CN102157268A - Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof - Google Patents
Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the technical field of photoelectrochemistry and photovoltaics and in particular provides a tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as a preparation method and an application thereof. The method is characterized by firstly adding tungstic acid solution to titanium isopropoxide, obtaining a tungsten-doped titanium dioxide colloid through treatment in water and then forming the nanocrystalline film through a hydrothermal method. The film and the preparation method have the following beneficial effects: the conduction band energy level of the titanium dioxide can be regulated after the tungsten is doped to ensure the conduction band energy level to be better matched with the excitation state energy level of the dye; the short circuit photocurrent and electron life of a dyed sensitized solar cell can be obviously improved when the nanocrystalline film is used for assembling the cell, thus substantially improving the energy conversion efficiency; and the defect that some dyes are unmatched with the conduction band energy level of the titanium dioxide can be overcome, and the preparation method has a good application prospect.
Description
Technical field
The invention belongs to Optical Electro-Chemistry and photovoltaic technology field, be specifically related to nano-crystalline titanium dioxide film that a kind of tungsten mixes and preparation method thereof and application.
Background technology
Dye-sensitized solar cells is the nearest twenties years a kind of solar cells of developing based on plant chlorophyll photosynthesis principle that grow up.This battery utilizes the strong absorption of dyestuff to visible light by being adsorbed onto on the semiconductor surface by dyestuff, semi-conductive spectral response can be widened the visual field, thereby obtain desirable electricity conversion.At present, oneself can be stabilized in the highest electricity conversion of DSSC more than 10 %, life-span can reach 10 ~ 20 years, and its manufacturing cost is 1/5 ~ 1/10 of a silicon solar cell only, be study in the present new material fullest, the most ripe, near the solar cell of industrialization state.Yet the peak efficiency of dye-sensitized solar cells just reached 10 % in 1993, and to also just having brought up to 12 % recently, the efficient that therefore further improves dye-sensitized solar cells is significant.
Up to the present, the nano-crystalline titanium dioxide of Detitanium-ore-type is the semi-conducting electrode material of the best dye-sensitized solar cells of performance.Therefore a lot of researchs concentrate on how to improve its performance to improve the overall electricity conversion of battery, and wherein metal-doped is a kind of up-and-coming method.The dissimilar metal atom can be replaced titanium atom by mixing, thereby change the band structure of titanium dioxide.Discover, can significantly improve injection, transfer efficiency and the transmission performance of nanocrystalline titanium dioxide film by mixing metallic zinc, aluminium, zirconium, neodymium.Charge recombination in the nano-crystalline titanium dioxide is a kind of mechanism of important destruction battery performance, yet seldom discovers and metal-dopedly can effectively suppress charge recombination.And the research that the tungsten doping nano crystal titanium dioxide is used in dye-sensitized solar cells still less, and do not find that tungsten mixes and can regulate and control the conduction level of titanium dioxide, suppresses charge recombination, significantly improves these functions of battery performance.The present invention is by being doped to tungsten in the titanium dioxide, different doping contents can be finely tuned the conduction level of titanium dioxide, thereby excited level better matching with dyestuff, significantly improved the performance of dye-sensitized solar cells, and issued the effect that has good inhibition charge recombination now at low doping concentration.
Summary of the invention
The object of the present invention is to provide a kind of tungsten doping nano crystal titanium dioxide semiconductive thin film that can significantly improve the dye-sensitized solar cells performance and preparation method thereof and application.
Tungsten doping nano crystal titanium dioxide semiconductive thin film provided by the invention, wherein, tungsten, Ti content mass ratio are: 0＜W/Ti＜25%, preferred 1%＜W/Ti＜20%; Nanocrystalline particle diameter scope is 5-50 nm, and such thin-film material thickness is 2-20 μ m, is water white transparency or white film.
The preparation method of tungsten doping nano crystal titanium dioxide film provided by the invention, concrete steps are:
1. the preparation of wolframic acid colloidal sol:
In beaker, take by weighing sodium tungstate and add in the deionized water, be mixed with the solution that mole solubility is 0-2.5 M, the solution water white transparency, be communicated with nitrogen with the glass dropper, insert beaker bottom, blow with nitrogen and be no less than 1 minute, in solution, drip equimolar hydrochloric acid then, produce white precipitate, and change yellow mercury oxide gradually into, logical again nitrogen blows and is no less than 1 minute.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the liquor argenti nitratis ophthalmicus of known solubility.Add deionized water at the product that filters, fully stir with magnetic stirring apparatus under the room temperature, getting concentration is the wolframic acid colloidal sol of 0-2.5 M.The concentration of wolframic acid colloidal sol is preferably 0.01-2.5 M.
2. the preparation of tungsten doping nano crystal titanium dioxide film
Dropwise be added drop-wise to the different third oxygen titanium in the deionized water, and stirring reaction is no less than 1 hour at ambient temperature, fully generate white precipitate, white precipitate is filtered, obtain titanium dioxide precipitation, this precipitation is transferred in the reaction bulb, drip the tetramethylammonium hydroxide aqueous solution of equivalent, add the wolframic acid solution of step 1 preparation again, add the deionized water constant volume at last.In 100-150 ℃ of oil bath powerful stirring reaction 1-5 hour, naturally cool to room temperature, the white colloid that obtains after reaction is finished is transferred in the autoclave and constant volume, under 150-300 ℃ condition hydrothermal treatment consists 6-24 hour.Take out behind the natural cooling and carry out sonicated, obtain milky TiO 2 sol, and on clean conductive glass, form one deck sol pellicle by rotation film forming or pulling film forming method.Dried film is put into Muffle furnace, and temperature is warming up to 450-550 ℃, and constant temperature 0.5-10 hour, naturally cool to room temperature, promptly obtain the nano-crystalline titanium dioxide film that tungsten mixes.Nanocrystalline form in the film and particle diameter characterize by an X-ray diffractometer and a saturating Electronic Speculum of emission.
The present invention also provides the application of above-mentioned tungsten doping nano crystal titanium dioxide film in dye-sensitized solar cells, the tungsten doping nano crystal titanium dioxide film that is about to the present invention's preparation is assembled dye-sensitized solar cells according to standard method, records each performance parameter of dye-sensitized solar cells under the AM1.5 simulated solar irradiation.Tungsten mixes and has significantly improved electron injection efficiency and short-circuit photocurrent, has improved the electron recombination life-span in the nano-crystalline titanium dioxide, has effectively suppressed the electron recombination in the nanocrystalline titanium dioxide film.Than the DSSC of the nanocrystalline titanium dioxide film preparation of Doped Tungsten not, mix performances such as the short-circuit photocurrent of DSSC of nanocrystalline titanium dioxide film preparation of tungsten and electricity conversion and be greatly improved.
To sum up, the present invention can regulate and control the conduction level of titanium dioxide after tungsten mixes, make it the excited level better matching with dyestuff.Utilize this nano-crystal film assembling dye-sensitized solar cells, can significantly improve the short-circuit photocurrent and the electron lifetime of battery, thereby energy conversion efficiency is significantly improved.This invention can remedy some dyestuff and the unmatched shortcoming of titanium dioxide conduction level, has very strong application prospect.
Description of drawings
Fig. 1. tungsten doping nano crystal titanium dioxide film X-ray diffraction spectrum.
Fig. 2. the nanocrystalline titanium dioxide film sem image that 0.1 % (left figure) and 1 % (right figure) tungsten mix.
Fig. 3. the structure chart of dyestuff NKX-2883.
Embodiment
Embodiment 10.01 the preparation of the wolframic acid colloidal sol of M
Described wolframic acid solution is formed by following prepared: take by weighing 0.147 g sodium tungstate and be dissolved in the 50 mL deionized waters in beaker, mixed solution is a colourless transparent solution, be communicated with nitrogen with the glass dropper, insert beaker bottom, blew 5 minutes with nitrogen, in solution, drip concentrated hydrochloric acid 20 mL of 1 M then, produce a large amount of white precipitates, be transformed into yellow mercury oxide gradually, logical again nitrogen blew 5 minutes.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the silver nitrate of 0.2 M.Add deionized water at the product that filters, make cumulative volume reach 50 mL, stir on magnetic stirring apparatus under the normal temperature, promptly getting concentration is the wolframic acid colloidal sol of 0.01 M.
Embodiment 20.02 the preparation of the wolframic acid colloidal sol of M
Described wolframic acid solution is formed by following prepared: take by weighing 0.294 g sodium tungstate and be dissolved in the 50 mL deionized waters in beaker, mixed solution is a colourless transparent solution, be communicated with nitrogen with the glass dropper, insert beaker bottom, blew 5 minutes with nitrogen, in solution, drip concentrated hydrochloric acid 20 mL of 1 M then, produce a large amount of white precipitates, be transformed into yellow mercury oxide gradually, logical again nitrogen blew 5 minutes.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the silver nitrate of 0.2 M.Add deionized water at the product that filters, make cumulative volume reach 50 mL, stir on magnetic stirring apparatus under the normal temperature, promptly getting concentration is the wolframic acid colloidal sol of 0.02 M.
Embodiment 30.05 the preparation of the wolframic acid colloidal sol of M
Described wolframic acid solution is formed by following prepared: take by weighing 0.735 g sodium tungstate and be dissolved in the 50 mL deionized waters in beaker, mixed solution is a colourless transparent solution, be communicated with nitrogen with the glass dropper, insert beaker bottom, blew 5 minutes with nitrogen, in solution, drip concentrated hydrochloric acid 20 mL of 1 M then, produce a large amount of white precipitates, be transformed into yellow mercury oxide gradually, logical again nitrogen blew 5 minutes.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the silver nitrate of 0.2 M.Add deionized water at the product that filters, make cumulative volume reach 50 mL, stir on magnetic stirring apparatus under the normal temperature, promptly getting concentration is the wolframic acid colloidal sol of 0.05 M.
Embodiment 40.1 the preparation of the wolframic acid colloidal sol of M
Described wolframic acid solution is formed by following prepared: take by weighing 1.47 g sodium tungstates and be dissolved in the 50 mL deionized waters in beaker, mixed solution is a colourless transparent solution, be communicated with nitrogen with the glass dropper, insert beaker bottom, blew 5 minutes with nitrogen, in solution, drip concentrated hydrochloric acid 20 mL of 1 M then, give birth to a large amount of white precipitates, be transformed into yellow mercury oxide gradually, logical again nitrogen blew 5 minutes.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the silver nitrate of 0.2 M.Add deionized water at the product that filters, make cumulative volume reach 50 mL, stir on magnetic stirring apparatus under the normal temperature, promptly getting concentration is the wolframic acid colloidal sol of 0.1 M.
Embodiment 50.2 the preparation of the wolframic acid colloidal sol of M
Described wolframic acid solution is formed by following prepared: take by weighing 2.94 g sodium tungstates and be dissolved in the 50 mL deionized waters in beaker, mixed solution is a colourless transparent solution, be communicated with nitrogen with the glass dropper, insert beaker bottom, blew 5 minutes with nitrogen, in solution, drip concentrated hydrochloric acid 20 mL of 1 M then, produce a large amount of white precipitates, be transformed into yellow mercury oxide gradually, logical again nitrogen blew 5 minutes.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the silver nitrate of 0.2 M.Add deionized water at the product that filters, make cumulative volume reach 50 mL, stir on magnetic stirring apparatus under the normal temperature, promptly getting concentration is the wolframic acid colloidal sol of 0.2 M.
Embodiment 60.5 the preparation of the wolframic acid colloidal sol of M
Described wolframic acid solution is formed by following prepared: take by weighing 7.35 g sodium tungstates and be dissolved in the 50 mL deionized waters in beaker, mixed solution is a colourless transparent solution, be communicated with nitrogen with the glass dropper, insert beaker bottom, blew 5 minutes with nitrogen, in solution, drip concentrated hydrochloric acid 20 mL of 1 M then, produce a large amount of white precipitates, be transformed into yellow mercury oxide gradually, logical again nitrogen blew 5 minutes.Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have white precipitate to produce fully with the silver nitrate of 0.2 M.Add deionized water at the product that filters, make cumulative volume reach 50 mL, stir on magnetic stirring apparatus under the normal temperature, promptly getting concentration is the wolframic acid colloidal sol of 0.5 M.
Embodiment 7The preparation of nanocrystalline titanium dioxide film
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip tetramethylammonium hydroxide aqueous solution 3.65 g, it is 40 g that the adding deionized water is adjusted to gross mass.Powerful stirring reaction is 3 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 450 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 0.01 % tungsten mixes.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 21 nm.It is 25 nm that field transmission electron microscope characterizes the particle diameter of finding nano particle, shown in accompanying drawing 2 right figure.
Embodiment 8Content is the preparation of the nanocrystalline titanium dioxide film of 0.1 % tungsten doping
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip the aqueous solution 3.65 g, wolframic acid colloidal sol 5 mL that add embodiment 1 preparation again, adding deionized water at last, to be adjusted to gross mass be 40 g.Powerful stirring reaction is 2 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 500 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 0.1 % tungsten mixes.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 18 nm.
Embodiment 9Content is the preparation of the nanocrystalline titanium dioxide film of 0.2 % tungsten doping
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip tetramethylammonium hydroxide aqueous solution 3.65 g, wolframic acid colloidal sol 5 mL that add embodiment 1 preparation again, adding deionized water at last, to be adjusted to gross mass be 40 g.Powerful stirring reaction is 2 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 450 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 0.2 % tungsten mixes.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 22 nm.
Embodiment 10Content is the preparation of the nanocrystalline titanium dioxide film of 0.5 % tungsten doping
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip tetramethylammonium hydroxide aqueous solution 3.65 g, wolframic acid colloidal sol 5 mL that add embodiment 1 preparation again, adding deionized water at last, to be adjusted to gross mass be 40 g.Powerful stirring reaction is 3 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 500 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 0.5 % tungsten mixes.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 23 nm.
Embodiment 11Content is the preparation of the nanocrystalline titanium dioxide film of 1 % tungsten doping
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip tetramethylammonium hydroxide aqueous solution 3.65 g, wolframic acid colloidal sol 5 mL that add embodiment 1 preparation again, adding deionized water at last, to be adjusted to gross mass be 40 g.Powerful stirring reaction is 3 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 500 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 1 % tungsten mixes.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 16 nm.Field transmission electron microscope characterizes the particle diameter of finding nano particle and is about 20 nm, shown in accompanying drawing 2 right figure.
Embodiment 12Content is the preparation of the nanocrystalline titanium dioxide film of 2 % tungsten doping
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip tetramethylammonium hydroxide aqueous solution 3.65 g, wolframic acid colloidal sol 5 mL that add embodiment 1 preparation again, adding deionized water at last, to be adjusted to gross mass be 40 g.Powerful stirring reaction is 3 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 500 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 2 % tungsten mix.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 18 nm.
Embodiment 13Content is the preparation of the nanocrystalline titanium dioxide film of 5% tungsten doping
Take by weighing the different third oxygen titanium of 14 g, dropwise be added drop-wise in the 50 mL deionized waters, stirring reaction is 2 hours under the room temperature, and the adularescent precipitation generates.The white precipitate that generates is carried out suction filtration, obtain titanium dioxide moist precipitate 24 g, moist precipitate is transferred in the there-necked flask, slowly drip tetramethylammonium hydroxide aqueous solution 3.65 g, wolframic acid colloidal sol 5 mL that add embodiment 1 preparation again, adding deionized water at last, to be adjusted to gross mass be 40 g.Powerful stirring reaction is 2 hours in 120 ℃ of oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is adjusted to 50 mL and is transferred in the 100 mL autoclaves, and hydrothermal treatment consists is 8 hours under 220 ℃ condition.Take out behind the natural cooling and carried out sonicated 20 minutes, obtain milky TiO 2 sol, and by rotation, lift and on clean conductive glass, form one deck sol pellicle.Dried film is put into Muffle furnace, and temperature slowly is warming up to 450 ℃, is incubated 2 hours, naturally cools to room temperature, and promptly obtaining content is the nanocrystalline titanium dioxide film that 5 % tungsten mix.Film characterizes through X-ray diffractometer and finds that as shown in Figure 1, prepared titanium dioxide nanocrystalline is an anatase crystal, and nano particle diameter is 19 nm.
Embodiment 140.1 % tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterization
The nanocrystalline titanium dioxide film that utilizes embodiment 7 preparations is according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.64 V, and short-circuit photocurrent is 8.0 mA/cm
2, fill factor, curve factor is 75 %, photoelectric conversion efficiency is 4.2 %.The dark current test shows is in 0.7 V bias voltage following time, and current strength is 2.7 mA/cm
2Record at light intensity 45 W/m by the intensity modulated photovoltaic spectrum
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 3.75 ms.
Embodiment 150.1 % tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterization
The 0.1 % tungsten doping nano crystal titanium dioxide film that utilizes embodiment 8 preparations is according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.63 V, and short-circuit photocurrent is 9.7 mA/cm
2, fill factor, curve factor is 58 %, photoelectric conversion efficiency is 4.6 %.The dark current test shows is in 0.7 V bias voltage following time, and current strength is 2.02 mA/cm
2Recording in light intensity by the intensity modulated photovoltaic spectrum is 45 W/m
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 3.82 ms.
Embodiment 160.2% tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterization
The 0.2 % tungsten doping nano crystal titanium dioxide film that utilizes embodiment 9 preparations is according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.63 V, and short-circuit photocurrent is 10.0 mA/cm
2, fill factor, curve factor is 65 %, photoelectric conversion efficiency is 5.1 %.The dark current test shows is in 0.7 V bias voltage following time, and current strength is 6.42 mA/cm
2Recording in light intensity by the intensity modulated photovoltaic spectrum is 45 W/m
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 16.8 ms.
Embodiment 170.5 % tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterization
The 0.5 % tungsten doping nano crystal titanium dioxide film that utilizes embodiment 10 preparations is according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.65 V, and short-circuit photocurrent is 8.6 mA/cm
2, fill factor, curve factor is 67 %, photoelectric conversion efficiency is 4.4 %.The dark current test shows is in 0.7V bias voltage following time, and current strength is 4.21 mA/cm
2Recording in light intensity by the intensity modulated photovoltaic spectrum is 45 W/m
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 52.3 ms.
Embodiment 181% tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterization
The 1% tungsten doping nano crystal titanium dioxide film that utilizes embodiment 11 preparations is according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.64 V, and short-circuit photocurrent is 9.1 mA/cm
2, fill factor, curve factor is 67 %, photoelectric conversion efficiency is 4.3 %.Recording in light intensity by the intensity modulated photovoltaic spectrum is 45 W/m
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 49.6 ms.
Embodiment 192 % tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterizations
The 2 % tungsten doping nano crystal titanium dioxide films that utilize embodiment 12 preparations are according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.63 V, and short-circuit photocurrent is 10.2 mA/cm
2, fill factor, curve factor is 58 %, photoelectric conversion efficiency is 4.1 %.Recording in light intensity by the intensity modulated photovoltaic spectrum is 45 W/m
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 57.1 ms.
Embodiment 205 % tungsten doping nano crystal titanium dioxide film radical dye sensitization solar cell performance characterizations
The 5 % tungsten doping nano crystal titanium dioxide films that utilize embodiment 13 preparations are according to existing standard method assembling dye-sensitized solar cells, and wherein dyestuff adopts NKX-2883(Fig. 3), electrolyte 0.1 M LiI/0.05 M I
2/ 0.5 M/ is to tert .-butylpyridine/0.6 M iodo 1, and the acetonitrile solution of 2-dimethyl-3-n-pro-pyl imidazoles is a platinum to electrode, and cell area is 0.25 cm
2Record the dye-sensitized solar cells current-voltage curve that contains different tungsten components under the AM1.5 simulated solar irradiation, the photovoltage that obtains opening a way is 0.57 V, and short-circuit photocurrent is 10.1 mA/cm
2, fill factor, curve factor is 53 %, photoelectric conversion efficiency is 3.2 %.Recording in light intensity by the intensity modulated photovoltaic spectrum is 45 W/m
2, under the wavelength 532 nm light source irradiation, the electron recombination life-span is 157 ms.
Claims (3)
1. the nano-crystalline titanium dioxide semiconductive thin film that mixes of a tungsten, it is characterized in that in this nanometer crystal semiconductor film, the mass ratio of tungsten, Ti content is: 0＜W/Ti＜25 %, nanocrystalline particle diameter scope is 5-50 nm, film thickness is 2-20 μ m, water white transparency or white.
2. the preparation method of the nano-crystalline titanium dioxide semiconductive thin film that mixes of a tungsten as claimed in claim 1 is characterized in that concrete steps are:
Preparation wolframic acid colloidal sol
In beaker, take by weighing sodium tungstate and add in the deionized water, be mixed with the solution that molar concentration is 0-2.5 M, be communicated with nitrogen with the glass dropper, insert beaker bottom, blow with nitrogen and to be no less than 1 minute, in solution, drip equimolar hydrochloric acid then, produce white precipitate, and changing yellow mercury oxide gradually into, logical again nitrogen blows and is no less than 1 minute; Suspension-turbid liquid is filtered, filtrate is carried out titration, in filtrate, do not have the white precipitate generation fully with the liquor argenti nitratis ophthalmicus of concentration known; Add deionized water in the product that filters, fully stir with magnetic stirring apparatus under the room temperature, obtaining concentration is the wolframic acid colloidal sol of 0-2.5 M;
Preparation tungsten doping nano crystal titanium dioxide film
The different third oxygen titanium dropwise is added drop-wise in the deionized water, and stirring reaction is no less than 1 hour at ambient temperature, fully generates white precipitate; White precipitate is filtered, obtain titanium dioxide precipitation; This titanium dioxide precipitation is transferred in the reaction bulb, is slowly dripped the tetramethylammonium hydroxide aqueous solution of equivalent, add again by step (1) preparation wolframic acid solution, add the deionized water constant volume at last; In 100-150 ℃ of oil bath stirring reaction 1-5 hour, naturally cool to room temperature, the white colloid that obtains after reaction is finished is transferred in the autoclave and constant volume, under 150-300 ℃ condition hydrothermal treatment consists 6-24 hour; Take out behind the natural cooling and carry out sonicated, obtain milky TiO 2 sol; On electro-conductive glass, form one deck sol pellicle by rotation film forming or pulling film forming method again; Dried film is put into Muffle furnace, and temperature rises to 450-550 ℃, and constant temperature 0.5-10 hour, naturally cool to room temperature, promptly obtain the nano-crystalline titanium dioxide semiconductive thin film that tungsten mixes.
One kind according to claim 1 the nano-crystalline titanium dioxide film that mixes of tungsten in the preparation DSSC, use.
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| CN103030304A (en) * | 2013-01-09 | 2013-04-10 | 华北电力大学 | Preparation method of titanium dioxide nano porous film material |
| CN104071831A (en) * | 2014-06-25 | 2014-10-01 | 复旦大学 | Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays |
| CN104310793A (en) * | 2014-10-18 | 2015-01-28 | 中山市创科科研技术服务有限公司 | Silver-doped titanium dioxide nano film glass and preparation method thereof |
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| CN101478035A (en) * | 2009-01-09 | 2009-07-08 | 中国科学院上海硅酸盐研究所 | Electrode material used for organic inorganic composite cell and manufacturing process |
| CN101567271A (en) * | 2009-05-08 | 2009-10-28 | 上海大学 | Method for preparing nano-crystalline Fe-doped meso-porous TiO* thick film electrode |
| CN101593627A (en) * | 2009-07-13 | 2009-12-02 | 北京化工大学 | The preparation method of metal-doped low-energy gap nanocrystalline semiconductor photo-anode film |
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| CN101567271A (en) * | 2009-05-08 | 2009-10-28 | 上海大学 | Method for preparing nano-crystalline Fe-doped meso-porous TiO* thick film electrode |
| CN101593627A (en) * | 2009-07-13 | 2009-12-02 | 北京化工大学 | The preparation method of metal-doped low-energy gap nanocrystalline semiconductor photo-anode film |
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| CN103030304A (en) * | 2013-01-09 | 2013-04-10 | 华北电力大学 | Preparation method of titanium dioxide nano porous film material |
| CN104071831A (en) * | 2014-06-25 | 2014-10-01 | 复旦大学 | Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays |
| CN104310793A (en) * | 2014-10-18 | 2015-01-28 | 中山市创科科研技术服务有限公司 | Silver-doped titanium dioxide nano film glass and preparation method thereof |
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