CN103739011A - Method for preparing three-dimensional multistage titanium dioxide slurry with micro-nano structure by one-pot method - Google Patents
Method for preparing three-dimensional multistage titanium dioxide slurry with micro-nano structure by one-pot method Download PDFInfo
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Abstract
The invention relates to a method for preparing three-dimensional multistage titanium dioxide slurry with a micro-nano structure by a one-pot method. The method comprises the following steps: (1) slowly adding titanium sources while stirring mixed liquor of organic amine, hydrochlorides and ethanol, and carrying out reflux at 50-70 DEG C for 2-5 hours to obtain a titanium dioxide colloid; (2) adding alkalis to the obtained titanium dioxide colloid, and carrying out hydrothermal reaction at 150-180 DEG C for 10-20 hours to obtain three-dimensional multistage titanium dioxide sol with a micro-nano structure; (3) dissolving the obtained three-dimensional multistage titanium dioxide sol with the micro-nano structure in a solvent after centrifuging and washing, adding a dispersing agent and a binding agent, and removing the solvent through evaporation after uniform dispersing, thus obtaining the three-dimensional multistage titanium dioxide slurry with the micro-nano structure. The method has the beneficial effects that the slurry is prepared by adopting the one-pot method without the step of after-treatment of a titanium dioxide precursor; the method is simple in preparation process and can achieve mass production; moreover, three-dimensional multistage titanium dioxide with the micro-nano structure, which is prepared by the method, not only contains titanium dioxide particles with nano structures but also contains micron-sized particles of nano aggregates.
Description
Technical field
The invention belongs to technical field of new energies, relate to a kind of one kettle way and prepare the method for three-dimensional multistage micro-nano-structure titanium dioxide slurry and the application in solar cell thereof.
Background technology
Shortage of resources and environmental pollution are two large Tough questions of 21 century facing mankind, and pollution-free reproducible green energy resource has become the focal issue of global concern, and sun power is inexhaustible and become focus with it.Solar cell has been realized the conversion of solar energy to electrical, receives in recent years numerous investigators' concern.In various dissimilar solar cells, dye sensitization solar battery is high with its photoelectric transformation efficiency, and preparation technology is simple, with low cost, intensity of illumination is relied on to the advantage such as little and be subject to extensive concern.
Dye sensitization solar battery mainly comprises semiconductor optical anode, to electrode and at semiconductor optical anode with to the ionogen between electrode.Wherein, semiconductor optical anode is its important component part, and it is not only the carrier of absorbing dye, is also the carrier of transmission electronic.At present, the semiconductor material that semiconductor photo-anode film is conventional is anatase octahedrite nano titanium oxide, and it has with low cost, and source is abundant, nontoxic pollution-free, the premium propertiess such as stable and erosion resistance.For dye sensitization titanium dioxide solar cell, the microstructure of its photoelectric transformation efficiency and titanium dioxide electrodes has close relationship.When forming the TiO 2 particles size of electrode, increase to when suitable with visible wavelength, because its enhancing to visible ray scattering process has extended light path, thereby be conducive to improve the capture rate of dye molecule to light.But when being beneficial to scattering of light, the increase of TiO 2 particles size also reduced the specific surface area of titanium dioxide.And the TiO of little nano-scale
2particle has large specific surface area, but is unfavorable for the scattering effect of visible ray.Therefore, traditional technology is to utilize nanoparticle and the combination of macrobead titanium dioxide to prepare electrode.
Chinese patent (publication number CN1909261A) discloses a kind of preparation method of photoabsorption reinforced membranes, and this film light anode comprises the composite structure of the first layer compact titanium dioxide film and second layer macroporous titanium dioxide film.Yet when this film of preparation, need to repeatedly apply, filming technology is complicated, is unfavorable for industrial applications.
Chinese patent (publication number CN1841792A) discloses a kind of method that spherical pore-forming material and titanium dioxide small-particle colloid are mixed with light scattering thin film electrode.Yet the titanium deoxid film light anode making with aforesaid method and the bonding force of conductive substrates are poor, thereby affect the work-ing life of dye sensitization solar battery.
Summary of the invention
The object of the invention is, in order to overcome above-mentioned the deficiencies in the prior art, provides a kind of one kettle way to prepare the method for three-dimensional multistage micro-nano-structure titanium dioxide slurry.
At this, the invention provides a kind of method that one kettle way is prepared three-dimensional multistage micro-nano-structure titanium dioxide slurry, comprising:
(1) in the mixed solution of organic amine, hydrochloride, ethanol, under stirring, slowly add titanium source, and reflux and within 2～5 hours, obtain colloidal tio 2 at 50～70 ℃;
(2) in the colloidal tio 2 of gained, add alkali, and within 10～20 hours, obtain three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol 150～180 ℃ of hydro-thermal reactions; And
(3) the three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol of gained is dissolved in solvent after centrifugal, washing, steams except described solvent after adding dispersion agent and binding agent to be uniformly dispersed, and obtains three-dimensional multistage micro-nano-structure titanium dioxide slurry.
The present invention adopts one kettle way to prepare slurry, post-processing step without TiO 2 precursor, preparation technology is simple, can large production, and the three-dimensional multistage micro-nano-structure titanium dioxide that makes of the method both contained the titanium dioxide granule of nanostructure, contain again the micron-scale particle of Micelle-like Nano-structure of Two.This structure both can guarantee the specific surface area of material, and the accumulation hole that has again aggregate mutually to pile up to form, is conducive to mass transfer, thereby can increases the photoelectric transformation efficiency of dye sensitization solar battery prepared therefrom, for example can be up to 8.99%.
Preferably, in step (1), described organic amine is at least one in amino dodecane, cetylamine and stearylamine.
Preferably, in step (1), described hydrochloride is KCl and/or CaCl
2.
Preferably, in step (1), described titanium source is titanium alkoxide, comprises tetrabutyl titanate and/or titanium isopropylate.
Preferably, in step (1), the mol ratio of described hydrochloride and described organic amine is 1:30～1:60.
Preferably, in step (1), the mol ratio in described organic amine and described titanium source is 1:1～1:4.
Preferably, in step (1), the volume ratio of described titanium source and described mixed solution is 1:40～1:50.
The mol ratio in the described titanium source in the described alkali preferably, adding in step (2) and step (1) is 1:1～1:4.
Preferably, in step (2), described alkali is at least one in ammoniacal liquor, Tetramethylammonium hydroxide and TBAH.
Preferably, in step (3), described solvent is ethanol, and described dispersion agent is Terpineol 350, and described binding agent is ethyl cellulose; In described slurry, titanium dioxide mass content is 20%, and ethyl cellulose mass content is 8%, and Terpineol 350 mass content is 72%.
Prepared according to the methods of the invention three-dimensional multistage micro-nano-structure titanium dioxide slurry can be for the preparation of individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode, a this kind of slurry skim can replace the two-layer composite of traditional the first layer compact titanium dioxide film and second layer macroporous titanium dioxide film, filming technology is simple, low cost of manufacture, is applicable to heavy industrialization application.And this slurry and conductive glass (are for example mixed fluorine SnO
2) surface bonding power is good, one-step print thickness can reach 20 μ m and not ftracture, extended the work-ing life of dye sensitization solar battery, and the photoelectric transformation efficiency of the dye sensitization solar battery of being prepared by this individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode is higher, for example can be up to 8.99%.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 1;
Fig. 2 is the X ray diffracting spectrum of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 2;
Fig. 3 a is field transmission Electronic Speculum (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 1;
Fig. 3 b is field transmission Electronic Speculum (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 1;
Fig. 3 c is field transmission Electronic Speculum (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 1;
Fig. 4 a is field transmission Electronic Speculum (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 3;
Fig. 4 b is field transmission Electronic Speculum (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 3;
Fig. 4 c is field transmission Electronic Speculum (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 3;
Fig. 5 is the graph of pore diameter distribution of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that makes of embodiment 1.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The invention provides a kind of one kettle way and prepare the method for three-dimensional multistage micro-nano-structure titanium dioxide slurry.In addition, the prepared three-dimensional multistage micro-nano-structure titanium dioxide slurry of the present invention can also be applied to the preparation of individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode, and the making that is further applied to dye sensitization solar battery.Particularly, as example, method of the present invention can comprise the following steps.
1. one kettle way is prepared three-dimensional multistage micro-nano-structure titanium dioxide slurry:
1.1 join organic amine, hydrochloride, ethanol in reaction vessel, under agitation slowly add titanium source, at 50～70 ℃, reflux and within 2～5 hours, obtain colloidal tio 2.Wherein, the organic amine adopting includes but not limited to one or more amines such as amino dodecane, cetylamine, stearylamine.The hydrochloride adopting includes but not limited to KCl and/or CaCl
2deng.In addition, the form that this hydrochloride also can the aqueous solution adds, and the concentration of this aqueous solution can be 0.1～0.2M.The titanium source adopting includes but not limited to the titanium alkoxide of the titaniferous such as tetrabutyl titanate and/or titanium isopropylate.The hydrochloride adding and the mol ratio of organic amine can be 1:30～1:60.The mol ratio in the organic amine adding and titanium source can be 1:1～1:4.The volume ratio of the mixed solution of the titanium source adding again, and organic amine, hydrochloride, ethanol can be 1:40～1:50.
1.2 for improving the degree of crystallinity of titanium dioxide, adds alkali lye in above-mentioned gained colloidal tio 2, is then placed in hydrothermal reaction kettle and within 10～20 hours, obtains three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol 150～180 ℃ of hydro-thermal reactions.Wherein, the alkali lye adopting includes but not limited to the alkali lye such as ammoniacal liquor, Tetramethylammonium hydroxide and/or TBAH, is preferably ammoniacal liquor.The mol ratio in the alkali lye adding and titanium source can be 1:1～1:4.
For example, after 1.3 the good three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol of hydro-thermal is centrifugal, collecting precipitation thing washing (using washing with alcohol), be dissolved in solvent, add binding agent and dispersion agent, after being uniformly dispersed, steaming desolventizes and obtains three-dimensional multistage micro-nano-structure titanium dioxide slurry.Finely dispersed mode can be for example high-shear and ultrasonic dispersion.The mode that steaming desolventizes can be for example that low pressure is revolved steaming.In order to make this slurry even, can also roll to it three-dimensional multistage micro-nano-structure titanium dioxide slurry that (for example rolling with three roll machine) obtains mixing.In one example, the solvent adopting is ethanol.In another example, the binding agent adopting is ethyl cellulose, and the dispersion agent adopting is Terpineol 350.In another example, in the slurry making, titanium dioxide mass content is 20%, and ethyl cellulose mass content is 8%, and Terpineol 350 mass content is 72%.
Fig. 1 and Fig. 2 illustrate respectively the X ray diffracting spectrum of three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by the method for two examples according to the present invention.Titanium dioxide in prepared slurry is pure anatase octahedrite as shown in Figure 1, without Rutile Type diffraction peak, occurs.Titanium dioxide in prepared slurry had both contained anatase octahedrite and had also contained Rutile Type as shown in Figure 2.Again, (101) peak is very sharp-pointed, and (103) and (112) peak energy and (004) peak are separately, illustrates that in slurry prepared by the present invention, titanium dioxide granule degree of crystallinity is all relatively good.
Fig. 3 a～3b illustrates the TEM figure of three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by the method for an example according to the present invention.It is probably 1 μ m that nanometer in the known three-dimensional multistage micro-nano-structure titanium dioxide of Fig. 3 a～3b slurry is piled up spherolite footpath, particle is uniformly dispersed, and this piles up, and ball is comprised of little nano particle, the general 25nm left and right of particle diameter (particle size range 10～50nm) of nano particle, from surface, can see hole, thereby be conducive to mass transfer.In addition in this three-dimensional multistage micro-nano-structure titanium dioxide slurry, also contain the nano particle of 10～50nm, this nano particle better crystallinity degree, particle is uniformly dispersed, and has high-specific surface area.In addition, known after tested, in this example, the BET specific surface area of three-dimensional multistage micro-nano-structure titanium dioxide can reach 55.2m
2/ g, median size is 28.3nm left and right, porosity is 30.2%.
Fig. 5 illustrates the graph of pore diameter distribution of three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by the method for an example according to the present invention.As shown in Figure 5, aperture mainly concentrates on 6nm left and right, but all occurs from the aperture between 20～140nm, and it is relevant that this forms accumulation microballoon with small-particle.
The method that the three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared according to the present invention is applied to prepare individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode is below described, and the method that is further applied to make dye sensitization solar battery.Should be understood that these methods are only for effect of the present invention is described, and unrestricted the present invention.
2. the preparation of individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode:
By above-mentioned three-dimensional multistage micro-nano-structure titanium dioxide slurry by screen printing technique printing for example, to the clean conductive glass (SnO of doped with fluorine
2transparent conducting glass or indium tin oxide transparent conductive semiconductor glass) surface, the thickness of printing can be 15～20 microns; At 90 ℃～120 ℃, dry after 5～10 minutes, be placed at 450 ℃～550 ℃ and calcine 1～2 hour, obtain individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode.
3. the preparation of dye sensitization solar battery:
The preparation of 3.1 dye sensitization individual layer three-dimensional multistage micro-nano titanium deoxid film light anodes:
By the above-mentioned individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode making, washing after taking out, dry, obtains the light anode after sensitization.The dye solution adopting can be the ruthenium complex dye solution of 0.1～0.4mmol/L.The solvent of this dye solution can be the mixing solutions of ethanol, DMSO or the trimethyl carbinol and acetonitrile etc.In addition, soak time can be more than 24 hours.
The preparation of 3.2 electrolyte solutions:
Electrolyte solution can be comprised of three parts: organic solvent, redox electron pair and additive.In one example, the proportioning of electrolyte solution is: 0.05mol/L iodine, 0.5mol/L lithium iodide, 0.5mol/L4-tert .-butylpyridine (4-TBP), 0.3mol/L1,2-dimethyl-3-propyl imidazole iodine (DMPII), solvent is the mixing solutions of the trimethyl carbinol and acetonitrile.
The assembling of 3.3 batteries:
Dye sensitization individual layer three-dimensional multistage micro-nano titanium deoxid film light anode, with together with electrode assembling, is injected to electrolyte solution between them, form dye sensitization solar battery.Wherein, to electrode, can be the differing materials such as graphite, platinum or conductive polymers.The platinum electrode that for example can prepare for pyrolysis method.
The performance test of dye sensitization solar battery
Can adopt following testing tool and method: CEP-1500 type quantum efficiency of solar battery test macro is incident monochromatic ray-electronic switch efficiency of test dye sensitization solar battery at room temperature.YSS-150A type solar simulator and ADCMT-6246 type tester be the current-voltage curve of test dye sensitization solar battery at room temperature, then draw the open circuit voltage of battery, short-circuit current, packing factor, and calculate thus the photoelectric transformation efficiency of battery, the intensity of light source is a sunlight, and the useful area of battery is 0.1884cm
2.Known after tested, according to the battery efficiency of the prepared dye sensitization solar battery of aforesaid method, can reach 8.99%, quite even more excellent with battery prepared by common double layer film.
A kind of one kettle way provided by the invention is prepared the preparation method of three-dimensional multistage micro-nano-structure titanium dioxide slurry, its preparation technology is simple, one kettle way makes the titanium dioxide granule that both contains nanostructure, the micron-scale particle that contains again Micelle-like Nano-structure of Two, both can guarantee the specific surface area of material, the accumulation hole that has again aggregate mutually to pile up to form, is conducive to mass transfer.When this slurry is applied to prepare titanium deoxid film light anode, a this kind of slurry skim can replace the two-layer composite of traditional the first layer compact titanium dioxide film and second layer macroporous titanium dioxide film, filming technology is simple, is applicable to heavy industrialization application.And this slurry and conductive glass (are for example mixed fluorine SnO
2) surface bonding power is good, one-step print thickness can reach 20 μ m and not ftracture, and has extended the work-ing life of dye sensitization of solar.In addition, the battery efficiency of the dye sensitization solar battery of being prepared by this slurry can reach 8.99%, quite even more excellent with battery prepared by common double layer film.Therefore, the present invention can effectively be applied in solar cell.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameters such as the concrete quality of following example, concentration, time, temperature etc. are only also examples in OK range, be that those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
The measuring method of using and instrument are: the diffracting spectrum of D/max2550V type X-ray diffractometer analysis self-control three-dimensional multistage micro-nano-structure titanium dioxide.JEM-2100F type field transmission electron microscope observation forms the microstructure of the titanium dioxide of three-dimensional multistage micro-nano-structure titanium dioxide slurry.CEP-1500 type quantum efficiency of solar battery test macro is incident monochromatic ray-electronic switch efficiency of test dye sensitization solar battery at room temperature.YSS-150A type solar simulator and ADCMT-6246 type tester be the current-voltage curve of test dye sensitization solar battery at room temperature, then draw the open circuit voltage (Voc) of battery, short-circuit current (Jsc), packing factor (FF), and calculate thus the photoelectric transformation efficiency (Eff) of battery, the intensity of light source is a sunlight, and the useful area of battery is 0.1884cm
2.The specific surface area of ASAP2020 specific surface instrument test three-dimensional multistage micro-nano-structure titanium dioxide, size distribution etc.
Embodiment 1
Prepare three-dimensional multistage micro-nano-structure titanium dioxide slurry: get 5g cetylamine, 3mlKCl solution (0.15M) and 800ml ethanol and join in there-necked flask, then 16ml tetrabutyl titanate is splashed in above-mentioned mixed solution, 50 ℃ of backflow 2h, then 25% the ammoniacal liquor that adds 1ml, is placed in hydrothermal reaction kettle in 160 degree hydro-thermal 12 hours;
The colloidal tio 2 that hydro-thermal is good is dissolved in ethanol through centrifugal washing with alcohol, add ethyl cellulose and Terpineol 350, through high-shear and ultrasonic dispersion, revolve and steam ethanol and obtain titanium dioxide dope, with three roll machine, roll the titania slurry that obtains mixing.The titania slurry mass content obtaining is 20%, and ethyl cellulose cellulose content is 8%, and Terpineol 350 content is 72%.
The preparation of individual layer three-dimensional multistage micro-nano-structure titanium dioxide film: use indium tin oxide-coated glass is conductive substrates, the mixing solutions ultrasonic cleaning conductive glass surface 10min that is 1:1 by dehydrated alcohol and acetone volume ratio, after cleaning, with deionized water drip washing three times, then in 100 ℃ of baking ovens, dry.By silk screen printing, titania slurry is printed to conductive glass surface, the thickness of titanium dioxide film is 20 microns, after drying, 500 ℃ of calcinings 30 minutes, obtains individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode in 100 ℃ of baking ovens.
The preparation of dye sensitization individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode: individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode is immersed in the ethanolic soln of 0.3mmol/L N719 dyestuff, take out with dehydrated alcohol drip washing after 48 hours and dry.
Electrolytical preparation: it is in the trimethyl carbinol of 1:1 and the mixing solutions of acetonitrile that 0.05mol/L iodine and 0.5mol/L lithium iodide are dissolved in to volume ratio, add 0.5mol/L4-tert .-butylpyridine (4-TBP) and 0.3mol/L1,2-dimethyl-3-propyl imidazole iodine (DMPII), ultrasonic dispersion 1 hour, thing precipitates until electrolytic solution is uniformly dispersed then on shaking table, to disperse 24 hours.
The assembling of dye sensitization solar battery: cover silicone resin film on platinum electrode, in the square opening of silicone resin film central authorities, drip an electrolytic solution, dye sensitization individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode surface is fitted with the platinum electrode that has dripped electrolytic solution down, both sides are fixed with black clip, are assembled into dye sensitization solar battery.
Embodiment 2
According to the method in embodiment 1, except following steps have change, other steps are identical: prepare three-dimensional multistage micro-nano-structure titanium dioxide slurry and add the ammonia soln that 0.5ml concentration is 25%.
Embodiment 3
According to the method in embodiment 1, except following steps have change, other steps are identical: while preparing three-dimensional multistage micro-nano-structure titanium dioxide slurry, add the TBAH solution that 10ml concentration is 10%.Hydrothermal temperature is 180 degree, and the hydro-thermal time is 16h.
Comparative example 1
This comparative example is for the preparation method of existing two-layer nano-crystalline titanium dioxide film light anode is described.According to the method in embodiment 1, except following steps have change, other steps are identical: while preparing TiO 2 sol, 90g acetic acid is joined in the there-necked flask that 1.5mol tetrabutyl titanate is housed, 60 degree are incubated half an hour; Then this mixture is joined in the 10L reactor that 6L pure water is housed, magnetic agitation one hour, stirring velocity is 300rpm.Preparation salpeter solution, method is that the nitric acid of 40g65% mixes with 650g water, this salpeter solution is joined in 10L reactor, start heating and carry out dispergation, it is 120 degree that oil bath temperature is controlled, the dispergation time is 6 hours, obtains finely dispersed titanium dioxide granule, after autoclave hydro-thermal, obtains colloidal tio 2.Slurry 1 is in the TiO 2 sol of above-mentioned centrifugal washing, to add ethyl cellulose and Terpineol 350, through high-shear and ultrasonic dispersion, revolves and steams ethanol and obtain titanium dioxide dope, rolls the titania slurry 1 that obtains mixing with three roll machine.The titania slurry mass content obtaining is 20%, and ethyl cellulose cellulose content is 8%, and Terpineol 350 content is 72%.Slurry 2 is according to 20% of titanium dioxide mass content, to add 200-300nm macrobead to mix in slurry 1.While preparing titanium dioxide photo anode, first with silk screen ST325 printing one deck slurry 1,100 degree, dry 5 minutes, then print successively three layers of slurry 2.
Analytical test result:
What Fig. 1 and Fig. 2 showed is respectively the XRD result of the three-dimensional multistage micro-nano-structure titanium dioxide slurry of embodiment 1 and embodiment 2 preparations, and the slurry of embodiment 1 preparation is pure anatase octahedrite, without Rutile Type diffraction peak, occurs.The slurry of embodiment 2 preparations had both contained anatase octahedrite and had also contained Rutile Type.(101) peak is very sharp-pointed, and (103) and (112) peak energy and (004) peak are separately, illustrate that particle degree of crystallinity prepared by embodiment mono-and embodiment bis-is all relatively good.
That Fig. 3 a～3b shows is the TEM figure of the three-dimensional multistage micro-nano-structure titanium dioxide slurry of embodiment 1 preparation.From these figure, it is probably 1 μ m that nanometer in three-dimensional multistage micro-nano-structure titanium dioxide slurry is piled up spherolite footpath, particle is uniformly dispersed, and this piles up, and ball is comprised of little nano particle, the general 25nm left and right of particle diameter (particle size range 10～50nm) of nano particle, can see hole from surface.In addition in this three-dimensional multistage micro-nano-structure titanium dioxide slurry, also contain the nano particle of 10～50nm, this nano particle better crystallinity degree, particle is uniformly dispersed, and has high-specific surface area.
That Fig. 4 a～4b shows is the TEM figure of the three-dimensional multistage micro-nano-structure titanium dioxide slurry of embodiment 3 preparations.From these figure, the micron order nanometer that contains 1 μ m in this slurry is piled up ball ball and nano level titanium dioxide granule.This micron order nanometer is piled up ball and is comprised of little nano particle, but particle degree of crystallinity does not have the degree of crystallinity of embodiment 1 preparation high.
What Fig. 5 showed is the graph of pore diameter distribution of the three-dimensional multistage micro-nano-structure titanium dioxide slurry of embodiment 1 preparation.Aperture mainly concentrates on 6nm left and right, but all occurs from the aperture between 20～140nm, and it is relevant that this forms accumulation microballoon with small-particle.
What table 1 showed is BET, aperture, particle diameter, the porosity test result of the three-dimensional multistage micro-nano-structure titanium dioxide slurry of embodiment 1 preparation.Result shows that the BET specific surface area of this slurry reaches 55.2g/cm
2;
BET, aperture, particle diameter, the porosity test result of the three-dimensional multistage micro-nano-structure titanium dioxide slurry of table 1 embodiment 1 preparation:
What table 2 showed is the I-V test result of the three-dimensional multistage micro-nano-structure titanium dioxide film of embodiment 1 preparation and the common double layer film of comparative example 1 preparation.The battery efficiency of the three-dimensional multistage micro-nano-structure titanium dioxide film assembling of embodiment 1 preparation can reach 8.99%, suitable with the battery that in comparative example 1 prepared by common double layer film;
The I-V test result of the common double layer film of the three-dimensional multistage micro-nano-structure titanium dioxide film of table 2 embodiment 1 preparation and comparative example 1 preparation:
Industrial applicability: the present invention adopts one kettle way to prepare slurry, preparation technology is simple, can large production, and the three-dimensional multistage micro-nano-structure titanium dioxide that makes of the method both contained the titanium dioxide granule of nanostructure, contained the micron-scale particle of Micelle-like Nano-structure of Two.This structure both can guarantee the specific surface area of material, and the accumulation hole that has again aggregate mutually to pile up to form, is conducive to mass transfer.The three-dimensional multistage micro-nano-structure titanium dioxide film of being prepared by this slurry has been realized individual layer printing sintering masking, has replaced traditional multilayer filming technology, and preparation technology is simple, and low cost of manufacture can be applicable to the fields such as solar cell.
Claims (10)
1. one kettle way is prepared the method for three-dimensional multistage micro-nano-structure titanium dioxide slurry, it is characterized in that, comprising:
(1) in the mixed solution of organic amine, hydrochloride, ethanol, under stirring, slowly add titanium source, and reflux and within 2～5 hours, obtain colloidal tio 2 at 50～70 ℃;
(2) in the colloidal tio 2 of gained, add alkali, and within 10～20 hours, obtain three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol 150～180 ℃ of hydro-thermal reactions;
(3) the three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol of gained is dissolved in solvent after centrifugal, washing, steams except described solvent after adding dispersion agent and binding agent to be uniformly dispersed, and obtains three-dimensional multistage micro-nano-structure titanium dioxide slurry.
2. method according to claim 1, is characterized in that, in step (1), described organic amine is at least one in amino dodecane, cetylamine and stearylamine.
3. method according to claim 1 and 2, is characterized in that, in step (1), described hydrochloride is KCl and/or CaCl
2.
4. according to the method in any one of claims 1 to 3, it is characterized in that, in step (1), described titanium source is titanium alkoxide, comprises tetrabutyl titanate and/or titanium isopropylate.
5. according to the method described in any one in claim 1 to 4, it is characterized in that, in step (1), the mol ratio of described hydrochloride and described organic amine is 1:30～1:60.
6. according to the method described in any one in claim 1 to 5, it is characterized in that, in step (1), the mol ratio in described organic amine and described titanium source is 1:1～1:4.
7. according to the method described in any one in claim 1 to 6, it is characterized in that, in step (1), the volume ratio of described titanium source and described mixed solution is 1:40～1:50.
8. according to the method described in any one in claim 1 to 7, it is characterized in that, the mol ratio in the described titanium source in the described alkali adding in step (2) and step (1) is 1:1～1:4.
9. according to the method described in any one in claim 1 to 8, it is characterized in that, in step (2), described alkali is at least one in ammoniacal liquor, Tetramethylammonium hydroxide and TBAH.
10. according to the method described in any one in claim 1 to 9, it is characterized in that, in step (3), described solvent is ethanol, and described dispersion agent is Terpineol 350, and described binding agent is ethyl cellulose; In described slurry, titanium dioxide mass content is 20%, and ethyl cellulose mass content is 8%, and Terpineol 350 mass content is 72%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601484A (en) * | 2016-12-10 | 2017-04-26 | 三峡大学 | Iodine-doping titanium dioxide microsphere electrode and manufacturing method thereof |
| CN107367527A (en) * | 2017-06-29 | 2017-11-21 | 滨州学院 | It is a kind of that there is highly sensitive spindle zinc oxide gas sensitive to triethylamine |
| CN107385880A (en) * | 2017-08-22 | 2017-11-24 | 海宁滴滴箱包智能科技有限公司 | A kind of load of high-crystallinity rice-shaped TiO 2 particles except the preparation method of formaldehyde composite fibre |
| CN108821335A (en) * | 2018-08-29 | 2018-11-16 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of high-dispersion nano titanium dioxide |
| CN109233521A (en) * | 2018-09-20 | 2019-01-18 | 徐冬 | A kind of exterior wall heat-insulating paint |
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| CN101770869A (en) * | 2010-02-09 | 2010-07-07 | 新奥科技发展有限公司 | Method for preparing titanium dioxide films for dye-sensitized solar battery |
| CN102145920A (en) * | 2011-04-18 | 2011-08-10 | 东华大学 | Method for preparing oil-soluble anatase titanium dioxide nanoparticles with two-step process |
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| CN101770869A (en) * | 2010-02-09 | 2010-07-07 | 新奥科技发展有限公司 | Method for preparing titanium dioxide films for dye-sensitized solar battery |
| CN102145920A (en) * | 2011-04-18 | 2011-08-10 | 东华大学 | Method for preparing oil-soluble anatase titanium dioxide nanoparticles with two-step process |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106601484A (en) * | 2016-12-10 | 2017-04-26 | 三峡大学 | Iodine-doping titanium dioxide microsphere electrode and manufacturing method thereof |
| CN106601484B (en) * | 2016-12-10 | 2018-06-19 | 三峡大学 | I2 doping titanium dioxide microballoon sphere electrode and preparation method thereof |
| CN107367527A (en) * | 2017-06-29 | 2017-11-21 | 滨州学院 | It is a kind of that there is highly sensitive spindle zinc oxide gas sensitive to triethylamine |
| CN107385880A (en) * | 2017-08-22 | 2017-11-24 | 海宁滴滴箱包智能科技有限公司 | A kind of load of high-crystallinity rice-shaped TiO 2 particles except the preparation method of formaldehyde composite fibre |
| CN107385880B (en) * | 2017-08-22 | 2020-05-19 | 海宁滴滴箱包智能科技有限公司 | Preparation method of high-crystallinity rice-shaped titanium dioxide particle-loaded formaldehyde-removing composite fiber |
| CN108821335A (en) * | 2018-08-29 | 2018-11-16 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of high-dispersion nano titanium dioxide |
| CN109233521A (en) * | 2018-09-20 | 2019-01-18 | 徐冬 | A kind of exterior wall heat-insulating paint |
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