CN1278941C - Bi2Te3 nanometer capsule and preparation thereof - Google Patents

Bi2Te3 nanometer capsule and preparation thereof Download PDF

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Publication number
CN1278941C
CN1278941C CN 200410073387 CN200410073387A CN1278941C CN 1278941 C CN1278941 C CN 1278941C CN 200410073387 CN200410073387 CN 200410073387 CN 200410073387 A CN200410073387 A CN 200410073387A CN 1278941 C CN1278941 C CN 1278941C
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nanocapsule
bi2te3
preparation
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nanometers
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CN1644509A (en
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赵新兵
孙霆
朱铁军
吉晓华
曹一琦
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention discloses an Bi2Te3 nanometer capsule which is a seamless hollow capsule whose ratio of length to diameter is from 2 to 5. The Bi2Te3 nanometer capsule comprises the constituents of the atom percentage content: 39.8 to 40.3% of Bi and 59.7 to 60.2% of Te. The Bi2Te3 nanometer capsule is prepared by adopting a wet chemistry method. The Bi2Te3 nanometer capsule with hollow tube type structural is possible to improve the thermoelectric properties of semiconductors, and the Bi2Te3 nanometer capsule can be used for preparing thermoelectric material with high performance and is widely used in the fields of material, physics, chemistry, microelectronics, etc.

Description

A kind of Bi 2Te 3Nanocapsule and preparation method thereof
Technical field
The present invention relates to semi-conductor Bi 2Te 3Nanocapsule and preparation method thereof.
Background technology
From Japanese carbonization scholar Iijima in 1991 since (S.Lijima) find carbon nanotube (CNTs) first, people have carried out extensive and deep research to synthetic, structure, performance and the application etc. of carbon nanotube.Carbon nanotube has the seamless tubular shaped structure that unique one dimension hollow graphite sheet is curled into because of it, and have a series of peculiar properties, as the height chemical stability, (Theoretical Calculation shows high physical strength, its tensile strength is 100 times of steel, and density have only steel 1/6), special electric property (different according to caliber and helicity, can be the conductor not worse than copper, also can be semi-conductor).Carbon nanotube is the material that a class has the applications well prospect, nowadays has been widely used in a plurality of high-tech areas such as physics, chemistry, material, electronic technology.
Since carbon nanotube, other various one dimension tubular nanometer materials are because its special structure and application prospects also receive much concern BN, BC 3, BC 2N, WS 2, MoS 2Emerge in succession Deng nanotube, but still do not satisfy the demand of a plurality of researchs and Application Areas, the nanotube of more materials and type still awaits R and D.
Bi 2Te 3It is one of binary mineral compound of present known nucleidic mass maximum.Bi 2Te 3The base alloy also is the best room temperature type thermoelectric material of present performance, is used to make semiconductor cooling device or thermoelectric power generation device.There are some researches prove that the nanometer of material (as: superlattice, nano wire etc.) can further improve Bi 2Te 3The thermoelectricity capability of sill.Existing solvent thermal or the synthetic Bi of hydrothermal method of adopting 2Te 3Nanotube, and be used to prepare the research report of high performance thermoelectric material.
Summary of the invention
The objective of the invention is Application Areas, and a kind of Bi is provided for the expansion nano material 2Te 3Nanocapsule and preparation method thereof.
Bi of the present invention 2Te 3Nanocapsule is that L/D ratio is 2～5 seamless hollow capsules, and its component and atomic percentage conc are:
Bi 39.8～40.3％，
Te 59.7～60.2％。
Bi 2Te 3The diameter of nanocapsule is 50～200 nanometers, wall thickness 5～20 nanometers, length 200～1000 nanometers.
Bi of the present invention 2Te 3The preparation method of nanocapsule adopts wet chemistry method, and its step is as follows:
1) compound of Bi element and the pure Te powder ratio according to Bi and Te atomic percentage conc is placed in the reaction vessel, add the deionized water of 80～850 times of Te weight, and mix;
2) in above-mentioned mixed solution, add 0.25～2.5 times the complexing agent that is equivalent to Te weight, add alkaline conditioner and make the pH value of solution value be in 12～14, add 0.5～3 times the reductive agent that is equivalent to Te weight;
3) be heated to the interior setting temperature of reaction of 55～85 ℃ of scopes, react after 6～100 hours, cool to room temperature stops to stir;
4) collect the interior solid reaction product of reaction vessel, behind cleaning-drying, obtain material of the present invention.
The compound of above-mentioned Bi element can be muriate, nitrate, vitriol or carbonate; Said alkaline conditioner can be NaOH or KOH; Complexing agent can adopt disodium ethylene diamine tetraacetate (hereinafter to be referred as EDTA); Said reductive agent can adopt NaBH 4Or KBH 4
In above-mentioned preparation process, the stirring of mixed solution from step 1), is lasted till that always reaction finishes.Used reaction vessel can be Glass Containers or acidproof, alkaline-resisting, heat-stable plastic containers.
The present invention has developed novel Bi 2Te 3Nanocapsule, length-to-diameter ratio is significantly less than nanotube, and its particular structure is expected to improve Bi 2Te 3The semiconductor heat electrical property of nano material, and can be widely used in fields such as physics, chemistry, material, microelectronics.
Description of drawings
Fig. 1 is at 85 ℃ of following synthetic Bi 2Te 3The field emission scanning electron microscope of nanocapsule and transmission electron microscope photo;
Fig. 2 is at 55 ℃ of following synthetic Bi 2Te 3The transmission electron microscope of nanocapsule and high-resolution electron microscopy photo.
Embodiment
Below in conjunction with embodiment the present invention is done further to state in detail.
Embodiment 1
1) in the glass beaker of a 800ml capacity, adds the 200ml deionized water successively, 3.83g Te powder (about 30 mmoles, 99.99% purity are crossed 30 μ m sieve), 6.31g BiCl 3(about 20 mmoles, analytical pure), and mix liquid with the 120rpm rotating speed with magnetic stirrer.
2) interpolation 1g EDTA in beaker, and interpolation NaOH makes the pH value of solution value reach 12, and then adds 2g NaBH 4
3) be heated to solution temperature with the speed of 5 ℃/min and reach 85 ℃ and maintain this temperature.
4) during 85 ℃ of isothermal reactions, keep the 120rpm stirring velocity, and prevent that with plastics film covering beaker solvent from excessively volatilizing.
5) reaction stops heating after 6 hours, naturally cools to room temperature.Collect the Powdered reaction product in the beaker, clean repeatedly for several times with deionized water, dehydrated alcohol and acetone successively, get Bi after the room temperature vacuum-drying 2Te 3Nanocapsule.
Adopt IRIS Intrepid II type XSP plasma emission spectrometry, the result shows that the atomic percentage conc of institute's synthetic nanocapsule is: 40.2%Bi and 59.8%Te.Adopt SIRION-FEI type field emission scanning electron microscope and JEM-2010 type transmission electron microscope observation nanocapsule form, as shown in Figure 1, nanocapsule length is between 200～800nm, and diameter is between 50～160nm, and thickness of pipe is 8～10nm.Adopt Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer to analyze the nanocapsule crystalline structure, the result is single-phase Bi 2Te 3Structure.
Get 0.6g and adopt above-mentioned route synthetic Bi 2Te 3Nanocapsule, by 250 ℃, 50MPa, 30min vacuum hotpressing, the acquisition diameter is 10mm, the disk shape sample of the about 1.2mm of thickness.At room temperature measure electric property after the cutting, the thermoelectric coefficient absolute value is 2.1 * 10 -4V/K, resistivity is 2.5 * 10 -5Ω m has typical pyroelectric material performance feature.
Embodiment 2
1) in the glass beaker of a 800ml capacity, adds the 450ml deionized water successively, 0.765g Te powder (about 6 mmoles, 99.99% purity are crossed 30 μ m sieve), 1.58g Bi (NO 3) 3(about 4 mmoles, analytical pure), and mix liquid with the 100rpm rotating speed with magnetic stirrer.
2) be heated to solution temperature with the speed of 5 ℃/min and reach 55 ℃ and maintain this temperature.
3) interpolation 1.9g EDTA in beaker, and interpolation KOH makes the pH value of solution value reach 14, and then adds 2.3g KBH 4
4) during 55 ℃ of isothermal reactions, keep the 100rpm stirring velocity, and prevent that with plastics film covering beaker solvent from excessively volatilizing.
5) reaction stops heating after 100 hours, naturally cools to room temperature.Collect the Powdered reaction product in the beaker, clean repeatedly for several times with deionized water, dehydrated alcohol and acetone successively, get Bi after the room temperature vacuum-drying 2Te 3Nanocapsule.
Adopt IRIS Intrepid II type XSP plasma emission spectrometry, the result shows that the atomic percentage conc of institute's synthetic nanocapsule is: 39.9%Bi and 60.1%Te.Adopt JEM-2010 type transmission electron microscope and JEOL-4000EX type high resolution transmission electron microscopy to observe the nanocapsule form, as shown in Figure 2, nanocapsule length is between 300～1000nm, and diameter is between 80～200nm, and thickness of pipe is 5～8nm.Adopt Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer to analyze the nanocapsule crystalline structure, the result is single-phase Bi 2Te 3Structure.
Get 0.6g and adopt above-mentioned route synthetic Bi 2Te 3Nanocapsule, by 250 ℃, 50MPa, 30min vacuum hotpressing, the acquisition diameter is 10mm, the disk shape sample of the about 1.2mm of thickness.At room temperature measure electric property after the cutting, the thermoelectric coefficient absolute value is 1.4 * 10 -4V/K, resistivity is 9.2 * 10 -6Ω m has typical pyroelectric material performance feature.

Claims (5)

1. Bi 2Te 3Nanocapsule is characterized in that it is that L/D ratio is 2～5 seamless hollow capsules, and its component and atomic percentage conc are:
Bi 39.8～40.3％，Te 59.7～60.2％。
2. Bi according to claim 1 2Te 3Nanocapsule is characterized in that capsular diameter in 50～200 nanometers, wall thickness 5～20 nanometers, and length is in 200～1000 nanometers.
3. the described Bi of claim 1 2Te 3The preparation method of nanocapsule, its step is as follows:
1) compound of Bi element and the pure Te powder ratio according to Bi and Te atomic percentage conc is placed in the reaction vessel, add the deionized water of 80～850 times of Te weight, and mix;
2) in above-mentioned mixed solution, add 0.25～2.5 times the complexing agent that is equivalent to Te weight, add alkaline conditioner and make the pH value of solution value be in 12～14, add 0.5～3 times the reductive agent that is equivalent to Te weight;
3) be heated to the interior setting temperature of reaction of 55～85 ℃ of scopes, react after 6～100 hours, cool to room temperature stops to stir;
4) collect the interior solid reaction product of reaction vessel, behind cleaning-drying, obtain Bi 2Te 3The nanocapsule material.
4. Bi according to claim 3 2Te 3The preparation method of nanocapsule, the compound that it is characterized in that said Bi element is muriate, nitrate, vitriol or carbonate.
5. Bi according to claim 3 2Te 3The preparation method of nanocapsule is characterized in that said reductive agent is NaBH 4Or KBH 4
CN 200410073387 2004-12-08 2004-12-08 Bi2Te3 nanometer capsule and preparation thereof Expired - Fee Related CN1278941C (en)

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CN103400932B (en) * 2008-08-29 2016-08-10 Lg化学株式会社 Novel thermo-electric converting material and preparation method thereof, and use the thermoelectric conversion element of this novel thermo-electric converting material
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

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