CN105152143A - Combustion synthesis method of Bi2SeO2-based thermoelectric material and combustion improver for Bi2SeO2-based thermoelectric material - Google Patents

Combustion synthesis method of Bi2SeO2-based thermoelectric material and combustion improver for Bi2SeO2-based thermoelectric material Download PDF

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CN105152143A
CN105152143A CN201510433936.8A CN201510433936A CN105152143A CN 105152143 A CN105152143 A CN 105152143A CN 201510433936 A CN201510433936 A CN 201510433936A CN 105152143 A CN105152143 A CN 105152143A
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pbo
thermoelectric material
bi2seo2
synthesis method
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CN105152143B (en
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唐新峰
杨东旺
胡铁铮
苏贤礼
鄢永高
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Wuhan University of Technology WUT
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Abstract

The invention discloses a combustion synthesis method of a Bi2SeO2-based thermoelectric material and a combustion improver for the Bi2SeO2-based thermoelectric material. By taking Bi, Se and Bi2O3 as raw materials, the method adopts a PbO compound as the combustion improver to promote combustion synthesis reaction to prepare the Bi2(1-x)Pb2xSeO2 thermoelectric material. The method disclosed by the invention has the advantages of being short in preparation time, simple in process, low in requirement on equipment, energy-saving and environmental-friendly, suitable for scaled production and the like, thereby laying a good foundation for scaled preparation and application of the Bi2SeO2-based thermoelectric material.

Description

A kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material and ignition dope thereof
Technical field
The invention belongs to thermoelectric material preparing technical field, be specifically related to a kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material and ignition dope thereof.
Background technology
Increasingly serious due to energy shortage and environmental pollution, studies and tap a new source of energy material and new forms of energy transformation technology become at present the focus of extensive concern in the world.Thermoelectric material is a kind of eco-friendly new energy materials, has commercial applications prospect widely in thermoelectric power generation and thermoelectric refrigeration technology.The efficiency of conversion of thermoelectric material is by zero dimension thermoelectric figure of merit ZT (ZT=α 2wherein α is Seebeck coefficient to σ T/ κ, σ is specific conductivity, κ is thermal conductivity, T is absolute temperature) determine, ZT is larger, and the conversion efficiency of thermoelectric of material is higher.
Bi 2seO 2compound is the N-shaped thermoelectric material with excellent heat electrical property developed in recent years, matches the potentiality used, therefore enjoy the concern of investigator because it has the p-type oxide thermoelectric material BiCuSeO based compound the most excellent with thermoelectricity capability.Bi 2seO 2compound crystal structure belongs to tetragonal system, and (BiO) n is stacking along c-axis, and Se occupies inter-layer position.So a kind of superstructure, makes it have extremely low thermal conductivity, is low to moderate 0.7-0.75W.m when 800K -1k -1.There is medium specific conductivity, high Seebeck coefficient simultaneously, make it have excellent thermoelectricity capability, when 773K, ZT max=0.12.Not only thermoelectricity capability is superior, and it is as seleno oxide, has good high high-temp stability and chemical stability, and this provides guarantee for its long service.
At present, Bi is prepared 2seO 2compound mainly adopts long-time solid reaction process, and preparation cycle is longer, temperature required higher, time consumption and energy consumption, and higher and degree of dependence is high to equipment requirements, mass-producing preparation cost is high, limits field and the scope of its mass-producing application greatly.Therefore, developing the supper-fast technology of preparing of new low cost is Bi 2seO 2the major subjects that base thermoelectricity material commercial applications faces.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material and ignition dope thereof, the technique related to is simple, and preparation process is supper-fast, low for equipment requirements, suitability for scale production.
For solving the problem of above-mentioned proposition, the technical solution used in the present invention is:
A kind of conbustion synthesis Bi 2seO 2the ignition dope of base thermoelectricity material, this ignition dope is PbO compound.
A kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material, it is with Bi, Se, Bi 2o 3for raw material, PbO compound is adopted to promote combustion synthesis reaction occurs as ignition dope, obtained described Bi 2seO 2base thermoelectricity material.
By such scheme, described raw material Bi, Se, Bi 2o 3, mol ratio between PbO is (2-2x): 3:(2-2x): 6x, wherein x is 0.02 ~ 0.1.
By such scheme, the method for described combustion synthesis reaction is: by Bi, Se, Bi 2o 3, PbO mixes as reactant, in a vacuum or inert atmosphere, adopts the mode of one end igniting to cause Self-propagating Sintering Synthetic reaction or thermal explosion 2 ~ 3min, the Bi cooling described under 500 ~ 900 DEG C of conditions 2seO 2base thermoelectricity material.
By such scheme, thermal expousure can be caused under the condition of 500 ~ 600 DEG C, obtained described Bi 2seO 2base thermoelectricity material powder, reduces temperature of reaction greatly.
By such scheme, the block that described reactant is powder or is become by pressed by powder.
According to Bi prepared by such scheme 2seO 2in base thermoelectricity material, Pb element occupies part Bi position with replacement form, gained Bi 2seO 2the chemical constitution of base thermoelectricity material can be expressed as Bi 2 (1-x)pb 2xseO 2.
Based on foregoing, under the prerequisite not departing from basic fundamental thought of the present invention, according to ordinary technical knowledge and the means of this area, the amendment of various ways, replacement or change can also be had to its content.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention makes public for the first time a kind of conbustion synthesis Bi 2seO 2the ignition dope of base thermoelectricity material, this ignition dope is PbO compound, under the effect of PbO compound, raw material Bi, Se, Bi 2o 3between combustion reactions more abundant, promote that reaction generates Bi 2 (1-x)pb 2xseO 2thermoelectric material.
2) in the present invention, PbO compound is not only ignition dope, and be effective doping agent, Pb occupies Bi position simultaneously, for system provides current carrier, optimizes thermoelectricity capability.
3) the present invention has that preparation time is ultrashort, technique is simple, low for equipment requirements, energy-conserving and environment-protective, is applicable to the advantages such as large-scale production, is Bi 2seO 2the mass-producing preparation of base thermoelectricity material and large-scale application are had laid a good foundation.
Figure of description
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom A, B, C, D.
Fig. 2 is the field emission scanning electron microscope photo of embodiment 1 products therefrom C.
Fig. 3 is the XRD figure spectrum of embodiment 2 products therefrom A, B, C, D.
Fig. 4 is the field emission scanning electron microscope photo of embodiment 2 products therefrom B.
Fig. 5 is the XRD figure spectrum of embodiment 3 products therefrom A, B, C, D.
Fig. 6 is the field emission scanning electron microscope photo of embodiment 3 products therefrom D.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In following examples, the Bi powder of employing, Se powder, Bi 2o 3powder and PbO powder are commercially available prod, and purity is 5N.
Embodiment 1
A kind of conbustion synthesis Bi 2seO 2the ignition dope of base thermoelectricity material, this ignition dope is PbO powder.
A kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material, with Bi, Se, Bi 2o 3for raw material, adopt PbO compound as ignition dope, attempt Self-propagating Sintering Synthetic reaction, preparation Bi 2 (1-x)pb 2xseO 2thermoelectric material powder, concrete steps are as follows:
1) by (2-2x): 3:(2-2x): the mol ratio of 6x (wherein x is respectively 0,0.04,0.06,0.1) takes Bi, Se, Bi 2o 3, PbO powder 4 parts, each 5g, is numbered A, B, C, D respectively.Then they are mixed, obtain reactant A, B, C, D respectively, and in 4MPa pressurize 5min, be pressed into the cylindrical ingot body that diameter is 10mm;
2) under room temperature, by step 1) gained ingot body is vacuum-sealed in quartz glass tube, coal gas flame ignition is shifted in Glass tubing bottom, all observes spreading (namely causing Self-propagating Sintering Synthetic reaction) of combustion wave, obtain product A, B, C and D respectively.
In above-mentioned synthetic reaction process, the rate of propagation of A sample is about 1mm/s, and after mixing PbO, rate of propagation can be increased to 1.3mm/s, the carrying out of visible PbO compound energy accelerate combustion reaction.Carry out material phase analysis respectively to the present embodiment products therefrom A, B, C and D, result as shown in Figure 1.Do not mix unreacted in the reactant A of PbO complete, product A Raw Bi 2o 3for main component, simultaneously containing a large amount of intermediate product Bi 2se 3, end product Bi 2seO 2content is less.After mixing PbO (reactant B, C, D), intermediate product Bi 2se 3all change into end product Bi 2seO 2, all occurred a small amount of PbSe in product (B, C, D), and along with the increase of PbO volume, PbSe increases gradually.This is because PbO can be reduced to Pb atom by the Bi in raw material, active high, except a part enters Bi 2seO 2lattice, also has part to change PbSe into the raw material Se powdered reaction compared with strong oxidizing property.A small amount of Bi in product 2o 3caused by Bi is oxidized by PbO, not raw material Bi 2o 3unreacted is complete.This generated in-situ a small amount of PbSe second-phase may strengthen the scattering of phonon further, reduce thermal conductivity.
Fig. 2 is the field emission scanning electron microscope photo of the present embodiment products therefrom C, and in figure, crystal grain is very large, in the form of sheets, and this and Bi 2seO 2layered crystal structure is consistent.
Embodiment 2
A kind of conbustion synthesis Bi 2seO 2the ignition dope of base thermoelectricity material, this ignition dope is PbO powder.
A kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material, with Bi, Se, Bi 2o 3for raw material, adopt PbO compound as ignition dope, attempt causing thermal expousure, preparation Bi 2 (1-x)pb 2xseO 2thermoelectric material powder, concrete steps are as follows:
1) by (2-2x): 3:(2-2x): the mol ratio of 6x (wherein x is respectively 0,0.04,0.06,0.1) takes Bi, Se, Bi 2o 3, PbO powder 4 parts, each 5g, is numbered A, B, C, D respectively and mixes, respectively reactant A, B, C, D, and under 4MPa pressurize 5min, be pressed into the cylindrical ingot body that diameter is 10mm;
2) by step 1) gained ingot body is vacuum-sealed in quartz glass tube, put into all rapidly after 500 DEG C of retort furnaces are incubated 2min and take out immediately, naturally cooling, respectively product A, B, C and D.
Carry out material phase analysis respectively to the present embodiment products therefrom A, B, C and D, result as shown in Figure 3.Described in result and embodiment 1, result is similar: the reactant A unreacted not mixing PbO is complete, product A Raw Bi 2o 3for main component, simultaneously containing a large amount of intermediate product Bi 2se 3, end product Bi 2seO 2content is less; After mixing PbO (product B, C, D), intermediate product Bi 2se 3all change into end product Bi 2seO 2, there is a small amount of Bi 2o 3.Mix in PbO after product and all occurred a small amount of PbSe, and along with the increase of PbO volume, PbSe increases gradually.
Fig. 4 is the field emission scanning electron microscope photo of the present embodiment products therefrom B, and in figure, crystal grain is very large, and in the form of sheets, thickness is about 200nm.
Embodiment 3
A kind of conbustion synthesis Bi 2seO 2the ignition dope of base thermoelectricity material, this ignition dope is PbO powder.
A kind of Bi 2seO 2the burning synthesis method of base thermoelectricity material, with Bi, Se, Bi 2o 3for raw material, adopt PbO compound as ignition dope, attempt causing thermal expousure under condition of different temperatures, preparation Bi 1.8pb 0.2seO 2thermoelectric material powder, concrete steps are as follows:
1) raw material Bi, Se, Bi is taken by the mol ratio of 3:5:3:1 2o 3, PbO powder 4 parts, each 5g, is numbered A, B, C, D respectively, mixes, respectively reactant A, B, C, D, and in 4MPa pressurize 5min, be pressed into the cylindrical ingot body that diameter is 10mm;
2) by step 1) gained ingot body is vacuum-sealed in quartz glass tube, raw material A is put into rapidly 500 DEG C of retort furnaces and be incubated 3min, raw material B puts into rapidly 700 DEG C of retort furnaces and is incubated 3min, raw material C puts into rapidly 800 DEG C of retort furnaces and is incubated 2min, raw material D puts into rapidly 800 DEG C of retort furnaces and is incubated 3min, take out immediately, naturally cooling, obtain product A, B, C and D respectively.
Respectively material phase analysis is carried out to the present embodiment products therefrom A, B, C and D, as shown in Figure 5.Result shows: in products therefrom, principal phase is Bi 2seO 2, only have a small amount of Bi 2o 3.Similarly, all occurred a small amount of PbSe in product, this is relevant to the combustion-supporting mechanism of PbO.Fig. 6 is the field emission scanning electron microscope photo of product D, and crystal grain is very large, in the form of sheets.
The above is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some improvement and conversion, these all belong to protection scope of the present invention.

Claims (5)

1. a conbustion synthesis Bi 2seO 2the ignition dope of base thermoelectricity material, is characterized in that, described ignition dope is PbO compound.
2. a Bi 2seO 2the burning synthesis method of base thermoelectricity material, is characterized in that, it is with Bi, Se, Bi 2o 3for raw material, PbO compound is adopted to promote combustion synthesis reaction occurs as ignition dope, obtained described Bi 2seO 2base thermoelectricity material.
3. burning synthesis method according to claim 2, is characterized in that, described Bi, Se, Bi 2o 3, mol ratio between PbO is (2-2x): 3:(2-2x): 6x, wherein x is 0.02 ~ 0.1.
4. burning synthesis method according to claim 2, is characterized in that, the method for described combustion synthesis reaction is: by Bi, Se, Bi 2o 3, PbO mixes as reactant, in a vacuum or inert atmosphere, adopts the mode of one end igniting to cause Self-propagating Sintering Synthetic reaction or thermal explosion 2 ~ 3min, the Bi cooling described under 500 ~ 900 DEG C of conditions 2seO 2base thermoelectricity material.
5. the Bi that described in any one of Claims 1 to 4, burning synthesis method prepares 2seO 2base thermoelectricity material.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107793154A (en) * 2016-09-07 2018-03-13 武汉理工大学 A kind of supper-fast preparation Cu2The method of Se/BiCuSeO block composite thermoelectric materials

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CN103436724A (en) * 2013-09-22 2013-12-11 武汉理工大学 New method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material
CN103910339A (en) * 2014-01-20 2014-07-09 武汉理工大学 Ultrafast preparation method of high-performance BiCuSeO-based blocky thermoelectric material having nanometer layered structure
CN104261357A (en) * 2014-09-23 2015-01-07 清华大学 Bi2O2Se-based thermoelectric material and preparation method thereof

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CN103215466A (en) * 2013-04-12 2013-07-24 武汉理工大学 Method for one-step preparation of single-phase BiCuSeO thermoelectric material powder by mechanical alloying
CN103436724A (en) * 2013-09-22 2013-12-11 武汉理工大学 New method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material
CN103910339A (en) * 2014-01-20 2014-07-09 武汉理工大学 Ultrafast preparation method of high-performance BiCuSeO-based blocky thermoelectric material having nanometer layered structure
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN107793154A (en) * 2016-09-07 2018-03-13 武汉理工大学 A kind of supper-fast preparation Cu2The method of Se/BiCuSeO block composite thermoelectric materials
CN107793154B (en) * 2016-09-07 2020-06-19 武汉理工大学 Ultra-fast preparation of Cu2Method for Se/BiCuSeO block composite thermoelectric material

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