CN109628794B - Low-temperature synthesis of Mg3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) material preparation method - Google Patents
Low-temperature synthesis of Mg3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) material preparation method Download PDFInfo
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- CN109628794B CN109628794B CN201910037961.2A CN201910037961A CN109628794B CN 109628794 B CN109628794 B CN 109628794B CN 201910037961 A CN201910037961 A CN 201910037961A CN 109628794 B CN109628794 B CN 109628794B
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Abstract
The invention relates to low-temperature synthesis of Mg3‑xZnxSb2(0≤x≤0.3) a method of producing a material, comprising the steps of: 1) according to Mg3‑ xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3), weighing the stoichiometric ratio of atoms, grinding and uniformly mixing the stoichiometric ratio of atoms, and pressing uniformly mixed powder into blocks; 2) putting the block obtained in the step 1) into a BN crucible, sealing the BN crucible in a glass tube in vacuum, then putting the BN crucible into a reaction furnace, preserving heat for 5 hours at the temperature of 410 ℃, and then raising the temperature to 500 ℃ and preserving heat for 15 hours; 3) grinding the obtained product into powder, treating in the step 2) and putting into the reaction furnace again, and preserving heat at 600 ℃ for 20h to obtain single-phase Mg3‑xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) thermoelectric material. The invention provides a method for doping Mg-containing matrix material with low melting point, non-powder state and higher ductility elements for the first time, and lays a good foundation for low-temperature synthesis and preparation of more related element-doped Mg-based thermoelectric materials in the future.
Description
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to low-temperature synthesis of Mg3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) material.
Background
With the development of human society, environmental destruction and depletion of fossil energy have become important issues of high human interest. The strategy of sustainable development is proposed as a prospective result in compliance with the development demand of the current human society. In order to alleviate the situation of environmental destruction and energy consumption, many scientists around the world are focusing their attention on finding and developing new renewable energy sources.
The thermoelectric conversion technology can realize direct conversion between electric energy and heat energy through the Seebeck effect and the Peltier effect of thermoelectric materials, and has important application prospects in the aspects of recycling industrial waste heat, automobile exhaust waste heat and the like as an environment-friendly energy conversion technology. Meanwhile, the device has the advantages of no transmission part, small volume, no noise, good reliability and the like. The conversion efficiency of thermoelectric materials is mainly determined by the thermoelectric figure of meritZTIt is decided that,ZT=α 2 Tσ/κwhereinαIs the Seebeck coefficient,σIs the electrical conductivity,κIs the heat conductivity,TIs the absolute temperature. The element doping can adjust the carrier concentration and the thermal conductivity of the thermoelectric material, so as to optimize the electrical property, the thermal property and the thermoelectric figure of merit.
Mg3Sb2The thermoelectric material of the system has higher Seebeck coefficient and excellent thermal property, thereby having higher Seebeck coefficientZTThe value is obtained. Meanwhile, the material system has the advantages of rich raw material, low price, no toxicity, no pollution and the like.
At present, Mg is prepared3Sb2The thermoelectric material mainly adopts a high-temperature melting method, a mechanical alloying method (ball milling) and discharge plasma sintering (SPS). However, the high saturation vapor pressure and the strong reactivity of Mg make the high-temperature melting method unable to precisely control its composition (volatilization and oxidation of Mg, etc.). The mechanical alloying method (ball milling) improves the volatilization of Mg well, but it easily introduces impurities, causes oxidation, and raw material simple substances easily adhere to the ball pot and the grinding balls. In addition, the powder state of the Zn simple substance is very serious (the raw material Zn powder provided by many companies and manufacturers is very serious and can not meet the experimental requirements), and only Zn particles or Zn blocks with higher purity can be adopted as the initial raw material. However, bulk Zn or particulate Zn has relatively good ductility and the synthesis of such materials by mechanical alloying (ball milling) is not feasible. Therefore, a method for doping a high-ductility element having a low melting point phase in a non-powder state, which can effectively prevent Mg from being volatilized and impurities from being introducedMg3Sb2Materials, appear to be very important.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing Mg at low temperature aiming at the defects of the prior art3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) and has the advantages of good composition control, high repeatability and the like.
The technical scheme adopted by the invention for solving the problems is as follows:
low-temperature synthesis of Mg3-xZnxSb2(0. ltoreq. x. ltoreq.0.3) a process for producing a material comprising the steps of:
1) according to Mg3(1+0.04)-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) weighing the stoichiometric ratio of atoms (Mg powder, Sb powder and Zn particles), then grinding and uniformly mixing the atoms, and cold-pressing the uniform mixture powder into blocks (Zn is small particles);
2) putting the block obtained in the step 1) into a BN crucible, sealing the BN crucible in a glass tube in vacuum, putting the glass tube into a reaction furnace, and performing a reaction process: keeping the temperature at 410 +/-5 ℃ for 5h, and then keeping the temperature at 500 ℃ for 15 h;
3) grinding the product obtained in the step 2) into powder, cold-pressing the powder into blocks, putting the blocks into a BN crucible, vacuum-sealing the blocks in a glass tube, putting the glass tube into a reaction furnace, and performing a reaction process: keeping the temperature at 600 ℃ for 20h to obtain single-phase Mg3-xZnxSb2A compound is provided.
In the scheme, the mass purities of the Mg powder and the Sb powder in the step 1) are both more than or equal to 99.9%, and the mass purities of the Zn particles are more than or equal to 99.9%.
In the scheme, the step 2) of putting the glass tube sealed with the cold-pressed block body into a reaction furnace, wherein the reaction process comprises the following steps: the heating rate is 5 ℃/min, the temperature is kept at 410 ℃ for 5h, and then the temperature is kept at 500 ℃ for 15 h.
In the scheme, the step 3) of putting the glass tube sealed with the cold-pressed block body into a reaction furnace, wherein the reaction process comprises the following steps: the heating rate is 5 ℃/min, and the temperature is kept at 600 ℃ for 20 h.
The preparation method can obtain single-phase Mg3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) material.
Based on the above, the contents may be modified, replaced or changed in various ways according to the common technical knowledge and means in the field without departing from the basic technical idea of the present invention, for example, the temperature and the incubation time of the solid phase reaction may be changed within a certain range.
The invention needs Zn elemental elements to carry out diffusion reaction with surrounding Mg and Sb atoms under the solid condition before the Zn elemental elements are not completely melted (otherwise, Zn is precipitated in a liquid form and adhered to the crucible wall to cause Zn deficiency), namely, the temperature of the first stage is set at 410 ℃ (the Zn melting point is 420 ℃), and the diffusion reaction with the surrounding atoms is carried out at the temperature which is not more than the Zn melting point and is as high as possible; the temperature of the second stage is 500 ℃, and the main phase is Zn-doped Mg3Sb2Compound formation, but the block uniformity is not good at this time, but elemental Zn with better ductility already forms compound; the temperature of 600 ℃ in the third stage is set by performing furnace reaction after the materials are ground and cold-pressed again, and the temperature is lower than the melting point of 650 ℃ of Mg and the melting point of 631 ℃ of Sb, and the main function is to make the product more uniform. After the third stage reaction is finished, single-phase Mg with uniform components is obtained3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) thermoelectric material.
With the existing Mg3Sb2Compared with the preparation method, the invention has the advantages that:
firstly, the invention adopts a low-temperature reaction synthesis method to prepare Mg for the first time3-xZnxSb2(x is more than or equal to 0 and less than or equal to 0.3) thermoelectric material;
secondly, the method has the advantages of effectively inhibiting Mg volatilization, avoiding introducing impurities, having good repeatability and the like;
thirdly, the invention provides a method for doping Mg-containing matrix material with low melting point, non-powder state and higher ductility elements.
Fourthly, the invention mainly adopts Mg powder and Sb powder, and has low price.
Drawings
FIG. 1 shows the reaction of step 3) and the calcination of step 4) in example 1XRD patterns of the samples after the sintering, and FIGS. 2 (a) and (b) are respectively microscopic morphology SEM images of different magnifications of the fracture surface of the block body after the sintering in the step 4); FIG. 3 is XRD patterns of samples after the step 3) reaction and the step 4) sintering in example 2, and FIGS. 4 (a) and (b) are SEM images of different magnifications of the fracture surface of the block after the step 4) sintering, respectively. As can be seen from FIGS. 1 and 2, the resulting product before and after sintering is single phase Mg3Sb2Compound, the sintered block sample is compact; as can be seen from FIGS. 3 and 4, the resulting product before and after sintering is single phase Mg2.8Zn0.2Sb2The compound, and the bulk sample after sintering was dense. FIG. 5 is an XRD pattern of the sample after the reaction of step 3) in examples 1 and 2. As can be seen from FIG. 5, the resulting sample was single-phase Mg3Sb2And Mg2.8Zn0.2Sb2A compound is provided.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
In the following examples, the mass purities of Mg powder and Sb powder are both not less than 99.9%, and the mass purities of Zn particles are not less than 99.9%.
Example 1
Low-temperature synthesis of Mg3-xZnxSb2(x = 0) method of material:
1) according to Mg3(1+0.04)Sb2(the excess of Mg is 4% to compensate the volatilization loss of Mg) the stoichiometric ratio of each atom is weighed, the total mass is 3g, then the atoms are ground and mixed evenly, and the evenly mixed powder is pressed into a cylindrical block with the diameter of 10mm (6 MPa for 10min of pressure maintaining);
2) putting the block obtained in the step 1) into a BN crucible, sealing the block in a glass tube in vacuum, putting the glass tube into a reaction furnace, heating to 410 ℃ at a speed of 5 ℃/min, preserving heat for 5h at the temperature of 410 ℃, then heating to 500 ℃ at the same speed, and preserving heat for 15 h;
3) grinding the obtained product into powder, processing the powder by the method in the step 2) (cold pressing the powder into blocks, putting the blocks into a BN crucible, and vacuum sealing the blocks in a glass tube), putting the blocks into a reaction furnace, heating the blocks to 600 ℃ at a speed of 5 ℃/min, and preserving heat for 20 hours;
4) grinding the block obtained in the step 3) into powder and sintering the powder into a block, and performing phase (XRD) and fracture surface microstructure (SEM) characterization on the sample before and after sintering.
FIG. 1 is sample Mg3Sb2XRD patterns before and after sintering show that after the sample powder is subjected to heat preservation at 410 ℃ for 5 hours, at 500 ℃ for 15 hours and at 600 ℃ for 20 hours, the obtained sample powder is single-phase Mg3Sb2The composition of the compound is unchanged after sintering treatment. FIGS. 2 (a) and (b) are SEM images of the fracture surface of the sintered block at different magnifications, respectively, and it can be seen that the obtained block is dense and has no pores, inclusions or other significant second phases.
Example 2
A method for synthesizing Mg3-xZnxSb2(x =0.2) material at low temperature comprises the following steps:
1) according to Mg3(1+0.04)-0.2Zn0.2Sb2(the excess of Mg is 4% to compensate the volatilization loss of Mg) the stoichiometric ratio of each atom is weighed, the total mass is 3g, then the atoms are ground and mixed evenly, and the evenly mixed powder is pressed into a cylindrical block with the diameter of 10mm (6 MPa for 10min of pressure maintaining);
2) putting the block obtained in the step 1) into a BN crucible, sealing the block in a glass tube in vacuum, putting the glass tube into a reaction furnace, heating to 410 ℃ at a speed of 5 ℃/min, preserving heat for 5h at the temperature of 410 ℃, then heating to 500 ℃ at the same speed, and preserving heat for 15 h;
3) grinding the obtained product into powder, processing the powder by the method (cold pressing the powder into blocks, putting the blocks into a BN crucible, and sealing the blocks in a glass tube in vacuum) in the step 2), putting the processed blocks into a reaction furnace, heating the blocks to 600 ℃ at the speed of 5 ℃/min, and preserving the heat for 20 hours;
4) grinding the block obtained in the step 3) into powder and sintering the powder into a block, and performing phase (XRD) and fracture surface microstructure (SEM) characterization on the sample before and after sintering.
FIG. 3 shows Mg before and after sintering2.8Zn0.2Sb2XRD pattern of (1), from whichTherefore, after the sample powder is subjected to heat preservation at 410 ℃ for 5 hours, at 500 ℃ for 15 hours and at 600 ℃ for 20 hours, the obtained sample powder is single-phase, and the composition of the sample is unchanged after sintering treatment. Fig. 4 (a) and (b) are SEM images of the fracture surface of the sintered block, respectively, and it can be seen that the resulting block is dense and free of pores, inclusions or other significant secondary phases.
Claims (5)
1. Low-temperature synthesis of Mg3-xZnxSb2(x =0.2) method of material, characterized in that it comprises the following steps:
1) according to Mg3(1+0.04)-xZnxSb2(x =0.2) weighing Mg powder, Sb powder and Zn particles in each atomic stoichiometric ratio, then grinding and mixing them, and cold-pressing the homogeneous mixture powder into a block;
2) putting the block obtained in the step 1) into a BN crucible, sealing the BN crucible in a glass tube in vacuum, putting the glass tube into a reaction furnace, and performing a reaction process: keeping the temperature at 410 +/-5 ℃ for 5h, and then keeping the temperature at 500 ℃ for 15 h;
3) grinding the product obtained in the step 2) into powder, cold-pressing the powder into blocks, putting the blocks into a BN crucible, vacuum-sealing the blocks in a glass tube, putting the glass tube into a reaction furnace, and performing a reaction process: keeping the temperature at 600 ℃ for 20h to obtain single-phase Mg3-xZnxSb2A compound is provided.
2. Low temperature synthesis of Mg according to claim 13-xZnxSb2(x =0.2), characterized in that the mass purities of Mg powder and Sb powder in the step 1) are both more than or equal to 99.9%, and the mass purity of Zn particles is more than or equal to 99.9%; the cold press molding process comprises the following steps: maintaining the pressure at 10MPa for 6 min.
3. Low temperature synthesis of Mg according to claim 13-xZnxSb2(x =0.2) method of material, characterized in that said step 2) puts the glass tube with vacuum-sealed cold-pressed block into the reaction furnace, the reaction process: the heating rate is 5 ℃/min, the temperature is kept at 410 ℃ for 5h, and then the temperature is kept at 500 ℃ for 15 h.
4. Low temperature synthesis of Mg according to claim 13-xZnxSb2(x =0.2) method of material, characterized in that said step 3) puts the glass tube with vacuum-sealed cold-pressed block into the reaction furnace, the reaction process: the heating rate is 5 ℃/min, and the temperature is kept at 600 ℃ for 20 h.
5. Single-phase Mg3-xZnxSb2(x =0.2) compound produced by the production method according to claim 1.
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| CN107176589A (en) * | 2017-03-31 | 2017-09-19 | 太原理工大学 | One kind prepares nanosizing Mg3Sb2The new method of thermoelectric material |
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| WO2009131323A2 (en) * | 2008-04-25 | 2009-10-29 | 주식회사 메가젠임플란트 | Hyaluronic acid bone-filling complex and fabrication method thereof |
| CN107176589A (en) * | 2017-03-31 | 2017-09-19 | 太原理工大学 | One kind prepares nanosizing Mg3Sb2The new method of thermoelectric material |
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