CN101478035B - Electrode material used for organic inorganic composite cell and manufacturing process - Google Patents
Electrode material used for organic inorganic composite cell and manufacturing process Download PDFInfo
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- CN101478035B CN101478035B CN 200910045113 CN200910045113A CN101478035B CN 101478035 B CN101478035 B CN 101478035B CN 200910045113 CN200910045113 CN 200910045113 CN 200910045113 A CN200910045113 A CN 200910045113A CN 101478035 B CN101478035 B CN 101478035B
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Abstract
The invention relates to an electrode material used for organic/inorganic composite battery and provides a simple and low-cost preparation method thereof. The preparation method is characterized in that a stable precursor solution is adopted to synthesize the TiO2-based electrode material with controllable composition and excellent performance by liquid-phase method or solid-phase reaction. The TiO2 can be doped with one of the transition metals selected from Zr, Hf, V, Nb, Ta, Cr, Mo, W or Sc, with a doping concentration of 0 to 30 mol%, to adjust the band structure of the TiO2 and improve the charge separation transportation capability of the TiO2, thereby improving the conversion efficiency of solar batteries. The maximal photoelectrical conversion efficiency is improved by 27.2% than that of the non-doped material.
Description
Technical field
The present invention relates to a kind of electrode material and manufacture method that is used for organic inorganic composite cell.The electrode material performance of this method preparation significantly is superior to the most frequently used electrode material at present, is specifically related to a kind ofly be equipped with the titania-based electrode material of composition and controllable structure through stable reaction precursor system, belongs to the photoelectric device field of materials.
Background technology
Increasingly serious along with environmental pollution and energy crisis; Be that the research of the clean energy resource of representative has received widely and paying close attention to solar energy; And traditional silicon solar cell is because its preparation technology requires factors such as harsh and cost height to restrict its development; The compound solar cell of the simple organic-inorganic of preparation technology with low cost arises at the historic moment under this background, and has obtained extensive studies.From engineering institutes such as Lausanne, SUI height in 1991
Professor has reported that a kind of conversion efficiency based on titanium dioxide nanocrystalline has reached (O ' Regan, B.and M. since 7.1% the compound solar cell of organic-inorganic
Nature 1991; 353:737-740.); The compound solar cell of organic-inorganic that with the dye-sensitized solar cells is representative has obtained paying close attention to widely and having obtained significant progress with its less cost and high conversion rate relatively; The monolithic small size efficient of dye-sensitized solar cells can reach 11%, sub-modular (25cm at present
2) efficient surpassed 8%.
Organic inorganic composite cell is mainly by inorganic semiconductor film, sensitizer, electrolyte, form electrode and conductive substrates.Wherein, dye-sensitized solar cells is mainly by nanocrystalline porous semiconductive thin film, dye sensitizing agent, redox electrolytes matter, form several parts such as electrode and conductive substrates.Its operation principle is: dye molecule absorbs behind the sunlight from the ground state transition to excitation state; The electronics of excitation state dyestuff is injected in the conduction band of Nano semiconductor; Transfer to conductive substrates subsequently, be transferred to electrode through external loop, the dyestuff that is in oxidation state is reduced the electrolyte reducing/regenerating of attitude; The electrolyte of oxidation state is reduced in that electrode is accepted electronics, thereby has accomplished a cyclic process of electron transport.In these processes, two of simultaneous back of the body reaction: be injected into electronics and the recombination reaction of the electron acceptor in oxidation state dyestuff or the electrolyte in the semiconductor conduction band.The how positive reaction of strengthening electronic transport process suppresses the back of the body reaction of charge recombination, is an emphasis of current dye-sensitized solar cells research work.
The maximum characteristics that with the dye-sensitized solar cells are the organic inorganic composite cell of representative are that its light absorption and separation of charge transmission are accomplished by sensitizer and porous semiconductor electrode film respectively; Charge transfer leans on majority carrier to accomplish, and its open circuit voltage depends on the quasi-Fermi level of Nano semiconductor and the energy level difference of electrolytical oxidation-reduction pair.
The main effect of porous semiconductor electrode film is to utilize its huge surface area to adsorb sensitizer; It simultaneously also is the carrier that photogenerated charge separates and transmits; The open circuit voltage of solar cell is directly related with semi-conductive quasi-Fermi level again in addition, so the semi-conducting electrode material plays a part very important in organic inorganic composite cell.
Have a large amount of corrective measures of having researched and proposed, mainly comprise the modification of titanium dioxide electrodes material and exploration two aspects of non-titanium dioxide system material to the semi-conducting electrode material.And up to the present, also fail to synthesize other semi-conducting electrode materials that performance can be compared with titanium dioxide mutually, use the widest, photoelectric conversion efficiency is the highest, also is that the semi-conducting electrode material that has industrialization prospect most is still titanium dioxide; Aspect the modification of titanium dioxide; Be the problem that the researcher pays close attention to how through the composition of simple process adjustments material, the pattern of controlled material always; And existing method often need adopt expensive and unsettled reactant; Perhaps need complicated preparation technology, and fail to obtain the satisfactory effect of improving.Therefore, through simple and cost low-cost preparation method thereof, the synthetic semi-conducting electrode material that can be used for the compound solar cell of organic-inorganic of forming controllable structure, excellent performance of design just seems particularly important.
Summary of the invention
The object of the present invention is to provide a kind of electrode material that can be used for organic inorganic composite cell, to improve the photoelectric properties of solar cell.
Another object of the present invention is to provide the simple of a kind of above-mentioned material and the cost low-cost preparation method thereof.
Describe the present invention below in detail.
The present invention adopts a kind of stable precursor solution to form titania-based electrode material controlled, excellent performance through simple liquid phase method technology or solid phase reaction are synthetic.
A) preparation of stable dopant precursor liquid solution
Solvent adopts the mixed solution of aqueous slkali and hydrogen peroxide, and wherein aqueous slkali comprises the mixed solution of any two kinds or several kinds in sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution, cesium hydroxide solution, ammoniacal liquor and the above-mentioned 5 kinds of aqueous slkalis; Solute adopts transition metal simple substance (Zr, Hf, V, Nb, Ta, Cr, Mo, W, Sc), its metal hydroxides, halide, nitrate, carboxylate and alkoxide.The solute of difference amount is joined in the above-mentioned solvent, obtain the precursor solution of various concentration in the cold bath after stirring a period of time, concentration range is at 0.001～10M.The concentration range of described aqueous slkali is 10
-4～20M, the concentration range of hydrogen peroxide is 10
-3～20M, the mol ratio of aqueous slkali and hydrogen peroxide is: 1: 0.02～200.
B) mixed liquor of basis material and dopant preparation
With the titanium dioxide source material, comprise Titanium, titanium dioxide, titanium hydroxide, Titanium Nitrate, titanium sulfate, titan yellow, halogenated titanium, carboxylic acid titanium and titanium alkoxide join in the described dopant precursor liquid solution of step a), stir.Then mixeding liquid temperature is increased to 60～100 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid behind stirring 0.5～5h.
C) titania-based electrode material is synthetic
1., the titania-based electrode material of liquid phase method prepared
The suspension-turbid liquid of step b) gained is moved in the reaction vessel, 80～450 ℃ of temperature range internal reactions 1～240 hour the target sediment, with washing of precipitate, be drying to obtain titania-based electrode material, temperature rate is not limit.
2., solid phase reaction prepares titania-based electrode material
The suspension-turbid liquid of step b) gained is moved in the reaction vessel; Get rid of moisture down for 100 ℃; Heat treatment got target product in 0.5～150 hour in 120～1200 ℃ of temperature ranges then, and product is washed, is drying to obtain titania-based electrode material, and temperature rate is not limit.。
D) making of electrode and battery assembling test
Powder and ethyl cellulose, polyethylene glycol and the turpentine oil of step c) gained are passed through the slurry that alcohol is mixed with stable uniform; On transparent conducting glass, prepare the semiconductor precursor film through silk screen printing or knife coating; Get the semiconductor anode film of porous through drying and annealing, controllable film thickness is built in 1～20 μ m.
Film after the annealing floods the porous anode film that 0.5～48h gets sensitization in sensitizer.With the solar cell that electrode is assembled into sandwich structure, to the electrodes use noble metal (Pt, Au, Ag, Cu, Mo) or carbon (C) load on the electro-conductive glass, the battery that obtains carries out battery performance test under analog light source.
This shows that electrode material 1. provided by the invention is base with titanium dioxide, that the containing transition metal element forms is anatase structured, rutile structure or non crystalline structure;
2. described transition metal is Zr, Hf, V, Nb, Ta, Cr, Mo, W or Sc, and the concentration of doping is 0～30mol%;
3. the particle diameter of described titanium dioxide powder is granular, bar-shaped, the sheet of 5nm-50 μ m or monocrystalline, polycrystalline, amorphous or the mixed crystal material of tubulose;
4. described titania-based electrode material through doping regulate titanium dioxide band structure, improve the separation of charge transmittability of titanium dioxide, thereby improve the conversion efficiency of solar cell.It is that high-photoelectric transformation efficiency is more unadulterated has improved 27.2%.(seeing embodiment 1-6 for details)
Beneficial effect of the present invention is:
The present invention has adopted simply and cheaply preparation technology, through the band structure of mixing and regulating titanium dioxide, improves the separation of charge transmittability of titanium dioxide, thereby has improved the conversion efficiency of solar cell.
Description of drawings
Fig. 1 is that the Nb doping that 180 ℃ of hydro-thermal reaction 20h obtain is respectively 0mol%, 2.5mol%, and 5mol%, 7.5mol%, the X ray diffracting spectrum of the titanium dioxide powder of 10mol% shows that the titania-doped electrode material of niobium is the anatase structured of pure phase.
Fig. 2 (a) is the transmission electron microscope image of the unadulterated titanium dioxide powder that obtains of 180 ℃ of hydro-thermal reaction 20h, shows that the powder that obtains is a nano powder, and average grain diameter is slightly less than 10nm; Fig. 2 (b) is that the Nb doping that 180 ℃ of hydro-thermal reaction 20h obtain is the transmission electron microscope image of the titanium dioxide powder of 10mol%, shows that the powder that obtains is a nano powder, and average grain diameter is about 12nm.
Embodiment
Introduce embodiments of the invention below, to understanding of the present invention, but the present invention is limited to embodiment absolutely not with further increase.
Embodiment 1:
Butyl titanate is added drop-wise to (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), fully stir clear solution, then temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtain suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain unadulterated titanium dioxide powder material.Through characterizing, the powder of gained is the anatase structured of pure phase, and is as shown in Figure 1, and powder is the nano particle of particle size distribution homogeneous, and average grain diameter is slightly less than 10nm, and its microcosmic TEM photo is shown in Fig. 2 (a).
Gained powder and ethyl cellulose, polyethylene glycol and turpentine oil are passed through the slurry that alcohol is mixed with stable uniform; On transparent conducting glass, prepare the semiconductor precursor film through silk screen printing; Get the semiconductor anode film of porous through drying and annealing, the film after the annealing is flooded the porous anode film that 24h gets sensitization in the N719 dyestuff.With the solar cell that electrode is assembled into sandwich structure, the battery that obtains carries out battery performance test under the AM1.5 analog light source, and the photoelectric conversion efficiency that records is 6.11%.
Embodiment 2:
1mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), the concentration that obtains homogeneous in the cold bath after stirring a period of time is the niobium precursor solution of 0.02M.It is 2.5mol% that the 39mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, fully stirs clear solution, then mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 2.5mol%.Through characterizing, the powder of gained is the anatase structured of pure phase, and the XRD diffraction pattern is as shown in Figure 1.
Gained powder and ethyl cellulose, polyethylene glycol and turpentine oil are passed through the slurry that alcohol is mixed with stable uniform; On transparent conducting glass, prepare the semiconductor precursor film through silk screen printing or knife coating; Get the semiconductor anode film of porous through drying and annealing, the film after the annealing is flooded the porous anode film that 24h gets sensitization in the N719 dyestuff.With the solar cell that electrode is assembled into sandwich structure, the battery that obtains carries out battery performance test under the AM1.5 analog light source, and the photoelectric conversion efficiency that records is 6.77%, more unadulterated titanium dioxide electrodes material, and battery performance has improved 10.8%.
Embodiment 3:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), the concentration that obtains homogeneous in the cold bath after stirring a period of time is the niobium precursor solution of 0.04M.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content; Fully stir clear solution; Then mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid behind the stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is the anatase structured of pure phase, and is as shown in Figure 1.
Powder is used for the making and the assembled battery testing photoelectronic performance of electrode, and under the AM1.5 analog light source, the photoelectric conversion efficiency that records is 7.21%, and more unadulterated titanium dioxide performance has improved 18.0%.
Embodiment 4:
3mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), the concentration that obtains homogeneous in the cold bath after stirring a period of time is the niobium precursor solution of 0.06M.It is 7.5mol% that the 37mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content; Fully stir clear solution; Then mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid behind the stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 7.5mol%.Through characterizing, the powder of gained is the anatase structured of pure phase, and is as shown in Figure 1.
Powder is used for the making and the assembled battery testing photoelectronic performance of electrode, and under the AM1.5 analog light source, the photoelectric conversion efficiency that records is 7.77%, and more unadulterated titanium dioxide performance has improved 27.2%.
Embodiment 5:
4mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), the concentration that obtains homogeneous in the cold bath after stirring a period of time is the niobium precursor solution of 0.08M.It is 10mol% that the 36mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content; Fully stir clear solution; Then mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid behind the stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 10mol%.Through characterizing, the powder of gained is the anatase structured of pure phase, and is as shown in Figure 1, and powder is the nano particle of particle size distribution homogeneous, and average grain diameter is about 12nm, and its microcosmic TEM photo is shown in Fig. 2 (b).
Powder is used for the making and the assembled battery testing photoelectronic performance of electrode, and under the AM1.5 analog light source, the photoelectric conversion efficiency that records is 6.14%, and more unadulterated titanium dioxide performance has improved 0.5%.
Embodiment 6:
8mmol metal simple-substance niobium is joined (NH in the mixed solvent of 500ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.016M after stirring a period of time in the cold bath.It is 20mol% that the 32mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content; Fully stir clear solution; Then mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid behind the stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 20mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 7:
2mmol metal simple-substance tantalum is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added in the above-mentioned tantalum precursor solution control tantalum doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the tantalum doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 8:
2mmol metal simple-substance zirconium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the zirconium precursor liquid solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added in the above-mentioned zirconium precursor liquid solution control zirconium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the zirconium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 9:
2mmol metal simple-substance tungsten is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the tungsten precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added in the above-mentioned tungsten precursor solution control tungsten doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the tungsten doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured
Embodiment 10:
The 2mmol vanadium metal is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the vanadium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol isopropyl titanate is added in the above-mentioned vanadium precursor solution control vanadium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 120 ℃ of following insulation reaction 240h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the vanadium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 11:
2mmol ethanol niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol titanium hydroxide is added in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 12:
The 2mmol columbium pentachloride is added drop-wise to (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, stir behind the 2h suspension-turbid liquid.Suspension-turbid liquid is moved in the agitated reactor, and at 180 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 13:
2mmol five water nitric acid molybdenums are joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the molybdenum precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol titanium tetrachloride is added drop-wise in the above-mentioned molybdenum precursor solution control molybdenum doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 80 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the molybdenum doping is 5.0mol%.Through characterizing, the powder of gained is non-crystal titanium dioxide.
Embodiment 14:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, fully stir after mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtain suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 300 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 15:
Get 5mmolNaOH and be dissolved in (30%) in the 50ml hydrogen peroxide, 2mmol metal simple-substance tantalum is joined in the above-mentioned solution, obtain the tantalum precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned tantalum precursor solution control tantalum doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 120 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 16:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the reaction vessel, and 100 ℃ are continued down to stir eliminating moisture, and then at 120 ℃ of following insulation reaction 1h, natural cooling gets target product, grinds promptly to get the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing the non-crystal titanium dioxide of the powder of gained.
Embodiment 17:
2mmol there is not (NH in the mixed solvent that niobium chloride joins 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the reaction vessel, and 100 ℃ are continued down to stir eliminating moisture, and then at 120 ℃ of following insulation reaction 150h, natural cooling gets target product, grinds promptly to get the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing the non-crystal titanium dioxide of the powder of gained.
Embodiment 18:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the reaction vessel, and 100 ℃ are continued down to stir eliminating moisture, and then at 600 ℃ of following insulation reaction 12h, natural cooling gets target product, grinds promptly to get the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is anatase structured.
Embodiment 19:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 50ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 5), obtain the niobium precursor solution that concentration is 0.04M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the reaction vessel, and 100 ℃ are continued down to stir eliminating moisture, and then at 1200 ℃ of following insulation reaction 6h, natural cooling gets target product, grinds promptly to get the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is a rutile structure.
Embodiment 20:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 400ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=1: 100), obtain the niobium precursor solution that concentration is 0.005M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content; After fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance; Obtain suspension-turbid liquid after stirring 2h, suspension-turbid liquid is moved in the agitated reactor, at 120 ℃ of following insulation reaction 50h; Natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is the anatase structured of pure phase.
Embodiment 21:
2mmol metal simple-substance niobium is joined (NH in the mixed solvent of 400ml ammoniacal liquor (25-28%) and hydrogen peroxide (30%)
3H
2O: H
2O
2=20: 1), obtain the niobium precursor solution that concentration is 0.005M after stirring a period of time in the cold bath.It is 5.0mol% that the 38mmol butyl titanate is added drop-wise in the above-mentioned niobium precursor solution control niobium doping content, after fully stirring mixeding liquid temperature is increased to 80 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtains suspension-turbid liquid after stirring 2h.Suspension-turbid liquid is moved in the agitated reactor, and at 120 ℃ of following insulation reaction 20h, natural cooling gets the target sediment, with precipitate with deionized water washing 3～5 times, be drying to obtain the titanium dioxide powder material that the niobium doping is 5.0mol%.Through characterizing, the powder of gained is the anatase structured of pure phase.
Claims (5)
1. electrode material that is used for organic inorganic composite solar battery is characterized in that described electrode material is base with titanium dioxide, and that the containing transition metal element forms is anatase structured, rutile structure or non crystalline structure;
Described transition metal is Zr, Hf, V, Nb, Ta, Cr, Mo, W or Sc, and the concentration of doping is 0～30mol%, but does not comprise 0mol%;
Described titanium dioxide powder is that particle diameter is granular, bar-shaped, the sheet of 5nm-50 μ m or monocrystalline, polycrystalline, amorphous or the mixed crystal material of tubulose;
Described titania-based electrode material through doping regulate titanium dioxide band structure, improve the separation of charge transmittability of titanium dioxide, thereby improve the conversion efficiency of solar cell.
2. preparation is characterized in that like each described method that is used for the electrode material of organic inorganic composite solar battery in the claim 1 concrete steps are:
A) preparation of stable dopant precursor liquid solution
Solvent adopts the mixed solution of aqueous slkali and hydrogen peroxide, and wherein aqueous slkali is a kind of in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, cesium hydroxide solution or the ammoniacal liquor or their combination; Solute adopts transition metal with simple substance, metal hydroxides, halide, nitrate, carboxylate or pure salt form; The solute of difference amount is joined in the above-mentioned solvent; In cold bath, obtain the precursor solution of various concentration after stirring a period of time, concentration range is at 0.001-10M;
B) mixed liquor of basis material and dopant preparation
With the titanium dioxide source material, join in the described dopant precursor liquid solution of step a), stir, then mixeding liquid temperature is increased to 60-100 ℃ to get rid of unnecessary hydrogen peroxide and organic substance, obtain suspension-turbid liquid behind the stirring 0.5-5h;
C) titania-based electrode material is synthetic
1., the titania-based electrode material of liquid phase method prepared
The suspension-turbid liquid of step b) gained is moved in the reaction vessel, get the target sediment, with washing of precipitate, be drying to obtain titania-based electrode material at 80-450 ℃ of temperature range internal reaction;
2., solid phase reaction prepares titania-based electrode material
The suspension-turbid liquid of step b) gained is moved in the reaction vessel, under 100 ℃ of conditions, get rid of moisture, heat treatment gets target product in 120-1200 ℃ of temperature range then, and product is washed, is drying to obtain titania-based electrode material.
3. get electrode material and get the preparation method by the described organic inorganic composite solar battery that is used for of claim 2, it is characterized in that said that the titanium dioxide source material comprise Titanium, titanium dioxide, titanium hydroxide, Titanium Nitrate, titanium sulfate, titan yellow, halogenated titanium, carboxylic acid titanium or titanium alkoxide.
4. get electrode material and get the preparation method by the described organic inorganic composite solar battery that is used for of claim 2, the concentration range that it is characterized in that aqueous slkali described in said the step a is 10
-4-20M, the concentration range of hydrogen peroxide is 10
-3-20M, the solute in the aqueous slkali and the mol ratio of hydrogen peroxide are: 1: 0.02-200.
5. get electrode material and get the preparation method by the described organic inorganic composite solar battery that is used for of claim 2, it is characterized in that:
When (1) liquid phase method prepares titania-based electrode material among the step c, 80-450 ℃ of temperature range internal reaction 1-240 hour;
When (2) solid phase reaction prepared titania-based electrode material among the step c, heat treatment time was 0.5-150 hour.
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| CN102157268B (en) * | 2010-11-23 | 2012-08-01 | 复旦大学 | Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof |
| CN102360961B (en) * | 2011-08-23 | 2013-01-30 | 奇瑞汽车股份有限公司 | Preparation method and modification process of sizing agent of scattering layer of dye-sensitized solar cell |
| ES2944935T3 (en) * | 2012-02-23 | 2023-06-27 | Treadstone Tech Inc | Corrosion resistant and electrically conductive metal surface |
| CN103594693B (en) * | 2013-11-19 | 2016-03-02 | 大连海事大学 | A kind of titanium dioxide/niobium-titanium oxide composite material and Synthesis and applications thereof |
| CN104715928B (en) * | 2015-02-15 | 2017-07-28 | 辽宁工业大学 | A kind of Li doping TiO2The preparation method of nanometer rods light anode |
| RU2726713C2 (en) * | 2015-12-21 | 2020-07-15 | Имек Фзв | Alloyed titanate |
| WO2017155070A1 (en) * | 2016-03-09 | 2017-09-14 | Ｄｏｗａエレクトロニクス株式会社 | Solution and method for manufacturing same, and method for manufacturing active material for secondary cell |
| CN106449988B (en) * | 2016-11-29 | 2019-04-19 | 宁波大学 | A kind of perovskite solar battery of super-thin electronic transport layer structure |
| CN107134575B (en) * | 2017-03-30 | 2020-05-15 | 中南大学 | Preparation method of sodium ion battery negative electrode material |
| CN109286000A (en) * | 2018-09-04 | 2019-01-29 | 江南大学 | Lithium ion battery mixes anatase titania negative electrode material and preparation method thereof with molybdenum |
| CN111244289B (en) * | 2020-01-15 | 2022-09-30 | 重庆文理学院 | Preparation method of organic photovoltaic device with ZnO film as interface layer |
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