CN104851593A - Preparation method for disperse titania nano-tube compound photo-anode with high light scattering effect - Google Patents
Preparation method for disperse titania nano-tube compound photo-anode with high light scattering effect Download PDFInfo
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Abstract
The invention discloses a preparation method for a disperse titania nano-tube compound photo-anode with high light scattering effect. The method comprises: using a two-step electrochemical anodic oxidation method on a titanium substrate to obtain a titania nano-tube array, and then through ultrasound, forming dispersed state titania nano-tubes, and through drying and high-temperature heat treatment in sequence, adding the obtained pure anatase phase high crystallinity degree titania nano-tube powders and titanium dioxide nano-particles into an alcohol mixed liquor, coating the formed composite slurry of pure anatase phase high crystallinity degree titania nano-tubes and titanium dioxide nano-particles on a transparent conductive substrate, and naturally drying and then sintering, and performing dye sensitization processing on a composite film of the obtained titania nano-tubes and titanium dioxide nano-particles, so as to obtain a disperse titania nano-tube compound photo-anode with high light scattering effect. By using a dye-sensitized solar cell prepared by the method, photoelectric conversion efficiency of the cell reaches up to 6%.
Description
Technical field
The present invention relates to field of dye-sensitized solar cells, refer in particular to a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect for DSSC.
Background technology
In typical DSSC, nanostructure light anode is very important part.The function of light anode primarily of three because usually characterizing: catching of light, from excitation state dyestuff to the electron injection of semiconductor, and the diffusion of electronics in light anode and collection.In DSSC, normally used smooth anode is made up of mesoporous TiO 2 nano particle, and it can provide large specific area for adsorpting dye molecule, and has unique band structure, and light induced electron can effectively shift in interface.But for titania nanoparticles, because electron diffusion length is effective, and the absorption coefficient of light of dyestuff is less, causes the photon energy in solar radiation not also to be fully used.Incident light is greatly had to penetrate titania nanoparticles film, particularly for the light of long wavelength.Therefore, the light capture ability strengthening light anode is most important for the photoelectric conversion efficiency improving solar cell, and the light scattering ability improving light anode is a kind of very important method that enhancing light is caught.
The titania nanotube adopting anode oxidation method to prepare has been widely used in DSSC, and it has intrinsic light scattering ability.But titania nanotube is applied in DSSC and also there are some technical barriers.Such as, in the pertinent literature of existing titania nanotube light anode preparation method, document (Huang Chanyan, Chen Xin, Tao Junchao, Sun Yan, Dai Ning.The preparation method of the nano compound film of titania nanotube and nanocrystalline composition, CN201010107419,2010) preparation method of the nano compound film of titania nanotube and nanocrystalline composition is proposed, the method directly utilizes growth at the on-chip titania nanotube of titanium, titania nanoparticles is poured in titania nanotube inner as light anode, battery prepared by this method can only adopt back illumination mode, causing incident light utilization ratio, lower (omissions or missing parts is repaiied, Sun Peng, Hu Guo, He Zuoli.To shift and titanium dioxide nano-pipe array thin film to the conductive glass surface that bonds prepares the method for light anode, CN201310004017,2013).Therefore need titania nanotube to strip down from titanium substrate, prepare the battery of positive radiation modality.
Document (repair, Sun Peng, Hu Guo, He Zuoli by omissions or missing parts.A kind ofly to shift and titanium dioxide nano-pipe array thin film to the conductive glass surface that bonds prepares the method for light anode, CN201310004017,2013) a kind of to shift and titanium dioxide nano-pipe array thin film to the conductive glass surface that bonds prepares the method for light anode is proposed in.The method achieve positive radiation modality, but the titanium dioxide nano-pipe array thin film of preparation has many electron trap centers, thus cause poor charge collection efficiency, reduce performance (the P. Docampo of titania nanotube light anode, S. Guldin, U. Steiner, H.J. Snaith, Charge transport limitations in self-assembled TiO2 photoanodes for dye-sensitized solar cells, J. Phys. Chem. Lett., 4 (2013) 698 – 703.).We have prepared titanium dioxide nano-tube powder, and improve its degree of crystallinity by high-temperature heat treatment, overcome above-mentioned difficulties, prepare the battery of positive radiation modality, and reduce electron trap center, improve the performance of battery.
In addition, document (Zhang Jingchang, Han Zhiyue, Wang Siqi, Yang Xiuying, Cao Weiliang.The preparation method of the titanium dioxide nanotube dye-sensitized photoanode thin film of modification, CN201010597806, 2010) preparation method of the titanium dioxide nanotube dye-sensitized photoanode thin film of modification is proposed in, the method adopts hydro thermal method to prepare titania nanotube, the tube diameters obtained is less, be about tens nanometer, the wavelength of the visible ray of ratio is much little, thus light scattering effect is very poor, cause not high (the K.C. Sun of the absorption efficiency of light, M.B. Qadir, S.H. Jeong, Hydrothermal synthesis of TiO2 nanotubes and their application as an over-layer for dye-sensitized solar cells, RSC Adv., 4 (2014) 23223 – 23230.).And hydro thermal method manufacturing cycle is long, complicated process of preparation, preparation in about 100 hours several grams.The titanium dioxide nano-tube powder that we prepare, its caliber is hundreds of nanometer, has excellent light scattering property, can improve the absorption efficiency of light.Used material comprises low-purity titanium sheet, ethylene glycol and ammonium fluoride, has the advantages that cost is low.And the productive rate of titanium dioxide nano-tube powder is very high, for the titanium substrate of 10 centimetres of * 10 centimetres of sizes, the productive rate of titanium dioxide nano-tube powder is about 5 Grams Per Hours, further by increase titanium substrate size, can realize large-scale production.
Summary of the invention
The object of the invention is to solve above-mentioned (1) back illumination mode, (2) a large amount of electron trap center, (3) poor light scattering property, (4) cost is high, technical problems such as productive rate is low and a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect is provided, the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of this preparation method's gained, there is positive radiation modality, high-crystallinity and less electron trap center, high light scattering titania nanotube, reduce the electron trap center of light anode, enhance the light scattering ability of light anode, thus improve the collection efficiency that it is prepared into the light capture rate after DSSC and electronics, and significantly can improve efficiency and the performance of DSSC.In addition, this preparation method has that cost is low, productive rate advantages of higher.
Technical scheme of the present invention
Have a preparation method for the dispersed titanium dioxide nanotube complex light anode of high light scattering effect, concrete steps are as follows:
(1), on titanium substrate, two-step electrochemical anode oxidation method is adopted to prepare the Nano tube array of titanium dioxide that thickness is 15-30 μm;
Described on titanium substrate, adopt two-step electrochemical anode oxidation method to prepare the Nano tube array of titanium dioxide that thickness is 15-30 μm, step is as follows:
The titanium substrate of thickness 1mm is cleaned successively in water, absolute ethyl alcohol, acetone; Then in the electrolyte be made up of ammonium fluoride, water and ethylene glycol, normal temperature, anodic oxidation voltage are carry out first time anodic oxidation 1h under the condition of 60 volts, then at normal temperatures, ultrasonic power is 50-200W, ultrasonic 5min in absolute ethyl alcohol, obtains the titanium substrate that there is pit on surface;
Be proceed second time anodic oxidation 1-3h under the condition of 60 volts by the surface of gained by the titanium substrate of pit normal temperature, anodic oxidation voltage in the electrolyte be made up of ammonium fluoride, water and ethylene glycol again, obtaining is the titanium substrate of the Nano tube array of titanium dioxide of 15-30 μm with thickness;
Above-mentioned first time anodic oxidation and the used electrolyte be made up of ammonium fluoride, water and ethylene glycol of second time anodic oxidation identical, calculate in mass ratio, i.e. ammonium fluoride: water: ethylene glycol is 0.5:3:100;
(2), with supersonic wave cleaning machine at normal temperatures, ultrasonic power is 50-200W, be the Nano tube array of titanium dioxide of 15-30 μm with thickness titanium substrate carries out ultrasonic disperse process 5-15min in absolute ethyl alcohol to step (1) gained, make the on-chip Nano tube array of titanium dioxide of titanium be distributed in absolute ethyl alcohol, obtain the titania nanotube ethanolic solution that concentration is the dispersity of 30-50g/L;
(3) rotating speed, is controlled to be 4000-10000r/min by the concentration of step (2) gained is the titania nanotube solution centrifugal 5-10min of the dispersity of 30-50g/L, the precipitation of gained respectively cleans 3 times with deionized water and absolute ethyl alcohol successively, and then controlled pressure is 10
-1-10Pa, temperature are carry out vacuumize 12-15h under 110-130 DEG C of condition, obtain pure dispersity titanium dioxide nano-tube powder;
(4), under air conditions, pure for step (3) gained dispersity titanium dioxide nano-tube powder being controlled heating rate is that 1-3 DEG C/min is warming up to 700-800 DEG C and heat-treats 1-3h, and then to control rate of temperature fall be that 1-3 DEG C/min is down to room temperature, obtain the high-crystallinity titanium dioxide nano-tube powder of pure Anatase;
(5), by isopropyl alcohol and n-butanol by volume for 1:3-5 carries out being mixed to get alcoholic solution;
The alcoholic solution mixing that particle diameter is the titania nanoparticles of 15-30nm, the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained and above-mentioned gained, use magnetic stirrer to carry out stirring 18-25h with 150-300rpm speed, obtain the high-crystallinity titania nanotube of Anatase and the composite mortar of titania nanoparticles;
Above-mentioned particle diameter used is the titania nanoparticles of 15-30nm, the high-crystallinity titanium dioxide nano-tube powder of pure Anatase of step (4) gained and the amount of alcoholic solution, is the titania nanoparticles of 15-30nm: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained in particle diameter: alcoholic solution is that the ratio of 100g:10-300g:1-2L calculates;
(6), use knife coating, the high-crystallinity titania nanotube of the Anatase of step (5) gained and titania nanoparticles composite mortar are coated in electrically conducting transparent substrate, coating thickness is 8-12 μm, then by the natural drying in atmosphere together with film of electrically conducting transparent matrix, then electrically conducting transparent matrix and dried film control temperature are 450-500 DEG C and carry out sintering 1-3h, obtaining based on the thickness of electrically conducting transparent substrate is the titania nanotube of 7-10 μm and the laminated film of titania nanoparticles, then dye sensitization process is carried out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had,
Described electrically conducting transparent substrate is fluorine doped tin oxide (FTO) electro-conductive glass or tin indium oxide (ITO) electro-conductive glass;
Described sensitized treatment, concrete steps are as follows:
Be that the titania nanotube of 7-10 μm and the laminated film of titania nanoparticles are immersed in N719 dye solution by thickness, dye sensitization process 24h is carried out under room temperature, then take out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had;
The concentration of described N719 dye solution is 0.3mmol/L, and solute is N719 dyestuff, and solvent is mixed liquor that 1:1 forms by acetonitrile and the tert-butyl alcohol by volume.
On covering on the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of above-mentioned gained, platinum is to electrode, filling electrolyte between two electrodes, and encapsulates with heat sealing film, just defines DSSC.
Beneficial effect of the present invention
A kind of dispersed titanium dioxide nanotube complex light anode with high light scattering effect of the present invention, owing to have employed technical scheme unlike the prior art, therefore has technique effect more better than prior art:
(1) directly utilize growth to prepare battery light anode at the on-chip titania nanotube of titanium, back illumination mode can only be adopted.The present invention is combined titanium dioxide nano-tube powder with titania nanoparticles, prepared the battery of positive radiation modality, added incident light utilization ratio.
(2) titanium dioxide nano-pipe array thin film has many electron trap centers, and cannot improve its degree of crystallinity by high annealing, thus causes poor charge collection efficiency.The present invention, by carrying out high-temperature heat treatment to the titania nanotube of pulverulence, improves the degree of crystallinity of titania nanotube, reduces electron trap center, adds the collection efficiency of electronics, improves the performance of battery.
(3) the present invention uses the titania nanotube of dispersity to serve as light-scattering component, the caliber less with the titania nanotube adopting hydro thermal method to prepare is compared with poor light scattering effect, titanium dioxide nano-tube powder prepared by the present invention, its caliber is hundreds of nanometer, there is excellent light scattering property, to catch more incident light, significantly strengthen light absorption and then improve battery efficiency.
(4) hydro thermal method manufacturing cycle is long, complicated process of preparation, and cost is higher.Material used by preparation method of the present invention comprises low-purity titanium sheet, ethylene glycol and ammonium fluoride, has the advantages that cost is low, and the productive rate of titanium dioxide nano-tube powder is very high, is applicable to large-scale production.
Accompanying drawing explanation
Use reason ripple 94023A solar simulator and Keithley 2400 digital sourcemeter under air quality AM1.5G standard illumination condition, measure the I-V curve chart of gained after the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of Fig. 1, embodiment 2 gained is assembled into DSSC.
Use reason ripple 94023A solar simulator and Keithley 2400 digital sourcemeter under air quality AM1.5G standard illumination condition, measure the I-V curve chart of gained after the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of Fig. 2, embodiment 1 gained is assembled into DSSC.
Use reason ripple 94023A solar simulator and Keithley 2400 digital sourcemeter under air quality AM1.5G standard illumination condition, measure the I-V curve chart of gained after the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of Fig. 3, embodiment 3 gained is assembled into DSSC.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
embodiment 1
Have a preparation method for the dispersed titanium dioxide nanotube complex light anode of high light scattering effect, concrete steps are as follows:
(1), on titanium substrate, adopt the preparation of two-step electrochemical anode oxidation method perpendicular to titanium substrate, be highly the Nano tube array of titanium dioxide of 15 μm; Nano tube array of titanium dioxide prepared by the method is perpendicular to titanium substrate, and wherein anode oxidation method is a kind of widely used technology, in field of dye-sensitized solar cells, for the preparation of titania nanotube;
Described on titanium substrate, adopt the preparation of two-step electrochemical anode oxidation method to be the Nano tube array of titanium dioxide of 15 μm perpendicular to titanium substrate, thickness, step is as follows:
The titanium substrate of thickness 1mm is cleaned successively in water, absolute ethyl alcohol, acetone; Then in the electrolyte be made up of ammonium fluoride, water and ethylene glycol, normal temperature, anodic oxidation voltage are carry out first time anodic oxidation 1h under the condition of 60 volts, then at normal temperatures, ultrasonic power is 100W, ultrasonic 5min in absolute ethyl alcohol, obtains the titanium substrate that there is pit on surface;
Be proceed second time anodic oxidation 1h under the condition of 60 volts by the surface of gained by the titanium substrate of pit normal temperature, anodic oxidation voltage in the electrolyte be made up of ammonium fluoride, water and ethylene glycol again, obtaining is the titanium substrate of the Nano tube array of titanium dioxide of 15 μm with thickness, and Nano tube array of titanium dioxide is perpendicular to titanium substrate;
Above-mentioned first time anodic oxidation and the used electrolyte be made up of ammonium fluoride, water and ethylene glycol of second time anodic oxidation identical, calculate in mass ratio, i.e. ammonium fluoride: water: ethylene glycol is 0.5:3:100;
(2), with supersonic wave cleaning machine at normal temperatures, ultrasonic power is 100W, be the Nano tube array of titanium dioxide of 15 μm with thickness titanium substrate carries out ultrasonic disperse process 10min in absolute ethyl alcohol to step (1) gained, make the on-chip Nano tube array of titanium dioxide of titanium be distributed in absolute ethyl alcohol, obtain the titania nanotube ethanolic solution that concentration is the dispersity of 30g/L;
(3) rotating speed, is controlled to be 4000r/min by the concentration of step (2) gained is the titania nanotube solution centrifugal 10min of the dispersity of 30g/L, the precipitation of gained respectively cleans 3 times to remove impurity remaining in dispersity titania nanotube with deionized water and ethanol successively, then controlled pressure is 10Pa, temperature is carry out vacuumize 12h under 120 DEG C of conditions, obtains pure dispersity titanium dioxide nano-tube powder;
(4), under air conditions, pure for step (3) gained dispersity titanium dioxide nano-tube powder being controlled heating rate is that 2 DEG C/min is warming up to 700 DEG C and heat-treats 2h, and then to control rate of temperature fall be that 2 DEG C/min is down to room temperature, obtain the high-crystallinity titanium dioxide nano-tube powder of pure Anatase;
(5), by isopropyl alcohol and n-butanol by volume for 1:4 carries out being mixed to get alcoholic solution;
The alcoholic solution mixing that 100g particle diameter is the titania nanoparticles of 20nm, the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of 10g step (4) gained and the above-mentioned gained of 1L, use magnetic stirrer to carry out stirring 24h with 200rpm speed, obtain the high-crystallinity titania nanotube of Anatase and the composite mortar of titania nanoparticles;
High-crystallinity titanium dioxide nano-tube powder, the particle diameter of the pure Anatase of above-mentioned step used (4) gained are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained in particle diameter: alcoholic solution is that the ratio of 100g:10g:1L calculates;
(6), use knife coating, the high-crystallinity titania nanotube of the Anatase of step (5) gained and titania nanoparticles composite mortar are coated in electrically conducting transparent substrate, coating thickness is 9 μm, then in by the natural drying in atmosphere together with film of electrically conducting transparent matrix, then electrically conducting transparent matrix and dried film control temperature are 450-500 DEG C and carry out sintering 2h, obtaining based on the thickness of electrically conducting transparent substrate is the titania nanotube of 8 μm and the laminated film of titania nanoparticles, then dye sensitization process is carried out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had,
Described electrically conducting transparent substrate is fluorine doped tin oxide (FTO) electro-conductive glass;
Described sensitized treatment, concrete steps are as follows:
By the thickness of above-mentioned gained be the titania nanotube of 8 μm and titania nanoparticles be immersed in N719 dye solution, dye sensitization process 24h is carried out under room temperature, then take out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had;
The concentration of described N719 dye solution is 0.3mmol/L, and solute is N719 dyestuff, and solvent is mixed liquor that 1:1 forms by acetonitrile and the tert-butyl alcohol by volume.
embodiment 2
Have a preparation method for the dispersed titanium dioxide nanotube complex light anode of high light scattering effect, concrete steps are as follows:
(1), on titanium substrate, adopt the preparation of two-step electrochemical anode oxidation method perpendicular to titanium substrate, be highly the Nano tube array of titanium dioxide of 15 μm; Nano tube array of titanium dioxide prepared by the method is perpendicular to titanium substrate, and wherein anode oxidation method is a kind of widely used technology, in field of dye-sensitized solar cells, for the preparation of titania nanotube;
Described on titanium substrate, adopt the preparation of two-step electrochemical anode oxidation method to be the Nano tube array of titanium dioxide of 15 μm perpendicular to titanium substrate, thickness, step is as follows:
The titanium substrate of thickness 1mm is cleaned successively in water, absolute ethyl alcohol, acetone; Then in the electrolyte be made up of ammonium fluoride, water and ethylene glycol, normal temperature, anodic oxidation voltage are carry out first time anodic oxidation 1h under the condition of 60 volts, then at normal temperatures, ultrasonic power is 100W, ultrasonic 5min in absolute ethyl alcohol, obtains the titanium substrate that there is pit on surface;
Be proceed second time anodic oxidation 1h under the condition of 60 volts by the surface of gained by the titanium substrate of pit normal temperature, anodic oxidation voltage in the electrolyte be made up of ammonium fluoride, water and ethylene glycol again, obtaining is the titanium substrate of the Nano tube array of titanium dioxide of 15 μm with thickness, and Nano tube array of titanium dioxide is perpendicular to titanium substrate;
Above-mentioned first time anodic oxidation and the used electrolyte be made up of ammonium fluoride, water and ethylene glycol of second time anodic oxidation identical, calculate in mass ratio, i.e. ammonium fluoride: water: ethylene glycol is 0.5:3:100;
(2), with supersonic wave cleaning machine at normal temperatures, ultrasonic power is 100W, be the Nano tube array of titanium dioxide of 15 μm with thickness titanium substrate carries out ultrasonic disperse process 10min in absolute ethyl alcohol to step (1) gained, make the on-chip Nano tube array of titanium dioxide of titanium be distributed in absolute ethyl alcohol, obtain the titania nanotube ethanolic solution that concentration is the dispersity of 30g/L;
(3) rotating speed, is controlled to be 4000r/min by the concentration of step (2) gained is the titania nanotube solution centrifugal 10min of the dispersity of 30g/L, the precipitation of gained respectively cleans 3 times to remove impurity remaining in dispersity titania nanotube with deionized water and ethanol successively, then controlled pressure is 10Pa, temperature is carry out vacuumize 12h under 120 DEG C of conditions, obtains pure dispersity titanium dioxide nano-tube powder;
(4), under air conditions, pure for step (3) gained dispersity titanium dioxide nano-tube powder being controlled heating rate is that 2 DEG C/min is warming up to 700 DEG C and heat-treats 2h, and then to control rate of temperature fall be that 2 DEG C/min is down to room temperature, obtain the high-crystallinity titanium dioxide nano-tube powder of pure Anatase;
(5), by isopropyl alcohol and n-butanol by volume for 1:4 carries out being mixed to get alcoholic solution;
The alcoholic solution mixing that 100g particle diameter is the titania nanoparticles of 20nm, the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of 100g step (4) gained and the above-mentioned gained of 1L, use magnetic stirrer to carry out stirring 24h with 200rpm speed, obtain the high-crystallinity titania nanotube of Anatase and the composite mortar of titania nanoparticles;
High-crystallinity titanium dioxide nano-tube powder, the particle diameter of the pure Anatase of above-mentioned step used (4) gained are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained in particle diameter: alcoholic solution is that the ratio of 100g:100g:1L calculates;
(6), use knife coating, the high-crystallinity titania nanotube of the Anatase of step (5) gained and titania nanoparticles composite mortar are coated in electrically conducting transparent substrate, coating thickness is 9 μm, then in by the natural drying in atmosphere together with film of electrically conducting transparent matrix, then electrically conducting transparent matrix and dried film control temperature are 450-500 DEG C and carry out sintering 2h, obtaining based on the thickness of electrically conducting transparent substrate is the titania nanotube of 8 μm and the laminated film of titania nanoparticles, then dye sensitization process is carried out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had,
Described electrically conducting transparent substrate is fluorine doped tin oxide (FTO) electro-conductive glass;
Described sensitized treatment, concrete steps are as follows:
By the thickness of above-mentioned gained be the titania nanotube of 8 μm and titania nanoparticles be immersed in N719 dye solution, dye sensitization process 24h is carried out under room temperature, then take out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had;
The concentration of described N719 dye solution is 0.3mmol/L, and solute is N719 dyestuff, and solvent is mixed liquor that 1:1 forms by acetonitrile and the tert-butyl alcohol by volume.
embodiment 3
Have a preparation method for the dispersed titanium dioxide nanotube complex light anode of high light scattering effect, concrete steps are as follows:
(1), on titanium substrate, adopt the preparation of two-step electrochemical anode oxidation method perpendicular to titanium substrate, be highly the Nano tube array of titanium dioxide of 15 μm; Nano tube array of titanium dioxide prepared by the method is perpendicular to titanium substrate, and wherein anode oxidation method is a kind of widely used technology, in field of dye-sensitized solar cells, for the preparation of titania nanotube;
Described on titanium substrate, adopt the preparation of two-step electrochemical anode oxidation method to be the Nano tube array of titanium dioxide of 15 μm perpendicular to titanium substrate, thickness, step is as follows:
The titanium substrate of thickness 1mm is cleaned successively in water, absolute ethyl alcohol, acetone; Then in the electrolyte be made up of ammonium fluoride, water and ethylene glycol, normal temperature, anodic oxidation voltage are carry out first time anodic oxidation 1h under the condition of 60 volts, then at normal temperatures, ultrasonic power is 100W, ultrasonic 5min in absolute ethyl alcohol, obtains the titanium substrate that there is pit on surface;
Be proceed second time anodic oxidation 1h under the condition of 60 volts by the surface of gained by the titanium substrate of pit normal temperature, anodic oxidation voltage in the electrolyte be made up of ammonium fluoride, water and ethylene glycol again, obtaining is the titanium substrate of the Nano tube array of titanium dioxide of 15 μm with thickness, and Nano tube array of titanium dioxide is perpendicular to titanium substrate;
Above-mentioned first time anodic oxidation and the used electrolyte be made up of ammonium fluoride, water and ethylene glycol of second time anodic oxidation identical, calculate in mass ratio, i.e. ammonium fluoride: water: ethylene glycol is 0.5:3:100;
(2), with supersonic wave cleaning machine at normal temperatures, ultrasonic power is 100W, be the Nano tube array of titanium dioxide of 15 μm with thickness titanium substrate carries out ultrasonic disperse process 10min in absolute ethyl alcohol to step (1) gained, make the on-chip Nano tube array of titanium dioxide of titanium be distributed in absolute ethyl alcohol, obtain the titania nanotube ethanolic solution that concentration is the dispersity of 30g/L;
(3) rotating speed, is controlled to be 4000r/min by the concentration of step (2) gained is the titania nanotube solution centrifugal 10min of the dispersity of 30g/L, the precipitation of gained respectively cleans 3 times to remove impurity remaining in dispersity titania nanotube with deionized water and ethanol successively, then controlled pressure is 10Pa, temperature is carry out vacuumize 12h under 120 DEG C of conditions, obtains pure dispersity titanium dioxide nano-tube powder;
(4), under air conditions, pure for step (3) gained dispersity titanium dioxide nano-tube powder being controlled heating rate is that 2 DEG C/min is warming up to 700 DEG C and heat-treats 2h, and then to control rate of temperature fall be that 2 DEG C/min is down to room temperature, obtain the high-crystallinity titanium dioxide nano-tube powder of pure Anatase;
(5), by isopropyl alcohol and n-butanol by volume for 1:4 carries out being mixed to get alcoholic solution;
The alcoholic solution mixing that 100g particle diameter is the titania nanoparticles of 20nm, the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of 300g step (4) gained and the above-mentioned gained of 1L, use magnetic stirrer to carry out stirring 24h with 200rpm speed, obtain the high-crystallinity titania nanotube of Anatase and the composite mortar of titania nanoparticles;
High-crystallinity titanium dioxide nano-tube powder, the particle diameter of the pure Anatase of above-mentioned step used (4) gained are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained in particle diameter: alcoholic solution is that the ratio of 100g:300g:1L calculates;
(6), use knife coating, the high-crystallinity titania nanotube of the Anatase of step (5) gained and titania nanoparticles composite mortar are coated in electrically conducting transparent substrate, coating thickness is 9 μm, then in by the natural drying in atmosphere together with film of electrically conducting transparent matrix, then electrically conducting transparent matrix and dried film control temperature are 450-500 DEG C and carry out sintering 2h, obtaining based on the thickness of electrically conducting transparent substrate is the titania nanotube of 8 μm and the laminated film of titania nanoparticles, then dye sensitization process is carried out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had,
Described electrically conducting transparent substrate is fluorine doped tin oxide (FTO) electro-conductive glass;
Described sensitized treatment, concrete steps are as follows:
By the thickness of above-mentioned gained be the titania nanotube of 8 μm and titania nanoparticles be immersed in N719 dye solution, dye sensitization process 24h is carried out under room temperature, then take out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had;
The concentration of described N719 dye solution is 0.3mmol/L, and solute is N719 dyestuff, and solvent is mixed liquor that 1:1 forms by acetonitrile and the tert-butyl alcohol by volume.
application Example 1
On the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of above-described embodiment 2 gained, cover platinum to electrode, filling electrolyte between two electrodes, and encapsulate with heat sealing film, just define DSSC.
application comparative examples 1
On traditional titania nanoparticles light anode, cover platinum to electrode, filling electrolyte between two electrodes, and encapsulate with heat sealing film, just define the DSSC of contrast.
Reason ripple 94023A solar simulator and Keithley 2400 digital sourcemeter is used to measure the DSSC of the DSSC of above-mentioned Application Example 1 gained and application comparative examples 1 gained under air quality AM1.5G standard illumination condition, the I-V curve of gained as shown in Figure 1, in figure, nano particle light anode represents the DSSC of the contrast of application comparative examples 1 gained, 100g:100g:1L nanotube complex light anode represents the DSSC of Application Example 1 gained, as can be known from Fig. 1 because the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of the embodiment of the present invention 2 gained has high light scattering effect and high charge collection efficiency, therefore the photoelectric conversion efficiency of its DSSC be prepared from is utilized to be 6%, and the photoelectric conversion efficiency of the DSSC utilizing traditional titania nanoparticles light anode to be prepared from is only 4.65%, namely DSSC prepared by the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of the present invention is utilized, its photoelectric conversion efficiency can improve 29%.
Adopt with the identical mode of Application Example 1, respectively by embodiment 1 and embodiment 3 gained there is the dispersed titanium dioxide nanotube complex light anode of high light scattering effect cover platinum above to electrode, filling electrolyte between two electrodes, and encapsulate with heat sealing film, just the DSSC of corresponding embodiment 1 and embodiment 3 is defined, with apply in comparative examples 1 utilize traditional titania nanoparticles light anode to be prepared from DSSC in contrast, reason ripple 94023A solar simulator and Keithley 2400 digital sourcemeter is used to measure the above-mentioned DSSC corresponding to embodiment 1 and embodiment 3 under air quality AM1.5G standard illumination condition, the I-V curve of gained respectively as shown in Figures 2 and 3, in figure, nano particle light anode represents the DSSC of the contrast of application comparative examples 1 gained, 100g:10g:1L nanotube complex light anode corresponds to the DSSC of embodiment 1 gained, 100g:300g:1L nanotube complex light anode corresponds to the DSSC of embodiment 3 gained, photoelectric conversion efficiency is respectively 5.20% and 4.72%, all be better than the photoelectric conversion efficiency 4.65% of the DSSC that traditional titania nanoparticles light anode is prepared from.
In sum, a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect of the present invention, when titania nanotube is applied in DSSC, solve (1) back illumination mode, (2) a large amount of electron trap center, (3) poor light scattering property, (4) cost is high, the series of technical such as productive rate is low, the dispersed titanium dioxide nanotube complex light anode with high light scattering effect of gained, there is positive radiation modality, high-crystallinity and less electron trap center, high light scattering titania nanotube, reduce the electron trap center of light anode, enhance the light scattering ability of light anode, thus significantly improve efficiency and the performance of DSSC.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (5)
1. there is a preparation method for the dispersed titanium dioxide nanotube complex light anode of high light scattering effect, it is characterized in that concrete steps are as follows:
(1), on titanium substrate, two-step electrochemical anode oxidation method is adopted to prepare the Nano tube array of titanium dioxide that thickness is 15-30 μm;
Described on titanium substrate, adopt two-step electrochemical anode oxidation method to prepare the Nano tube array of titanium dioxide that thickness is 15-30 μm, step is as follows:
The titanium substrate of thickness 1mm is cleaned successively in water, absolute ethyl alcohol, acetone; Then in the electrolyte be made up of ammonium fluoride, water and ethylene glycol, normal temperature, anodic oxidation voltage are carry out first time anodic oxidation 1h under the condition of 60 volts, then at normal temperatures, ultrasonic power is 50-200W, ultrasonic 5min in absolute ethyl alcohol, obtains the titanium substrate that there is pit on surface;
Be proceed second time anodic oxidation 1-3h under the condition of 60 volts by the surface of gained by the titanium substrate of pit normal temperature, anodic oxidation voltage in the electrolyte be made up of ammonium fluoride, water and ethylene glycol again, obtaining is the titanium substrate of the Nano tube array of titanium dioxide of 15-30 μm with thickness;
Above-mentioned first time anodic oxidation and the used electrolyte be made up of ammonium fluoride, water and ethylene glycol of second time anodic oxidation identical, calculate in mass ratio, i.e. ammonium fluoride: water: ethylene glycol is 0.5:3:100;
(2), with supersonic wave cleaning machine at normal temperatures, ultrasonic power is 50-200W, be the Nano tube array of titanium dioxide of 15-30 μm with thickness titanium substrate carries out ultrasonic disperse process 5-15min in absolute ethyl alcohol to step (1) gained, make the on-chip Nano tube array of titanium dioxide of titanium be distributed in absolute ethyl alcohol, obtain the titania nanotube ethanolic solution that concentration is the dispersity of 30-50g/L;
(3) rotating speed, is controlled to be 4000-10000r/min by the concentration of step (2) gained is the titania nanotube solution centrifugal 5-10min of the dispersity of 30-50g/L, the precipitation of gained respectively cleans 3 times with deionized water and absolute ethyl alcohol successively, and then controlled pressure is 10
-1-10Pa, temperature are carry out vacuumize 12-15h under 110-130 DEG C of condition, obtain pure dispersity titanium dioxide nano-tube powder;
(4), under air conditions, pure for step (3) gained dispersity titanium dioxide nano-tube powder being controlled heating rate is that 1-3 DEG C/min is warming up to 700-800 DEG C and heat-treats 1-3h, and then to control rate of temperature fall be that 1-3 DEG C/min is down to room temperature, obtain the high-crystallinity titanium dioxide nano-tube powder of pure Anatase;
(5), by isopropyl alcohol and n-butanol by volume for 1:3-5 carries out being mixed to get alcoholic solution;
The alcoholic solution mixing that particle diameter is the titania nanoparticles of 15-30nm, the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained and above-mentioned gained, use magnetic stirrer to carry out stirring 18-25h with 150-300rpm speed, obtain the high-crystallinity titania nanotube of Anatase and the composite mortar of titania nanoparticles;
Above-mentioned particle diameter used is the amount of the titania nanoparticles of 15-30nm, the high-crystallinity titanium dioxide nano-tube powder of pure Anatase and alcoholic solution, is the titania nanoparticles of 15-30nm in particle diameter: the high-crystallinity titanium dioxide nano-tube powder of pure Anatase: alcoholic solution is that the ratio of 100g:10-300g:1-2L calculates;
(6), use knife coating, the high-crystallinity titania nanotube of the Anatase of step (5) gained and titania nanoparticles composite mortar are coated in electrically conducting transparent substrate, coating thickness is 8-12 μm, then by the natural drying in atmosphere together with film of electrically conducting transparent matrix, then electrically conducting transparent matrix and dried film control temperature are 450-500 DEG C and carry out sintering 1-3h, obtaining based on the thickness of electrically conducting transparent substrate is the titania nanotube of 7-10 μm and the laminated film of titania nanoparticles, then dye sensitization process is carried out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had,
Described sensitized treatment, concrete steps are as follows:
Be that the titania nanotube of 7-10 μm and the laminated film of titania nanoparticles are immersed in N719 dye solution by the thickness of above-mentioned gained, dye sensitization process 24h is carried out under room temperature, then take out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had;
The concentration of described N719 dye solution is 0.3mmol/L, and solute is N719 dyestuff, and solvent is mixed liquor that 1:1 forms by acetonitrile and the tert-butyl alcohol by volume.
2. a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect as claimed in claim 1, is characterized in that:
In step (1), on titanium substrate, the preparation of two-step electrochemical anode oxidation method is adopted to be the Nano tube array of titanium dioxide of 15 μm perpendicular to titanium substrate, thickness;
In step (2), with supersonic wave cleaning machine at normal temperatures, ultrasonic power is 100W, be the Nano tube array of titanium dioxide of 15 μm with thickness titanium substrate carries out ultrasonic disperse process 10min in absolute ethyl alcohol to step (1) gained, make the on-chip Nano tube array of titanium dioxide of titanium be distributed in absolute ethyl alcohol, obtain the titania nanotube ethanolic solution that concentration is the dispersity of 30g/L;
In step (3), control rotating speed to be 4000r/min by the concentration of step (2) gained be the titania nanotube solution centrifugal 10min of the dispersity of 30g/L, the precipitation of gained respectively cleans 3 times to remove impurity remaining in dispersity titania nanotube with deionized water and ethanol successively, then controlled pressure is 10Pa, temperature is carry out vacuumize 12h under 120 DEG C of conditions, obtains pure dispersity titanium dioxide nano-tube powder;
In step (4), under air conditions, pure for step (3) gained dispersity titanium dioxide nano-tube powder being controlled heating rate is that 2 DEG C/min is warming up to 700 DEG C and heat-treats 2h, and then to control rate of temperature fall be that 2 DEG C/min is down to room temperature, obtain the high-crystallinity titanium dioxide nano-tube powder of pure Anatase;
In step (5), by isopropyl alcohol and n-butanol by volume for 1:4 carries out being mixed to get alcoholic solution;
The high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained used, particle diameter are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm in particle diameter: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained: alcoholic solution is that the ratio of 100g:10-300g:1L calculates;
In step (6), use knife coating, the high-crystallinity titania nanotube of the Anatase of step (5) gained and titania nanoparticles composite mortar are coated in electrically conducting transparent substrate, coating thickness is 9 μm, then in by the natural drying in atmosphere together with film of electrically conducting transparent matrix, then electrically conducting transparent matrix and dried film control temperature are 450-500 DEG C and carry out sintering 2h, obtaining based on the thickness of electrically conducting transparent substrate is the titania nanotube of 8 μm and the laminated film of titania nanoparticles, then dye sensitization process is carried out, the dispersed titanium dioxide nanotube complex light anode of high light scattering effect must be had,
Described electrically conducting transparent substrate is fluorine doped tin oxide electro-conductive glass.
3. a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect as claimed in claim 2, it is characterized in that in step (5), the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained used, particle diameter are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm in particle diameter: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained: alcoholic solution is that the ratio of 100g:10g:1L calculates.
4. a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect as claimed in claim 2, it is characterized in that in step (5), the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained used, particle diameter are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm in particle diameter: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained: alcoholic solution is that the ratio of 100g:300g:1L calculates.
5. a kind of preparation method with the dispersed titanium dioxide nanotube complex light anode of high light scattering effect as claimed in claim 2, it is characterized in that in step (5), the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained used, particle diameter are the titania nanoparticles of 20nm and the amount of alcoholic solution, are the titania nanoparticles of 20nm in particle diameter: the high-crystallinity titanium dioxide nano-tube powder of the pure Anatase of step (4) gained: alcoholic solution is that the ratio of 100g:100g:1L calculates.
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| WO2007065480A1 (en) * | 2005-12-09 | 2007-06-14 | Technische Universität Braunschweig | Dye sensitized solar cell |
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| WO2007065480A1 (en) * | 2005-12-09 | 2007-06-14 | Technische Universität Braunschweig | Dye sensitized solar cell |
| CN101140957A (en) * | 2007-10-18 | 2008-03-12 | 清华大学 | Dye sensitization solar cell based on titanic oxide nano bar light scattering thin film electric pole and its preparing method |
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