CN114249304A - High-performance BiTe-based composite thermoelectric material and preparation method thereof - Google Patents
High-performance BiTe-based composite thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 8
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
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Abstract
Disclosed herein are a BiTe-based composite thermoelectric material having high performance and a method for preparing the same. Having the general formula BixSb2‑xTe3‑ ySeyMz(ii) a Wherein, M is an alloy formed by one or more of Bi, Sb, Te and Se and one or more of I, Br, Cu, Ag, Cd, Y and Yb, or an alloy formed by one or more of I, Br, Cu, Ag, Cd, Y and Yb; x, y and z are mole molecules and range from 0 to 1. The Bi2Te3The base thermoelectric material is put into a ball milling tank, firstly ball milling is carried out for 1 h-5 h under the condition of the rotating speed of 100 rpm-400 rpm, then ball milling is carried out for 5 h-20 h under the condition of 400 rpm-800 rpm, alloyed thermoelectric material powder is obtained, the powder is cold-pressed into alloy blocks by a cold press under the condition of 100 MPa-500 MPa, and then the alloy blocks are placedThe electric plasma sinters into a dense mass. Bi of the present invention2Te3The base thermoelectric composite material has the advantages of simple preparation method, high production efficiency, high conductivity and power factor, low thermal conductivity, good thermoelectric property and the like.
Description
Technical Field
The invention relates to the field of thermoelectricity, in particular to a multi-metal co-doped BiTe-based thermoelectric material and a preparation method thereof.
Background
In recent years, the rapid growth of population and the rapid development of industry, the excessive exploitation of fossil fuels, the more remarkable energy and environmental problems, and the energy crisis and the environmental crisis have attracted attention from various countries. However, about 70% of the energy consumed annually worldwide is wasted in the form of waste heat, which if effectively recycled would greatly alleviate the energy shortage problem. The thermoelectric material can directly convert heat energy into electric energy, has the advantages of no transmission part, small volume, no noise, no pollution, good reliability and the like, and has huge application prospect in the aspects of automobile waste heat recycling and industrial waste heat power generation.
The thermoelectric technology can realize the mutual conversion between heat energy and electric energy, and has wide application prospect as a clean energy technology. The performance of a thermoelectric material can be measured by a dimensionless thermoelectric figure of merit, ZT, (S) calculated from the following equation2σ/κ) T, where S is Seebeck coefficient, σ is electrical conductivity, T is temperature, κ is thermal conductivity, power factor PF ═ S2And sigma. Good thermoelectric materials require high electrical conductivity, high Seebeck coefficient and low thermal conductivity. The thermoelectric performance can be improved by increasing the power factor (S)2σ) and reducing thermal conductance.
Bi2Te3Is a classic room temperature thermoelectric material, is first discovered in 1954, has a bismuth telluride structure, and belongs to
Space group, indirect bandgap of about 0.15eV, consisting of a series of Te along the c-axis1-Bi-Te2-Bi-Te1Five atomic layers are stacked. Bi atoms and Te atoms are strongly bonded by ion-covalent bonds, and two layers of Te atoms are bonded by weak van der Waals forces. Bi having a layered structure2Te3The anisotropy is significant. In addition, the，Bi2Te3Can be easily alloyed with Sb or Se to form a high-performance p-type BiSbTe alloy and n-type BiTeSe alloy, thereby making a device which is generally used for refrigeration or power generation in the vicinity of room temperature and has high refrigeration efficiency.
In the 60's of the 20 th century, the thermoelectric performance of p-type BiSbTe alloy was high, and the maximum ZT value reached 1.1 around 300K. With the development of material synthesis technology, the thermoelectric performance of the BiSbTe alloy is further improved. In 2008, Poudel et al prepared BiSbTe nanocrystals by ball milling-hot pressing, reduced thermal conductivity and bipolar effect, and increased the maximum ZT value to 1.4 (373K). In 2015, Kim et al prepared Bi0.5Sb1.5Te3When the excess Te is added, and then melting and SPS sintering are carried out, a compact dislocation array is manufactured in a parent material, intermediate frequency phonons are effectively scattered, the lattice thermal conductivity is further reduced, the maximum ZT value is improved to 1.86, and the numerical value needs to be further confirmed. Compared with p-type BiSbTe alloy, the maximum ZT value of n-type BiTeSe alloy is about 1.0. However, the materials are affected by high-temperature melting and unstable rapid cooling in the preparation process, the requirements on equipment are high, the preparation process is complex, the repeatability of the prepared materials is poor, and the performance of the prepared materials is unstable. The material prepared by the invention can be completely repeated, has stable performance and can solve the problems.
Disclosure of Invention
The invention solves the problems: the invention overcomes the defects of the prior art, prepares the BiTe-based thermoelectric material with good thermoelectric performance by adopting multi-metal co-doping measurement, directly doping metal in an alloy form and optimizing the preparation process, has very high electric conductivity and power factor and lower thermal conductivity, and is suitable for thermoelectric temperature difference power generation and semiconductor refrigeration.
The technical scheme of the invention is as follows:
a polymetal co-doped BiTe-based thermoelectric composite material has a general formula of BixSb2-xTe3-ySeyMz(ii) a Wherein M is I, Br, Cu, Ag, Cd, Y, Yb elementOne or more of biotin; x, y and z are molar molecules and are all 0-1.
A polymetal co-doped BiTe-based thermoelectric composite material has a general formula of BixSb2-xTe3-ySeyMz(ii) a Wherein, M is an alloy formed by one or more of Bi, Sb, Te and Se and one or more of I, Br, Cu, Ag, Cd, Y and Yb, or an alloy formed by one or more of I, Br, Cu, Ag, Cd, Y and Yb; x, y and z are mole molecules and range from 0 to 1.
Preferably, x ranges from 0.3 to 0.7, y ranges from 0 to 0.5, and z ranges from 0 to 0.3.
A preparation method of the multi-metal co-doped BiTe-based thermoelectric composite material comprises the following steps:
canning: according to BixSb2-xTe3-ySeyMzWeighing high-purity (the purity is 99.999%) powder corresponding to the simple substance element according to the element and the mole fraction, filling the powder into a ball milling tank, inflating and deflating the ball milling tank for 3 times, and sealing the ball milling tank;
ball milling: putting the sealed ball milling tank into a planetary ball mill for ball milling alloying, firstly carrying out ball milling at a low rotating speed, and then carrying out ball milling at a high rotating speed to obtain alloyed powder;
cold pressing: taking out the alloying powder under the protection of Ar gas, and then carrying out primary cold pressing on the alloying powder by a cold press under the condition of certain pressure intensity to form an alloy block;
and (3) sintering: directly placing the cold-pressed alloy block into a sintered graphite mold, then placing the mold into a discharge plasma sintering furnace, pressurizing the mold to a set pressure, vacuumizing to 1-5Pa, then heating with current, raising the temperature to the sintering temperature, keeping the sintering temperature for a period of time, then reducing the current, cooling to room temperature, finishing sintering, and obtaining the Bi after sinteringxSb2-xTe3-ySeyMzA thermoelectric material;
the rotation speed of the low-speed ball milling is 100 rpm-400 rpm, and the low-speed ball milling time is 1 h-5 h; the high-speed ball milling speed is 400 rpm-800 rpm, and the high-speed ball milling time is 5 h-20 h.
When M is an alloy, the preparation method of the multi-metal co-doped BiTe-based thermoelectric composite material comprises the following steps:
canning: weighing high-purity powder (the purity is 99.999%) corresponding to the simple substance element according to the element and the mole fraction in the M, filling the powder into a ball milling tank, and sealing the ball milling tank;
ball milling: putting the sealed ball milling tank into a ball mill for ball milling alloying, firstly carrying out ball milling at a low rotating speed, and then carrying out ball milling at a high rotating speed to obtain M alloying powder;
according to BixSb2-xTe3-ySeyMzIn the presence of elements other than M and mole fraction, repeating the steps a-b to obtain BixSb2-xTe3-ySeyMzAlloying powder of other elements except M, and mixing with the M alloying powder;
cold pressing: cold-pressing the mixed alloying powder into an alloy block by a cold press;
and (3) sintering: placing the cold-pressed alloy block into a sintering mold, then placing the mold into a discharge plasma sintering furnace for sintering to obtain the BixSb2-xTe3-ySeyMzA thermoelectric material;
the rotation speed of the low-speed ball milling is 100 rpm-400 rpm, and the low-speed ball milling time is 1 h-5 h; the high-speed ball milling speed is 400 rpm-800 rpm, and the high-speed ball milling time is 5 h-20 h.
Preferably, in the cold pressing step, the pressure of the cold pressing is 100 MPa-500 MPa.
Preferably, in the sintering step, after the alloy block is placed in a mold, the mold is pressurized and vacuumized to 1-5Pa, then the temperature is raised from room temperature to 573K-873K at the temperature raising rate of 1.5K/min-5K/min under the protection of argon, the temperature is kept for 1-30min, then the temperature is lowered to room temperature, the sintering is finished, and the Bi is obtained after the sinteringxSb2-xTe3-ySeyMzA thermoelectric material. Preferred temperature and time energyEnsures the material to be completely sintered, thereby ensuring high density of the material and preventing the material from decomposing.
Preferably, the set pressure of the die is 30-100MPa, and the optimized pressure is 50MPa, so that the material has high density, and the material is not broken after sintering.
The thermoelectric composite material is applied to the fields of thermoelectric power generation and semiconductor refrigeration.
Advantageous effects
The invention provides multi-metal doped BixSb2-xTe3-ySeyMzThe thermoelectric material effectively improves the electric conductivity of the BiTe-based thermoelectric material by metal doping, and the electric conductivity of the thermoelectric material is further improved by doping metal in an alloy form; bixSb2-xTe3-ySeyMzHas high power factor and low thermal conductivity, which makes BixSb2-xTe3-ySeyMzHas higher thermoelectric figure of merit and good thermoelectric application potential.
The invention obtains the alloyed thermoelectric material powder by using the planetary ball mill, the powder is cold-pressed into alloy blocks by a cold press, and then the alloy blocks are sintered into compact blocks by discharge plasma, so that the material can be rapidly sintered and molded, and the thermoelectric material with uniform alloy grains, high density and good mechanical property is obtained.
Bi of the present invention2Te3The base thermoelectric composite material has the advantages of simple preparation method, high production efficiency, high conductivity and power factor, low thermal conductivity, good thermoelectric property and the like.
The performance of a thermoelectric material can be measured by a dimensionless thermoelectric figure of merit, ZT, (S) calculated from the following equation2σ/κ) T, where S is Seebeck coefficient, σ is electrical conductivity, T is temperature, κ is thermal conductivity, power factor PF ═ S2And sigma. Good thermoelectric materials require high electrical conductivity, high Seebeck coefficient and low thermal conductivity. The thermoelectric performance can be improved by increasing the power factor (S)2σ) and reducing thermal conductance.The electric conductivity of the thermoelectric material can be improved by doping trace element, but the Seebeck coefficient of the thermoelectric material is not changed too much, so that the performance of the thermoelectric material is improved but limited. The micro-doping is carried out in the form of alloy, so that the electric conductivity of the thermoelectric material can be improved, the Seebeck coefficient of the thermoelectric material can be obviously improved, the heat conductivity of the thermoelectric material can be reduced, and the performance of the material can be improved.
Drawings
FIG. 1 is a graph of the electrical conductivity σ as a function of temperature for examples 1,2 and 3 of the present invention;
FIG. 2 is a graph showing the Seebeck coefficient S with respect to temperature for examples 1,2 and 3 of the present invention;
FIG. 3 is a graph of power factor versus temperature for examples 1,2 and 3 of the present invention;
FIG. 4 is a graph of the thermal conductivity κ as a function of temperature for examples 1,2 and 3 of the invention;
FIG. 5 is a graph of thermoelectric figure of merit (ZT) as a function of temperature for examples 1,2 and 3 of the present invention;
FIG. 6 is a graph showing thermoelectric figure of merit (ZT) of comparative example 1 according to the present invention as a function of temperature.
Detailed Description
The raw materials used in the following examples are all conventional products commercially available from Alfa Aesar.
The invention successfully prepares a novel high-performance thermoelectric material, and the chemical general formula of the thermoelectric material is BixSb2-xTe3-ySeyMzWherein M is one or more than two of Bi, Sb, Te, Se, I, Br, Cu, Ag, Cd, Y and Yb elements, wherein x, Y and z are molar numbers and range from 0 to 1. The number of the mols x is 0.3 to 0.7, the number of the mols y is 0 to 0.5, and the number of the mols z is 0 to 0.3.
The invention prepares single-metal or multi-metal doped Bi by ball milling, cold pressing and spark plasma sintering technologyxSb2-xTe3-ySeyMzThermoelectric material with effective improvement of BiTe-based heat by metal dopingElectrical conductivity of electrical materials, BixSb2- xTe3-ySeyMzHas high power factor and low thermal conductivity, which makes BixSb2-xTe3-ySeyMzHas higher thermoelectric figure of merit and good thermoelectric application potential.
The embodiment of the invention comprises three steps of ball milling, cold pressing and spark plasma sintering, and the detailed embodiment is as follows:
1) ball milling and mixing: according to the chemical ratio Bi in the chemical formulaxSb2-xTe3-ySeyMzFirstly, weighing required elementary substance powder of Bi, Sb, Te, Se and M, putting the powder into a ball milling tank, carrying out ball milling for 4 hours under the condition of 260 revolutions per minute (rpm) to fully mix the elementary substance powder, and then carrying out ball milling for 12 hours under the condition of 550 revolutions per minute (rpm) to fully alloy the elementary substance.
2) Taking out the alloyed powder under the protection of Ar gas, and then carrying out primary cold pressing on the alloyed powder by a cold press under the condition of 260MPa of pressure to form an alloy block, wherein the time is 2 hours.
3) Solid sintering: and further sintering the alloy blocks obtained by the cold pressing reaction into blocks by using a Spark Plasma Sintering (SPS) technology. Firstly, selecting a graphite mould, adding a layer of carbon paper for protecting the mould in the graphite mould, putting the powder into the mould, compacting by using a graphite pressure head, then putting the mould into a discharge plasma sintering device, applying a certain pressure within the pressure range of 30-100MPa, vacuumizing, and starting to heat up and sinter when the pressure is less than 5 Pa. Slowly increasing current to raise the temperature from room temperature to 773K at a rate of 15-25K/min after 20-30min, maintaining the temperature at the sintering temperature for a period of time, generally 5min, and then cooling. After cooling to room temperature, Bi having a high density is obtainedxSb2-xTe3-ySeyMz bulk thermoelectric materials.
Example 1
P-type Bi0.5Sb1.5Te3The preparation method comprises the following steps:
1) ball milling and mixing: according to the formula BixSb2-xTe3-ySeyMzWeighing elementary powder of Bi, Sb, Te, Se, I, Br, Cu, Ag, Cd, Y and Yb according to the conditions that x is 0.5, Y is 0 and z is 0, wherein the total mass is 10g, putting the powder into a ball milling tank, filling argon for protection, carrying out ball milling for 4h at 260rpm, and carrying out ball milling for 12h at 550 rpm.
2) Cold pressing: taking out under the protection of Ar gas, and then carrying out primary cold pressing on the alloy block by a cold press under the condition of 260MPa pressure for 2 hours.
3) Solid sintering: adding a layer of carbon paper in a mold, directly placing a block material obtained by cold pressing into a graphite mold with the inner diameter of 12.7mm, placing the graphite mold into an SPS device, pressurizing at two ends of the mold, wherein the pressure is 50MPa, vacuumizing to 5Pa, starting to heat up, heating to 773K at a rate of 20K/min, then preserving heat for 5min, then starting to cool down, keeping the pressure at 50MPa, gradually reducing the current to gradually reduce the temperature, cooling to room temperature, and then taking out.
Example 2
P type (Bi)0.5Sb1.5Te3)Cu0.005The preparation method of the thermoelectric composite material comprises the following steps
1) Doping and mixing: doping Cu powder to Bi of example one0.5Sb1.5Te3In accordance with the formula (Bi)0.5Sb1.5Te3)CunWeighing the powder with the total mass of 10g when n is 0.005, putting the powder into a ball milling tank, introducing argon for protection, ball milling the powder for 4 hours at 260rpm, and ball milling the powder for 12 hours at 550 rpm.
2) The remaining steps are the same as step 2 and step 3 of example one.
Example 3
P type (Bi)0.5Sb1.5Te3)(AgSbTe2) A method for preparing an n (n-0.004) thermoelectric composite material, comprising the steps of:
1) ball milling: firstly according to the general formula AgSbTe2Weighing Ag, Sb and Te elementary substance powder with the total mass of 10g, putting the powder into a ball milling tank, filling argon for protection, ball milling for 4 hours at 260rpm, and then milling at 550rpmThen, the mixture is ball-milled for 12 hours.
2) Doping and mixing: the AgSbTe obtained in the step one2Powder doping to example-Bi0.5Sb1.5Te3In the powder according to the general formula (Bi)0.5Sb1.5Te3)(AgSbTe2) And n is 0.004, the total mass is 10g, the mixture is placed into a ball milling tank, argon is filled into the ball milling tank for ball milling for 4 hours at 260rpm, and then the ball milling is carried out for 12 hours at 550 rpm.
3) The remaining steps are the same as step 2 and step 3 of example one.
Comparative example 1
P-type Bi0.5Sb1.504Te3.008Ag0.004The preparation method comprises the following steps:
1) ball milling and mixing: according to the formula Bi0.5Sb1.504Te3.008Ag0.004Weighing elementary substance powder with corresponding mole fractions of Bi, Sb, Te and Ag, wherein the total mass is 10g, then placing the powder into a ball milling tank, introducing argon for protection, carrying out ball milling for 4h at 260rpm, and carrying out ball milling for 12h at 550 rpm.
2) The remaining steps are the same as step 2 and step 3 of example one.
Electric properties
The electrical properties of examples 1,2,3, including conductivity σ and Seebeck coefficient S, were systematically tested as shown in fig. 1-3. The instrument used for the electrical test was ULVAC ZEM-3. Example 1 the maximum Power factor is 32. mu.W/cmK2Examples 2 and 3 showed very high conductivity and power factor with a maximum power factor of 40. mu.W/cmK2。
Thermal conductivity property
As shown in FIG. 1, the thermal diffusivity, D, and specific heat, C, of examples 1,2, and 3 were measured by laser light scattering analysis (LFA) and Differential Scanning Calorimetry (DSC), respectivelypUsing the formula k ═ Cpρ D (where ρ is the density of the thermoelectric material), the thermal conductivity κ of the thermoelectric material is obtained by calculation. The instruments used in the test were NETZSCH LFA 457 and NETZSCH STA, temperature range: 300-. As can be seen from FIG. 4, example 3 has a lower thermal conductanceThe minimum rate is 1.08W/mK.
From the thermal conductivity and electrical data, the thermoelectric figure of merit ZT can be calculated. FIG. 5 is a graph of thermoelectric figure of merit versus temperature for examples 1,2, and 3. It can be seen from fig. 5 that the ZT value of example 1 is lower and is only 0.8, and as the alloy is doped, ZT is greatly improved, and the ZT values of examples 2 and 3 are improved to 1.0 and 1.25 at 400K, which is higher than ZT value (0.98) of comparative example, which indicates that the alloy doping has better thermoelectric performance than non-alloy doping.
Claims (8)
1. A preparation method of a multi-metal co-doped BiTe-based thermoelectric composite material is characterized by comprising the following steps: the general formula of the material is BixSb2-xTe3-ySeyMz(ii) a Wherein M is one or more of elements I, Br, Cu, Ag, Cd, Y and Yb; x, y and z are molar molecules and are all 0-1;
the preparation method of the material comprises the following steps:
a) canning: according to BixSb2-xTe3-ySeyMzWeighing powder corresponding to the simple substance elements according to the elements and the mole fraction, filling the powder into a ball milling tank, and sealing the ball milling tank;
b) ball milling: putting the sealed ball milling tank into a ball mill for ball milling alloying, firstly carrying out ball milling at a low rotating speed, and then carrying out ball milling at a high rotating speed to obtain alloyed powder;
c) cold pressing: cold-pressing the alloying powder into an alloy block by a cold press;
d) and (3) sintering: placing the cold-pressed alloy block into a sintering mold, then placing the mold into a discharge plasma sintering furnace for sintering to obtain the BixSb2-xTe3-ySeyMzA thermoelectric material;
the rotation speed of the low-speed ball milling is 100 rpm-400 rpm, and the low-speed ball milling time is 1 h-5 h; the high-speed ball milling speed is 400 rpm-800 rpm, and the high-speed ball milling time is 5 h-20 h.
2. Multi-metal alloyThe doped BiTe-based thermoelectric composite material is characterized in that: the general formula of the material is BixSb2- xTe3-ySeyMz(ii) a Wherein, M is an alloy formed by one or more of Bi, Sb, Te and Se and one or more of I, Br, Cu, Ag, Cd, Y and Yb, or an alloy formed by one or more of I, Br, Cu, Ag, Cd, Y and Yb; x, y and z are mole molecules and range from 0 to 1.
3. The production method according to claim 1 or the thermoelectric composite material according to claim 2, characterized in that: the range of x is 0.3-0.7, the range of y is 0-0.5, and the range of z is 0-0.3.
4. A method of making a thermoelectric composite material as recited in claim 2, comprising the steps of:
a) canning: weighing powder corresponding to the simple substance element according to the element and the mole fraction in the M, filling the powder into a ball milling tank, and sealing the ball milling tank;
b) ball milling: putting the sealed ball milling tank into a ball mill for ball milling alloying, firstly carrying out ball milling at a low rotating speed, and then carrying out ball milling at a high rotating speed to obtain M alloying powder;
c) according to BixSb2-xTe3-ySeyMzIn the presence of elements other than M and mole fraction, repeating the steps a-b to obtain BixSb2- xTe3-ySeyMzAlloying powder of other elements except M, and mixing with the M alloying powder;
d) cold pressing: cold-pressing the mixed alloying powder into an alloy block by a cold press;
e) and (3) sintering: placing the cold-pressed alloy block into a sintering mold, then placing the mold into a discharge plasma sintering furnace for sintering to obtain the BixSb2-xTe3-ySeyMzA thermoelectric material;
the rotation speed of the low-speed ball milling is 100 rpm-400 rpm, and the low-speed ball milling time is 1 h-5 h; the high-speed ball milling speed is 400 rpm-800 rpm, and the high-speed ball milling time is 5 h-20 h.
5. The method according to claim 1 or 4, wherein in the cold pressing step, the pressure of the cold pressing is 100MPa to 500 MPa.
6. The method according to claim 1 or 4, wherein in the sintering step, after the alloy ingot is placed in the mold, the mold is pressurized and evacuated to 1-5 Pa; then under the protection of argon, heating the sintering furnace from room temperature to 573K-873K at the heating rate of 1.5K/min-5K/min, keeping the temperature for 1-30min, then cooling to room temperature, finishing sintering, and obtaining the Bi after sinteringxSb2-xTe3-ySeyMzA thermoelectric material.
7. The method of claim 6, wherein the die set pressure is 30-100 MPa.
8. Use of a thermoelectric composite material prepared by the method of claim 1 or the thermoelectric composite material of claim 2, wherein: the thermoelectric composite material is applied to the fields of thermoelectric power generation and semiconductor refrigeration.
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