CN103165287B - Photocuring prepares the method for Nano-titania Porous Films - Google Patents
Photocuring prepares the method for Nano-titania Porous Films Download PDFInfo
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- CN103165287B CN103165287B CN201310075246.0A CN201310075246A CN103165287B CN 103165287 B CN103165287 B CN 103165287B CN 201310075246 A CN201310075246 A CN 201310075246A CN 103165287 B CN103165287 B CN 103165287B
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Abstract
The present invention relates to the method utilizing photocuring technology to prepare Nano-titania Porous Films, belong to technical field of function materials, also belong to light polymerization technique field.The monomer material of nano titanium oxide colloid and photopolymerization is mixed and made into colloidal titania dispersion by it, is coated on substrate surface, through the irradiation polymerization film-forming of ultraviolet light, defines the nano-titanium dioxide film of loose structure finally by heat treatment.The invention provides a kind of method being prepared Nano-titania Porous Films by photocuring organic-inorganic mixed system coating, the method meets " 5E " principle of photocuring technology, simultaneously by changing the reaction conditions such as monomeric species, light trigger kind, monomer addition and coating method, realize the regulation and control to film morphology, thickness, pore-size etc., the Nano-titania Porous Films of preparation has the advantages such as incrust, high-specific surface area, all even porosity of surfacing are large.The present invention can be applicable to DSSC, and loose structure can increase the absorption of dyestuff, strengthens the scattering of light, and then improves the photoelectric conversion efficiency of battery, has very high practical value and application prospect.
Description
Technical field
The present invention relates to the method utilizing photocuring technology to prepare Nano-titania Porous Films, belong to technical field of function materials, also belong to light polymerization technique field, particularly utilize photocuring technology to prepare the method that can be used for the Nano-titania Porous Films of dye-sensitized solar cell anode.
Background technology
Since the eighties in 20th century, the federal Instituto Superior Technico of Lausanne, SUI
the seminar of professor is devoted to the research of dye sensitization porous nano electrode always, and they, with porous nano titanium dioxide film adsorb transition metal Ru Complex dyes, select suitable oxidation-reduction electrolyte, have developed a kind of dye sensitized nano crystal hull cell.Based on this principle battery research made a breakthrough in 1991, O'Regan and
nature reports this kind of novel low-cost photovoltaic cell, and under AM1.5 solar simulated is irradiated, its total photoelectric conversion efficiency can reach 7.1 ~ 7.9%.1993,
seminar reports the DSSC that photoelectric conversion efficiency reaches 10% again.The development appearing as photoelectrochemical cell of this battery brings revolutionary innovation, and the major advantage of DSSC is the cost of its cheapness and simple technique, and cost of manufacture is only 1/5 ~ 1/10 of silicon solar cell.
DSSC has the structure of similar sandwich: the Nano-titania Porous Films light anode being adsorbed with dyestuff, load catalyst to the electrolyte containing redox couple between electrode and the two poles of the earth.Under the irradiation of incident light, the light-sensitive coloring agent being adsorbed in nano titanium oxide surface absorbs suitable photon, transit to excitation state, then the conduction band to titanium dioxide injects electronics, dyestuff becomes the cation of oxidation state, electronics spreads and reaches in the collectors such as electro-conductive glass in photo-anode film, electric current is formed to electrode subsequently by external circuit, electronics on electrode is transferred in the oxidant in electrolyte through catalytic reaction, in electrolyte solution the electronics of reducing agent then accept by dyestuff cation, dyestuff is lived again, forms a complete circulation.In whole process, apparent upper chemical substance does not change, and light energy conversion has become electric energy.
In order to the photoelectric conversion efficiency of the photocatalysis performance and DSSC that improve titanium dioxide, preparation is usually needed to have the nano-titanium dioxide film of loose structure.On the one hand, Nano-titania Porous Films has large specific area, can increase the adsorbance of dyestuff, thus improves the absorption efficiency to sunlight; On the other hand, sunlight can repeatedly reflect in loose structure, increases dyestuff to the absorption of sunlight, thus improves the utilization ratio to sunlight.This preparation method with the Nano-titania Porous Films of high-specific surface area mainly contains two classes at present: (one) powder coated method (as Japanese Unexamined Patent Publication 10-212120 publication), is dispersed into suspension load at substrate surface by nano titanium oxide.The method technique is simple, with low cost, but the contact area of the nano-titanium dioxide film adopting powder coated legal system standby and base material is little, and not strong to the adhesive force of base material, nano-titanium dioxide film easily peels off.(2) sol-gel process (as Japanese Unexamined Patent Publication 11-310898 publication), utilizes sol-gal process directly to prepare nano-titanium dioxide film at substrate surface.What generally adopt at present is sol-gel process, obtained nano-titanium dioxide film is evenly distributed, good film-forming property, but the method itself also has some to be difficult to the shortcoming overcome, as complex process, inefficiency, cannot effectively control nano-titanium dioxide film surface topography, in addition the nano-titanium dioxide film pore structure adopting sol-gal process to prepare is less, specific area is little, dyestuff is difficult to enter nano-titanium dioxide film inside, thus have impact on the photoelectric conversion efficiency of DSSC.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide and utilize photocuring technology to prepare the method that can be used for the Nano-titania Porous Films of dye-sensitized solar cell anode.The method technique is simple, good film-forming property, take full advantage of the advantage of photocuring technology, obtained Nano-titania Porous Films and the strong adhesion of base material, pattern, size are controlled, there is loose structure, high-specific surface area, there is very high practical value and application prospect in DSSC.
The photocuring technology that utilizes provided by the invention prepares the method with the nano-titanium dioxide film of loose structure, nano titanium oxide colloid is mixed the obtained colloidal titania dispersion that can apply film forming by it with the monomer of photopolymerization, make coating carry out photopolymerization reaction film-forming after being coated on substrate surface, form Nano-titania Porous Films finally by heat treatment.Based on foregoing, the method specifically comprises the following steps:
(1) base material preliminary treatment: base material ultrasonic cleaning is clean, is soaked in aqueous isopropanol for subsequent use.
Base material is successively according to the order ultrasonic cleaning 10 ~ 20min respectively of washing agent, deionized water, acetone, deionized water, ethanol and deionized water.
(2) aqueous colloidal dispersion is prepared: be dispersed in by nano titanium oxide in the mixed solution of ethanol and isopropyl alcohol and obtain a, the volume ratio scope of ethanol and isopropyl alcohol is 2 ~ 5:5; Monomer and light trigger to be dissolved in the mixed solution of ethanol and DMF to obtain b, and the molar ratio of ethanol and DMF is 1:1, adds in a afterwards by b, mix that obtain can the colloidal titania dispersion of film.
Nano titanium oxide is one or more in titania nanoparticles, titania nanotube, titanium dioxide nano-rod or titanium dioxide nano thread.
In the aqueous colloidal dispersion of gained, the molar ratio of ethanol, isopropyl alcohol and DMF is 2 ~ 5:2:1 ~ 5, and the mass ratio range of monomer, light trigger and titanium dioxide is 1 ~ 2.5:0.02 ~ 0.1:0.5 ~ 2.0.
Monomer is one or more in simple function group, difunctional and multi-functional acrylate or methacrylate.
Light trigger is one or more in benzil and derivative, acetophenone derivs, α – hydroxy-ketone derivative, α – amido ketone derivatives, benzophenone and derivative/tertiary amine, thioxanthone and derivative/tertiary amine thereof, anthraquinone and derivative/tertiary amine thereof.
(3) film forming is applied: the base material be soaked in aqueous isopropanol takes out nitrogen and dries up the base material obtaining load nano-titanium dioxide film, and being coated on pretreated base material of colloidal titania dispersion homogeneous obtained in above-mentioned steps (2) is formed the uniform coating of a layer thickness.
The method that base material is formed coating includes knife coating, spin-coating method, dip-coating method and spraying process.
(4) radiation curing: under the base material being coated with colloidal titania dispersion coating obtained in step (3) is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.
The exposure time of UV light source is 2 ~ 15min, and light intensity is 5 ~ 200mW/cm
2, the radiation modality in point, line or face is taked in the irradiation of UV light source.
(5) heat treatment: the cured film obtained through step (4) is placed in box Muffle furnace heat-treats, be warming up to temperature gradually by room temperature to be arbitrary temp in 500 ~ 750 DEG C of intervals and to be incubated 1 ~ 3h to sinter, last stove is cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.
Heating rate is 1 ~ 10 DEG C/min, and is be incubated 15 ~ 60min respectively in 100 ~ 200 DEG C and 300 ~ 400 DEG C of intervals in temperature.
The present invention introduces the monomer that can carry out photopolymerization reaction in nanometer titanium dioxide colloid solution, utilizes light polymerization technique to make it in substrate surface photocuring film forming, forms Nano-titania Porous Films eventually through heat treatment organics removal matter.Be compared to the existing method preparing nano-titanium dioxide film in this area, preparation method of the present invention avoids the shortcoming existed in previous methods, its advantage is: the present invention is by changing monomeric species, content of monomer, light trigger kind, nano-titania particle pattern, coating method, light application time, the reaction conditions such as illumination methods, can very simply realize film morphology, thickness, the control of pore-size, this method technique is simple, good film-forming property, make full use of the advantage of photocuring technology, obtained has the titanium deoxid film of loose structure and the strong adhesion of base material, pattern, size is controlled, there is loose structure, high-specific surface area, the absorption of dyestuff can be increased, strengthen the scattering of light, and then improve the photoelectric conversion efficiency of DSSC.
Accompanying drawing explanation
Fig. 1 is scanning electron microscopy (SEM) photo of nano-titanium dioxide film heat treatment front surface prepared in embodiments of the invention 1.
Fig. 2 is the SEM photo of nano-titanium dioxide film heat treatment rear surface prepared in embodiments of the invention 1.
Fig. 3 is the SEM photo in cross section after the nano-titanium dioxide film heat treatment prepared by embodiments of the invention 1.
By surface topography and the Cross Section Morphology of the nano-titanium dioxide film prepared by sem observation.Fig. 1 is the SEM photo of nano-titanium dioxide film heat treatment front surface prepared in embodiment 1, can observe the polymer that in the nano-titanium dioxide film before photocuring after-baking, nano-titania particle is formed by polymerization reaction be wrapped in.Fig. 2 is the SEM photo of nano-titanium dioxide film heat treatment rear surface prepared in embodiment 1, after can observing photocuring, in the nano-titanium dioxide film of Overheating Treatment, nano-titania particle arrangement is loosened, and has a lot of out-of-shape, hole not of uniform size between particle.Fig. 3 is the SEM photo in cross section after the nano-titanium dioxide film heat treatment prepared by embodiment 1, and after can observing heat treatment, the thickness of nano-titanium dioxide film is about 5 μm.
Embodiment
Embodiment 1
By FTO transparent conducting glass successively according to the order ultrasonic cleaning 15min respectively of blue moon washing agent, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.0g titania nanoparticles is dispersed in the mixed solution of 6.0mL ethanol and 15.0mL isopropyl alcohol and obtains a; 2.0g monomer pentaerythritol triacrylate (PETA) and 0.025g light trigger 2-hydroxy-2-methyl-1-phenylacetone (HMPP) are dissolved in 6.0mL ethanol and 8.0mLN, obtain b in the mixed solution of dinethylformamide (DMF).Afterwards b is added dropwise in a, mixes the colloidal titania dispersion of obtained film.Nitrogen dries up the FTO transparent conducting glass be soaked in aqueous isopropanol, the obtained uniform coating of a layer thickness on the FTO transparent conducting glass utilizing knife coating to be coated on uniformly by aqueous colloidal dispersion to clean up.Under the FTO electro-conductive glass being coated with colloidal titania dispersion coating is placed in UV lamp, obtain cured film through ultraviolet radiation.The irradiation time of UV light source is 5min, and light intensity is 50mW/cm
2, a radiation modality is taked in the irradiation of UV light source.Then the cured film obtained is heat-treated, to be heated up gradually by room temperature with the heating rate of 2 DEG C/min and be incubated 30min respectively 150 DEG C and 400 DEG C, finally be warming up to 600 DEG C and be incubated 2h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the TiO after sintering
2porous membrane is cooled to 100 DEG C, immerses 24h in 0.5mMN719 dye solution (solvent is the tert-butyl alcohol and the acetonitrile of volume ratio 1:1) under airtight darkroom.The painted TiO that nitrogen dries up
2perforated membrane faces up placement, then by platinum to electrode surface towards being placed down in, slightly staggering and clamping with folder is assembled into DSSC.Electrolyte (0.6MBMII, 0.03MI is instilled from the seam of two cube electrodes
2, 0.1M guanidinium isothiocyanate and 0.5M4-tert .-butylpyridine, solvent is acetonitrile and the valeronitrile of volume ratio 85:15), until diffusion is full of whole battery.Light source is tungsten halogen lamp, and incident intensity is 100mW/cm
2.Record V
oc=731mV, I
sc=15.53mA/cm
2, ff=0.70, therefore the photoelectric conversion efficiency of battery is η (%)=7.9.
Embodiment 2
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 15min respectively of five clean powder, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.0g titanium dioxide nano-rod is dispersed in the mixed solution of 6.0mL ethanol and 15.0mL isopropyl alcohol and obtains a; 2.0g monomer pentaerythritol triacrylate and 0.03g light trigger 2-hydroxy-2-methyl-1-phenylacetone are dissolved in 6.0mL ethanol and 8.0mLN, obtain b in the mixed solution of dinethylformamide.Afterwards b is added dropwise in a, mixes the colloidal titania dispersion of obtained film.Nitrogen dries up the base material that FTO electro-conductive glass obtains load thin film, the aqueous colloidal dispersion coating utilizing dip-coating method to obtain one deck to be evenly distributed at substrate surface.Under the painting be coated on FTO electro-conductive glass is placed on UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 5min, and light intensity is 50mW/cm
2, a radiation modality is taked in the irradiation of UV light source.Then the cured film obtained is placed in box Muffle furnace and heat-treats, to be heated up gradually by room temperature with the heating rate of 5 DEG C/min and be incubated 30min respectively 150 DEG C and 400 DEG C, finally be warming up to 600 DEG C and be incubated 2h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=705mV, I
sc=12.93mA/cm
2, ff=0.70, therefore the photoelectric conversion efficiency of battery is η (%)=6.4.
Embodiment 3
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 20min respectively of hand cleanser, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.0.75g titania nanoparticles is dispersed in the mixed solution of 5.0mL ethanol and 12.0mL isopropyl alcohol and obtains a; 1.0g monomer pentaerythritol triacrylate and 0.02g light trigger benzophenone are dissolved in 5.0mL ethanol and 7.0mLN, obtain b in the mixed solution of dinethylformamide.Afterwards b is added in a, mix the colloidal titania dispersion of obtained film.Nitrogen dries up FTO electro-conductive glass, utilizes knife coating obtained aqueous colloidal dispersion to be coated on uniformly the substrate surface cleaned up.Under the colloidal titania dispersion coating be coated on FTO electro-conductive glass is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 5min, and light intensity is 30mW/cm
2, line radiation modality is taked in the irradiation of UV light source.The cured film obtained is placed in box Muffle furnace and heat-treats, to be heated up gradually by room temperature with the heating rate of 2 DEG C/min and be incubated 60min respectively 150 DEG C and 400 DEG C, finally be warming up to 550 DEG C and be incubated 2h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=669mV, I
sc=13.16mA/cm
2, ff=0.73, therefore the photoelectric conversion efficiency of battery is η (%)=6.4.
Embodiment 4
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 15min respectively of five clean powder, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.0g titania nanoparticles is dispersed in the mixed solution of 6.0mL ethanol and 15.0mL isopropyl alcohol and obtains a; 2.0g monomer third is oxidized tri methylol triacrylate and 0.025g light trigger α, α '-dimethyl benzil ketals is dissolved in 6.0mL ethanol and 8.0mLN, obtains b in the mixed solution of dinethylformamide.Afterwards b is added in a, mix the colloidal titania dispersion of obtained film.Nitrogen dries up FTO electro-conductive glass, utilizes spin-coating method to be coated on uniformly on base material by obtained aqueous colloidal dispersion and forms one deck coating.Under the FTO electro-conductive glass being coated with colloidal titania dispersion is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 10min, and light intensity is 20mW/cm
2, face radiation modality is taked in the irradiation of UV light source.The cured film obtained is placed in box Muffle furnace and heat-treats, to be heated up gradually by room temperature with the heating rate of 5 DEG C/min and be incubated 30min respectively 120 DEG C and 350 DEG C, finally be warming up to 550 DEG C and be incubated 1h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=695mV, I
sc=12.24mA/cm
2, ff=0.69, therefore the photoelectric conversion efficiency of battery is η (%)=5.9.
Embodiment 5
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 10min respectively of five clean powder, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.5g titania nanoparticles is dispersed in the mixed solution of 15mL ethanol and 16mL isopropyl alcohol and obtains a; 4.0g monomer triethylene-glycol dimethylacrylate and 0.06g light trigger α, α '-diethoxy acetophenone is dissolved in 15mL ethanol and 20mLN, obtains b in the mixed solution of dinethylformamide.Afterwards b is added in a, mix the colloidal titania dispersion of obtained film.Nitrogen dries up the base material that FTO electro-conductive glass obtains load thin film, utilizes spraying process to apply one deck aqueous colloidal dispersion coating uniformly at substrate surface.Under the FTO electro-conductive glass film being coated with colloidal titania dispersion coating is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 15min, and light intensity is 50mW/cm
2, face radiation modality is taked in the irradiation of UV light source.The cured film obtained is heat-treated, to be heated up gradually by room temperature with the heating rate of 10 DEG C/min and be incubated 60min respectively 200 DEG C and 400 DEG C, finally be warming up to 700 DEG C and be incubated 1h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=697mV, I
sc=14.17mA/cm
2, ff=0.68, therefore the photoelectric conversion efficiency of battery is η (%)=6.7.
Embodiment 6
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 15min respectively of blue moon washing agent, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.0g titania nanoparticles is dispersed in the mixed solution of 6.0mL ethanol and 10.0mL isopropyl alcohol and obtains a; 2.0g monomer tri (propylene glycol) diacrylate and 0.03g light trigger 1-hydroxy cyclohexyl phenylketone are dissolved in 6.0mL ethanol and 8.0mLN, obtain b in the mixed solution of dinethylformamide.Afterwards b is added in a, mix the colloidal titania dispersion of obtained film.Nitrogen dries up FTO electro-conductive glass, and the base material utilizing knife coating to be coated on uniformly by obtained aqueous colloidal dispersion to clean up forms the uniform coating of a layer thickness.Under the aqueous colloidal dispersion coated film be coated on FTO electro-conductive glass is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 15min, and light intensity is 10mW/cm
2, a radiation modality is taked in the irradiation of UV light source.The cured film obtained is placed in box Muffle furnace and heat-treats, to be heated up gradually by room temperature with the heating rate of 5 DEG C/min and be incubated 30min respectively 150 DEG C and 300 DEG C, finally be warming up to 550 DEG C and be incubated 2h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=665mV, I
sc=13.09mA/cm
2, ff=0.63, therefore the photoelectric conversion efficiency of battery is η (%)=5.5.
Embodiment 7
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 20min respectively of hand cleanser, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.25g titania nanoparticles is dispersed in the mixed solution of 8.0mL ethanol and 15mL isopropyl alcohol and obtains a; 3.0g monomeric acrylic isodecyl ester and 0.05g light trigger 2-methyl isophthalic acid-(4-first mercaptophenyl)-2-morpholine-1-acetone solution, in 8.0mL ethanol and 10mLN, obtain b in the mixed solution of dinethylformamide.Afterwards b is added in a, mix the colloidal titania dispersion of obtained film.Nitrogen dries up FTO electro-conductive glass, utilizes spin-coating method that obtained aqueous colloidal dispersion is coated on substrate surface uniformly.Under the FTO electro-conductive glass being coated with colloidal titania dispersion coating is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 2min, and light intensity is 100mW/cm
2, line radiation modality is taked in the irradiation of UV light source.The cured film obtained is placed in box Muffle furnace and heat-treats, to be heated up gradually by room temperature with the heating rate of 5 DEG C/min and be incubated 60min respectively 100 DEG C and 300 DEG C, finally be warming up to 500 DEG C and be incubated 3h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=705mV, I
sc=10.45mA/cm
2, ff=0.75, therefore the photoelectric conversion efficiency of battery is η (%)=5.5.
Embodiment 8
By FTO electro-conductive glass successively according to the order ultrasonic cleaning 15min respectively of blue moon washing agent, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be finally soaked in aqueous isopropanol for subsequent use.1.5g titania nanoparticles is dispersed in the mixed solution of 10mL ethanol and 15mL isopropyl alcohol and obtains a; 2.0g monomer tetramethylol methane tetraacrylate and 0.04g light trigger TMDPO are dissolved in 10mL ethanol and 14mLN, obtain b in the mixed solution of dinethylformamide.Afterwards b is added in a, mix the colloidal titania dispersion of obtained film.Nitrogen dries up FTO electro-conductive glass, utilizes knife coating to apply one deck colloidal titania dispersion coating uniformly at substrate surface.Under the painting be coated on FTO electro-conductive glass is placed on UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film.The irradiation time of UV light source is 10min, and light intensity is 30mW/cm
2, face radiation modality is taked in the irradiation of UV light source.The cured film obtained is heat-treated, to be heated up gradually by room temperature with the heating rate of 2 DEG C/min and be incubated 60min respectively 150 DEG C and 400 DEG C, finally be warming up to 700 DEG C and be incubated 2h and sinter, be cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.By the same terms assembling DSSC in embodiment 1, record V
oc=699mV, I
sc=13.17mA/cm
2, ff=0.73, therefore the photoelectric conversion efficiency of battery is η (%)=6.7.
Claims (8)
1. photocuring prepares the method for Nano-titania Porous Films, it is characterized in that the method comprises the following steps:
(1) base material preliminary treatment: by base material successively according to the order ultrasonic 10 ~ 20min respectively of washing agent, deionized water, acetone, deionized water, ethanol and deionized water, be soaked in aqueous isopropanol for subsequent use after cleaning up;
(2) aqueous colloidal dispersion is prepared: be dispersed in by nano titanium oxide in the mixed solution of ethanol and isopropyl alcohol and obtain a, the volume ratio of ethanol and isopropyl alcohol is 2 ~ 5:5; Monomer and light trigger are dissolved in the mixed solution of ethanol and DMF and obtain b, and the molar ratio of ethanol and DMF is 1:1, adds in a afterwards by b, mixes the colloidal titania dispersion of obtained film; Described monomer is one or more in simple function group, difunctional and multi-functional acrylate or methacrylate;
(3) apply film forming: nitrogen dries up and cleans up base material for subsequent use, is coated on base material by colloidal titania dispersion, make its surface form the uniform coating of a layer thickness;
(4) radiation curing: under the base material being coated with colloidal titania dispersion coating that step (3) obtains is placed in UV lamp, carries out polymerization reaction through ultraviolet radiation and obtain cured film;
(5) heat treatment: the cured film obtained through step (4) is placed in box Muffle furnace heat-treats, be warming up to the arbitrary temperature in 500 ~ 750 DEG C of intervals gradually by room temperature and be incubated 1 ~ 3h and sinter, be finally cooled to the nano-titanium dioxide film that namely room temperature obtains having loose structure.
2. method according to claim 1, is characterized in that: the nano titanium oxide described in step (2) is one or more in titania nanoparticles, titania nanotube, titanium dioxide nano-rod or titanium dioxide nano thread.
3. method according to claim 1, it is characterized in that: ethanol, isopropyl alcohol and N in the colloidal titania dispersion described in step (2), the molar ratio of dinethylformamide is 2 ~ 5:2:1 ~ 5, and the mass ratio of monomer, light trigger and titanium dioxide is 1 ~ 2.5:0.02 ~ 0.1:0.5 ~ 2.0.
4. method according to claim 1, is characterized in that: the initator described in step (2) is one or more in benzil and derivative, acetophenone derivs, α – hydroxy-ketone derivative, α – amido ketone derivatives, benzophenone and derivative/tertiary amine, thioxanthone and derivative/tertiary amine thereof, anthraquinone and derivative/tertiary amine thereof.
5. method according to claim 1, is characterized in that: the method forming coating on base material described in step (3) is one or more in knife coating, spin-coating method, dip-coating method or spraying process.
6. method according to claim 1, is characterized in that: the exposure time of the ultraviolet source described in step (4) is 2 ~ 15min, and light intensity is 5 ~ 200mW/cm
2.
7. method according to claim 1, is characterized in that: the radiation modality in point, line or face is taked in the irradiation of the UV light source described in step (4).
8. method according to claim 1, is characterized in that: the heating rate described in step (5) is 1 ~ 10 DEG C/min, and is incubated 15 ~ 60min respectively 100 ~ 200 DEG C and 300 ~ 400 DEG C.
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| CN103588243B (en) * | 2013-09-11 | 2015-10-07 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of nano-titanium dioxide powder |
| CN103474242B (en) * | 2013-09-26 | 2016-01-20 | 华北电力大学 | A kind of anode film of dye-sensitized solar cells |
| CN105036072B (en) * | 2015-05-22 | 2017-03-22 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105753336B (en) * | 2016-01-25 | 2018-01-16 | 浙江大学 | A kind of surface has carbon-oxidation nickel composite film of array loose structure and preparation method thereof |
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