CN103165287A - Method for manufacturing nano titanium dioxide thin film through photocuring - Google Patents
Method for manufacturing nano titanium dioxide thin film through photocuring Download PDFInfo
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- CN103165287A CN103165287A CN2013100752460A CN201310075246A CN103165287A CN 103165287 A CN103165287 A CN 103165287A CN 2013100752460 A CN2013100752460 A CN 2013100752460A CN 201310075246 A CN201310075246 A CN 201310075246A CN 103165287 A CN103165287 A CN 103165287A
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Abstract
The invention belongs to the technical field of functional materials and photopolymerization and relates to a method for manufacturing a nano titanium dioxide thin film through photocuring. According to the method, a nano titanium dioxide colloid and a photopolymerisable monomer material are mixed to manufacture a colloid titanium dioxide dispersoid, the colloid titanium dioxide dispersoid is coated on the surface of a base material and polymerized and curied through radiation of ultraviolet to manufacture a film, and finally, the porous nano titanium dioxide thin film is obtained by performing thermal treatment on the film. The invention also provides a method for manufacturing the porous nano titanium dioxide thin film by photocuring an organic and inorganic mixed system coating. The method accords with a '5E' principal of a photocuring technology, the morphology, the thickness, the pore dimension and the like of the thin film are regulated and controlled by changing reaction conditions such as types of a monomer and a photoinitiator, the monomer addition amount, a film coating method and the like; the manufactured porous nano titanium dioxide thin film has the advantages of high specific surface area, smooth and uniform surface, high porosity and the like and is difficultly peeled. The method can be applied to a dye-sensitized solar cell; through a porous structure, the dye adsorption capacity can be enhanced, the light scattering performance is enhanced, and the photoelectric conversion efficiency of the cell is improved; and the manufactured thin film has a high practical value and a application prospect.
Description
Technical field
The present invention relates to utilize photocuring technology to prepare the method for Nano-titania Porous Films, belong to technical field of function materials, also belong to the light polymerization technique field, particularly utilize the photocuring technology preparation to can be used for the method for the Nano-titania Porous Films of dye-sensitized solar cell anode.
Background technology
Since the eighties in 20th century, Lausanne, SUI federal Instituto Superior Technico
Professor's seminar is devoted to the research of dye sensitization porous nano electrode always, and they select suitable oxidation-reduction electrolyte with porous nano titanium dioxide film absorption transition metal Ru complex compound dyestuff, have developed a kind of dye sensitized nano crystal hull cell.Research made a breakthrough in 1991 based on the battery of this principle, O'Regan and
Reported this class novel low-cost photovoltaic cell on Nature, under the irradiation of AM1.5 solar simulated, its total photoelectric conversion efficiency can reach 7.1～7.9%.1993,
Seminar has reported that again photoelectric conversion efficiency reaches 10% DSSC.The development that appears as photoelectrochemical cell of this battery has brought revolutionary innovation, and the major advantage of DSSC is cost and the simple technique of its cheapness, and cost of manufacture is only 1/5～1/10 of silicon solar cell.
DSSC has the structure of similar sandwich: absorption has the Nano-titania Porous Films light anode of dyestuff, load catalyst to the electrolyte that contains redox couple between electrode and the two poles of the earth.Under the irradiation of incident light, be adsorbed in the suitable photon of light-sensitive coloring agent absorption on nano titanium oxide surface, transit to excitation state, then the conduction band to titanium dioxide injects electronics, dyestuff becomes the cation of oxidation state, electronics spreads in photo-anode film in collectors such as reaching electro-conductive glass, forming electric current by external circuit subsequently arrives electrode, electronics on electrode is transferred in oxidant in electrolyte through catalytic reaction, in electrolyte solution, the electronics of reducing agent is accepted by the dyestuff cation, make dyestuff live again, form a complete circulation.In whole process, apparent upper chemical substance does not change, and light energy conversion has become electric energy.
For the photocatalysis performance that improves titanium dioxide and the photoelectric conversion efficiency of DSSC, usually need preparation 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, thereby improves the absorption efficiency to sunlight; On the other hand, sunlight can reflect in loose structure repeatedly, increases dyestuff to sun Optical Absorption, thereby improves the utilization ratio to sunlight.This preparation method with Nano-titania Porous Films of high-specific surface area mainly contains two classes at present: (one) powder coated method (as Japanese kokai publication hei 10-212120 communique) is dispersed into suspension with nano titanium oxide and loads on substrate surface.The method technique is simple, with low cost, but adopts the contact area of the standby nano-titanium dioxide film of powder coated legal system and base material little, and not strong to the adhesive force of base material, nano-titanium dioxide film easily peels off.(2) sol-gel process (as Japanese kokai publication hei 11-310898 communique), utilize sol-gal process directly to prepare nano-titanium dioxide film at substrate surface.What generally adopt at present is sol-gel process, the nano-titanium dioxide film that makes is evenly distributed, good film-forming property, but the method itself also has some shortcomings that are difficult to overcome, as complex process, inefficiency, can't effectively control the nano-titanium dioxide film surface topography, adopt in addition the nano-titanium dioxide film pore structure of sol-gal process preparation less, specific area is little, dyestuff is difficult to enter nano-titanium dioxide film inside, thereby has affected the photoelectric conversion efficiency of DSSC.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the method for utilizing the photocuring technology preparation to can be used for the Nano-titania Porous Films of dye-sensitized solar cell anode is provided.The method technique is simple, good film-forming property, take full advantage of the advantage of photocuring technology, the Nano-titania Porous Films that makes and the strong adhesion of base material, pattern, size are controlled, have loose structure, high-specific surface area has very high practical value and application prospect aspect DSSC.
The method of utilizing photocuring technology to prepare the nano-titanium dioxide film with loose structure provided by the invention, it mixes the nano titanium oxide colloid and makes the colloidal titania dispersion that can apply film forming with the monomer of photopolymerization, make coating carry out the photopolymerization reaction film-forming after being coated on substrate surface, form Nano-titania Porous Films by heat treatment at last.Based on foregoing, the method specifically comprises the following steps:
(1) base material preliminary treatment: the base material ultrasonic cleaning is clean, be soaked in aqueous isopropanol standby.
Base material is to distinguish ultrasonic cleaning 10～20min according to the order of washing agent, deionized water, acetone, deionized water, ethanol and deionized water successively.
(2) preparation aqueous colloidal dispersion: nano titanium oxide is dispersed in the mixed solution of ethanol and isopropyl alcohol to get a, the volume ratio scope of ethanol and isopropyl alcohol is 2～5:5; Monomer and light trigger are dissolved in the mixed solution of ethanol and DMF to get b, and the molar ratio of ethanol and DMF is 1:1, afterwards b is added in a, mixes to make the colloidal titania dispersion that can 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 scope 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) apply film forming: the base material taking-up nitrogen that is soaked in aqueous isopropanol dries up the base material that obtains the load nano-titanium dioxide film, the colloidal titania dispersion that makes in above-mentioned steps (2) is coated on uniformly forms the uniform coating of a layer thickness on pretreated base material.
The method that forms coating on base material includes knife coating, spin-coating method, dip-coating method and spraying process.
(4) radiation curing: the base material that is coated with the colloidal titania dispersion coating that obtains in step (3) is placed under the 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 of point, line or face is taked in the irradiation of UV light source.
(5) heat treatment: the cured film that obtains through step (4) is placed in box Muffle furnace heat-treats, by room temperature be warming up to gradually temperature be 500～750 ℃ in the interval arbitrary temp and be incubated 1～3h and carry out sintering, last stove is cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.
Heating rate is 1～10 ℃/min, and is incubated respectively 15～60min in temperature is 100～200 ℃ and 300～400 ℃ of intervals.
The present invention introduces the monomer that can carry out photopolymerization reaction in nanometer titanium dioxide colloid solution, utilize light polymerization technique to make it in substrate surface photocuring film forming, finally removes organic substance by heat treatment and forms Nano-titania Porous Films.be compared to the existing method for preparing nano-titanium dioxide film in this area, preparation method of the present invention has avoided the shortcoming that exists in the previous methods, its advantage is: the present invention can be by changing monomeric species, content of monomer, the light trigger kind, the 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, take full advantage of the advantage of photocuring technology, the titanium deoxid film with loose structure that makes and the strong adhesion of base material, pattern, size is controlled, has loose structure, high-specific surface area, can increase the absorption of dyestuff, strengthen scattering of light, and then the photoelectric conversion efficiency of raising DSSC.
Description of drawings
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 prepared in embodiments of the invention 1 nano-titanium dioxide film heat treatment rear surface.
Fig. 3 is the SEM photo in cross section after nano-titanium dioxide film heat treatment prepared in embodiments of the invention 1.
Surface topography and Cross Section Morphology by the prepared nano-titanium dioxide film of sem observation.Fig. 1 is the SEM photo of nano-titanium dioxide film heat treatment front surface prepared in embodiment 1, can observe nano-titania particle in the nano-titanium dioxide film before the photocuring after-baking and be aggregated the polymer that reaction forms and be wrapped in.Fig. 2 is the SEM photo of prepared in embodiment 1 nano-titanium dioxide film heat treatment rear surface, can observe photocuring and arrange loosely by nano-titania particle in the nano-titanium dioxide film of Overheating Treatment, a lot of out-of-shapes, hole not of uniform size are arranged between particle.Fig. 3 is the SEM photo in cross section after nano-titanium dioxide film heat treatment prepared in embodiment 1, can observe that the thickness of nano-titanium dioxide film is about 5 μ m after heat treatment.
Embodiment
Embodiment 1
Successively according to the order difference ultrasonic cleaning 15min of blue moon washing agent, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO transparent conducting glass.The 1.0g titania nanoparticles is dispersed in the mixed solution of 6.0mL ethanol and 15.0mL isopropyl alcohol to get a; 2.0g monomer pentaerythritol triacrylate (PETA) and 0.025g light trigger 2-hydroxy-2-methyl-1-phenylacetone (HMPP) are dissolved in the mixed solution of 6.0mL ethanol and 8.0mL DMF (DMF) to get b.Afterwards b is added dropwise in a, mixes the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the FTO transparent conducting glass that is soaked in aqueous isopropanol, utilizes knife coating that aqueous colloidal dispersion is coated on uniformly and makes the uniform coating of a layer thickness on the FTO transparent conducting glass that cleans up.The FTO electro-conductive glass that is coated with the colloidal titania dispersion coating is placed under the UV lamp, obtains 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 that obtains is heat-treated, heating rate with 2 ℃/min is heated up gradually by room temperature and is incubated respectively 30min at 150 ℃ and 400 ℃, finally be warming up to 600 ℃ and the insulation 2h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.With the TiO after sintering
2Porous membrane is cooled to 100 ℃, immerses 24h in 0.5mM N719 dye solution (solvent is the tert-butyl alcohol and the acetonitrile of volume ratio 1:1) under airtight darkroom.The painted TiO that nitrogen is dried up
2The perforated membrane placement that faces up, then with platinum to electrode surface towards being placed down in, slightly staggering and using to clamp is assembled into DSSC.Splash into electrolyte (0.6M BMII, 0.03M I 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
2Record V
oc=731mV, I
sc=15.53mA/cm
2, ff=0.70 is therefore the photoelectric conversion efficiency of battery is η (%)=7.9.
Embodiment 2
Successively according to the order difference ultrasonic cleaning 15min of five clean powder, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 1.0g titanium dioxide nano-rod is dispersed in the mixed solution of 6.0mL ethanol and 15.0mL isopropyl alcohol to get a; 2.0g monomer pentaerythritol triacrylate and 0.03g light trigger 2-hydroxy-2-methyl-1-phenylacetone are dissolved in the mixed solution of 6.0mL ethanol and 8.0mL DMF to get b.Afterwards b is added dropwise in a, mixes the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the base material that the FTO electro-conductive glass obtains load thin film, utilizes dip-coating method to make the aqueous colloidal dispersion coating that one deck is evenly distributed at substrate surface.Be placed under the UV lamp being coated on being coated with on the FTO electro-conductive glass, carry 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 that obtains is placed in box Muffle furnace and heat-treats, heating rate with 5 ℃/min is heated up gradually by room temperature and is incubated respectively 30min at 150 ℃ and 400 ℃, finally be warming up to 600 ℃ and the insulation 2h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=705mV, I
sc=12.93mA/cm
2, ff=0.70 is therefore the photoelectric conversion efficiency of battery is η (%)=6.4.
Embodiment 3
Successively according to the order difference ultrasonic cleaning 20min of hand cleanser, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 0.75g titania nanoparticles is dispersed in the mixed solution of 5.0mL ethanol and 12.0mL isopropyl alcohol to get a; 1.0g monomer pentaerythritol triacrylate and 0.02g light trigger benzophenone are dissolved in the mixed solution of 5.0mL ethanol and 7.0mL DMF to get b.Afterwards b is added in a, mix the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the FTO electro-conductive glass, utilizes knife coating that the aqueous colloidal dispersion that makes is coated on the substrate surface that cleans up uniformly.The colloidal titania dispersion coating that is coated on the FTO electro-conductive glass is placed under the 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, the line radiation modality is taked in the irradiation of UV light source.The cured film that obtains is placed in box Muffle furnace heat-treats, heating rate with 2 ℃/min is heated up gradually by room temperature and is incubated respectively 60min at 150 ℃ and 400 ℃, finally be warming up to 550 ℃ and the insulation 2h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=669mV, I
sc=13.16mA/cm
2, ff=0.73 is therefore the photoelectric conversion efficiency of battery is η (%)=6.4.
Embodiment 4
Successively according to the order difference ultrasonic cleaning 15min of five clean powder, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 1.0g titania nanoparticles is dispersed in the mixed solution of 6.0mL ethanol and 15.0mL isopropyl alcohol to get a; 2.0g monomer the third oxidation tri methylol triacrylate and 0.025g light trigger α, α '-dimethyl benzil ketals is dissolved in the mixed solution of 6.0mL ethanol and 8.0mL DMF to get b.Afterwards b is added in a, mix the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the FTO electro-conductive glass, utilizes spin-coating method that the aqueous colloidal dispersion that makes is coated on uniformly and forms one deck coating on base material.The FTO electro-conductive glass that is coated with the colloidal titania dispersion is placed under the 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, the face radiation modality is taked in the irradiation of UV light source.The cured film that obtains is placed in box Muffle furnace heat-treats, heating rate with 5 ℃/min is heated up gradually by room temperature and is incubated respectively 30min at 120 ℃ and 350 ℃, finally be warming up to 550 ℃ and the insulation 1h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=695mV, I
sc=12.24mA/cm
2, ff=0.69 is therefore the photoelectric conversion efficiency of battery is η (%)=5.9.
Embodiment 5
Successively according to the order difference ultrasonic cleaning 10min of five clean powder, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 1.5g titania nanoparticles is dispersed in the mixed solution of 15mL ethanol and 16mL isopropyl alcohol to get a; 4.0g monomer triethylene-glycol dimethylacrylate and 0.06g light trigger α, α '-diethoxy acetophenone are dissolved in the mixed solution of 15mL ethanol and 20mL DMF to get b.Afterwards b is added in a, mix the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the base material that the FTO electro-conductive glass obtains load thin film, utilizes spraying process to apply uniformly one deck aqueous colloidal dispersion coating at substrate surface.The FTO electro-conductive glass film that is coated with the colloidal titania dispersion coating is placed under the 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, the face radiation modality is taked in the irradiation of UV light source.The cured film that obtains is heat-treated, heating rate with 10 ℃/min is heated up gradually by room temperature and is incubated respectively 60min at 200 ℃ and 400 ℃, finally be warming up to 700 ℃ and the insulation 1h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=697mV, I
sc=14.17mA/cm
2, ff=0.68 is therefore the photoelectric conversion efficiency of battery is η (%)=6.7.
Embodiment 6
Successively according to the order difference ultrasonic cleaning 15min of blue moon washing agent, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 1.0g titania nanoparticles is dispersed in the mixed solution of 6.0mL ethanol and 10.0mL isopropyl alcohol to get a; 2.0g monomer tri (propylene glycol) diacrylate and 0.03g light trigger 1-hydroxy cyclohexyl phenylketone are dissolved in the mixed solution of 6.0mL ethanol and 8.0mL DMF to get b.Afterwards b is added in a, mix the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the FTO electro-conductive glass, utilizes knife coating that the aqueous colloidal dispersion that makes is coated on uniformly and forms the uniform coating of a layer thickness on the base material that cleans up.The aqueous colloidal dispersion coated film that is coated on the FTO electro-conductive glass is placed under the 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 that obtains is placed in box Muffle furnace heat-treats, heating rate with 5 ℃/min is heated up gradually by room temperature and is incubated respectively 30min at 150 ℃ and 300 ℃, finally be warming up to 550 ℃ and the insulation 2h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=665mV, I
sc=13.09mA/cm
2, ff=0.63 is therefore the photoelectric conversion efficiency of battery is η (%)=5.5.
Embodiment 7
Successively according to the order difference ultrasonic cleaning 20min of hand cleanser, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 1.25g titania nanoparticles is dispersed in the mixed solution of 8.0mL ethanol and 15mL isopropyl alcohol to get a; 3.0g monomer isodecyl acrylate and 0.05g light trigger 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone solution gets b in the mixed solution of 8.0mL ethanol and 10mL DMF.Afterwards b is added in a, mix the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the FTO electro-conductive glass, utilizes spin-coating method that the aqueous colloidal dispersion that makes is coated on substrate surface uniformly.The FTO electro-conductive glass that is coated with the colloidal titania dispersion coating is placed under the UV lamp, carries out polymerization reaction through ultraviolet radiation and obtained cured film.The irradiation time of UV light source is 2min, and light intensity is 100mW/cm
2, the line radiation modality is taked in the irradiation of UV light source.The cured film that obtains is placed in box Muffle furnace heat-treats, heating rate with 5 ℃/min is heated up gradually by room temperature and is incubated respectively 60min at 100 ℃ and 300 ℃, finally be warming up to 500 ℃ and the insulation 3h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=705mV, I
sc=10.45mA/cm
2, ff=0.75 is therefore the photoelectric conversion efficiency of battery is η (%)=5.5.
Embodiment 8
Successively according to the order difference ultrasonic cleaning 15min of blue moon washing agent, deionized water, acetone, deionized water, 95% (v/v) ethanol and deionized water, be soaked at last in aqueous isopropanol standby the FTO electro-conductive glass.The 1.5g titania nanoparticles is dispersed in the mixed solution of 10mL ethanol and 15mL isopropyl alcohol to get a; 2.0g monomer tetramethylol methane tetraacrylate and 0.04g light trigger TMDPO are dissolved in the mixed solution of 10mL ethanol and 14mL DMF to get b.Afterwards b is added in a, mix the colloidal titania dispersion that makes the use of filming.Nitrogen dries up the FTO electro-conductive glass, utilizes knife coating to apply uniformly one deck colloidal titania dispersion coating at substrate surface.Be placed under the UV lamp being coated on being coated with on the FTO electro-conductive glass, carry out polymerization reaction through ultraviolet radiation and obtained cured film.The irradiation time of UV light source is 10min, and light intensity is 30mW/cm
2, the face radiation modality is taked in the irradiation of UV light source.The cured film that obtains is heat-treated, heating rate with 2 ℃/min is heated up gradually by room temperature and is incubated respectively 60min at 150 ℃ and 400 ℃, finally be warming up to 700 ℃ and the insulation 2h carry out sintering, be cooled to the nano-titanium dioxide film that room temperature namely obtains having loose structure.Press the same terms assembling DSSC in embodiment 1, record V
oc=699mV, I
sc=13.17mA/cm
2, ff=0.73 is 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: successively according to the ultrasonic 10～20min of order difference of washing agent, deionized water, acetone, deionized water, ethanol and deionized water, be soaked in aqueous isopropanol standby after cleaning up base material;
(2) preparation aqueous colloidal dispersion: nano titanium oxide is dispersed in the mixed solution of ethanol and isopropyl alcohol to get 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 to get b, and the molar ratio of ethanol and DMF is 1:1, afterwards b is added in a, mixes the colloidal titania dispersion that makes the use of filming; 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 standby base material, and the colloidal titania dispersion is coated on base material, makes its surface form the uniform coating of a layer thickness;
(4) radiation curing: the base material that is coated with the colloidal titania dispersion coating that step (3) is obtained is placed under the UV lamp, carries out polymerization reaction through ultraviolet radiation and obtains cured film;
(5) heat treatment: the cured film that obtains through step (4) is placed in box Muffle furnace heat-treats, be warming up to gradually the arbitrary temperature in 500～750 ℃ of intervals and be incubated 1～3h by room temperature and carry out sintering, be cooled at last the nano-titanium dioxide film that room temperature namely obtains having loose structure.
2. method according to claim 1, it 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, it 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 that forms 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, it is characterized in that: the exposure time of the ultraviolet source described in step (4) is 2～15min, light intensity is 5～200mW/cm
2
7. method according to claim 1, it is characterized in that: the radiation modality of point, line or face is taked in the irradiation of the UV light source described in step (4).
8. method according to claim 1, it is characterized in that: the heating rate described in step (5) is 1～10 ℃/min, and is incubated respectively 15～60min at 100～200 ℃ and 300～400 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588243A (en) * | 2013-09-11 | 2014-02-19 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nano titanium dioxide powder |
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| CN103474242B (en) * | 2013-09-26 | 2016-01-20 | 华北电力大学 | A kind of anode film of dye-sensitized solar cells |
| CN105036072A (en) * | 2015-05-22 | 2015-11-11 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105753336A (en) * | 2016-01-25 | 2016-07-13 | 浙江大学 | Carbon-nickel oxide composite thin film with array porous structure on surface and preparation method of thin film |
| 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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| CN111012581A (en) * | 2019-12-17 | 2020-04-17 | 苏州涂冠镀膜科技有限公司 | Medical ear hook and preparation method thereof |
| CN116640505A (en) * | 2023-06-12 | 2023-08-25 | 中轻检验认证有限公司 | Functional photo-curable leather finishing agent system and preparation method and application thereof |
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