CN103739011B - 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 method and application in solar cells thereof that a kind of one kettle way prepares three-dimensional multistage micro-nano-structure titanium dioxide slurry.
Background technology
Shortage of resources and environmental pollution are two large Tough questions of 21 century facing mankind, and the green energy resource of non-polluting renewable has become the focal issue of global concern, and sun power is inexhaustible and become focus with it.Solar cell achieves the conversion of solar energy to electrical, receives the concern of numerous investigator in recent years.In various dissimilar solar cell, dye sensitization solar battery is high with its photoelectric transformation efficiency, and preparation technology is simple, with low cost, relies on the advantage such as little be subject to extensive concern to intensity of illumination.
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.The premium propertiess such as at present, the semiconductor material that semiconductor photo-anode film is conventional is anatase octahedrite nano titanium oxide, and it has with low cost, abundance, nontoxic pollution-free, stable and erosion resistance.For dye-sensitized titania solar cell, the microstructure of its photoelectric transformation efficiency and titanium dioxide electrodes has close relationship.When the TiO 2 particles size forming electrode increases to suitable with visible wavelength, because it extends light path to the enhancing of visible ray scattering process, thus be conducive to improving dye molecule to the capture rate of light.But also reduce the specific surface area of titanium dioxide while the increase of TiO 2 particles size is beneficial to scattering of light.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 utilizes nanoparticle and macrobead titanium dioxide to combine 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.But need repeatedly to apply when preparing this film, 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.But, the titanium dioxide thin film photo-anode obtained with aforesaid method and the bonding force of conductive substrates poor, thus 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, to provide 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 prepares three-dimensional multistage micro-nano-structure titanium dioxide slurry, comprising:
(1) slowly add titanium source under stirring in the mixed solution of organic amine, hydrochloride, ethanol, and within 2 ~ 5 hours, obtain colloidal tio 2 50 ~ 70 DEG C of backflows;
(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 DEG C 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, adds after dispersion agent and binding agent are uniformly dispersed and steams except described solvent, obtain three-dimensional multistage micro-nano-structure titanium dioxide slurry.
The present invention adopts one kettle way to prepare slurry, without the need to the post-processing step of TiO 2 precursor, preparation technology is simple, can large production, and the titanium dioxide granule of three-dimensional multistage micro-nano-structure titanium dioxide both containing nanostructure that the method obtains, the micron-size particles again containing Micelle-like Nano-structure of Two.This structure both can ensure the specific surface area of material, had again the accumulation hole that aggregate is piled up mutually, was conducive to mass transfer, thus can increase the photoelectric transformation efficiency of dye sensitization solar battery prepared therefrom, such as can 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 alkoxides, 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.
Preferably, the mol ratio in the described titanium source in the described alkali added 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 may be used for preparing 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 (such as mix fluorine SnO
2) surface bonding power is good, one-step print thickness can reach 20 μm and not ftracture, extend the work-ing life of dye sensitization solar battery, and the photoelectric transformation efficiency of the dye sensitization solar battery to be prepared by this individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode is higher, such as can 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 embodiment 1 obtains;
Fig. 2 is the X ray diffracting spectrum of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 2 obtains;
Fig. 3 a is Flied emission transmission electron microscope (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 1 obtains;
Fig. 3 b is Flied emission transmission electron microscope (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 1 obtains;
Fig. 3 c is Flied emission transmission electron microscope (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 1 obtains;
Fig. 4 a is Flied emission transmission electron microscope (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 3 obtains;
Fig. 4 b is Flied emission transmission electron microscope (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 3 obtains;
Fig. 4 c is Flied emission transmission electron microscope (TEM) photo of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 3 obtains;
Fig. 5 is the graph of pore diameter distribution of the three-dimensional multistage micro-nano-structure titanium dioxide slurry that embodiment 1 obtains.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention provides a kind of method that one kettle way prepares three-dimensional multistage micro-nano-structure titanium dioxide slurry.In addition, the three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by 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 is applied to the making of dye sensitization solar battery further.Particularly, exemplarily, method of the present invention can comprise the following steps.
1. one kettle way prepares three-dimensional multistage micro-nano-structure titanium dioxide slurry:
Organic amine, hydrochloride, ethanol join in reaction vessel by 1.1, under agitation slowly add titanium source, within 2 ~ 5 hours, obtain colloidal tio 2 50 ~ 70 DEG C of backflows.Wherein, the organic amine adopted includes but not limited to one or more amines such as amino dodecane, cetylamine, stearylamine.The hydrochloride adopted includes but not limited to KCl and/or CaCl
2deng.In addition, this hydrochloride also can add in form of an aqueous solutions, and the concentration of this aqueous solution can be 0.1 ~ 0.2M.The titanium source adopted includes but not limited to the Titanium alkoxides of the titaniferous such as tetrabutyl titanate and/or titanium isopropylate.The hydrochloride added and the mol ratio of organic amine can be 1:30 ~ 1:60.The mol ratio in the organic amine added and titanium source can be 1:1 ~ 1:4.Again, the volume ratio of the mixed solution of the titanium source added and organic amine, hydrochloride, ethanol can be 1:40 ~ 1:50.
1.2, for improving the degree of crystallinity of titanium dioxide, add alkali lye, are then placed in hydrothermal reaction kettle and within 10 ~ 20 hours, obtain three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol 150 ~ 180 DEG C of hydro-thermal reactions in above-mentioned gained colloidal tio 2.Wherein, the alkali lye adopted 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 added and titanium source can be 1:1 ~ 1:4.
Centrifugal for three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol good for hydro-thermal, collecting precipitation thing is washed (such as using washing with alcohol) and dissolves afterwards in a solvent by 1.3, 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 such as high-shear and ultrasonic disperse.Steaming the mode desolventized can be such as that low pressure revolves steaming.In order to make this slurry even, the three-dimensional multistage micro-nano-structure titanium dioxide slurry that (such as rolling with three roll machine) obtains mixing can also be rolled to it.In one example, the solvent adopted is ethanol.In another example, the binding agent adopted is ethyl cellulose, and the dispersion agent adopted is Terpineol 350.In another example, in obtained slurry, 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 illustrates the X ray diffracting spectrum of the three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared according to the method for the present invention's two examples respectively.Titanium dioxide in slurry prepared is as shown in Figure 1 pure anatase octahedrite, occurs without Rutile Type diffraction peak.Titanium dioxide in slurry prepared as shown in Figure 2 both also contained Rutile Type containing anatase octahedrite.Again, (101) peak is very sharp-pointed, and (103) and (112) peak energy is separated with (004) peak, 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 the three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared according to the method for the present invention's example.Pile up spherolite footpath by the nanometer in Fig. 3 a ~ 3b known three-dimensional multistage micro-nano-structure titanium dioxide slurry and be probably 1 μm, Granular composite is even, and this piles up ball and to be made up of little nano particle, general about the 25nm of particle diameter (particle size range 10 ~ 50nm) of nano particle, can hole be seen from surface, thus be conducive to mass transfer.In addition the nano particle also containing 10 ~ 50nm in this three-dimensional multistage micro-nano-structure titanium dioxide slurry, this nano particle better crystallinity degree, Granular composite is even, 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 about 28.3nm, and porosity is 30.2%.
Fig. 5 illustrates the graph of pore diameter distribution of the three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared according to the method for the present invention's example.As shown in Figure 5, aperture mainly concentrates on about 6nm, but all occurs from the aperture between 20 ~ 140nm, and it is relevant that this forms accumulation microballoon with small-particle.
Below illustrate and the three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by the present invention is applied to the method preparing individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode, and be applied to the method making dye sensitization solar battery further.Should be understood that these methods only for illustration of effect of the present invention, and unrestricted the present invention.
2. the preparation of individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode:
By the conductive glass (SnO of such as doped with fluorine that above-mentioned three-dimensional multistage micro-nano-structure titanium dioxide slurry is extremely cleaned by screen printing technique printing
2transparent conducting glass or indium tin oxide transparent conductive semiconductor glass) surface, the thickness of printing can be 15 ~ 20 microns; Dry at 90 DEG C ~ 120 DEG C after 5 ~ 10 minutes, calcine 1 ~ 2 hour at being placed in 450 DEG C ~ 550 DEG C, 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 dioxide thin film photo-anode:
By above-mentioned obtained individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode, washing after taking out, drying, obtain the light anode after sensitization.The dye solution adopted can be the ruthenium complex dye solution of 0.1 ~ 0.4mmol/L.The solvent of this dye solution can be the mixing solutions etc. of ethanol, DMSO or the trimethyl carbinol and acetonitrile.In addition, soak time can be more than 24 hours.
The preparation of 3.2 electrolyte solutions:
Electrolyte solution can be made up 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:
By dye sensitization individual layer three-dimensional multistage micro-nano titanium dioxide thin film photo-anode with together with electrode assembling, inject electrolyte solution between which, form dye sensitization solar battery.Wherein, can be the differing materials such as graphite, platinum or conductive polymers to electrode.The platinum electrode such as can prepared for pyrolysis method.
The performance test of dye sensitization solar battery
Following testing tool and method can be adopted: the incident monochromatic ray-electronic switch efficiency of CEP-1500 type quantum efficiency of solar battery test macro at room temperature test dye sensitization solar battery.The current-voltage curve of YSS-150A type solar simulator and ADCMT-6246 type tester at room temperature test dye sensitization solar battery, then the open circuit voltage of battery is drawn, short-circuit current, packing factor, and calculate the photoelectric transformation efficiency of battery thus, the intensity of light source is a sunlight, and the useful area of battery is 0.1884cm
2.Known after tested, the battery efficiency of the dye sensitization solar battery prepared by aforesaid method can reach 8.99%, quite even more excellent with the battery of general dual layer film preparation.
A kind of one kettle way provided by the invention prepares the preparation method of three-dimensional multistage micro-nano-structure titanium dioxide slurry, its preparation technology is simple, one kettle way obtains the titanium dioxide granule both containing nanostructure, micron-size particles again containing Micelle-like Nano-structure of Two, both the specific surface area of material can have been ensured, there is again the accumulation hole that aggregate is piled up mutually, be conducive to mass transfer.When this slurry being applied to preparation titanium dioxide thin film photo-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 (such as mix fluorine SnO
2) surface bonding power is good, one-step print thickness can reach 20 μm and not ftracture, and extends the work-ing life of dye sensitization of solar.In addition, the battery efficiency of the dye sensitization solar battery prepared by this slurry can reach 8.99%, quite even more excellent with the battery of general dual layer film preparation.Therefore, the present invention can effectively be applied in solar cell.
Exemplify embodiment below further 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 parameter etc. such as the concrete quality of following example, concentration, time, temperature is also only an example in OK range, namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
The measuring method used and instrument are: the diffracting spectrum of D/max2550V type X-ray diffractometer analysis self-control three-dimensional multistage micro-nano-structure titanium dioxide.The microstructure of the titanium dioxide of JEM-2100F type Flied emission transmission electron microscope observation composition three-dimensional multistage micro-nano-structure titanium dioxide slurry.Incident monochromatic ray-electronic switch the efficiency of CEP-1500 type quantum efficiency of solar battery test macro at room temperature test dye sensitization solar battery.The current-voltage curve of YSS-150A type solar simulator and ADCMT-6246 type tester at room temperature test dye sensitization solar battery, then the open circuit voltage (Voc) of battery is drawn, short-circuit current (Jsc), packing factor (FF), and calculate the photoelectric transformation efficiency (Eff) of battery thus, the intensity of light source is a sunlight, and the useful area of battery is 0.1884cm
2.The specific surface area, size distribution etc. of ASAP2020 specific surface instrument test three-dimensional multistage micro-nano-structure titanium dioxide.
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 instilled in above-mentioned mixed solution, 50 DEG C of backflow 2h, then add the ammoniacal liquor of 25% of 1ml, be placed in hydrothermal reaction kettle in 160 degree of hydro-thermals 12 hours;
The colloidal tio 2 that hydro-thermal is good dissolves in ethanol through centrifugal washing with alcohol, add ethyl cellulose and Terpineol 350, through high-shear and ultrasonic disperse, revolve and steam ethanol and obtain titanium dioxide dope, roll the titania slurry obtaining mixing with three roll machine.The titania slurry mass content obtained is 20%, and 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, with the mixing solutions ultrasonic cleaning conductive glass surface 10min that dehydrated alcohol and acetone volume ratio are 1:1, with deionized water drip washing three times after cleaning, then dry in 100 DEG C of baking ovens.By silk screen printing by titania slurry printing to conductive glass surface, the thickness of titanium dioxide film is 20 microns, in 100 DEG C of baking ovens dry after 500 DEG C calcining 30 minutes, obtain individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode.
The preparation of dye sensitization individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode: immersed by individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode in the ethanolic soln of 0.3mmol/L N719 dyestuff, taking-up dehydrated alcohol drip washing after 48 hours is also dried.
Electrolytical preparation: 0.05mol/L iodine and 0.5mol/L lithium iodide being dissolved in volume ratio is in the trimethyl carbinol of 1:1 and the mixing solutions of acetonitrile, add 0.5mol/L4-tert .-butylpyridine (4-TBP) and 0.3mol/L1,2-dimethyl-3-propyl imidazole iodine (DMPII), ultrasonic disperse 1 hour, then on shaking table disperse 24 hours until electrolytic solution is uniformly dispersed thing precipitation.
The assembling of dye sensitization solar battery: cover silicone resin film on platinum electrode, an electrolytic solution is dripped in the square opening of silicone resin film central authorities, dye sensitization individual layer three-dimensional multistage micro-nano-structure titanium dioxide film light anode surface is fitted with the platinum electrode dripping electrolytic solution down, both sides black clip is fixed, and is namely assembled into dye sensitization solar battery.
Embodiment 2
According to the method in embodiment 1, except following steps have change, other steps are identical: preparing three-dimensional multistage micro-nano-structure titanium dioxide slurry interpolation 0.5ml concentration is the ammonia soln of 25%.
Embodiment 3
According to the method in embodiment 1, except following steps have change, other steps are identical: when 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 the preparation method for 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: when preparing TiO 2 sol, joined by 90g acetic acid in the there-necked flask that 1.5mol tetrabutyl titanate is housed, and 60 degree are incubated half an hour; Then being joined by this mixture is equipped with in the 10L reactor of 6L pure water, and 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 controls, the dispergation time is 6 hours, obtains finely dispersed titanium dioxide granule, after autoclave hydro-thermal, obtain colloidal tio 2.Slurry 1 adds ethyl cellulose and Terpineol 350 in the TiO 2 sol that above-mentioned centrifugal water is washed, through high-shear and ultrasonic disperse, revolves and steam ethanol and obtain titanium dioxide dope, roll the titania slurry 1 obtaining mixing with three roll machine.The titania slurry mass content obtained is 20%, and cellulose content is 8%, and Terpineol 350 content is 72%.Slurry 2 in slurry 1, adds 200-300nm macrobead according to 20% of titanium dioxide mass content mix.When preparing titanium dioxide photo anode, first print one deck slurry 1,100 degree of oven dry 5 minutes with silk screen ST325, then print three layers of slurry 2 successively.
Analytical test result:
Fig. 1 and Fig. 2 display be the XRD result of three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by embodiment 1 and embodiment 2 respectively, slurry prepared by embodiment 1 is pure anatase octahedrite, occurs without Rutile Type diffraction peak.Slurry prepared by embodiment 2 both also contained Rutile Type containing anatase octahedrite.(101) peak is very sharp-pointed, and (103) and (112) peak energy is separated with (004) peak, illustrates that grain crystalline degree prepared by embodiment one and embodiment two is all relatively good.
Fig. 3 a ~ 3b show be embodiment 1 prepare three-dimensional multistage micro-nano-structure titanium dioxide slurry TEM figure.From these figure, nanometer in three-dimensional multistage micro-nano-structure titanium dioxide slurry is piled up spherolite footpath and is probably 1 μm, Granular composite is even, and this piles up ball and to be made up of little nano particle, general about the 25nm of particle diameter (particle size range 10 ~ 50nm) of nano particle, can see hole from surface.In addition the nano particle also containing 10 ~ 50nm in this three-dimensional multistage micro-nano-structure titanium dioxide slurry, this nano particle better crystallinity degree, Granular composite is even, has high-specific surface area.
Fig. 4 a ~ 4b show be embodiment 3 prepare three-dimensional multistage micro-nano-structure titanium dioxide slurry TEM figure.From these figure, in this slurry, pile up ball ball and nano level titanium dioxide granule containing the micron order nanometer of 1 μm.This micron order nanometer is piled up ball and is made up of little nano particle, but the degree of crystallinity that grain crystalline degree does not have embodiment 1 to prepare is high.
Fig. 5 display be the graph of pore diameter distribution of three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by embodiment 1.Aperture mainly concentrates on about 6nm, but all occurs from the aperture between 20 ~ 140nm, and it is relevant that this forms accumulation microballoon with small-particle.
Embodiment 1 that what table 1 showed is prepare the BET of three-dimensional multistage micro-nano-structure titanium dioxide slurry, aperture, particle diameter, porosity test result.The BET specific surface area that result shows this slurry reaches 55.2g/cm
2;
The BET of three-dimensional multistage micro-nano-structure titanium dioxide slurry prepared by table 1 embodiment 1, aperture, particle diameter, porosity test result:
Three-dimensional multistage micro-nano-structure titanium dioxide film prepared by embodiment 1 that what table 2 showed is and the I-V test result of general dual layer film prepared by comparative example 1.The battery efficiency of three-dimensional multistage micro-nano-structure titanium dioxide film assembling prepared by embodiment 1 can reach 8.99%, suitable with the battery of general dual layer film preparation in comparative example 1;
The I-V test result of three-dimensional multistage micro-nano-structure titanium dioxide film prepared by table 2 embodiment 1 and general dual layer film prepared by comparative example 1:
Industrial applicability: the present invention adopts one kettle way to prepare slurry, preparation technology is simple, can large production, and the titanium dioxide granule of three-dimensional multistage micro-nano-structure titanium dioxide both containing nanostructure that the method obtains, the micron-size particles again containing Micelle-like Nano-structure of Two.This structure both can ensure the specific surface area of material, had again the accumulation hole that aggregate is piled up mutually, was conducive to mass transfer.The three-dimensional multistage micro-nano-structure titanium dioxide film prepared by this slurry achieves individual layer printing sintering masking, and instead of traditional multilayer filming technology, preparation technology is simple, and low cost of manufacture, can be applicable to the fields such as solar cell.
Claims (4)
1. one kettle way prepares the method for three-dimensional multistage micro-nano-structure titanium dioxide slurry, it is characterized in that, comprising:
(1) titanium source is slowly added under stirring in the mixed solution of organic amine, hydrochloride, ethanol, and within 2 ~ 5 hours, obtain colloidal tio 2 50 ~ 70 DEG C of backflows, the mol ratio of wherein said hydrochloride and described organic amine is 1:30 ~ 1:60, the mol ratio in described organic amine and described titanium source is 1:1 ~ 1:4, described organic amine is at least one in amino dodecane, cetylamine and stearylamine, and described hydrochloride is KCl and/or CaCl
2, described titanium source is Titanium alkoxides;
(2) in the colloidal tio 2 of gained, alkali is added, and within 10 ~ 20 hours, obtain three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol 150 ~ 180 DEG C of hydro-thermal reactions, the mol ratio in the described titanium source in the described alkali added in step (2) and step (1) is 1:1 ~ 1:4, and described alkali is at least one in ammoniacal liquor, Tetramethylammonium hydroxide and TBAH;
(3) gained three-dimensional multistage micro-nano-structure titanium dioxide colloidal sol through centrifugal, washing after be dissolved in solvent, adding after dispersion agent and binding agent are uniformly dispersed steams except described solvent, obtain three-dimensional multistage micro-nano-structure titanium dioxide slurry, in step (3), described solvent is ethanol, described dispersion agent is Terpineol 350, and described binding agent is ethyl cellulose.
2. method according to claim 1, is characterized in that, in step (1), described titanium source comprises tetrabutyl titanate and/or titanium isopropylate.
3. method according to claim 1 and 2, is characterized in that, in step (1), the volume ratio of described titanium source and described mixed solution is 1:40 ~ 1:50.
4. method according to claim 1 and 2, is characterized in that, in step (3), 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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| 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 |
| 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 |
| CN108821335B (en) * | 2018-08-29 | 2020-11-06 | 单潇 | 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 |
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