembled into " sandwich " knot and form DSSC.Described dye solution N719 dye solution, concentration is 3 * 10 -4mol/L, described solvent is that volume ratio is the acetonitrile of 1:1 and the mixed solution of the tert-butyl alcohol.
The TiO that the present invention is prepared 2nano particle/nanotube composite construction has carried out X-ray diffraction (XRD), scanning electron microscopy (SEM) is analyzed, the titanium oxide peak that has occurred as shown in Figure 2 Anatase in figure, after water treatment is described, before unannealed, there is Anatase to occur, the instrument that wherein X-ray diffraction analysis is used is D8Advance, and condition determination is the scanning of 0.001 °/step.The mensuration voltage of scanning electron microscope diagram 3 is to carry out under the condition of 20KV.The picture of scanning electron microscopy can be found out, water treatment has obtained good nanotube and nano particle composite construction, and by the DSSC assembling under the irradiation of 1.5AM analog light source, as shown in Figure 4, the transformation efficiency that records DSSCs reaches 7.3%.
Embodiment 1:TiO 2nano particle/nanotube electrode preparation flow is as follows:
(1) preliminary treatment of business titanium sheet: the commercial titanium sheet that is 0.2mm by thickness is cut into a certain size pectinate texture.Order with deionized water, acetone, alcohol, deionized water, carry out ultrasonic cleaning, the impurity of titanium plate surface is cleaned up.In air, with hair-dryer, dry up standby.In this experimental procedure, adopt cheap commercial titanium sheet (purity is 99.6%).In ultrasonic cleaning process, in each cleaning process, the ultrasonic processing time is 10 minutes, keeps the smooth of titanium plate surface as far as possible.
(2) preparation of anodic oxidation solution: by NH 4f is that 0.2wt% joins in analytically pure anhydrous organic solvent ethylene glycol according to mass percent, adds magnetic stir bar, room temperature be placed down on magnetic stirring apparatus, be stirred to mix standby.
TiO is prepared in (3) two step anodic oxidations 2nanotube, idiographic flow and process conditions are as follows:
A, once oxidation: pretreated titanium sheet and inert electrode are put into the reaction solution of above-mentioned preparation, external connection constant voltage power supply, supply voltage is 20V, under room temperature condition, reacts, the control time, inert electrode was graphite electrode at 8 hours.
B, remove once oxidation: the titanium sheet reacting completely is taken out, with deionized water, rinsing rear immersion concentration well is in 30wt% hydrogen peroxide solution ultrasonic 5 minutes, make oxide layer fully separated with titanium substrate, take out titanium sheet, with obtaining ganoid titanium sheet after deionized water rinsing.Under room temperature, with hair-dryer, dry up standby.
C, secondary oxidation: solution before the sample that removes once oxidation in step B is put into, under the same terms, control the reaction time, be oxidized for the second time.After oxidation completely, take out titanium sheet, with deionized water rinsing remained on surface organic substance, obtain the TiO based on titanium substrate 2nano-tube film.In this example, the secondary oxidation time is 24 hours, can see clearly that nanotube pore size is consistent, high-sequential from Fig. 3.
(4) TiO 2the peeling off, shift of nano-tube film
By the TiO obtaining in above-mentioned steps (3) 2it is 30% H that nano-tube film is put into mass percent 2o 2in solution, soak after 5 minutes and take out, will nanotube is separated with substrate with deionized water rinsing, obtain the good TiO of integrality 2nano-tube film.Adopt TiO 2colloid is by TiO 2on nano-tube film front, to the conducting surface that adheres to cleaned FTO electro-conductive glass, simple wipe samples, keeps the surface of whole FTO electro-conductive glass neatly standby.
(5) water treatment TiO 2nano-tube film
By the TiO based on FTO substrate preparing 2nano-tube film at high temperature 150 ℃ baking 3 hours, to strengthen its TiO 2the adhesiveness on nano-tube film and FTO surface.After taking out sample, put into analytically pure alcohol, 60 ℃ of high temperature baths heat 5 hours, obtain described TiO after taking-up 2nano particle/nanotube composite construction.
(6) TiO of growth in situ 2the DSSC assembling of nano particle/nanotube composite Nano array electrode
By the TiO preparing 2annealing crystallization under nano particle/nanotube compound structure film hot conditions, is 500 ℃ of bakings 5 hours, and soaks 24h in N719 dyestuff, with the Pt of magnetron sputtering deposition, electrode assembling is become to DSSC.
According to measuring crystal phase structure (XRD) and morphology characterization (SEM, TEM), show the described TiO that the present embodiment 1 has been made 2nano particle/nanotube composite construction.
Embodiment 2:TiO 2nano particle/nanotube electrode preparation flow is as follows:
(1) preliminary treatment of business titanium sheet: the commercial titanium sheet that is 0.3mm by thickness is cut into a certain size pectinate texture.The use deionized water of order, acetone, alcohol, deionized water carries out ultrasonic cleaning, and the impurity of titanium plate surface is cleaned up.In air, with hair-dryer, dry up standby.In this experimental procedure, adopting highly purified purity is 99.7% titanium sheet, and in ultrasonic cleaning process, in each cleaning process, the ultrasonic processing time is 15 minutes, keeps the smooth of titanium plate surface as far as possible.
(2) preparation of anodic oxidation solution: by NH 4f joins and analyzes in pure ethylene glycol solvent according to mass percent 0.2wt%, adds magnetic stir bar, room temperature be placed down on magnetic stirring apparatus, be stirred to mix standby.
TiO is prepared in (3) two step anodic oxidations 2nanotube, idiographic flow and process conditions are as follows:
A, once oxidation: pretreated titanium sheet and inert electrode are put into the reaction solution of above-mentioned preparation, external connection constant voltage power supply, supply voltage is 60V, under room temperature condition, reacts, the control time, inert electrode had stereotype at 2 hours.
B, remove once oxidation: the titanium sheet reacting completely is taken out, after rinsing well with deionized water, put into mass percent and be ultrasonic 10 minutes of the hydrogen peroxide oxalic acid of 20wt%, make oxide layer fully separated with titanium substrate, take out titanium sheet, with obtaining ganoid titanium sheet after deionized water rinsing.Under room temperature, with hair-dryer, dry up standby.
C, secondary oxidation: solution before the sample that removes once oxidation in step B is put into, under the same terms, control the reaction time, be oxidized for the second time.After oxidation completely, take out titanium sheet, with deionized water rinsing remained on surface organic substance, obtain the TiO based on titanium substrate 2nanotube.In this example, the secondary oxidation time is 12 hours, can see clearly that nanotube aperture is consistent, high-sequential from SEM figure.
(4) TiO 2the peeling off, shift of nanotube
By the TiO obtaining in above-mentioned steps 2nano-tube film is put into the H that mass fraction is 30wt% 2o 2in solution, soak after 10 minutes and take out, will nanotube is separated with substrate with deionized water rinsing, obtain the good TiO of integrality 2nano-tube film.Adopt TiO 2colloid is by TiO 2on nano-tube film front, to adhering to cleaned FTO conducting surface, simple wipe samples, keeps whole FTO surface neatly standby.
(5) water treatment TiO 2nano-tube film
By the TiO based on FTO substrate preparing 2nano-tube film toasts 5 hours at 150 ℃ of high temperature, to strengthen its TiO 2the adhesiveness on nano-tube film and FTO surface.Take out and to put into the alcoholic solution that the mass percent of water is 40wt% after sample, 60 ℃ of high-temperature heatings 4 hours, obtain described TiO after taking-up 2nanotube composite construction.
(6) TiO of growth in situ 2the DSSC assembling of nano particle/nanotube composite Nano array electrode
By the TiO preparing 2at 600 ℃ of nano particle/nanotube compound structure film high temperature, toast annealing crystallization in 5 hours, and soak 40h in N719 dyestuff, with the Pt of magnetron sputtering deposition, electrode assembling is become to DSSC.
According to measuring crystal phase structure (XRD) and morphology characterization (SEM, TEM), show the described TiO having made 2nano particle/nanotube composite construction.
Embodiment 3:TiO 2nano particle/nanotube electrode preparation flow is as follows:
(1) preliminary treatment of business titanium sheet: the commercial titanium sheet that is 0.25mm by thickness is cut into a certain size pectinate texture.The use deionized water of order, acetone, alcohol, deionized water carries out ultrasonic cleaning, and the impurity of titanium plate surface is cleaned up.In air, with hair-dryer, dry up standby.In this experimental procedure, adopt cheap commercial titanium sheet (purity is 99.4%).In ultrasonic cleaning process, in each cleaning process, the ultrasonic processing time is 20 minutes, keeps the smooth of titanium plate surface as far as possible.
(2) preparation of anodic oxidation solution: by ammonium fluoride, according to mass percent, be that 0.25wt% joins in analytically pure anhydrous organic solvent ethylene glycol, add magnetic stir bar, room temperature be placed down on magnetic stirring apparatus, be stirred to mix standby.
TiO is prepared in (3) two step anodic oxidations 2nanotube, idiographic flow and process conditions are as follows:
A, once oxidation: pretreated titanium sheet and inert electrode are put into the reaction solution of above-mentioned preparation, external connection constant voltage power supply, supply voltage is 50V, under room temperature condition, reacts, the control time, inert electrode was graphite cake in 4 hours.
B, remove once oxidation: the titanium sheet reacting completely is taken out, after rinsing well with deionized water, put into mass percent and be ultrasonic 8 minutes of the hydrogen peroxide solution of 50wt%, make oxide layer fully separated with titanium substrate, take out titanium sheet, with obtaining ganoid titanium sheet after deionized water rinsing.Under room temperature, with hair-dryer, dry up standby.
C, secondary oxidation: solution before the sample that removes once oxidation in step B is put into, under the same terms, control the reaction time, be oxidized for the second time.After oxidation completely, take out titanium sheet, with deionized water rinsing remained on surface organic substance, obtain the TiO based on titanium substrate 2nano-tube film.In this example, the secondary oxidation time is 24 hours, can see clearly that nanotube aperture is consistent, high-sequential from SEM figure.
(4) TiO 2nTAs peels off, shifts
By the TiO obtaining in above-mentioned steps 2nano-tube film is put into the H that mass percent is 50wt% 2o 2in solution, soak after 8 minutes and take out, will nanotube is separated with substrate with deionized water rinsing, obtain the good TiO of integrality 2nano-tube film.Adopt TiO 2colloid is by TiO 2on nano-tube film front, to the conducting surface that adheres to cleaned FTO electro-conductive glass, simple wipe samples, keeps the surface of whole FTO electro-conductive glass neatly standby.
(5) water treatment TiO 2nano-tube film
By the TiO based on FTO substrate preparing 2nano-tube film toasts 3 hours at 300 ℃ of high temperature, to strengthen its TiO 2the adhesiveness on NTAs film and FTO surface.Take out the alcoholic solution of putting into moisture (mass fraction of water is 20wt%) after sample, 200 ℃ of high-temperature heatings 30 minutes, obtain described TiO after taking-up 2nano particle/nanotube composite construction.
(6) TiO of growth in situ 2the DSSC assembling of nano particle/nanotube composite Nano array electrode
By the TiO preparing 2annealing crystallization under nano particle/nanotube compound structure film hot conditions, and soak 24h in N719 dyestuff, with the Pt of magnetron sputtering deposition, electrode assembling is become to DSSC.
According to measuring crystal phase structure (XRD) and morphology characterization (SEM, TEM), show the described TiO having made 2nano particle/nanotube composite construction.
Embodiment 4:TiO 2nano particle/nanotube electrode preparation flow is as follows:
(1) preliminary treatment of business titanium sheet: the commercial titanium sheet that is 0.3mm by thickness is cut into a certain size pectinate texture.The use deionized water of order, acetone, alcohol, deionized water carries out ultrasonic cleaning, and the impurity of titanium plate surface is cleaned up.In air, with hair-dryer, dry up standby.In this experimental procedure, adopt cheap commercial titanium sheet (purity is 99.5%).In cleaning process, the ultrasonic processing time of every step is 12 minutes, keeps the smooth of titanium plate surface as far as possible.
(2) preparation of anodic oxidation solution: by NaF, according to mass percent, be that 0.22wt% joins in analytically pure anhydrous organic solvent dimethyl sulfoxide (DMSO), add magnetic stir bar, room temperature be placed down on magnetic stirring apparatus, be stirred to mix standby.
TiO is prepared in (3) two step anodic oxidations 2nanotube, idiographic flow and process conditions are as follows:
A, once oxidation: pretreated titanium sheet and inert electrode are put into the reaction solution of above-mentioned preparation, external connection constant voltage power supply, supply voltage is 40V, under room temperature condition, reacts, the control time, inert electrode had stereotype at 5 hours.
B, remove once oxidation: the titanium sheet reacting completely is taken out, after rinsing well with deionized water, put into mass percent and be ultrasonic 10 minutes of the hydrogen peroxide solution of 30wt%, make oxide layer fully separated with titanium substrate, take out titanium sheet, with obtaining ganoid titanium sheet after deionized water rinsing.Under room temperature, with hair-dryer, dry up standby.
C, secondary oxidation: solution before the sample that removes once oxidation in step B is put into, under the same terms, control the reaction time, be oxidized for the second time.After oxidation completely, take out titanium sheet, with deionized water rinsing remained on surface organic substance, obtain the TiO based on titanium substrate 2nanotube.In this example, the secondary oxidation time is 24 hours, can see clearly that nanotube aperture is consistent, high-sequential from SEM figure.
(4) TiO 2the peeling off, shift of nanotube
By the TiO obtaining in above-mentioned steps 2nano-tube film is put into the H of certain mass percent 2o 2in solution, soak after 5 minutes and take out, will nanotube is separated with substrate with deionized water rinsing, obtain the good TiO of integrality 2nano-tube film.Adopt TiO 2colloid is by TiO 2on nano-tube film front, to adhering to cleaned FTO conducting surface, simple wipe samples, keeps whole FTO surface neatly standby.
(5) water treatment TiO 2nano-tube film
By the TiO based on FTO substrate preparing 2nano-tube film toasts 3 hours at 300 ℃ of high temperature, to strengthen its TiO 2the adhesiveness on NTAs film and FTO surface.The alcoholic solution that the mass percent of putting into water after taking-up sample is 30wt%, 150 ℃ of 2 times hour of high-temperature heating, obtains described TiO after taking-up 2nano particle/nanotube composite construction.
(6) TiO of growth in situ 2the DSSC assembling of nano particle/nanotube composite Nano array electrode
By the TiO preparing 2annealing crystallization under nano particle/nanotube compound structure film hot conditions, and soak 24h in N719 dyestuff, with the Pt of magnetron sputtering deposition, electrode assembling is become to DSSC.
According to measuring crystal phase structure (XRD) and morphology characterization (SEM, TEM), show the described TiO having made 2nano particle/nanotube composite construction.
The above embodiment is only the preferred embodiment for absolutely proving that the present invention lifts, and protection scope of the present invention is not limited to this.Being equal to that those skilled in the art do on basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.

Claims (9)

1. a growth in situ TiO 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that, described preparation method is specially:
Titanium sheet is placed in to anodic oxidation solution and carries out anodic oxidation reactions twice, obtain the TiO based on titanium substrate 2nanotube, and titanium substrate is peeled off and obtain TiO 2nano-tube film, then by TiO 2the film of nanotube is pasted on electro-conductive glass and reacts in rearmounted aqueous solution, obtains TiO 2nano particle/nanotube composite construction, finally carries out annealing crystallization by the composite construction obtaining, and after soaking in dye solution, is assembled into DSSC.
2. growth in situ TiO according to claim 1 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that,
The purity of described titanium sheet is more than 99.4%, and titanium sheet needed to carry out preliminary treatment before carrying out two step anodic oxidation reactionses, was specially, and titanium sheet is cut out to formation pectinate texture, then carries out drying up after ultrasonic cleaning standby.
3. growth in situ TiO according to claim 2 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that:
Described two step anodic oxidation reactionses specifically comprise:
A, once oxidation reaction: pretreated titanium sheet and inert electrode are put into anodic oxidation solution, and external connection constant voltage power supply reacts;
B, go once oxidation reaction: the titanium sheet reacting completely is taken out, clean the ultrasonic oxide layer that makes separated with titanium substrate, take out titanium sheet, clean and dry up standbyly, obtain the clean titanium sheet that removes once oxidation of surface clean;
C, secondary oxidation reaction: the titanium sheet that removes once oxidation is put into remaining anodic oxidation solution after steps A reaction, externally carry out secondary oxidation with once oxidation reacting phase with constant voltage source and react, after reacting completely, taking-up, obtains the TiO based on titanium substrate 2nanotube.
4. growth in situ TiO according to claim 3 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that:
Described anodic oxidation solution be the organic solvent of fluoride ion, by being that 0.2wt%-0.25wt % joins in anhydrous organic solvent and stirs and obtain by the chemical substance that contains fluoride ion according to mass percent.
5. growth in situ TiO according to claim 4 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that:
The chemical substance of described fluoride ion is NaF, HF or NH 4f; Described anhydrous organic solvent is anhydrous ethylene glycol, dimethyl sulfoxide (DMSO) or glycerol.
6. growth in situ TiO according to claim 5 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that: the described detailed process that titanium substrate is peeled off is:
By the TiO based on titanium substrate 2nanotube is placed in H 2o 2in solution, soak, and slowly rinse with deionized water, make TiO 2nanotube is separated with titanium substrate, obtains complete TiO 2nano-tube film, and adhered on the conducting surface of electro-conductive glass.
7. growth in situ TiO according to claim 5 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that: the detailed process of described treatment reaction is:
Stick to the TiO of the conducting surface of electro-conductive glass 2nano-tube film is put into the alcoholic solution below analytically pure alcohol or moisture mass fraction 40wt% after toasting under the high temperature of 150 ℃-300 ℃, after heating in water bath for reaction, obtain TiO 2nano particle/nanotube composite construction.
8. growth in situ TiO according to claim 7 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that: described annealing crystallization is specially at 500 ℃ of-600 ℃ of temperature and toasts more than 3 hours; Described dye solution is N719 dye solution, and the TiO after annealing crystallization 2nano particle/nanotube composite construction soaks and within 24 hours, carries out above electrode assembling again in dyestuff.
9. growth in situ TiO according to claim 8 2the preparation method of the DSSC of nano particle/nanotube, is characterized in that: the concentration of described N719 dye solution is 3 * 10 -4mol/L, solvent is that volume ratio is the acetonitrile of 1:1 and the mixed solution of the tert-butyl alcohol.
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