CN109022863B - Ga-filled skutterudite thermoelectric material and preparation method thereof - Google Patents

Ga-filled skutterudite thermoelectric material and preparation method thereof Download PDF

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CN109022863B
CN109022863B CN201810775076.XA CN201810775076A CN109022863B CN 109022863 B CN109022863 B CN 109022863B CN 201810775076 A CN201810775076 A CN 201810775076A CN 109022863 B CN109022863 B CN 109022863B
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CN109022863A (en
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姜晶
张蕊
王超
牛夷
周婷
潘燕
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University of Electronic Science and Technology of China
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Abstract

The hair isObviously discloses a Ga-filled CoSb3Cobaltosite thermoelectric material GaxCo4Sb12.3And a preparation method thereof, belonging to the field of thermoelectric materials. The invention aims to provide a method for improving CoSb content by filling gallium simple substance (Ga) to form filling skutterudite3A method for thermoelectric performance of a skutterudite material. The thermoelectric material can improve CoSb by adjusting parameters such as seebeck coefficient, electric conductivity and thermal conductivity by changing the content of elemental gallium (Ga)3The skutterudite material has thermoelectric property and simple preparation process, and is suitable for large-scale production.

Description

Ga-filled skutterudite thermoelectric material and preparation method thereof
Technical Field
The invention belongs to the field of thermoelectric materials, and particularly relates to a method for improving CoSb content by filling gallium simple substance (Ga) to form filled skutterudite3A method for thermoelectric performance of a skutterudite material.
Background
Thermoelectric materials can realize the mutual conversion between heat energy and electric energy, the method for generating electricity by using temperature difference is a potential energy utilization method, in addition, the accurate control of temperature can be realized by using electricity to convert heat, and the thermoelectric material has wide application prospect in sensors and integrated circuits.
There are many factors that affect the energy conversion efficiency of thermoelectric systems, such as: the type and performance of the thermoelectric element, the loss of heat, the overall accuracy of the device, etc., with the most critical factor being the performance of the thermoelectric material. Dimensionless thermoelectric figure of merit, zT, is often used to measure the performance of thermoelectric materials, and the expression is:
Figure BDA0001731177550000011
where, γ represents absolute temperature, α represents seebeck coefficient, σ represents electrical conductivity, and κ represents thermal conductivity.
It can thus be seen that a good thermoelectric material should have a large seebeck coefficient and electrical conductivity and as small a thermal conductivity as possible. However, there is a mutual dependency relationship among three parameters of the material, namely the seebeck coefficient, the electrical conductivity and the thermal conductivity: the Seebeck coefficient is increased but the electric conductivity is reduced by reducing the carrier concentration of the material, meanwhile, the electron thermal conductivity is also influenced by the electric conductivity, one of the parameters is changed, the other two parameters are changed, the optimization of the electric transport performance and the optimization of the thermal transport performance are coupled together, and therefore, the three parameters of the Seebeck coefficient, the electric conductivity and the thermal conductivity must be comprehensively considered together in order to optimize the thermoelectric performance of the material.
Thermoelectric materials having the crystal structure of Skurteudite, also known as Skutterudite materials, originally found in mineral form in Skurterude in Norway towns, are a class of materials having the general formula MX3Wherein M represents a metal element such As Ir, Co, Rh, Fe, etc., and X represents a group V element such As P, As, Sb, etc. Skutterudite is a cubic lattice structure originally derived from CoAs3Minerals and later extends to other compounds of the same family. One unit cell contains 8 AB3The molecule has 32 atoms, each unit cell has two larger gaps, and the filled skutterudite is formed by filling atoms into the gaps, so that the lattice thermal conductivity is reduced, and the electron transport condition is basically not influenced. At present, the method for improving the thermoelectric performance of skutterudite materials mainly comprises the following steps: doping (element replacement), reduction of thermal conductivity by forming a filled skutterudite material, low-dimensional treatment of a material, synthesis of a skutterudite material having micro pores, and the like.
Disclosure of Invention
The invention aims to provide a method for improving CoSb content by filling gallium simple substance (Ga) to form filling skutterudite3A method for thermoelectric performance of a skutterudite material. The thermoelectric material can improve CoSb by adjusting parameters such as seebeck coefficient, electric conductivity and thermal conductivity by changing the content of elemental gallium (Ga)3The skutterudite material has thermoelectric property and simple preparation process, and is suitable for large-scale production.
The technical scheme of the invention is as follows:
ga-filled skutterudite thermoelectric material GaxCo4Sb12.3Wherein the value range of x is as follows: 0.1 to 0.25; the seebeck coefficient, the electric conductivity and the thermal conductivity of the thermoelectric material are improved by adjusting the content of the elementary gallium (Ga).
Further, the thermoelectric material GaxCo4Sb12.3The preparation method comprises the following steps:
step 1: ga, Co and Sb in stoichiometric ratioxCo4Sb12.3Weighing, uniformly mixing, filling into a graphite crucible, filling the graphite crucible into a quartz tube, and vacuumizing and sealing the tube;
step 2: putting the sealed quartz tube obtained in the step 1 into a muffle furnace, heating to 1100 ℃, and preserving heat for 10-15 hours;
and step 3: continuously putting the quartz tube obtained in the step 2 after high-temperature melting into a muffle furnace, heating to 700 ℃, and annealing and preserving heat for 100-120 hours;
and 4, step 4: carrying out high-energy ball milling on the annealed block sample obtained in the step 3 for 3-6 hours;
and 5: the stoichiometric ratio obtained in the step 4 is GaxCo4Sb12.3The powder of (A) is subjected to pressure sintering under vacuum conditions to obtain a thermoelectric material GaxCo4Sb12.3。
Further, in order to prevent the simple substance metal from being oxidized, the weighing of the metal simple substance mentioned in the step 1 is carried out in a glove box filled with inert atmosphere;
further, the heating rate in the step 2 is 3 ℃ per minute;
further, the heating rate in the step 3 is 5 ℃ per minute;
further, the high-energy ball milling in the step 4 specifically refers to ball milling in a high-energy ball mill with the rotating speed of 1450 revolutions per minute for 3-6 hours;
further, the pressure sintering mode in the step 5 is hot-pressing sintering or discharge plasma sintering, the used mold is a graphite mold, the applied pressure is 50-80 MPa, and the sintering time is 2-20 minutes.
Write the thermoelectric Material Ga of the inventionxCo4Sb12.3The preparation method has the advantages of high electrical conductivity, small thermal conductivity, high seebeck coefficient, simple preparation process and suitability for large-scale production.
Drawings
FIG. 1 shows Ga elementary substance-filled skutterudite Ga in different stoichiometric ratiosxCo4Sb12.3Scanning electron micrograph (c). (A) For the filled skutterudite Ga obtained in example 1xCo4Sb12.3Scanning electron micrographs of the thermoelectric material; (B) for the filled skutterudite Ga obtained in example 2xCo4Sb12.3Scanning electron micrographs of the thermoelectric material; (C) for the filled skutterudite Ga obtained in example 3xCo4Sb12.3Scanning electron micrographs of the thermoelectric material; (D) for the filled skutterudite Ga obtained in example 4xCo4Sb12.3Scanning electron micrographs of the thermoelectric material; the clear cubic structure in the figure shows that the skutterudite thermoelectric materials are successfully synthesized in the examples 1 to 4;
FIG. 2 shows Ga in the filled skutterudite obtained in examplexCo4Sb12.3X-ray diffraction patterns of thermoelectric materials. (A) (B), (C) and (D) are filled skutterudites Ga obtained in examples 1 to 4, respectivelyxCo4Sb12.3The X-ray diffraction spectrum of the thermoelectric material only shows CoSb on the spectrum because the amount of the filled Ga is little3The characteristic diffraction peaks of skutterudite, combined with FIG. 1, demonstrate that the samples prepared in examples 1-4 are indeed filled with skutterudite GaxCo4Sb12.3A thermoelectric material;
FIG. 3 shows Ga in the filled skutterudite obtained in examplexCo4Sb12.3Conductivity-temperature characteristic curve of thermoelectric material, wherein0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3"curves for the filled skutterudites Ga obtained in examples 1 to 4xCo4Sb12.3Electrical conductivity-temperature characteristic curve of thermoelectric material. The prepared filled skutterudite Ga is shown in the figurexCo4Sb12.3The electric conductivity of the thermoelectric material can reach 286.68S/cm at most.
FIG. 4 shows Ga in the filled skutterudite obtained in examplexCo4Sb12.3Seebeck coefficient-temperature characteristic curve of thermoelectric material in which "Ga0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3"curves for the filled skutterudites Ga obtained in examples 1 to 4xCo4Sb12.3The seebeck coefficient-temperature characteristic of a thermoelectric material. The prepared filled skutterudite Ga is shown in the figurexCo4Sb12.3The Seebeck coefficient of the thermoelectric material can reach-336.4068 uV/K at most.
FIG. 5 shows Ga in the filled skutterudite obtained in examplexCo4Sb12.3Thermal conductivity-temperature characteristic curve of thermoelectric material, wherein0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3"curves for the filled skutterudites Ga obtained in examples 1 to 4xCo4Sb12.3Thermal conductivity-temperature characteristic curve of thermoelectric material. The prepared filled skutterudite Ga is shown in the figurexCo4Sb12.3The thermal conductivity of the thermoelectric material is at least 2.792W/(mK).
FIG. 6 shows Ga in the filled skutterudite obtained in examplexCo4Sb12.3ZT-temperature characteristic curve of thermoelectric material, wherein "Ga0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3"curves for the filled skutterudites Ga obtained in examples 1 to 4xCo4Sb12.3ZT-temperature characteristic curve of thermoelectric material. The prepared filled skutterudite Ga is shown in the figurexCo4Sb12.3The ZT of the thermoelectric material can reach 0.561 at most.
Detailed Description
The technical scheme of the invention is described in detail below by combining the drawings and the embodiment.
Example 1
Step 1: ga, Co and Sb in stoichiometric ratio0.1Co4Sb12.3Weighing, mixing uniformly, loading into a graphite crucible, loading the graphite crucible into a quartz tube, and vacuumizing and sealing the tube. In order to avoid the oxidation of the elemental metal, the weighing of the elemental metal mentioned in the step is carried out in a glove box filled with inert atmosphere;
step 2: putting the sealed quartz tube obtained in the step 1 into a muffle furnace, heating to 1100 ℃, wherein the heating rate is 3 ℃ per minute, and keeping the temperature for 10 hours;
and step 3: continuously putting the quartz tube obtained in the step 2 after high-temperature melting into a muffle furnace, heating to 700 ℃, wherein the heating rate is 5 ℃ per minute, and annealing and preserving heat for 100 hours;
and 4, step 4: carrying out high-energy ball milling on the annealed block sample obtained in the step 3 for 3 hours;
and 5: the stoichiometric ratio obtained in the step 4 is Ga0.1Co4Sb12.3The powder is sintered under vacuum to obtain the thermoelectric material of the present invention. The pressure sintering mode is hot-pressing sintering or discharge plasma sintering, the used mold is a graphite mold, the applied pressure is 70MPa, and the sintering time is 5 minutes
Filled skutterudite Ga obtained in example 10.1Co4Sb12.3The thermoelectric material has the conductivity of 255.66S/cm at 773K, the Seebeck coefficient of-336.4 uV/K at 473K and the lowest thermal conductivity of 3.335W/(mK) at 623K.
Example 2
Step 1: ga, Co and Sb in stoichiometric ratio0.15Co4Sb12.3Weighing and mixingAfter uniform combination, the mixture is put into a graphite crucible, and then the graphite crucible is put into a quartz tube for vacuumizing and tube sealing. In order to avoid the oxidation of the elemental metal, the weighing of the elemental metal mentioned in the step is carried out in a glove box filled with inert atmosphere;
step 2: putting the sealed quartz tube obtained in the step 1 into a muffle furnace, heating to 1100 ℃, wherein the heating rate is 3 ℃ per minute, and keeping the temperature for 15 hours;
and step 3: continuously putting the quartz tube obtained in the step 2 after high-temperature melting into a muffle furnace, heating to 700 ℃, wherein the heating rate is 5 ℃ per minute, and annealing and preserving heat for 110 hours;
and 4, step 4: carrying out high-energy ball milling on the annealed block sample obtained in the step 3 for 6 hours;
and 5: the stoichiometric ratio obtained in the step 4 is Ga0.15Co4Sb12.3The powder is sintered under vacuum to obtain the thermoelectric material of the present invention. The pressure sintering mode is hot-pressing sintering or discharge plasma sintering, the used mold is a graphite mold, the applied pressure is 60MPa, and the sintering time is 5 minutes
Example 2 the resulting filled skutterudite Ga0.15Co4Sb12.3The thermoelectric material has an electrical conductivity of 254.45S/cm at 773K, a Seebeck coefficient of-324.56 uV/K at 473K and a thermal conductivity of at least 2.822W/(mK) at 573K.
Example 3
Step 1: ga, Co and Sb in stoichiometric ratio0.2Co4Sb12.3Weighing, mixing uniformly, loading into a graphite crucible, loading the graphite crucible into a quartz tube, and vacuumizing and sealing the tube. In order to avoid the oxidation of the elemental metal, the weighing of the elemental metal mentioned in the step is carried out in a glove box filled with inert atmosphere;
step 2: putting the sealed quartz tube obtained in the step 1 into a muffle furnace, heating to 1100 ℃, wherein the heating rate is 3 ℃ per minute, and keeping the temperature for 12 hours;
and step 3: continuously putting the quartz tube obtained in the step 2 after high-temperature melting into a muffle furnace, heating to 700 ℃, wherein the heating rate is 5 ℃ per minute, and annealing and insulating for 120 hours;
and 4, step 4: carrying out high-energy ball milling on the annealed block sample obtained in the step 3 for 4 hours;
and 5: the stoichiometric ratio obtained in the step 4 is Ga0.2Co4Sb12.3The powder is sintered under vacuum to obtain the thermoelectric material of the present invention. The pressure sintering mode is hot-pressing sintering or discharge plasma sintering, the used mold is a graphite mold, the applied pressure is 80MPa, and the sintering time is 5 minutes
Ga-filled skutterudite obtained in example 30.2Co4Sb12.3The thermoelectric material has the conductivity of 280.22S/cm at 773K, the Seebeck coefficient of-322.2 uV/K at 473K, the lowest thermal conductivity of 2.991W/(mK) at 573K and finally the ZT value of 0.561 at 623K. Filling skutterudite Ga with the existing metal simple substance Ga single elementxCo4Sb12.3Compared with the thermoelectric property of the material, the thermoelectric property of the material is improved by 2-3 times, and the material is suitable for medium-temperature thermoelectric materials.
Example 4
Step 1: ga, Co and Sb in stoichiometric ratio0.25Co4Sb12.3Weighing, mixing uniformly, loading into a graphite crucible, loading the graphite crucible into a quartz tube, and vacuumizing and sealing the tube. In order to avoid the oxidation of the elemental metal, the weighing of the elemental metal mentioned in the step is carried out in a glove box filled with inert atmosphere;
step 2: putting the sealed quartz tube obtained in the step 1 into a muffle furnace, heating to 1100 ℃, wherein the heating rate is 3 ℃ per minute, and keeping the temperature for 14 hours;
and step 3: continuously putting the quartz tube obtained in the step 2 after high-temperature melting into a muffle furnace, heating to 700 ℃, wherein the heating rate is 5 ℃ per minute, and annealing and preserving heat for 1000 hours;
and 4, step 4: carrying out high-energy ball milling on the annealed block sample obtained in the step 3 for 5 hours;
and 5: the stoichiometric ratio obtained in the step 4 is Ga0.25Co4Sb12.3The powder is sintered under vacuum to obtain the thermoelectric material of the present invention. The pressure sintering mode is hot-pressing sintering or discharge plasma sintering, the used mold is a graphite mold, the applied pressure is 50MPa, and the sintering time is 5 minutes
Example 4 the resulting filled skutterudite Ga0.25Co4Sb12.3The thermoelectric material has an electrical conductivity of 258.77S/cm at 773K, a Seebeck coefficient of-334.93 uV/K at 473K and a lowest thermal conductivity of 2.792W/(mK) at 573K.

Claims (5)

1. Ga-filled skutterudite thermoelectric material GaxCo4Sb12.3Wherein the value range of x is as follows: 0.1 to 0.25; the seebeck coefficient, the electric conductivity and the thermal conductivity of the thermoelectric material are improved by adjusting the content of the elementary gallium (Ga);
the thermoelectric material GaxCo4Sb12.3The preparation method comprises the following steps:
step 1: ga, Co and Sb in stoichiometric ratioxCo4Sb12.3Weighing, uniformly mixing, filling into a graphite crucible, filling the graphite crucible into a quartz tube, and vacuumizing and sealing the tube;
step 2: putting the sealed quartz tube obtained in the step 1 into a muffle furnace, heating to 1100 ℃ at a rate of 3 ℃ per minute, and preserving heat for 10-15 hours;
and step 3: continuously putting the quartz tube obtained in the step 2 after high-temperature melting into a muffle furnace, heating to 700 ℃, and annealing and preserving heat for 100-120 hours;
and 4, step 4: carrying out high-energy ball milling on the annealed block sample obtained in the step 3 for 3-6 hours;
and 5: the stoichiometric ratio obtained in the step 4 is GaxCo4Sb12.3The powder of (A) is subjected to pressure sintering under vacuum conditions to obtain a thermoelectric material GaxCo4Sb12.3。
2. The Ga-filled skutterudite thermoelectric material according to claim 1GaxCo4Sb12.3And the method is characterized in that in order to avoid the oxidation of the elemental metal, the weighing of the elemental metal mentioned in the step 1 is carried out in a glove box filled with inert atmosphere.
3. The Ga-filled skutterudite thermoelectric material Ga according to claim 1xCo4Sb12.3And the method is characterized in that the temperature rise rate in the step 3 is 5 ℃ per minute.
4. The Ga-filled skutterudite thermoelectric material Ga according to claim 1xCo4Sb12.3The method is characterized in that the high-energy ball milling in the step 4 is specifically ball milling for 3-6 hours in a high-energy ball mill with the rotating speed of 1450 revolutions per minute.
5. The Ga-filled skutterudite thermoelectric material Ga according to claim 1xCo4Sb12.3The method is characterized in that the pressure sintering mode in the step 5 is discharge plasma sintering, the used mold is a graphite mold, the applied pressure is 50-80 MPa, and the sintering time is 2-20 minutes.
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CN101435029A (en) * 2008-12-26 2009-05-20 武汉理工大学 Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material

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CN101435029A (en) * 2008-12-26 2009-05-20 武汉理工大学 Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material

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Ga填充n型方钴矿化合物的结构及热电性能;苏贤礼等;《物理学报》;20081031;第57卷(第10期);第3部分,图3、5、7 *

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