CN113121234A - Mg3Sb 2-based thermoelectric material with high-temperature stability and preparation method thereof - Google Patents
Mg3Sb 2-based thermoelectric material with high-temperature stability and preparation method thereof Download PDFInfo
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Abstract
The invention provides Mg with high-temperature stability3Sb2A base thermoelectric material and a preparation method thereof relate to the technical field of thermoelectric materials. The Mg provided by the invention3Sb2The thermoelectric material includes Mg3~3.2Sb1.5Bi0.5‑xTexThermoelectric bulk material and deposited on said Mg3~3.2Sb1.5Bi0.5‑xTexA boron nitride coating on the surface of the thermoelectric block material; x is more than 0 and less than or equal to 0.06. The invention is at Mg3Sb2Introducing boron nitride coating and Mg into base thermoelectric material3Sb2The thermoelectric property of the base thermoelectric material is very stable at high temperature under the protection of the boron nitride coating, the Mg loss at high temperature can be effectively inhibited, and the Mg content is greatly improved3Sb2The working temperature of the thermoelectric material and thus the thermoelectric conversion efficiency at high temperature is ensured. The Mg provided by the invention3Sb2The thermoelectric material is very stable in thermoelectric performance even at a high temperature of 500 ℃.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to Mg with high-temperature stability3Sb2A base thermoelectric material and a method for producing the same.
Background
The thermoelectric material is a green environment-friendly functional material capable of realizing direct interconversion of heat energy and electric energy, the thermoelectric generator made of the semiconductor thermoelectric material can generate electricity as long as the temperature difference exists, and the thermoelectric generator has the advantages of cleanness, no noise pollution, no harmful substance emission, long service life, firmness, high reliability, stability and the like, and is a green environment-friendly energy with wide application range. In recent decades, thermoelectric materials have played an indispensable role in some special fields of miniaturization or miniaturization, such as electric power driving devices of space satellites, refrigeration systems of vehicle-mounted refrigerators, and micro medical devices.
Mg3Sb2The base material is a Zintle phase thermoelectric material, has the special performance of electronic crystal-phonon glass due to a complex network structure formed by chemical bonds and ionic bonds, and the raw materials are nontoxic, cheap and abundant elements. When the temperature is lowAt 1200K, Mg3Sb2The crystal structure is Mn2O3Form α phase, containing 3 Mg atoms and 2 Sb atoms per unit cell. In the presence of Mg3Sb2The Mg atom has two different positions, namely ionic Mg (I) and covalent Mg (II), and the Mg (II) forms [ Mg (II) ] with the Sb atom2Sb2]2-Layer, Mg (I) constituting Mg2+A cationic layer. Thus, Mg3Sb2The complex covalent bond and ionic bond network structure conforms to the characteristics of phonon glass-electronic crystal, and can obtain higher carrier mobility and stronger phonon scattering.
Tamaki, Ph, Japan Panasonic electric appliance, 2016, reported in Advanced Materials by inclusion of Mg3Sb2Te is introduced into the system to prepare a series of Mg3+δSb2-xBix-yTey(delta is more than or equal to 0 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 2, and y is more than or equal to 0 and less than or equal to 0.05) due to doping of Te3Sb2Becomes n-type, most importantly, the thermoelectric figure of merit is more than 0.5 at 300K, and the material price of the component is lower, and the specific performance is similar to that of Bi2Te3The price is reduced by 50%. Thus, Mg3Sb2The base thermoelectric material has attracted attention in the field of thermoelectricity. However, since the Mg element contained in the thermoelectric material is volatile at high temperature, so that the Mg element deviates from the stoichiometric ratio of the chemical components, Mg vacancy is introduced, and the thermoelectric performance is damaged at high temperature, the thermoelectric material can be generally applied only in the temperature environment lower than 500 ℃.
Disclosure of Invention
In view of the above, the present invention aims to provide Mg with high temperature stability3Sb2A base thermoelectric material and a method for producing the same. The Mg provided by the invention3Sb2The base thermoelectric material has high temperature stability, and the thermoelectric performance is very stable even at a high temperature of 500 ℃.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides Mg with high-temperature stability3Sb2Based thermoelectric materials, including Mg3~3.2Sb1.5Bi0.5- xTexThermoelectric bulk material and deposited on said Mg3~3.2Sb1.5Bi0.5-xTexA boron nitride coating on the surface of the thermoelectric block material; the Mg3~3.2Sb1.5Bi0.5-xTexIn the thermoelectric bulk material, x is more than 0 and less than or equal to 0.06.
Preferably, x is 0.01, 0.02, 0.03, 0.04, 0.05 or 0.06.
The invention provides Mg with high-temperature stability in the technical scheme3Sb2The preparation method of the base thermoelectric material comprises the following steps:
(1) mixing metal Mg, Sb, Bi and Te in a molar ratio of 3-3.2: 1.5:0.5-x: x in a protective atmosphere, and carrying out high-energy ball milling to obtain mixed powder;
(2) hot-pressing the mixed powder at the temperature of 750-800 ℃ to obtain Mg3~3.2Sb1.5Bi0.5-xTexA thermoelectric bulk material;
(3) under vacuum condition, the Mg is added3~3.2Sb1.5Bi0.5-xTexHeating the thermoelectric block material to 300-400 ℃, and introducing BCl3、NH3、H2And N2In the presence of Mg3~3.2Sb1.5Bi0.5-xTexPerforming chemical vapor deposition on the surface of the thermoelectric block material to form a boron nitride coating to obtain the Mg with high temperature stability3Sb2A base thermoelectric material.
Preferably, the purity of the metals Mg, Sb, Bi and Te in the step (1) is more than or equal to 99.99%.
Preferably, the time of high-energy ball milling in the step (1) is 10-24 h; the particle size of the mixed powder is less than 1 micron.
Preferably, the time for hot press molding in the step (2) is 2-5 min.
Preferably, after the hot-press molding in the step (2), the method further comprises the step of adding the obtained Mg3~3.2Sb1.5Bi0.5-xTexThermoelectric bulk materialAnd cleaning with high-purity nitrogen.
Preferably, the degree of vacuum of the vacuum condition in the step (3) is 1 × 10-2~8×10-2Pa。
Preferably, BCl in the mixed gas in the step (3)3The volume flow of (1) is 100-200 sccm, and the NH3、H2、N2And BCl3In a volume ratio of 3:1:6: 1; the gas pressure of the mixed gas is 4-5 kPa.
Preferably, the time of the chemical vapor deposition in the step (3) is 2-3 h.
The invention provides Mg with high-temperature stability3Sb2Based thermoelectric materials, including Mg3~3.2Sb1.5Bi0.5- xTexThermoelectric bulk material and deposited on said Mg3~3.2Sb1.5Bi0.5-xTexA boron nitride coating on the surface of the thermoelectric block material; the Mg3~3.2Sb1.5Bi0.5-xTexIn the thermoelectric bulk material, x is more than 0 and less than or equal to 0.06. The invention is at Mg3Sb2A boron nitride coating is introduced into the base thermoelectric material, the boron nitride coating has excellent oxidation resistance, the boron nitride coating starts to be oxidized at about 900 ℃ in the air, and the oxidation temperature can reach 2000 ℃ in vacuum; the ceramic has good dielectric property, is the best high-temperature insulating material in ceramics, and has a dielectric constant of 4; thermal shock resistance, coefficient of thermal expansion of 10-6(ii) a Good chemical stability and corrosion resistance, chemical inertness to almost all molten metals; it is due to these excellent properties that Mg3Sb2The thermoelectric property of the base thermoelectric material is very stable at high temperature under the protection of the boron nitride coating, the Mg loss at high temperature can be effectively inhibited, the thermoelectric property of the material is not attenuated, and the Mg is greatly improved3Sb2The working temperature of the thermoelectric material and thus the thermoelectric conversion efficiency at high temperature is ensured.
The results of the examples show that the invention provides Mg3Sb2The base thermoelectric material has high-temperature stability, the thermoelectric property is almost kept unchanged at the high temperature of 500 ℃, and the thermoelectric property is very stable.
The invention provides Mg with high-temperature stability in the technical scheme3Sb2The invention relates to a preparation method of a thermoelectric material, which adopts ball milling and high-temperature sintering methods to prepare Mg3~3.2Sb1.5Bi0.5-xTexThermoelectric bulk material, then deposited on Mg by chemical vapor deposition3~3.2Sb1.5Bi0.5-xTexThe boron nitride coating is deposited on the thermoelectric block material, the process is simple, the operation is easy, and the large-scale production is convenient.
Drawings
FIG. 1 is a graph of Mg deposited boron nitride coating and undeposited boron nitride coating of example 13.2Sb1.5Bi0.49Te0.01A graph of the conductivity change of the thermoelectric block material under 773K;
FIG. 2 is a graph of Mg deposited boron nitride coating versus undeposited boron nitride coating of example 23.2Sb1.5Bi0.47Te0.03A Seebeck coefficient change curve chart of the thermoelectric block material under 773K;
FIG. 3 is Mg of example 3 with and without a boron nitride coating deposited3.2Sb1.5Bi0.44Te0.06A power factor change curve chart of the thermoelectric block material under 773K;
FIG. 4 is Mg of example 3 with and without a boron nitride coating deposited3.2Sb1.5Bi0.44Te0.06Morphology of samples of thermoelectric bulk after the same time treatment at 773K, FIG. 4, (a) Mg without deposited boron nitride coating3.2Sb1.5Bi0.44Te0.06Topography of thermoelectric bulk material, (b) Mg for depositing boron nitride coating3.2Sb1.5Bi0.44Te0.06Topography of thermoelectric blocks.
Detailed Description
The invention provides Mg with high-temperature stability3Sb2Based thermoelectric materials, including Mg3~3.2Sb1.5Bi0.5- xTexThermoelectric bulk material and deposited on said Mg3~3.2Sb1.5Bi0.5-xTexA boron nitride coating on the surface of the thermoelectric block material; the Mg3~3.2Sb1.5Bi0.5-xTexIn the thermoelectric bulk material, x is more than 0 and less than or equal to 0.06.
In the present invention, x is preferably 0.01, 0.02, 0.03, 0.04, 0.05 or 0.06.
The invention is at Mg3Sb2Introducing boron nitride coating and Mg into base thermoelectric material3Sb2The thermoelectric property of the base thermoelectric material is very stable at high temperature under the protection of the boron nitride coating, the Mg loss at high temperature can be effectively inhibited, and the Mg content is greatly improved3Sb2The working temperature of the thermoelectric material and thus the thermoelectric conversion efficiency at high temperature is ensured. The Mg provided by the invention3Sb2The thermoelectric performance of the base thermoelectric material is very stable even at a high temperature of 500 ℃.
The invention provides Mg with high-temperature stability in the technical scheme3Sb2The preparation method of the base thermoelectric material comprises the following steps:
(1) mixing metal Mg, Sb, Bi and Te in a molar ratio of 3-3.2: 1.5:0.5-x: x in a protective atmosphere, and carrying out high-energy ball milling to obtain mixed powder;
(2) hot-pressing the mixed powder at the temperature of 750-800 ℃ to obtain Mg3~3.2Sb1.5Bi0.5-xTexA thermoelectric bulk material;
(3) under vacuum condition, the Mg is added3~3.2Sb1.5Bi0.5-xTexHeating the thermoelectric block material to 300-400 ℃, and introducing BCl3、NH3、H2And N2In the presence of Mg3~3.2Sb1.5Bi0.5-xTexPerforming chemical vapor deposition on the surface of the thermoelectric block material to form a boron nitride coating to obtain the Mg with high temperature stability3Sb2A base thermoelectric material.
In a protective atmosphere, mixing metal Mg, Sb, Bi and Te in a molar ratio of 3-3.2: 1.5:0.5-x: x, and performing high-energy ball milling to obtain mixed powder. The protective atmosphere is not particularly critical to the present invention and may be any protective atmosphere known to those skilled in the art, such as argon in particular. In the present invention, the purity of the metals Mg, Sb, Bi and Te is preferably 99.99% or more. In the present invention, the high energy ball milling is preferably performed in a high energy ball mill, and the operation method of performing the high energy ball milling under a protective atmosphere in the present invention has no particular requirement, and can be performed by an operation method well known to those skilled in the art. In the invention, the high-energy ball milling time is preferably 10-24 h, and more preferably 15-20 h; the particle size of the mixed powder is preferably less than 1 micron. The invention has no special requirements on the ball milling parameters of the high ball milling, and can obtain uniform mixed powder meeting the particle size requirement through high-energy ball milling.
After mixed powder is obtained, the mixed powder is subjected to hot press molding at the temperature of 750-800 ℃ to obtain Mg3~3.2Sb1.5Bi0.5-xTexThermoelectric bulk material. According to the invention, the mixed powder is preferably placed in a graphite mold, and then the graphite mold filled with the mixed powder is placed in hot-pressing equipment for hot-press molding. In the invention, the temperature of the hot-press molding is preferably 780-800 ℃; the time for hot press molding is preferably 2-5 min, and more preferably 2-3 min. In the hot press molding process, all metals in the mixed powder are melted and solidified, and a chemical reaction is carried out to form an alloy material. After hot press forming, the invention also preferably uses the obtained Mg3~3.2Sb1.5Bi0.5-xTexCleaning the thermoelectric block material by adopting high-purity nitrogen; the cleaning time is preferably 1-3 min.
Obtaining Mg3~3.2Sb1.5Bi0.5-xTexAfter thermoelectric bulk material, the invention adds the Mg under vacuum condition3~ 3.2Sb1.5Bi0.5-xTexHeating the thermoelectric block material to 300-400 ℃, and introducing BCl3、NH3、H2And N2In the presence of Mg3~3.2Sb1.5Bi0.5-xTexChemical vapor deposition is carried out on the surface of the thermoelectric block material to form the boron nitride coatingLayer of said Mg with high temperature stability3Sb2A base thermoelectric material. In the present invention, the degree of vacuum of the vacuum condition is preferably 1 × 10-2~8×10-2Pa; the invention is preferably evacuated to a vacuum of 1X 10 by means of mechanical and molecular pumps-2~8×10-2Pa. In the invention, the heating temperature is preferably 350-400 ℃; the heating is preferably carried out in a tube furnace. In the present invention, BCl in the mixed gas3The volume flow of the gas is preferably 100-200 sccm, more preferably 150-200 sccm; the NH3、H2、N2And BCl3Is preferably 3:1:6: 1; the gas pressure of the mixed gas is preferably 4 to 5kPa, and more preferably 4.5 kPa. In the present invention, BCl in the mixed gas3And NH3Reaction to boron nitride, H2And N2Plays a catalytic role. In the invention, the time of the chemical vapor deposition is preferably 2-3 h, and the chemical vapor deposition is carried out on Mg3~3.2Sb1.5Bi0.5- xTexAnd a uniform and compact boron nitride coating is formed on the surface of the thermoelectric block material.
The preparation method provided by the invention is simple in process, easy to operate and convenient for large-scale production.
The following examples are provided to illustrate Mg having high temperature stability according to the present invention3Sb2The base thermoelectric material and the method for producing the same are explained in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Mg with high-temperature stability3Sb2The preparation method of the base thermoelectric material comprises the following steps:
(1) weighing 99.99% metal Mg, Sb, Bi and Te according to the molar ratio of Mg to Sb to Te to be 3.2:1.5:0.49:0.01, adding 10g of the metal Mg, Sb, Bi and Te into a high-energy ball mill, and mixing and stirring for 10 hours under the protection of argon to obtain uniform mixed powder (the particle size is less than 1 micron);
(2) placing the mixed powder into graphite mold, rapidly placing into hot pressing equipment, and hot pressing at 800 deg.C for 2min to obtain the final productMg3.2Sb1.5Bi0.49Te0.01A thermoelectric bulk material;
(3) mg by using high-purity nitrogen3.2Sb1.5Bi0.49Te0.01Cleaning the thermoelectric block material for 1min, and then putting the thermoelectric block material into a tubular furnace; the mechanical pump and the molecular pump are started to vacuumize to 1X 10-2Pa;
(4) Mg is added under the vacuum condition formed in the step (3)3.2Sb1.5Bi0.49Te0.01Heating the thermoelectric block material to 300 ℃; BCl of 100sccm was introduced3Gas, other gases NH introduced3、H2And N2And BCl3Gas volume ratio of NH3:H2:N2:BCl3Adjusting the reaction pressure to 4.5kPa at 3:1:6:1, Mg heating to 300 deg.C3.2Sb1.5Bi0.49Te0.01Carrying out vapor deposition on the surface of the thermoelectric block material for 2h to form a compact boron nitride coating and obtain Mg with high-temperature stability3Sb2A base thermoelectric material.
Using a thermoelectric measurement system to obtain Mg with high temperature stability3Sb2Samples of the base thermoelectric material (with the boron nitride coating deposited) were tested for stability of conductivity at 773K (500 deg.C) and compared with Mg without the boron nitride coating deposited3.2Sb1.5Bi0.49Te0.01The electrical conductivities of the thermoelectric bulk materials were compared and the results of the tests are shown in the conductivity stability curve of fig. 1 (in fig. 1, σ)0Mg as initially undeposited boron nitride coating3.2Sb1.5Bi0.49Te0.01Electrical conductivity of the thermoelectric bulk material, σ being Mg without deposited boron nitride coating3.2Sb1.5Bi0.49Te0.01Thermoelectric bulk material or Mg deposited with boron nitride coating3.2Sb1.5Bi0.49Te0.01The electrical conductivity of the thermoelectric bulk material at 773K over time). As can be seen in FIG. 1, the Mg of the boron nitride coating was deposited3.2Sb1.5Bi0.49Te0.01The conductivity of the block hardly changed at 773K (true)The actual testing yielded Mg deposited boron nitride coatings3.2Sb1.5Bi0.49Te0.01The conductivity of the block is maintained at-1 × 10 at 773K4S/m); without depositing boron nitride coating Mg3.2Sb1.5Bi0.49Te0.01The conductivity of the bulk showed a significant decay with time at 773K.
Example 2
Mg with high-temperature stability3Sb2The preparation method of the base thermoelectric material comprises the following steps:
(1) weighing 99.99% metal Mg, Sb, Bi and Te according to the molar ratio of Mg to Sb to Te to be 3.2 to 1.5 to 0.47 to 0.03, adding 10g of the metal Mg, Sb, Bi and Te into a high-energy ball mill, and mixing and stirring for 17 hours under the protection of argon to obtain uniform mixed powder (the particle size is less than 1 micron);
(2) putting the mixed powder into a graphite mold, quickly putting the graphite mold into hot-pressing equipment, and hot-pressing at 800 ℃ for 2min to prepare Mg3.2Sb1.5Bi0.47Te0.03A thermoelectric bulk material;
(3) mg by using high-purity nitrogen3.2Sb1.5Bi0.47Te0.03Cleaning the thermoelectric block material for 2min, and then putting the thermoelectric block material into a tubular furnace; the mechanical pump and the molecular pump are started to vacuumize to 5 x 10-2Pa;
(4) Mg is added under the vacuum condition formed in the step (3)3.2Sb1.5Bi0.47Te0.03Heating the thermoelectric block material to 350 ℃; introducing 150sccm of BCl3Gas, other gases NH introduced3、H2And N2And BCl3Gas volume ratio of NH3:H2:N2:BCl3Adjusting the reaction pressure to 4.5kPa with 3:1:6:1, Mg heated to 350 ℃3.2Sb1.5Bi0.47Te0.03Carrying out vapor deposition on the surface of the thermoelectric block material for 2.5h to form a compact boron nitride coating and obtain Mg with high-temperature stability3Sb2A base thermoelectric material.
Using a pyroelectric measuring system for obtaining high temperature stabilityMg3Sb2Seebeck stability test was performed on samples of base thermoelectric materials (with boron nitride coating deposited) at 773K, and compared with Mg without boron nitride coating deposited3.2Sb1.5Bi0.47Te0.03The seebeck of the blocks were compared and the test results are shown in the seebeck stability curve of fig. 2 (in fig. 2, S)0Mg as initially undeposited boron nitride coating3.2Sb1.5Bi0.47Te0.03Seebeck, S of thermoelectric bulk material Mg without deposited boron nitride coating3.2Sb1.5Bi0.47Te0.03Thermoelectric bulk material or Mg deposited with boron nitride coating3.2Sb1.5Bi0.47Te0.03Seebeck of thermoelectric bulk material at 773K over time). As can be seen from FIG. 2, the Mg of the boron nitride coating was deposited3.2Sb1.5Bi0.47Te0.03The seebeck of the bulk showed little change at 773K (actual testing yielded Mg deposited boron nitride coatings3.2Sb1.5Bi0.47Te0.03The Seebeck of the thermoelectric bulk material is maintained at 773K to-270 μ V/K); without depositing boron nitride coating Mg3.2Sb1.5Bi0.47Te0.03Seebeck of the block showed significant fluctuations at 773K.
Example 3
Mg with high-temperature stability3Sb2The preparation method of the base thermoelectric material comprises the following steps:
(1) weighing 99.99% metal Mg, Sb, Bi and Te according to the molar ratio of Mg to Sb to Te to be 3.2:1.5:0.44:0.06, adding 10g of the metal Mg, Sb, Bi and Te into a high-energy ball mill, and mixing and stirring for 24 hours under the protection of argon to obtain uniform mixed powder (the particle size is less than 1 micron);
(2) putting the mixed powder into a graphite mold, quickly putting the graphite mold into hot-pressing equipment, and hot-pressing at 800 ℃ for 2min to prepare Mg3.2Sb1.5Bi0.44Te0.06A thermoelectric bulk material;
(3) mg by using high-purity nitrogen3.2Sb1.5Bi0.44Te0.06Cleaning thermoelectric block material for 3minThen putting the mixture into a tube furnace; the mechanical pump and the molecular pump are started to vacuumize to 8 x 10-2Pa;
(4) Mg is added under the vacuum condition formed in the step (3)3.2Sb1.5Bi0.44Te0.06Heating the thermoelectric block material to 400 ℃; BCl of 200sccm is introduced3Gas, other gases NH introduced3、H2And N2And BCl3Volume of gas you are NH3:H2:N2:BCl3Adjusting the reaction pressure to 4.5kPa at 3:1:6:1, Mg heating to 400 deg.C3.2Sb1.5Bi0.44Te0.06Carrying out vapor deposition on the surface of the thermoelectric block material for 3h to form a compact boron nitride coating and obtain Mg with high-temperature stability3Sb2A base thermoelectric material.
Using a thermoelectric measurement system to obtain Mg with high temperature stability3Sb2A sample of the base thermoelectric material (deposited with a boron nitride coating) was tested for power factor stability at 773K and compared with Mg without a deposited boron nitride coating3.2Sb1.5Bi0.44Te0.06The power factor of the blocks was compared and the test results are shown in the power factor stability curve of fig. 3 (in fig. 3, PF0Mg as initially undeposited boron nitride coating3.2Sb1.5Bi0.44Te0.06Power factor of thermoelectric bulk material, PF is Mg without deposited boron nitride coating3.2Sb1.5Bi0.44Te0.06Thermoelectric bulk material or Mg deposited with boron nitride coating3.2Sb1.5Bi0.44Te0.06Power factor of thermoelectric bulk material at 773K over time). As can be seen in FIG. 3, the Mg of the boron nitride coating was deposited3.2Sb1.5Bi0.44Te0.06The power factor of the bulk hardly changed at 773K (actual testing gave Mg deposited boron nitride coatings3.2Sb1.5Bi0.44Te0.06The power factor of the thermoelectric bulk material is maintained at 14 mu w/cmK under 773K2) (ii) a While depositing boron nitride coating Mg3.2Sb1.5Bi0.44Te0.06The power factor of the bulk shows a significant decay with time at 773K.
The obtained Mg having high temperature stability3Sb2Samples of base thermoelectric material (with boron nitride coating deposited) and Mg without boron nitride coating deposited3.2Sb1.5Bi0.44Te0.06The surface topography of the block after the same time treatment at 773K is shown in fig. 4 (b) and (a). As can be seen in FIG. 4, the Mg of the boron nitride coating was deposited3.2Sb1.5Bi0.44Te0.06No significant voids, i.e. no Mg loss, occurred in the bulk samples.
As can be seen from the above examples, the present invention provides Mg3Sb2The base thermoelectric material has high temperature stability, and the thermoelectric performance is still very stable even at a high temperature of 773K (500 ℃).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Mg with high-temperature stability3Sb2A thermoelectric material comprising Mg3~3.2Sb1.5Bi0.5-xTexThermoelectric bulk material and deposited on said Mg3~3.2Sb1.5Bi0.5-xTexA boron nitride coating on the surface of the thermoelectric block material; the Mg3~3.2Sb1.5Bi0.5-xTexIn the thermoelectric bulk material, x is more than 0 and less than or equal to 0.06.
2. Mg with high temperature stability according to claim 13Sb2A base thermoelectric material characterized in that x is 0.01, 0.02, 0.03, 0.04, 0.05 or 0.06.
3. Mg with high temperature stability according to claim 1 or 23Sb2The preparation method of the base thermoelectric material is characterized by comprising the following steps of:
(1) mixing metal Mg, Sb, Bi and Te in a molar ratio of 3-3.2: 1.5:0.5-x: x in a protective atmosphere, and carrying out high-energy ball milling to obtain mixed powder;
(2) hot-pressing the mixed powder at the temperature of 750-800 ℃ to obtain Mg3~3.2Sb1.5Bi0.5-xTexA thermoelectric bulk material;
(3) under vacuum condition, the Mg is added3~3.2Sb1.5Bi0.5-xTexHeating the thermoelectric block material to 300-400 ℃, and introducing BCl3、NH3、H2And N2In the presence of Mg3~3.2Sb1.5Bi0.5-xTexPerforming chemical vapor deposition on the surface of the thermoelectric block material to form a boron nitride coating to obtain the Mg with high temperature stability3Sb2A base thermoelectric material.
4. The production method according to claim 3, wherein the purity of the metals Mg, Sb, Bi and Te in the step (1) is 99.99% or more.
5. The preparation method according to claim 3, wherein the high-energy ball milling time in the step (1) is 10-24 h; the particle size of the mixed powder is less than 1 micron.
6. The preparation method according to claim 3, wherein the hot press molding in the step (2) is performed for 2-5 min.
7. The method as claimed in claim 3 or 6, wherein the step (2) further comprises subjecting the obtained Mg to hot press forming3~3.2Sb1.5Bi0.5-xTexThe thermoelectric block material is cleaned by high-purity nitrogen.
8. The method of claim 3The preparation method is characterized in that the vacuum degree of the vacuum condition in the step (3) is 1 multiplied by 10-2~8×10-2Pa。
9. The method according to claim 3, wherein BCl in the mixed gas of the step (3)3The volume flow of (1) is 100-200 sccm, and the NH3、H2、N2And BCl3In a volume ratio of 3:1:6: 1; the gas pressure of the mixed gas is 4-5 kPa.
10. The method according to claim 3, 8 or 9, wherein the time of the chemical vapor deposition in the step (3) is 2 to 3 hours.
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