CN1159212C - Nano level metal telluride preparing process - Google Patents

Nano level metal telluride preparing process Download PDF

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CN1159212C
CN1159212C CNB02121431XA CN02121431A CN1159212C CN 1159212 C CN1159212 C CN 1159212C CN B02121431X A CNB02121431X A CN B02121431XA CN 02121431 A CN02121431 A CN 02121431A CN 1159212 C CN1159212 C CN 1159212C
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nano level
hot pressure
pressure reaction
reaction still
nitric acid
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CN1384048A (en
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南策文
邓元
周西松
韦国丹
刘静
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Tsinghua University
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Abstract

The present invention relates to a preparing process for a nanosized metal telluride. In the process, nitrate or chlorinated salt of bismuth, tin or lead, and a simple substance Te are used as raw materials, N and N-dimethylformamide are used as solvents, the raw materials and the solvents react under the condition of the existence of alkali and a reducing agent at a temperature of 100 to 180 DEG C to synthesize a nanosized thermoelectric material M<x>Te<y>(M is equal to Bi, Sn, Pb) and a Bi2Te3 or PbTe base compound adulterated with Pb or Sn; spherical, quadrate and club-shaped nanocrystal particles can be conveniently obtained by controlling the reaction condition, and the particle size of the obtained nanocrystal particles is less than 100 nm. The process has the characteristics of simple operation (one-step feeding), low energy consumption (synthesized at a temperature of 100 to 180 DEG C), high crystallinity, small particle size (50 nm or so on average), controllable crystal form (products with the shapes of sticks, balls and sheets can be obtained); the prepared Bi2Te3 or PbTe base compound is a thermoelectric material with the highest thermoelectric conversion efficiency respectively in a room-temperature zone or a moderate-temperature zone after being sintered.

Description

A kind of preparation method of nano level metal telluride
Technical field
The present invention relates to a kind of preparation method of thermoelectric material, relate in particular to a kind of synthetic technology of nano level telluride.The technical fields such as cooling that can be used for thermo-electric generation (used heat utilization), thermoelectric refrigeration and microelectronic device (chip).
Background technology
Rowe is described in detail thermoelectric material in its " CRC Handbook of Thermoelectrics " that writes (being published by CRC Press1995) book.In present all thermoelectric materials, Tellurobismuthite (Bi 2Te 3) be and lead telluride (PbTe) based semiconductor material is respectively to generally acknowledge at present best room temperature, middle warm area thermoelectric material.Their conversion efficiency of thermoelectric represents with thermoelectric quality factor ZT, wherein Bi 2Te 3ZT be about 0.6 (pure Bi 2Te 3) and 1.0 (doping Bi 2Te 3), they have been the industrial standards of current commercial thermo-electric device.Know by the Fundamentals of Material Science theory: by carrier concentration in means such as the optimum doping control semi-conductor, strengthen semi-conductive electrical transmission performance to reach, strengthen scattering process simultaneously, be still the important channel of improving pyroelectric material performance phonon.So synthetic Bi 2Te 3Or the sosoloid of PbTe or its doped compound can improve the thermoelectricity capability of material.
And preparation technology is the basis of thermoelectric material technology.The telluride thermoelectric material has several preparation methods at present, roughly can divide solid phase method, liquid phase method and vapor phase process three major types.
Solid phase method is the most direct synthetic method, and it is that simple substance high temperature is directly synthetic.Rowe describes the various solid phase synthesis process of telluride thermoelectric material in detail in its book.Comprise scorification, powder metallurgic method, machine-alloying is pulverized and is mixed simple substance sintering process etc.
Because solid phase method synthetic temperature of reaction, the reaction times of growing relatively and the protection of rare gas element that need be higher, the chemical uniformity of material be bad, and is difficult to obtain the nano level compound.And the thermoelectricity capability of chemical ingredients homogeneity and material is closely related, and the nano level lead compound also helps reducing the sintering temperature of material.
Ritter has reported the method (Inorg.Chem.1995,34,4278) with the synthetic Tellurobismuthite of organometallic complex method.Raw material is Bi 2O 3, Te, tartrate and nitric acid etc., but it also needs the higher temperature of reaction and the reduction of hydrogen, contains impurity in the product, and the reactant cost is higher.
Warren etc. (J.Alloys Compd.1995,229,175) metal salt solution and H 2Tellurobismuthite has been synthesized in the Te reaction.This method has been used the big gaseous state H of toxicity 2Te, operation relative risk, toxicity is big, and H 2Unstable under the Te room temperature, easily be decomposed into hydrogen and simple substance tellurium, cause product impure.
Vapor phase process mainly adopts chemical vapour deposition.People such as Boulouz (J.Cryst.Growth 1998,194,336) have reported that with dimethyl tellurium and dimethyl bismuth be raw material, and vapour deposition obtains the telluride film.But it also needs higher temperature of reaction (greater than 400 ℃), and the reactant cost is higher.
Summary of the invention
The objective of the invention is in order to solve the problems that synthetic telluride thermoelectric material exists in the traditional method, adopt solution chemical processes (solvent-thermal method), the Tellurobismuthite, the lead telluride that directly synthesize Tellurobismuthite, lead telluride or tellurium tin and doping heavy atom at low temperatures, to reduce temperature of reaction, to shorten the reaction times, obtain the uniform nano level crystalline material of chemical ingredients, thereby reduce the sintering temperature of material, save the energy.
The present invention adopts following technical scheme: a kind of preparation method of nano level binary metal telluride compound, and this method is carried out as follows:
(1) by stoichiometric ratio soluble metal bismuth, tin or plumbous nitrate or chlorate are mixed mutually with the tellurium powder, take by weighing the POTASSIUM BOROHYDRIDE that is equivalent to tellurium powder molar weight again, above-mentioned raw materials is added in the hot pressure reaction still;
(2). add solvent N in the hot pressure reaction still, dinethylformamide is to 80～90% of the reactor capacity, and adding a certain amount of potassium hydroxide again, to make alkali concn be 1～2mol/L, 100 ℃～180 ℃ reactions 15～40 hours; Naturally cool to room temperature then, filter, water or ethanol thorough washing, vacuum-drying promptly gets the nano level Bi of different-shape 2Te 3Or SnTe or PbTe compound.
The present invention also provides a kind of preparation method of nano level ternary metal telluride compound, carries out as follows:
(1) solubility nitric acid or tin chloride or lead salt and nitric acid or bismuth chloride salt and tellurium powder are mixed mutually, its mol ratio is: solubility nitric acid or tin chloride or lead salt: nitric acid or bismuth chloride salt: tellurium powder=(0.02～0.5): 1: (1.52～2), add the POTASSIUM BOROHYDRIDE that is equivalent to tellurium powder molar weight again, above-mentioned raw materials is added in the hot pressure reaction still;
(2). in the hot pressure reaction still, add solvent N, dinethylformamide is to 80～90% of its capacity, taking by weighing a certain amount of potassium hydroxide again, to make alkali concn be 1～2mol/L, 100 ℃～180 ℃ reactions 15 hours～40 hours, naturally cool to room temperature then, filter water, ethanol thorough washing, vacuum-drying, the Bi of black nano level doping Pb or Sn 2Te 3Or PbTe compound.
Present method has (charging) simple to operate, energy consumption low (100～180 ℃ synthetic), degree of crystallinity height (product is a crystal), particle diameter little (about average 50 nanometers), characteristics such as crystalline form is controlled; By the control of reaction conditions, can obtain sphere, square and rod-like nano crystal particles easily.Prepared Bi 2Te 3, PbTe for the base compound be respectively room temperature, the highest thermoelectric material of middle warm area conversion efficiency of thermoelectric behind sintering.
Description of drawings
Fig. 1 differing temps synthetic Bi 2Te 3The XRD spectrum;
Fig. 2 Bi 2Te 3Nanometer rod TEM photo;
Fig. 3 Bi 2Te 3Nanometer ball TEM photo;
Fig. 4 Bi 2Te 3Nanometer ball TEM photo;
Fig. 5 Bi 2Te 3Nanometer sheet TEM photo;
The XRD spectrum of Fig. 6 synthetic SnTe;
The TEM photo of Fig. 7 synthetic SnTe;
Fig. 8 synthetic SnBi 2Te 4XRD spectrum;
Fig. 9 synthetic SnBi 2Te 4The TEM photo;
Figure 10 synthetic Sn 0.2Bi 2Te 3.2XRD spectrum
Figure 11 synthetic Sn 0.2Bi 2Te 3.2The TEM photo
Figure 11 synthetic Sn 0.2Bi 2Te 3.2The TEM photo
Figure 12 synthetic Pb 0.02Bi 2Te 3.02XRD spectrum
Figure 13 synthetic Pb 0.02Bi 2Te 3.02The TEM photo
Embodiment
All chemical are commercially available analytical pure, without being further purified.
Embodiment 1
BiCl 32H 2O (20mmol), Te powder (30mmol), KOH (90mmol) and KBH 4(30mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 90%, 100 ℃ of reaction of its capacity 24 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, vacuum-drying gets black Bi 2Te 3Powder.Compounds X RD spectrum is seen Fig. 1 a; Pattern is a rod-shpaed particle, and rod footpath 10 nanometers are grown up in 100 nanometer (see figure 2)s.(Fig. 1 changes)
Embodiment 2
BiCl 32H 2O (20mmol), Te powder (30mmol), KOH (120mmol) and KBH 4(30mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 90%, 130 ℃ of reaction of its capacity 24 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 60 ℃ of dryings of vacuum get black Bi 2Te 3Powder.Compounds X RD spectrum is seen Fig. 1 b; Pattern is a spheroidal particle, median size 20 nanometer (see figure 3)s.
Embodiment 3
Bi (NO 3) 35H 2O (20mmol), Te powder (30mmol), KOH (160mmol) and KBH 4(30mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 80%, 100 ℃ of reaction of its capacity 24 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 80 ℃ of dryings of vacuum get black Bi 2Te 3Powder.Compounds X RD spectrum is seen Fig. 1 c; Pattern is a spheroidal particle, median size 20 nanometer (see figure 4)s.
Embodiment 4
BiCl 32H 2O (20mmol), Te powder (30mmol), KOH (150mmol) and KBH 4(30mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 90%, 180 ℃ of reaction of its capacity 15 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 60 ℃ of dryings of vacuum get black Bi 2Te 3Powder.Compounds X RD spectrum is seen Fig. 1 d; Pattern is a platy shaped particle, mean length 400 nanometer (see figure 5)s.
Embodiment 5
SnCl 22H 2O (20mmol), Te powder (20mmol), KOH (90mmol) and KBH 4(20mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 90%, 180 ℃ of reaction of its capacity 40 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 60 ℃ of dryings of vacuum get black SnTe powder.Compounds X RD spectrum is seen Fig. 6; Pattern is a spheroidal particle, median size 30 nanometer (see figure 7)s.
Embodiment 6
SnCl 22H 2O (10mmol), BiCl 32H 2O (20mmol), Te powder (40mmol), KOH (140mmol) and KBH 4(40mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 90%, 100 ℃ of reaction of its capacity 40 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 60 ℃ of dryings of vacuum get black SnBi 2Te 4Powder.Compounds X RD spectrum is seen Fig. 8; Pattern is a spheroidal particle, median size 20 nanometer (see figure 9)s.
Embodiment 7
SnCl 22H 2O (2mmol), BiCl 32H 2O (20mmol), Te powder (32mmol), KOH (150mmol) and KBH 4(32mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 80%, 180 ℃ of reaction of its capacity 15 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 60 ℃ of dryings of vacuum get black Sn 0.2Bi 2Te 3.2Powder.Compounds X RD spectrum is seen Figure 10; Pattern is a spheroidal particle, median size 50 nanometers (seeing Figure 11).
Embodiment 8
Pb (NO 3) 2(1mmol), BiCl 32H 2O (100mmol), Te powder (150mmol), KOH (150mmol) and KBH 4(150mmol) join in the 100ml hot pressure reaction still, add solvent N, dinethylformamide (DMF) was to 90%, 180 ℃ of reaction of its capacity 30 hours.Naturally cool to room temperature, filter, water, ethanol thorough washing, 60 ℃ of dryings of vacuum get black Pb 0.02Bi 2Te 3.02Powder.Compounds X RD spectrum is seen Figure 12; Pattern is a spheroidal particle, median size 30 nanometers (seeing Figure 13).

Claims (2)

1. the preparation method of a nano level binary metal telluride, this method is carried out as follows:
(1) by stoichiometric ratio soluble metal bismuth, tin or plumbous nitrate or chlorate are mixed mutually with the tellurium powder, take by weighing the POTASSIUM BOROHYDRIDE that is equivalent to tellurium powder molar weight again, above-mentioned raw materials is added in the hot pressure reaction still;
(2) add solvent N in the hot pressure reaction still, dinethylformamide is to 80～90% of the reactor capacity, and adding a certain amount of potassium hydroxide again, to make alkali concn be 1～2mol/L, 100 ℃～180 ℃ reactions 15～40 hours; Naturally cool to room temperature then, filter, water or ethanol thorough washing, vacuum-drying promptly gets the nano level Bi of different-shape 2Te 3Or SnTe or PbTe compound.
2. the preparation method of a nano level ternary metal telluride, this method is carried out as follows:
(1) solubility nitric acid or tin chloride or lead salt and nitric acid or bismuth chloride salt and tellurium powder are mixed mutually, its mol ratio is: solubility nitric acid or tin chloride or lead salt: nitric acid or bismuth chloride salt: tellurium powder=(0.02～0.5): 1: (1.52～2), add the POTASSIUM BOROHYDRIDE that is equivalent to tellurium powder molar weight again, above-mentioned raw materials is added in the hot pressure reaction still;
(2) in the hot pressure reaction still, add solvent N, dinethylformamide is to 80～90% of its capacity, taking by weighing a certain amount of potassium hydroxide again, to make alkali concn be 1～2mol/L, 100 ℃～180 ℃ reactions 15 hours～40 hours, naturally cool to room temperature then, filter water, ethanol thorough washing, vacuum-drying, the Bi of black nano level doping Pb or Sn 2Te 3Or PbTe compound.
CNB02121431XA 2002-06-21 2002-06-21 Nano level metal telluride preparing process Expired - Fee Related CN1159212C (en)

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WO2004105144A1 (en) * 2003-05-20 2004-12-02 Matsushita Electric Industrial Co., Ltd. Thermoelectric material and method for producing same
CN100348755C (en) * 2003-12-25 2007-11-14 同济大学 Method for synthesizing tin white cobalt series thermoelectric material
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US7309830B2 (en) * 2005-05-03 2007-12-18 Toyota Motor Engineering & Manufacturing North America, Inc. Nanostructured bulk thermoelectric material
CN100355645C (en) * 2004-12-24 2007-12-19 同济大学 Method for preparing Nano lead telluride doped with silver and stibium or silver and bismuth
CN1333093C (en) * 2005-11-17 2007-08-22 钢铁研究总院 Preparation method of bismuth-tollurium base thromoelectric alloy
CN100585032C (en) * 2007-10-23 2010-01-27 南京航空航天大学 Method for preparing lead telluride nano-wire
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CN101602496B (en) * 2009-07-07 2011-05-25 同济大学 Synchronic preparation method of lead telluride thin film and nano powder
CN103058151B (en) * 2013-01-16 2015-02-04 吉林大学 Hiberarchy bismuth telluride nanocrystal and preparation method thereof
CN103274371B (en) * 2013-06-07 2015-01-07 吉林大学 Method for preparing oil-soluble telluride semiconductor nano-crystal by adopting alkyl amide as solvent
CN103569975B (en) * 2013-11-22 2015-09-09 北方民族大学 A kind of method of solvent-thermal process Tellurobismuthite polycrystalline Nano dish
CN108367922A (en) * 2015-06-01 2018-08-03 宝山钢铁股份有限公司 Manufacture the water-based process of metal chalogenides nano material
CN105200520B (en) * 2015-10-09 2017-07-21 广东工业大学 One kind prepares Bi2(SexTe1‑x)3The method of single crystal nanoplate
CN105819411B (en) * 2016-03-04 2018-01-23 山东科技大学 A kind of preparation method nanocrystalline as the octahedra SnTe of elementary cell using triangle
CN112723322A (en) * 2021-01-29 2021-04-30 河南科技大学 Method for preparing layered bismuth telluride nanoparticles by hydrothermal method
CN113582143A (en) * 2021-07-29 2021-11-02 西安石油大学 Metal telluride nanotube and universal preparation method thereof

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