CN103022336B

CN103022336B - Double-doped In4Se3-based thermoelectric material, and preparation method and application thereof

Info

Publication number: CN103022336B
Application number: CN201210539358.2A
Authority: CN
Inventors: 吴立明; 林志盛; 陈玲
Original assignee: Fujian Institute of Research on the Structure of Matter of CAS
Current assignee: Fujian Institute of Research on the Structure of Matter of CAS
Priority date: 2012-12-14
Filing date: 2012-12-14
Publication date: 2015-07-15
Anticipated expiration: 2032-12-14
Also published as: CN103022336A

Abstract

The invention relates to a double-doped In4Se3-based thermoelectric material In4-xPb0.01SnxSE3 (x=0.02-0.05), and the preparation method and the application thereof. Powder of Pb and Sn double-doped In4Se3 is synthesized through a high-temperature solid-phase two-step method, and the obtained powder is subjected to spark plasma sintering to obtain target block materials. The maximum thermoelectricity merit figure of the Pb and Sn double-doped In4Se3-based thermoelectric material can reach 1.4, the thermoelectricity performance is improved by 40% than that of a current commercial thermoelectric material system, and the material can be used for manufacturing efficient heat-electricity conversion apparatuses.

Description

Codope In 4se 3base thermoelectricity material and preparation thereof and purposes

Technical field

The invention belongs to material science, relate to a kind of new and effective thermoelectric material.

Background technology

World today's civilization is that high speed development, science and technology are highly developed, the energy and environmental problem oneself become the focus paid close attention in the whole world.Human society, while self-growth, also is faced with ecological deterioration gradually! The significant problems such as energy shortage.Along with non-renewable energy resources day by day reduce and the mankind to the increase of energy demand, energy crisis will become main crisis in 21 century.Thermoelectric material can realize the directly conversion mutually between heat energy and electric energy in the solid state, is the energy conversion material that a class has very big application prospect.Its main feature is environmentally safe and using energy source diversity, for alleviating two hang-ups---energy crisis and environmental pollution that the mankind face.At present, more thermoelectric material mainly semiconductor and alloy thereof is studied in the world, as Bi ₂te ₃sill, PbTe sill, AgSbTe ₂and (AgSbTe ₂) _1-x(GeTe) _xsolid solution, metal silicide (Mg/Mn/Fe) and SiGe alloy etc.In generation nineteen ninety, occurs that a class is referred to as the material of " phonon glasses electron crystal " (PGEC), and this kind of thermoelectric material mainly contains skutterudite, Runge-Kutta integration, β-Zn ₄sb ₃, Half-Heusler etc.With Bi ₂te ₃for stock, apply modern nanometer technology, prepared various low-dimension nano material, if ZT value during super crystal lattice material, 450 K of room temperature ZT value up to 2.4 is accurate one dimension laminar nano pipe and other high performance Bi comprising nanostructure of 1.0 ₂te ₃base thermoelectricity material.The Bi that current business-like thermoelectric material is ₂te ₃solid solution (thermoelectricity optimal value about 1.0), it is applied to semiconductor refrigerating.Be that the thermoelectric material of matrix mainly utilizes nanometer technology to reduce thermal conductivity to improve thermoelectricity optimal value with PbTe, although the particle at present by embedding each size can reduce its thermal conductivity greatly, but its thermal stability reduces greatly because of the high temperature polymerization maturation of nano particle, limits its useful life and application.To the Si of N-shaped _0.7ge _0.3material is 1.5 × 10 in carrier concentration ²²cm ^-3time, during 1100 K, its ZT can reach about 1.0.N-shaped pyroelectric material Ag Pb _msbTe _2+mseries compound, when being 18 as m and segregation can being separated out when the nano particle of the rich Ag-Sb being of a size of 1 ~ 10 nm (or a little more greatly or even micron dimension) from matrix, (Ag _1-xpb ₁₈sbTe ₂₀) reach as high as 2.2 in its ZT value of 800 K, be the body material that current ZT value is the highest.But its thermal stability also reduces greatly because of the high temperature polymerization maturation of nano particle.Therefore, what the exploration and being found to be of the thermoelectric material of novel and high-efficiency, good heat stability made high efficiency thermoelectric switching device provides possibility.

In ₄se ₃be a lamellar compound with anisotropic accurate two dimensional crystal structure, and its energy gap is about 0.5ev, substantially meets as excellent thermoelectric material candidate conditional, therefore cause interest and the extensive concern of scientific research man.In recent years, report research is had to prove In ₄se ₃be the Novel hot electric material that a class has a high potential, its Polycrystalline reaches 0.6 at the thermoelectric figure of merit (ZT) of 713 K, is widely studied the unadulterated thermoelectric figure of merit of even business-like system high a lot of than at present.Such as, in non-doping situation, PbTe maximum ZT value is the maximum ZT value of 0.50, SiGe is 0.5, and the maximum ZT value of skutterudite is only 0.04.But In ₄se ₃conductance is still less, and its charge carrier solubility is 4.13 × 10 ¹⁶cm ^-3, with best charge carrier solubility 1.0-5.0 × 10 ¹⁹cm ^-3differ three orders of magnitude, reduce its thermal conductivity so charge carrier solubility effectively can be regulated by the amount changing doping and embeds micro-nanophase, its thermoelectric figure of merit can be made to be further enhanced.Based on the research reported, we further improve synthetic method and realize Pb, Sn codope In ₄se ₃the acquisition of thermoelectric material, the thermoelectric figure of merit of its thermoelectric material can bring up to 1.4, higher by 40% than the thermoelectricity optimal value of current business-like thermoelectric material system.Related work, so far there are no bibliographical information.

Summary of the invention

The object of the invention: (1) provides a kind of codope In ₄se ₃base thermoelectricity material In _4-xpb _0.01sn _xse ₃(x=0.02-0.05), works as x=0.04, and the thermoelectric figure of merit of material reaches 1.4; (2) a kind of codope In is provided ₄se ₃the preparation method of base thermoelectricity material; (3) a kind of codope In of function admirable is provided ₄se ₃the purposes of base thermoelectricity material;

Technical scheme of the present invention is as follows:

Codope In prepared by the present invention ₄se ₃base thermoelectricity material In _4-xpb _0.01sn _xse ₃(x=0.02-0.05), works as x=0.04, and the thermoelectric figure of merit of material reaches 1.4.

The preparation method of described thermoelectric material, comprises the steps:

(1) In, Pb, Sn and Se tetra-kinds of raw materials are stoichiometrically mixed, adopt high temperature solid-state method, at 600-900 ° of C sintering, quenching, grinding, compressing tablet, then 400-500 ° of C annealing, obtained Pb, Sn codope In ₄se ₃powder.

(2) powder that step (1) is obtained is carried out discharge plasma sintering under 50-70 MPa, in the insulation of 400-450 degree, obtain target material.

Described thermoelectric material is applied to the making of High Efficiency Thermal-power conversion device.

The invention provides the purposes of this thermoelectric material, it is characterized in that: Pb, Sn codope In ₄se ₃base thermoelectricity material is higher by 40% than current business-like pyroelectric material performance due to its thermoelectricity capability, therefore can be applicable to the making of High Efficiency Thermal-power conversion device.

Accompanying drawing explanation

Fig. 1 is Pb, Sn codope In ₄se ₃thermoelectric material and In ₄se ₃the X-ray powder diffraction pattern of pure phase, wherein 1 is the X-ray powder diffraction pattern obtained according to crystal structure matching, and 2-5 is the Sn doping difference corresponding 0.02 to 0.05 and the In of doping 0.01Pb that adopt high temperature solid phase synthesis to obtain ₄se ₃sample last X-ray powder diffraction of pulverizing tests the collection of illustrative plates obtained.The model of x-ray powder diffraction instrument used is D/MAX2500, manufacturer: Rigaku Corporation.

Fig. 2 is In _4-xpb _0.01sn _xse ₃the graph of a relation of the electricity of (x=0.02-0.05), thermotransport and temperature, a) resistivity, b) Seebeck coefficient, c) power factor and d) thermal conductivity.Wherein, leg-of-mutton curve is the In of doping 0.01 mol% lead and 0.03 mol% tin ₄se ₃sample, the curve of rhombus is the In of doping 0.01 mol% lead and 0.04 mol% tin ₄se ₃sample, circular curve is the In of doping 0.01 mol% lead and 0.05 mol% tin ₄se ₃sample.: the test of thermal conductivity adopts resistance to (Netzsch, LFA427) thermal conductance instrument of speeding of Germany, and resistivity and Seebeck coefficient adopt thermoelectricity capability analyzer ZEM-3 (ULAC-RIKO, Inc.).

Fig. 3 is In _4-xpb _0.01sn _xse ₃the thermoelectricity optimal value of (x=0.02-0.05) and the relation of temperature.Wherein, leg-of-mutton curve is the In of doping 0.01 mol% lead and 0.03 mol% tin ₄se ₃sample, the curve of rhombus is the In of doping 0.01 mol% lead and 0.04 mol% tin ₄se ₃sample, circular curve is the In of doping 0.01 mol% lead and 0.05 mol% tin ₄se ₃sample.

Embodiment

Embodiment 1

Adopt high temperature solid phase synthesis synthesis Compound I n _4-xpb _0.01sn _xse ₃(x=0.02-0.05).

Concrete operation step is as follows: to be encapsulated in after stoichiometrically being mixed by In, Pb, Sn and Se tetra-kinds of raw material in quartz ampoule and to be placed in tube furnace, slowly be heated to 800 ° of C from room temperature, be incubated 30 hours, quenching, grinding, compressing tablet, then to anneal 7 days to obtain Pb and Sn codope In at 450 ° of C ₄se ₃powder.The powder of Pb and Sn codope is carried out discharge plasma sintering under 60 MPa, 450 degree of insulations 20 minutes, the block materials of target can be obtained.

Claims

1. a codope In ₄se ₃base thermoelectricity material, is characterized in that, the structure of described thermoelectric material is In _4-xpb _0.01sn _xse ₃, wherein, the span of x is 0.02-0.05.

2. codope In as claimed in claim 1 ₄se ₃base thermoelectricity material, wherein, x=0.04, the thermoelectric figure of merit of described material reaches 1.4.

3. the preparation method of the thermoelectric material described in claim 1 or 2, comprises the steps:

(1) In, Pb, Sn and Se tetra-kinds of raw materials are stoichiometrically mixed, adopt high temperature solid-state method, at 600-900 DEG C of sintering, quenching, grinding, compressing tablet, then 400-500 DEG C of annealing, obtained Pb, Sn codope In ₄se ₃powder;

(2) powder that step (1) is obtained is carried out discharge plasma sintering under 50-70MPa, in the insulation of 400-450 degree, obtain target material.

4. heat-power conversion device, it comprises the thermoelectric material described in claim 1 or 2.