CN101723351A - Method for preparing Bi2Te3/carbon nanotube composite material - Google Patents

Method for preparing Bi2Te3/carbon nanotube composite material Download PDF

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Publication number
CN101723351A
CN101723351A CN200910155794A CN200910155794A CN101723351A CN 101723351 A CN101723351 A CN 101723351A CN 200910155794 A CN200910155794 A CN 200910155794A CN 200910155794 A CN200910155794 A CN 200910155794A CN 101723351 A CN101723351 A CN 101723351A
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carbon nanotube
bi2te3
compound
nano tube
carbon nano
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CN200910155794A
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孙晨曦
张孝彬
周丽娜
赵新兵
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing a Bi2Te3/carbon nanotube composite material, which comprises the following steps: dissolving acidized carbon nanotubes into aqueous solution of surfactant EDTA, performing ultrasonic dispersion, and adding alkali to adjust the OH- concentration of the solution to between 0.1 and 1mol/L; in a determined molar ratio of Bi to Te of 2:3 through chemical composition analysis of Bi2Te3, dissolving a compound containing Bi element, a compound containing Te element or a Te simple substance into the aqueous solution, and adding a reducing agent NaBH4 with stirring to obtain mixed solution; and stirring and heating the mixed solution in a water bath, centrifugally separating, washing and collecting solid product after the reaction is finished, and drying. In the Bi2Te3/carbon nanotube composite material prepared by the method, the size of Bi2Te3 particles is about between 10 and 20nm; and the Bi2Te3/carbon nanotube composite material combines advantages of the carbon nanotubes and a thermoelectric material and is expected to improve figure of merit.

Description

A kind of Bi 2Te 3The preparation method of/carbon nano tube compound material
Technical field
The present invention relates to Bi 2Te 3The preparation method of/carbon nano tube compound material belongs to the semi-conductor thermoelectric material technical field.
Background technology
Thermoelectric material is a kind of semiconductor functional material, it can realize the mutual conversion of heat energy and electric energy, there is important use to be worth and application prospects (B.C.Sales.Thermoelectric materials-Smaller is cooler.Science at thermo-electric generation and focus refrigerating field, 2002,295 (5558): 1248-1249).And Bi 2Te 3Its ZT value can approach 1, is thermoelectric material best under the current room temperature state.The height of thermoelectric device performance directly depends on the size of thermoelectric figure of merit, and therefore, further improve thermoelectric figure of merit ZT is a central topic of thermoelectricity research always.Can effectively improve the performance of focus material by grain refining and reduction crystal grain dimension.
Reduction, the crystal grain thinning of crystal grain in the thermoelectric material (particle) size or make material nanoization; help strengthening the scattering process of phonon on the one hand to heat; thereby reduce thermal conductivity (amplitude is greater than the reduction of specific conductivity); thereby the scattering that can improve current carrier is on the other hand again promoted the Seebeck coefficient; thereby can improve thermoelectric figure of merit (the J.Jortner and C.N.R.Rao.Nanostructured advanced materials.Perspectives and directions.Pure Appl.Chem. of material; 2002,74 (9): 1491-1506.).Therefore with Bi 2Te 3The base thermoelectricity material nanometer has application potential too.
Carbon nanotube has become the domestic and international research focus rapidly owing to have excellent performance and exist multiple potential using value, carbon nanotube to have outstanding specific surface area and favorable mechanical, electricity, optical property.Because it has big specific surface area, coat the main means that other nano materials have become surface modification of carbon nanotube and disperseed compound nano-particle on its surface.
Summary of the invention
It is tiny to the purpose of this invention is to provide a kind of particle, helps improving the Bi of thermoelectric figure of merit 2Te 3The preparation method of/carbon nano tube compound material.
Bi of the present invention 2Te 3The preparation method of/carbon nano tube compound material, employing be that low temperature wet is learned synthesis technique, step is as follows:
1) with carbon nanotube at concentrated nitric acid, the vitriol oil or the above two nitration mixture are ultrasonic or reflow treatment 2-5h, or after 300 ℃ of oxide treatment again through pickling, filtering and washing is to neutral, oven dry obtains the carbon nanotube that the surface exists defective or functionalization;
2) carbon nanotube after the step 1) processing being dissolved in concentration is in 5-20g/L disodium ethylene diamine tetraacetate (EDTA) aqueous solution, ultra-sonic dispersion, and add alkali regulator solution OH -Concentration is 0.1-1mol/L;
3) according to Bi 2Te 3The determined Bi of chemical ingredients: the mol ratio of Te is 2: 3, and the compound or the Te simple substance that will contain the compound of Bi element and contain the Te element are dissolved in step 2) the aqueous solution in, stir down according to every mole of Bi 2Te 3Add 50-200g reductive agent NaBH 4, get mixed solution;
4) with mixed solution stirring heating 12-48h under 70-85 ℃ of water-bath, reaction finishes back centrifugation, washing, collection solid product, and oven dry obtains Bi 2Te 3/ carbon nano tube compound material.
Among the present invention, the compound of the said Bi of containing element is muriate, oxide compound, vitriol, nitrate or the carbonate that contains the Bi element.The compound of the said Te of containing element is muriate, oxide compound, vitriol, nitrate, nitrite or the carbonate that contains the Te element.
The Bi that the inventive method makes 2Te 3/ carbon nano tube compound material, its Bi 2Te 3Particle size is about 10-20nm, evenly is coated on carbon nano tube surface with stratiform, or is connected in the bunchy carbon nano tube surface with Granular forms.This Bi 2Te 3/ carbon nano tube compound material combines the advantage of carbon nanotube and thermoelectric material, is expected to improve thermoelectric figure of merit, is with a wide range of applications.
Description of drawings
Fig. 1 is Bi 2Te 3Be coated on the TEM image of single-root carbon nano-tube;
Fig. 2 is that bunchy carbon tube-surface coats Bi 2Te 3The TEM image.
Embodiment
Embodiment 1
1) with carbon nanotube ultrasonic 2h in concentrated nitric acid solution, filtering and washing is dried to neutral, obtains the carbon nanotube of functionalization.
2) carbon nanotube after the processing of 0.05g step 1) is dissolved in the EDTA aqueous solution that 100mL concentration is 20g/L, ultra-sonic dispersion 30min, and add NaOH, regulator solution OH -Concentration is 0.5mol/L;
3) according to Bi 2Te 3The determined Bi of chemical ingredients: the mol ratio of Te is 2: 3, with Bi (NO 3) 35H 2O and Na 2TeO 3Be dissolved in step 2) the aqueous solution in, stir down according to every mole of Bi 2Te 3Add 100g reductive agent NaBH 4, get mixed solution;
4) with mixed solution stirring heating 36h under 70 ℃ of water-baths.Reaction finishes the back centrifugation, uses deionized water, absolute ethanol washing, collection solid product, oven dry.Get Bi 2Te 3/ carbon nano tube compound material.
Adopt the thing phase of Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer assay products, its result is the Bi of hexagonal structure 2Te 3And carbon nanotube.Adopt 200KV/JEM-2010 (HR) type transmission electron microscopy product pattern, the result is Bi 2Te 3Nano particle evenly is coated on the carbon nano tube surface (see figure 1).The bunchy carbon nano tube surface is connected with dispersive Bi 2Te 3The nano particle (see figure 2).Bi 2Te 3Particle size is 10-20nm.
Embodiment 2
1) carbon nanotube reflux in concentrated nitric acid solution is handled 2h, filtering and washing is dried to neutral, obtains the carbon nanotube of functionalization.
2) carbon nanotube after the processing of 0.03g step 1) is dissolved in the EDTA aqueous solution that 100mL concentration is 10g/L, ultra-sonic dispersion 30min, and add NaOH, regulator solution OH -Concentration is 0.8mol/L;
3) according to Bi 2Te 3The determined Bi of chemical ingredients: the mol ratio of Te is 2: 3, with Bi (NO 3) 35H 2O and TeO 2Be dissolved in step 2) the aqueous solution in, stir down according to every mole of Bi 2Te 3Add 50g reductive agent NaBH 4, get mixed solution;
4) with mixed solution stirring heating 48h under 70 ℃ of water-baths.Reaction finishes the back centrifugation, uses deionized water, absolute ethanol washing, collection solid product, oven dry.Get Bi 2Te 3/ carbon nano tube compound material, Bi 2Te 3Particle size is 10-20nm.
Adopt the thing phase of Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer assay products, its result is the Bi of hexagonal structure 2Te 3And carbon nanotube.
Embodiment 3
1) with carbon nanotube ultrasonic 3h in concentrated sulfuric acid solution, filtering and washing is dried to neutral, obtains the carbon nanotube of functionalization.
2) carbon nanotube after the processing of 0.06g step 1) is dissolved in the EDTA aqueous solution that 100mL concentration is 15g/L, ultra-sonic dispersion 30min, and add NaOH, regulator solution OH -Concentration is 0.4mol/L;
3) according to Bi 2Te 3The determined Bi of chemical ingredients: the mol ratio of Te is 2: 3, with BiCl 3And Na 2TeO 3Be dissolved in step 2) the aqueous solution in, stir down according to every mole of Bi 2Te 3Add 80g reductive agent NaBH 4, get mixed solution;
4) with mixed solution at 80 ℃ of following stirring heating 24h of water-bath.Reaction finishes the back centrifugation, uses deionized water, absolute ethanol washing, collection solid product, oven dry.Get Bi 2Te 3/ carbon nano tube compound material.Bi 2Te 3Particle size is 10-20nm.
Adopt the thing phase of Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer assay products, its result is the Bi of hexagonal structure 2Te 3And carbon nanotube.
Embodiment 4
1) with carbon nanotube ultrasonic 3h in concentrated nitric acid solution, filtering and washing is dried to neutral.Obtain the carbon nanotube of functionalization.
2) carbon nanotube after the processing of 0.025g step 1) is dissolved in the EDTA aqueous solution that 100mL concentration is 5g/L, ultra-sonic dispersion 30min, and add NaOH, regulator solution OH -Concentration is 1mol/L;
3) according to Bi 2Te 3The determined Bi of chemical ingredients: the mol ratio of Te is 2: 3, with BiCl 3Be dissolved in step 2 with Te simple substance) the aqueous solution in, stir down according to every mole of Bi 2Te 3Add 60g reductive agent NaBH 4, get mixed solution;
4) with mixed solution at 85 ℃ of following stirring heating 12h of water-bath.Reaction finishes the back centrifugation, uses deionized water, absolute ethanol washing, collection solid product, oven dry.Get Bi 2Te 3/ carbon nano tube compound material.Bi 2Te 3Particle size is 10-20nm.
Adopt the thing phase of Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer assay products, its result is the Bi of hexagonal structure 2Te 3And carbon nanotube.

Claims (3)

1. Bi 2Te 3The preparation method of/carbon nano tube compound material, its step comprises:
1) with carbon nanotube at concentrated nitric acid, the vitriol oil or the above two nitration mixture are ultrasonic or reflow treatment 2-5h, or after 300 ℃ of oxide treatment again through pickling, filtering and washing is to neutral, oven dry obtains the carbon nanotube that the surface exists defective or functionalization;
2) carbon nanotube after the step 1) processing being dissolved in concentration is in the 5-20g/L disodium ethylene diamine tetra-acetic acid aqueous solution, ultra-sonic dispersion, and adding alkali regulator solution OH-concentration is 0.1-1mol/L;
3) according to Bi 2Te 3The determined Bi of chemical ingredients: the mol ratio of Te is 2: 3, and the compound or the Te simple substance that will contain the compound of Bi element and contain the Te element are dissolved in step 2) the aqueous solution in, stir down according to every mole of Bi 2Te 3Add 50-200g reductive agent NaBH 4, get mixed solution;
4) with mixed solution stirring heating 12-48h under 70-85 ℃ of water-bath, reaction finishes back centrifugation, washing, collection solid product, and oven dry obtains Bi 2Te 3/ carbon nano tube compound material.
2. Bi according to claim 1 2Te 3The preparation method of/carbon nano tube compound material, the compound that it is characterized in that the said Bi of containing element is muriate, oxide compound, vitriol, nitrate or the carbonate that contains the Bi element.
3. Bi according to claim 1 2Te 3The preparation method of/carbon nano tube compound material, the compound that it is characterized in that the said Te of containing element is muriate, oxide compound, vitriol, nitrate, nitrite or the carbonate that contains the Te element.
CN200910155794A 2009-12-18 2009-12-18 Method for preparing Bi2Te3/carbon nanotube composite material Pending CN101723351A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103738929A (en) * 2013-09-03 2014-04-23 吉林化工学院 Preparation of graded bismuth telluride micrometer structure with simple solvothermal method
CN105833859A (en) * 2016-04-22 2016-08-10 上海电机学院 Preparation method for Bi serial amorphous catalyst loaded on carbon nano tube
CN105859274A (en) * 2016-03-31 2016-08-17 山东大学 A temperature-controllable oxide thermoelectric material, a preparing method thereof and applications of the oxide thermoelectric material
CN108502870A (en) * 2018-05-25 2018-09-07 湖南大学 Modified carbon nano tube tube material and its preparation method and application
CN108675731A (en) * 2018-06-11 2018-10-19 青岛理工大学 Nano modification thermoelectricity mortar is protected with intelligent cathode with preparation method and thermoelectric structure and is deteriorated from monitoring system and preparation method
CN112316935A (en) * 2020-11-25 2021-02-05 正太新材料科技有限责任公司 Preparation method for degrading and separating flaky Bi-based catalytic pigment
CN115259139A (en) * 2022-06-14 2022-11-01 江西理工大学 Method for nano-crystallizing bismuth telluride and compounding nano-crystallized bismuth telluride and carbon nano tube film

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103738929A (en) * 2013-09-03 2014-04-23 吉林化工学院 Preparation of graded bismuth telluride micrometer structure with simple solvothermal method
CN105859274A (en) * 2016-03-31 2016-08-17 山东大学 A temperature-controllable oxide thermoelectric material, a preparing method thereof and applications of the oxide thermoelectric material
CN105833859A (en) * 2016-04-22 2016-08-10 上海电机学院 Preparation method for Bi serial amorphous catalyst loaded on carbon nano tube
CN108502870A (en) * 2018-05-25 2018-09-07 湖南大学 Modified carbon nano tube tube material and its preparation method and application
CN108675731A (en) * 2018-06-11 2018-10-19 青岛理工大学 Nano modification thermoelectricity mortar is protected with intelligent cathode with preparation method and thermoelectric structure and is deteriorated from monitoring system and preparation method
CN112316935A (en) * 2020-11-25 2021-02-05 正太新材料科技有限责任公司 Preparation method for degrading and separating flaky Bi-based catalytic pigment
CN112316935B (en) * 2020-11-25 2022-05-24 正太新材料科技有限责任公司 Preparation method for degrading and separating flaky Bi-based catalytic pigment
CN115259139A (en) * 2022-06-14 2022-11-01 江西理工大学 Method for nano-crystallizing bismuth telluride and compounding nano-crystallized bismuth telluride and carbon nano tube film
CN115259139B (en) * 2022-06-14 2024-02-02 江西理工大学 Bismuth telluride nanocrystallization and method for compounding bismuth telluride with carbon nano tube film

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Open date: 20100609