CN101899701B - Method for preparing composite material of copper sulfide and titanium dioxide nano-tube - Google Patents
Method for preparing composite material of copper sulfide and titanium dioxide nano-tube Download PDFInfo
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- CN101899701B CN101899701B CN2010102296420A CN201010229642A CN101899701B CN 101899701 B CN101899701 B CN 101899701B CN 2010102296420 A CN2010102296420 A CN 2010102296420A CN 201010229642 A CN201010229642 A CN 201010229642A CN 101899701 B CN101899701 B CN 101899701B
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Abstract
The invention provides a method for preparing a composite material of a copper sulfide and titanium dioxide nano-tube. The method comprises the following steps of putting a sanded titanium plate in acetone or absolute ethanol for ultrasonic cleaning, and is rinsed and aired with deionized water; anodizing a platinum plate serving as a cathode and the treated titanium plate serving as an anode in ethylene glycol solution with 0.25 weight percent of ammonium fluoride, namely a titanium dioxide nano-tube array grows on the surface of the titanium plate; putting the titanium plate growing the titanium dioxide nano-tube array in mixed solution filled with copper chloride and sodium thiosulfate, wherein molar concentrations of the copper chloride and the sodium thiosulfate in the mixed solution are the same, and are between 0.0025 and 0.01mol/L; and sealing the solution with an autoclave, heating the autoclave to the temperature of between 60 and 120 DEG C, and preserving the temperature for 12 to 24 hours. The nano composite material prepared by the method has high sunlight absorbing and utilizing capability, has good application prospect in the field of solar cells, and has simple manufacture process, low equipment requirement and low preparation cost.
Description
Technical field
The present invention relates to the preparation method of a kind of cupric sulfide and titania nanotube matrix material.
Background technology
Utilize the TiO of anonizing preparation
2Nanotube has high-sequential property, and it as the dye sensitization solar battery negative electrode, is compared with the sun power sensitization battery electrode that nano particle constitutes, and the electronics of its generation has the more long lifetime, and TiO
2The pipeline of nanotube better approach for electron transport is provided.But because existing titania nanotube is simple N-type semiconductor material, only photoabsorption can be arranged near UV-light, and can not absorb visible light, the absorption of sunshine is still waiting to improve with utilizing ability.Quantum dot sensitized solar cell based on titania nanotube was studied out in 2008, and it replaces dyestuff with semiconductor-quantum-point, had device architecture, the relative characteristic of simple of quantum dot sensitized process.
Summary of the invention
The present invention is the preparation method of a kind of cupric sulfide and titania nanotube composite nano materials.The nano composite material of this method preparation to the absorption of sunshine with utilize ability high, have good utilization prospect in area of solar cell.And its manufacture craft is simple, equipment requirements is low, and preparation cost is low.
The present invention is for realizing its goal of the invention, and the technical scheme that is adopted and the concrete practice are:
The preparation method of a kind of cupric sulfide and titania nanotube composite nano materials, its concrete practice is:
A. titanium sheet pre-treatment: with the titanium sheet of purity more than 99.0%, with sand paper with its surface be milled to light seamless after, put into acetone or absolute ethyl alcohol 20-40 minute ultrasonic cleaning, again with deionized water rinsing and air-dry;
B. electrochemical preparation titania nanotube: the titanium sheet of platinized platinum after as negative electrode, a step process carried out anodic oxidation as anode in the ethylene glycol solution of 0.25%wt Neutral ammonium fluoride; Voltage is 50-60v; Oxidization time 5-20 hour, promptly grow Nano tube array of titanium dioxide at titanium plate surface;
C. the preparation of matrix material: have the titanium sheet of Nano tube array of titanium dioxide to put into the mixing solutions that cupric chloride and Sulfothiorine are housed the growth of b step; The cupric chloride of mixing solutions is identical with the volumetric molar concentration of Sulfothiorine, and concentration range is 0.0025-0.01mol/L; After sealing with autoclave, put into stove and heat, the time is 12-24 hour, and temperature is 60-120 ℃.
Compared with prior art, the invention has the beneficial effects as follows:
Adopt the electrochemical production titania nanotube; Again Nano tube array of titanium dioxide is put into the mixing solutions of cupric chloride and Sulfothiorine; Under 60-120 ℃ temperature condition; The nano level cupric sulfide that produces in the mixing solutions is adsorbed on the titania nanotube surface, and forms the nanotube-shaped matrix material of cupric sulfide and titania nanotube.This composite material nanometer pipeline is similarly electron transport approach preferably is provided, and titania nanotube wherein is the N-type semiconductor material, the ability absorbing ultraviolet light; Produce photovoltage; And nano-copper sulfide wherein is the P-type semiconductor material, can absorb visible light, produces photovoltage; Make matrix material integral body absorbing ultraviolet light can absorb visible light again, produce photovoltage, to the absorption of sunshine with utilize ability to improve greatly.Thereby has good utilization prospect in area of solar cell.
Adopt the matrix material of Hydrothermal Preparation cupric sulfide and titania nanotube, temperature is low in the process, and save energy need not task equipment, and technology is simple, and preparation cost is low.
In the titanium sheet pre-treatment in above-mentioned a step, the titanium sheet with coated abrasive working after, also put it into polishing fluid and carry out 5-15 minute electrochemical etching, carry out ultrasonic cleaning again; Described polishing fluid is formulated by 3: 2: 5 volume ratio by the glacial acetic acid of 99.8% the vitriol oil, 40% hydrofluoric acid and purity 99.8%; Getting a titanium sheet during polishing in addition is negative electrode, and the titanium sheet of handling carries out the constant voltage electrochemical etching of 11-15V as anode to the titanium sheet of handling.
Polished finish makes titanium plate surface more smooth, makes the matrix material that makes more smooth, and pattern is good, and is better with contacting of battery electrode, and is higher with the battery useful output of its preparation.
Below in conjunction with accompanying drawing and embodiment the present invention is further described.
Description of drawings
Fig. 1 is the X ray diffracting spectrum that the inventive method is prepared into matrix material.Among the figure, ordinate zou is diffraction intensity (Intensity), A.U. (a.u.), and X-coordinate is diffraction angle 2 θ, and unit is degree (deg.).
Fig. 2 is the sem photograph with the titania nanotube of the inventive method before composite sulfuration copper.
Fig. 3 is the sem photograph of the inventive method prepared product.
Fig. 4 is a titania nanotube before the composite sulfuration copper and the material behind the composite sulfuration copper in the inventive method, under same light source, and the I-V graphic representation that opto-electronic conversion is exported, among the figure, ordinate zou is current density degree, unit, and X-coordinate is a voltage, and unit is V.Fig. 4 explains the material behind the composite sulfuration copper, and its short-circuit current density is 1.7 for mA/cm
2, and the short-circuit current density of simple titania nanotube is almost nil.It is thus clear that the nano composite material of present method preparation to the absorption of sunshine with utilize ability high, useful output is high.
Embodiment
Embodiment one
One embodiment of the present invention are, the preparation method of a kind of cupric sulfide and titania nanotube matrix material, and its concrete practice is:
A. titanium sheet pre-treatment: with the titanium sheet of purity 99.9%, with sand paper with its surface be milled to light seamless after, put into the ultrasonic cleaning in 30 minutes of acetone or absolute ethyl alcohol, again with deionized water rinsing and air-dry;
B. electrochemical preparation titania nanotube: the titanium sheet of platinized platinum after as negative electrode, a step process carried out anodic oxidation as anode in the ethylene glycol solution of 0.25%wt (being that weight percent is 0.25%) Neutral ammonium fluoride; Voltage is 55v; Oxidization time 13 hours promptly grows Nano tube array of titanium dioxide at titanium plate surface;
C. the preparation of matrix material: have the titanium sheet of Nano tube array of titanium dioxide to put into the mixing solutions that cupric chloride and Sulfothiorine are housed the growth of b step, the cupric chloride of mixing solutions is identical with the volumetric molar concentration of Sulfothiorine, and concentration is 0.005mol/L; After sealing with autoclave, put into stove and heat, the time is 17 hours, and temperature is 100 ℃.
In the titanium sheet pre-treatment in this routine a step, the titanium sheet with coated abrasive working after, also put it into polishing fluid and carry out 10 minutes electrochemical etchings, carry out ultrasonic cleaning again; Described polishing fluid is formulated by 3: 2: 5 volume ratio by the hydrofluoric acid of 99.8% (weight percent concentration) vitriol oil, 40% (weight percent concentration) and the glacial acetic acid of purity 99.8% (the ice shape crystal of anhydrous acetic acid); Getting a titanium sheet during polishing in addition is negative electrode, and the titanium sheet of handling carries out the constant voltage electrochemical etching of 11V as anode to the titanium sheet of handling.
Embodiment two
One embodiment of the present invention are, the preparation method of a kind of cupric sulfide and titania nanotube matrix material, and its concrete practice is:
A. titanium sheet pre-treatment: with the titanium sheet of purity 99.9%, with sand paper with its surface be milled to light seamless after, put into the ultrasonic cleaning in 20 minutes of acetone or absolute ethyl alcohol, again with deionized water rinsing and air-dry;
B. electrochemical preparation titania nanotube: the titanium sheet of platinized platinum after as negative electrode, a step process carried out anodic oxidation as anode in the ethylene glycol solution of 0.25%wt Neutral ammonium fluoride; Voltage is 50v; Oxidization time 5 hours promptly grows Nano tube array of titanium dioxide at titanium plate surface;
C. the preparation of matrix material: have the titanium sheet of Nano tube array of titanium dioxide to put into the mixing solutions that cupric chloride and Sulfothiorine are housed the growth of b step, the cupric chloride of mixing solutions is identical with the volumetric molar concentration of Sulfothiorine, and concentration is 0.0025mol/L; After sealing with autoclave, put into stove and heat, the time is 12 hours, and temperature is 60 ℃.
In the titanium sheet pre-treatment in this routine a step, the titanium sheet with coated abrasive working after, also put it into polishing fluid and carry out 5 minutes electrochemical etchings, carry out ultrasonic cleaning again; Described polishing fluid is formulated by 3: 2: 5 volume ratio by the hydrofluoric acid of the vitriol oil, 40% (weight percent concentration) of 99.8% (weight percent concentration) and the glacial acetic acid of purity 99.8% (the ice shape crystal of anhydrous acetic acid); Getting a titanium sheet during polishing in addition is negative electrode, and the titanium sheet of handling carries out the constant voltage electrochemical etching of 12V as anode to the titanium sheet of handling.
Embodiment three
One embodiment of the present invention are, the preparation method of a kind of cupric sulfide and titania nanotube matrix material, and its concrete practice is:
A. titanium sheet pre-treatment: with the titanium sheet of purity 99.0%, with sand paper with its surface be milled to light seamless after, put into the ultrasonic cleaning in 40 minutes of acetone or absolute ethyl alcohol, again with deionized water rinsing and air-dry;
B. electrochemical preparation titania nanotube: the titanium sheet of platinized platinum after as negative electrode, a step process carried out anodic oxidation as anode in the ethylene glycol solution of 0.25%wt Neutral ammonium fluoride; Voltage is 60v; Oxidization time 20 hours promptly grows Nano tube array of titanium dioxide at titanium plate surface;
C. the preparation of matrix material: have the titanium sheet of Nano tube array of titanium dioxide to put into the mixing solutions that cupric chloride and Sulfothiorine are housed the growth of b step, the cupric chloride of mixing solutions is identical with the volumetric molar concentration of Sulfothiorine, and concentration is 0.01mol/L; After sealing with autoclave, put into stove and heat, the time is 24 hours, and temperature is 120 ℃.
In the titanium sheet pre-treatment in this routine a step, the titanium sheet with coated abrasive working after, also put it into polishing fluid and carry out 15 minutes electrochemical etchings, carry out ultrasonic cleaning again; Described polishing fluid is formulated by 3: 2: 5 volume ratio by the glacial acetic acid of 99.8% the vitriol oil, 40% hydrofluoric acid and purity 99.8%; Getting a titanium sheet during polishing in addition is negative electrode, and the titanium sheet of handling carries out the constant voltage electrochemical etching of 15V as anode to the titanium sheet of handling.
Embodiment four
One embodiment of the present invention are, the preparation method of a kind of cupric sulfide and titania nanotube matrix material, and its concrete practice is:
A. titanium sheet pre-treatment: with the titanium sheet of purity 99.0%, with sand paper with its surface be milled to light seamless after, put into the ultrasonic cleaning in 25 minutes of acetone or absolute ethyl alcohol, again with deionized water rinsing and air-dry;
B. electrochemical preparation titania nanotube: the titanium sheet of platinized platinum after as negative electrode, a step process carried out anodic oxidation as anode in the ethylene glycol solution of 0.25%wt Neutral ammonium fluoride; Voltage is 57v; Oxidization time 15 hours promptly grows Nano tube array of titanium dioxide at titanium plate surface;
C. the preparation of matrix material: have the titanium sheet of Nano tube array of titanium dioxide to put into the mixing solutions that cupric chloride and Sulfothiorine are housed the growth of b step, the cupric chloride of mixing solutions is identical with the volumetric molar concentration of Sulfothiorine, and concentration is 0.008mol/L; After sealing with autoclave, put into stove and heat, the time is 22 hours, and temperature is 80 ℃.
In the titanium sheet pre-treatment in this routine a step, the titanium sheet with coated abrasive working after, also put it into polishing fluid and carry out 15 minutes electrochemical etchings, carry out ultrasonic cleaning again; Described polishing fluid is formulated by 3: 2: 5 volume ratio by the glacial acetic acid of 99.8% the vitriol oil, 40% hydrofluoric acid and purity 99.8%; Getting a titanium sheet during polishing in addition is negative electrode, and the titanium sheet of handling carries out the constant voltage electrochemical etching of 15V as anode to the titanium sheet of handling.
Fig. 1 is the X ray diffracting spectrum that the inventive method is prepared into matrix material.Among the figure, ordinate zou is diffraction intensity (Intensity), A.U. (a.u.), and X-coordinate is diffraction angle 2 θ, and unit is degree (deg.).Fig. 1 explains that the matrix material of present method preparation is the matrix material that cupric sulfide and titanium oxide constitute really;
Fig. 2 is the sem photograph with the titania nanotube of the inventive method before composite sulfuration copper.Fig. 3 is the sem photograph of the inventive method prepared product.
The prepared product that Fig. 2, Fig. 3 explain the inventive method really is the compound matrix material of nano copper sulfate particle on titania nanotube.
Fig. 4 is a titania nanotube before the composite sulfuration copper and the material behind the composite sulfuration copper in the inventive method, and under same light source, the I-V graphic representation that opto-electronic conversion is exported wherein is labeled as TiO
2Almost the curve of level is the I-V graphic representation of the titania nanotube before the composite sulfuration copper, and another is labeled as CuS-TiO
2Curve be the material I-V graphic representation behind the composite sulfuration copper; Among the figure, ordinate zou is current density degree, unit, and X-coordinate is a voltage, and unit is V.Fig. 4 explains the material behind the composite sulfuration copper, and its short-circuit current density is 1.7 for mA/cm
2, and the short-circuit current density of simple titania nanotube is almost nil.It is thus clear that the nano composite material of present method preparation to the absorption of sunshine with utilize ability high, useful output is high.
Claims (2)
1. one kind is used as the nano-copper sulfide of solar-electricity pool cathode and the preparation method of titania nanotube matrix material, and its concrete practice is:
A. titanium sheet pre-treatment: with the titanium sheet of purity more than 99.0%, with sand paper with its surface be milled to light seamless after, put into acetone or absolute ethyl alcohol 20-40 minute ultrasonic cleaning, again with deionized water rinsing and air-dry;
B. electrochemical preparation titania nanotube: the titanium sheet of platinized platinum after as negative electrode, a step process carried out anodic oxidation as anode in the ethylene glycol solution of 0.25%wt Neutral ammonium fluoride; Voltage is 50-60V; Oxidization time 5-20 hour, promptly grow Nano tube array of titanium dioxide at titanium plate surface;
C. the preparation of matrix material: have the titanium sheet of Nano tube array of titanium dioxide to put into the mixing solutions that cupric chloride and Sulfothiorine are housed the growth of b step; The cupric chloride of mixing solutions is identical with the volumetric molar concentration of Sulfothiorine, and concentration range is 0.0025-0.01mol/L; After sealing with autoclave, put into stove and heat, the time is 12-24 hour, and temperature is 60-120 ℃, promptly gets nano-copper sulfide and titania nanotube matrix material as the solar cell negative electrode.
2. according to claim 1 a kind of as the nano-copper sulfide of solar-electricity pool cathode and the preparation method of titania nanotube matrix material; It is characterized in that: in the titanium sheet pre-treatment in described a step; The titanium sheet with coated abrasive working after; Also put it into polishing fluid and carry out 5-15 minute electrochemical etching, carry out ultrasonic cleaning again; Described polishing fluid is formulated by 3: 2: 5 volume ratio by the glacial acetic acid of 99.8% the vitriol oil, 40% hydrofluoric acid and purity 99.8%; Getting a titanium sheet during polishing in addition is negative electrode, and the titanium sheet of handling carries out the constant voltage electrochemical etching of 11-15V as anode to the titanium sheet of handling.
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CN110359074B (en) * | 2019-07-19 | 2020-10-27 | 中原工学院 | Medical metal titanium or titanium alloy surface composite anticorrosive coating and preparation method thereof |
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CN101768771B (en) * | 2008-12-31 | 2011-12-21 | 北京大学 | Cylindrical and barrel-shaped titanium dioxide nanotube arrays and preparation method and application thereof |
CN101545129B (en) * | 2009-04-02 | 2010-08-11 | 桂林工学院 | A process for synthesizing crystalline titanic oxide nano-tubes |
CN101625930B (en) * | 2009-06-19 | 2012-04-11 | 东南大学 | Ordered nano-tube array structure electrode material, preparation method and stored energy application |
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