CN101327962B - Preparation of Bi2Sr2Co2Oy thermoelectric compounds - Google Patents

Preparation of Bi2Sr2Co2Oy thermoelectric compounds Download PDF

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CN101327962B
CN101327962B CN2008100484409A CN200810048440A CN101327962B CN 101327962 B CN101327962 B CN 101327962B CN 2008100484409 A CN2008100484409 A CN 2008100484409A CN 200810048440 A CN200810048440 A CN 200810048440A CN 101327962 B CN101327962 B CN 101327962B
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polyoxyethylene glycol
solution
thermoelectric
thermoelectric compound
presoma
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CN101327962A (en
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唐新峰
高文斌
张莉
张清杰
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The invention relates to a preparation method of Bi2Sr2Co2Oy thermoelectric compounds which is characterized by: preparing a gel by sol-gel method using polyethylene glycol as a dispersant; pre-burning the gel at 300-500 DEG C after the gel is dried, heating the obtained precursor to 800-900 DEG C at air atmosphere, taking out the precursor after insulation for 1-5 hours, obtaining the uniform nano flake Bi2Sr2Co2Oy thermoelectric compounds. The method has advantages of simple and easily controllable method, short reaction period, easily available of the materials, simple device, which is safeand no pollution. The obtained Bi2Sr2Co2Oy thermoelectric compounds are flake, as well as uniform distribution and high purity with a wafer diameter of 1-3mum and a wafer thickness of 200-400nm.

Description

Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound
Technical field
The invention belongs to the new energy materials field, be specifically related to a kind of Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound.
Background technology
Thermoelectric generation technology is to utilize the Seebeck effect of semi-conductor thermoelectric material heat energy to be directly changed into the technology of electric energy.Because it does not contain the needed huge transmission rig of other generation technology, have that volume is little, the life-span is long, reliability is high, manufacturing process is simple, manufacturing and characteristics such as running cost is low, wide application and be subjected to scientific worker's attention, at numerous areas vast potential for future development is arranged.
Bi 2Sr 2Co 2O yBe in being applicable to, a type oxide thermoelectric material of cold zone, have characteristics such as unique high temperature resistant, resistance to oxidation, high strength, environmentally safe, can long term operation under high temperature, oxidizing atmosphere.But the thermoelectric figure of merit of present this material is less relatively, and efficiency of conversion is lower.Therefore, need improve its thermoelectricity capability.Studies show that, for Bi 2Sr 2Co 2O yCompound also can improve its thermoelectricity capability by optimizing its microtexture except that by mixing.At present, for Bi 2Sr 2Co 2O yThe preparation method of polycrystalline compounds is mainly high-temperature solid phase reaction method, and (Solid state reaction SSR) and sol-gel method (Sol-gel method), but all difficultly obtains to be evenly distributed, thickness is the sheet Bi of nanoscale 2Sr 2Co 2O yCompound.
Summary of the invention
The purpose of this invention is to provide a kind ofly be evenly distributed, thickness is nanoscale, flaky Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound.
To achieve these goals, technical scheme of the present invention is: Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound is characterized in that it comprises the steps:
1). is to mix at 1: 1 analytical pure Glacial acetic acid and deionized water according to volume ratio, as solvent; Add analytically pure Co (NO then 3) 26H 2O, Sr (NO 3) 2And Bi (NO 3) 35H 2O, and mix, Co formed 2+, Sr 2+, Bi 3+Three metal ion species concentration are the solution A of 0.03～0.06mol/L;
2). the mass percent that accounts for polyoxyethylene glycol and solution A by polyoxyethylene glycol is 4%～6% (mass percent that solution A accounts for polyoxyethylene glycol and solution A is 94%～96%), chooses polyoxyethylene glycol, and polyoxyethylene glycol is poured in the solution A, stirs, and obtains mixing solutions B;
3). mixing solutions B was fully reacted 5～10 hours in 60～100 ℃ of water-baths, obtain the colloidal sol of homogeneous transparent; With colloidal sol in air in 60～120 ℃ of heating, make it become xerogel gradually;
4). the xerogel that step 3) is obtained in 300～500 ℃ of pre-burnings, obtains Bi under air atmosphere 2Sr 2Co 2O yThe presoma of thermoelectric compound;
5). the presoma that step 4) is obtained placed under 800～900 ℃ of retort furnace air atmospheres calcining 1～5 hour, promptly obtained the flaky Bi of even 2Sr 2Co 2O yThermoelectric compound (final product).
Bi 2Sr 2Co 2O yIn y be 7～9.
The Bi that the present invention obtains 2Sr 2Co 2O yThermoelectric compound can be applied to prepare Bi 2Sr 2Co 2O yThermoelectric material.
The present invention is a dispersion agent with polyoxyethylene glycol (PEG) at first, adopts sol-gel method to prepare gel; 300～500 ℃ of pre-burnings, the presoma that obtains is warming up to 800～900 ℃ under air atmosphere behind the gel drying, is incubated after 1～5 hour to take out, and gets final product.Selection polyoxyethylene glycol (PEG) can make the long molecular chain absorption of polyoxyethylene glycol for tensio-active agent or be coated on by the surface of discrete particles, produce sterically hindered, make particle be in homogeneously dispersed state, stop particulate to be reunited, reduce the size of final product, strengthen the homogeneity of product powder, thereby be evenly distributed, thickness is the sheet Bi of nanoscale 2Sr 2Co 2O yCompound.300～500 ℃ of pre-burnings are in order to remove organism, and obtain Bi 2Sr 2Co 2O yThe presoma of thermoelectric compound.Thereby 800～900 ℃ of calcinings are finally to form Bi in order to make presoma carry out solid state reaction 2Sr 2Co 2O yThe thermoelectric compound crystal.
The invention has the beneficial effects as follows: employing be the sol-gel method of dispersion agent with the polyoxyethylene glycol, its method is simple and easy to control, reaction time is short, starting material are easy to get, equipment is simple, safety non-pollution; The Bi that obtains 2Sr 2Co 2O yThermoelectric compound is a sheet, and be evenly distributed, the purity height, wafer diameter is 1～3 μ m, wafer thickness is 200～400nm.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the Bi of the embodiment of the invention 1 preparation 2Sr 2Co 2O yThe XRD figure spectrum of thermoelectric compound.
Fig. 3 is the Bi of the embodiment of the invention 1 preparation 2Sr 2Co 2O yThe SEM shape appearance figure of thermoelectric compound.
Fig. 4 is the Bi of the embodiment of the invention 2 preparations 2Sr 2Co 2O yThe XRD figure spectrum of thermoelectric compound.
Fig. 5 is the Bi of the embodiment of the invention 2 preparations 2Sr 2Co 2O yThe SEM shape appearance figure of thermoelectric compound.
Fig. 6 is the Bi of the embodiment of the invention 2 preparations 2Sr 2Co 2O yThe high multiple SEM shape appearance figure of thermoelectric compound.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with example, but content of the present invention not only is confined to the following examples.
Embodiment 1:
As shown in Figure 1, Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound, it comprises the steps:
1). is to mix at 1: 1 analytical pure Glacial acetic acid and deionized water according to volume ratio, as solvent; Add analytically pure Co (NO then 3) 26H 2O, Sr (NO 3) 2And Bi (NO 3) 35H 2O, and mix, Co formed 2+, Sr 2+, Bi 3+Three metal ion species concentration are the homogeneous transparent solution A of 0.03mol/L;
2). the mass percent that accounts for polyoxyethylene glycol and solution A by polyoxyethylene glycol is 5% (mass percent that solution A accounts for polyoxyethylene glycol and solution A is 95%), choose polyoxyethylene glycol, polyoxyethylene glycol is poured in the solution A, stirred, obtain the red-purple mixing solutions B of homogeneous transparent;
3). mixing solutions B was fully reacted 7 hours in 80 ℃ of water-baths, obtain the colloidal sol of homogeneous transparent; With colloidal sol in air in 90 ℃ of heating, make it become xerogel gradually;
4). the xerogel that step 3) is obtained in 400 ℃ of pre-burnings, obtains Bi under air atmosphere 2Sr 2Co 2O yThe presoma of thermoelectric compound;
5). the presoma that step 4) is obtained placed under 850 ℃ of retort furnace air atmospheres calcining 3 hours, promptly obtained the flaky Bi of even 2Sr 2Co 2O yThermoelectric compound (final product).
The Bi that obtains 2Sr 2Co 2O yThermoelectric compound is a sheet, and is evenly distributed, and wafer diameter is about 1～3 μ m, and wafer thickness is about 200～400nm.
Fig. 2 illustrates that resulting final product is single-phase Bi 2Sr 2Co 2O yThermoelectric compound (being the purity height); Fig. 3 illustrates that the gained sample size is evenly distributed, and is the sheet crystalline substance, and wafer diameter is about 1～3 μ m, and wafer thickness is about 200～400nm.
Embodiment 2:
Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound, it comprises the steps:
1). is to mix at 1: 1 analytical pure Glacial acetic acid and deionized water according to volume ratio, as solvent; Add analytically pure Co (NO then 3) 26H 2O, Sr (NO 3) 2And Bi (NO 3) 35H 2O, and mix, Co formed 2+, Sr 2+, Bi 3+Three metal ion species concentration are the homogeneous transparent solution A of 0.06mol/L;
2). the mass percent that accounts for polyoxyethylene glycol and solution A by polyoxyethylene glycol is 5% (mass percent that solution A accounts for polyoxyethylene glycol and solution A is 95%), choose polyoxyethylene glycol, polyoxyethylene glycol is poured in the solution A, stirred, obtain the red-purple mixing solutions B of homogeneous transparent;
3). mixing solutions B was fully reacted 7 hours in 80 ℃ of water-baths, obtain the colloidal sol of homogeneous transparent; With colloidal sol in air in 90 ℃ of heating, make it become xerogel gradually;
4). the xerogel that step 3) is obtained in 400 ℃ of pre-burnings, obtains Bi under air atmosphere 2Sr 2Co 2O yThe presoma of thermoelectric compound;
5). the presoma that step 4) is obtained placed under 850 ℃ of retort furnace air atmospheres calcining 3 hours, promptly obtained the flaky Bi of even 2Sr 2Co 2O yThermoelectric compound (final product).
The Bi that obtains 2Sr 2Co 2O yThermoelectric compound is a sheet, and is evenly distributed, and wafer diameter is 1～3 μ m, and wafer thickness is 200～400nm.
Fig. 4 illustrates that resulting final product is single-phase Bi 2Sr 2Co 2O yThermoelectric compound (being the purity height); Fig. 5 illustrates gained final product even size distribution, is the sheet crystalline substance, and wafer diameter is about 1～3 μ m, and wafer thickness is about 200～400nm; Fig. 6 illustrates that the wafer thickness of gained final product is about 200～400nm.
Embodiment 3:
Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound, it comprises the steps:
1). is to mix at 1: 1 analytical pure Glacial acetic acid and deionized water according to volume ratio, as solvent; Add analytically pure Co (NO then 3) 26H 2O, Sr (NO 3) 2And Bi (NO 3) 35H 2O, and mix, Co formed 2+, Sr 2+, Bi 3+Three metal ion species concentration are the homogeneous transparent solution A of 0.03mol/L;
2). the mass percent that accounts for polyoxyethylene glycol and solution A by polyoxyethylene glycol is 4% (mass percent that solution A accounts for polyoxyethylene glycol and solution A is 96%), choose polyoxyethylene glycol, polyoxyethylene glycol is poured in the solution A, stirred, obtain the red-purple mixing solutions B of homogeneous transparent;
3). mixing solutions B was fully reacted 10 hours in 60 ℃ of water-baths, obtain the colloidal sol of homogeneous transparent; With colloidal sol in air in 60 ℃ of heating, make it become xerogel gradually;
4). the xerogel that step 3) is obtained in 300 ℃ of pre-burnings, obtains Bi under air atmosphere 2Sr 2Co 2O yThe presoma of thermoelectric compound;
5). the presoma that step 4) is obtained placed under 800 ℃ of retort furnace air atmospheres calcining 5 hours, promptly obtained the flaky Bi of even 2Sr 2Co 2O yThermoelectric compound (final product).
Embodiment 4:
Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound, it comprises the steps:
1). is to mix at 1: 1 analytical pure Glacial acetic acid and deionized water according to volume ratio, as solvent; Add analytically pure Co (NO then 3) 26H 2O, Sr (NO 3) 2And Bi (NO 3) 35H 2O, and mix, Co formed 2+, Sr 2+, Bi 3+Three metal ion species concentration are the homogeneous transparent solution A of 0.04mol/L;
2). the mass percent that accounts for polyoxyethylene glycol and solution A by polyoxyethylene glycol is 6% (mass percent that solution A accounts for polyoxyethylene glycol and solution A is 94%), choose polyoxyethylene glycol, polyoxyethylene glycol is poured in the solution A, stirred, obtain the red-purple mixing solutions B of homogeneous transparent;
3). mixing solutions B was fully reacted 5 hours in 100 ℃ of water-baths, obtain the colloidal sol of homogeneous transparent; With colloidal sol in air in 120 ℃ of heating, make it become xerogel gradually;
4). the xerogel that step 3) is obtained in 500 ℃ of pre-burnings, obtains Bi under air atmosphere 2Sr 2Co 2O yThe presoma of thermoelectric compound;
5). the presoma that step 4) is obtained placed under 900 ℃ of retort furnace air atmospheres calcining 1 hour, promptly obtained the flaky Bi of even 2Sr 2Co 2O yThermoelectric compound (final product).

Claims (1)

1.Bi 2Sr 2Co 2O yThe preparation method of thermoelectric compound is characterized in that it comprises the steps:
1). is to mix at 1: 1 analytical pure Glacial acetic acid and deionized water according to volume ratio, as solvent; Add analytically pure Co (NO then 3) 26H 2O, Sr (NO 3) 2And Bi (NO 3) 35H 2O, and mix, Co formed 2+, Sr 2+, Bi 3+Three metal ion species concentration are the solution A of 0.03～0.06mol/L;
2). the mass percent that accounts for polyoxyethylene glycol and solution A by polyoxyethylene glycol is 4%～6%, chooses polyoxyethylene glycol, and polyoxyethylene glycol is poured in the solution A, stirs, and obtains mixing solutions B;
3). mixing solutions B was fully reacted 5～10 hours in 60～100 ℃ of water-baths, obtain the colloidal sol of homogeneous transparent; With colloidal sol in air in 60～120 ℃ of heating, make it become xerogel gradually;
4). the xerogel that step 3) is obtained in 300～500 ℃ of pre-burnings, obtains Bi under air atmosphere 2Sr 2Co 2O yThe presoma of thermoelectric compound;
5). the presoma that step 4) is obtained placed under 800～900 ℃ of retort furnace air atmospheres calcining 1～5 hour, promptly obtained the flaky Bi of even 2Sr 2Co 2O yThermoelectric compound, Bi 2Sr 2Co 2O yIn y be 7～9.
CN2008100484409A 2008-07-17 2008-07-17 Preparation of Bi2Sr2Co2Oy thermoelectric compounds Expired - Fee Related CN101327962B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117242A (en) * 2007-08-22 2008-02-06 武汉理工大学 Method for preparing ultra-thin sheet-like NaxCo2O4 thermoelectric compound powder
CN101157482A (en) * 2007-09-19 2008-04-09 哈尔滨工业大学 Modified Ca-Co-O system doped transition metal composite oxides and preparation method thereof
CN101157483A (en) * 2007-09-19 2008-04-09 哈尔滨工业大学 Transition metal composite oxides and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117242A (en) * 2007-08-22 2008-02-06 武汉理工大学 Method for preparing ultra-thin sheet-like NaxCo2O4 thermoelectric compound powder
CN101157482A (en) * 2007-09-19 2008-04-09 哈尔滨工业大学 Modified Ca-Co-O system doped transition metal composite oxides and preparation method thereof
CN101157483A (en) * 2007-09-19 2008-04-09 哈尔滨工业大学 Transition metal composite oxides and preparation method thereof

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Title
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李瑜煜 等.钴基氧化物热电材料研究现状与展望.电源技术30 8.2006,30(8),689-692.
李瑜煜等.钴基氧化物热电材料研究现状与展望.电源技术30 8.2006,30(8),689-692. *
马秋花 等.热电材料综述.电工材料 1.2004,(1),43-47.
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