CN108821771B - Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance - Google Patents

Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance Download PDF

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CN108821771B
CN108821771B CN201810534585.3A CN201810534585A CN108821771B CN 108821771 B CN108821771 B CN 108821771B CN 201810534585 A CN201810534585 A CN 201810534585A CN 108821771 B CN108821771 B CN 108821771B
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刘呈燕
王秀霞
苗蕾
伍少海
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Guilin University of Electronic Technology
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Abstract

The invention discloses a preparation method of a silver-selenium ternary compound polycrystalline block material with high thermoelectric performance, which synthesizes Ag by using a hydrothermal reaction methodxMSey(M is selected from any one of Sn, Cr, Bi, Ga and Al) black nano powder, further carrying out heat treatment in an atmosphere tube furnace, doping halogen atoms at high temperature after vacuum tube sealing of a quartz tube, optimizing the thermoelectric property of the quartz tube, and preparing the Ag with high thermoelectric property by a hot-pressing sintering processxMSeyThe method for synthesizing the polycrystalline block material has the advantages of simple synthesis process, rich raw material resources, higher product purity and stable high-temperature performance in a sample, and is a thermoelectric power generation material with high thermoelectric performance.

Description

Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance
The technical field is as follows:
the invention relates to the technical field of thermoelectric material science, in particular to a preparation method of a silver-selenium ternary compound polycrystalline block material with high thermoelectric performance.
Background art:
the global demand for alternative clean energy sources in the world has greatly driven the rapid development of Thermoelectric (TE) materials research, which may beWaste heat collection is achieved by applying a thermal gradient to generate electricity directly. The silver-selenium ternary compound crystal material is a well-known excellent Thermoelectric (TE) material, the unique bonding characteristics of the compound lead the compound to have rich structure, and weaker chemical bonds lead the compound to have lower sound velocity, and the compound can be an insulator, a semiconductor, an electronic conductor or even a superconductor according to the difference of the structure and the composition, and has important application in various aspects such as light, electricity, magnetism and the like. The conversion efficiency of TE devices is influenced by the carnot efficiency and dimensionless performance of the material, ZT ═ S2σT/(ke+kl)]Where S is the Seebeck coefficient, σ is the electrical conductivity, keIs the electron thermal conductivity, klLattice thermal conductivity, T is absolute temperature. High ZT values require a combination of high seebeck coefficient, high electrical conductivity and low thermal conductivity. However, all these parameters are interdependent and influence each other, so that it is difficult to improve the synchronization. The current research trend is to search for thermoelectric materials with lower intrinsic thermal conductivity and then optimize the power factor on the basis of the thermoelectric materials, so as to achieve the purpose of obtaining higher thermoelectric performance. The silver-selenium ternary compound has the thermal conductivity lower than the glass limit and the heat capacity C at high temperatureVLess than 3NkBWherein N is the number of Avogaridol, kBIs a boltzmann constant which embodies good seebeck coefficient (n-type) and electrical conductivity, and is a promising class of intermediate-temperature thermoelectric materials. At present, typical methods for preparing ternary silver-selenium compounds at home and abroad mainly comprise the following three fluxing agent methods, solid-phase synthesis methods and solvothermal methods.
The invention content is as follows:
the invention aims to provide a preparation method of a silver-selenium ternary compound polycrystalline block material with high thermoelectric property, which adopts a synthesis method of crystal growth by hydrothermal reaction, and the reaction raw materials react progressively to synthesize a target product, the size, the shape, the composition and the phase structure of the material can be effectively regulated and controlled by changing the reaction temperature and the reaction time, then the precursor is further thermally treated, foreign atoms are introduced to replace Se, defects are regulated and controlled, the carrier concentration is improved, thereby improving the conductivity, further optimizing the thermoelectric figure of merit ZT, enhancing the mechanical property thereof through a hot pressing sintering process, thereby preparing the silver-selenium ternary compound polycrystalline block material with high density, good mechanical strength and low thermal conductivity, and the synthesis temperature is low, and a surfactant and an organic auxiliary agent are not adopted in the preparation process, so that the energy is saved, the environment is protected, and the cost is low.
The invention is realized by the following technical scheme:
a chemical formula of Ag with high thermoelectric performancexMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that M is selected from any one of Sn, Cr, Bi, Ga and Al, and x and y are positive integers; when M is Sn, x is 8, y is 6; when M is Cr and Bi, x is 1, y is 2; when X is Ga and Al, X is 9 and y is 6; the method comprises the following steps:
(1) per AgxMSeyThe molar ratio of each element in the chemical formula is that Ag precursor AgNO3Precursor SeO of Se2Adding a solid raw material consisting of precursor of M and chloride salt containing M into a polytetrafluoroethylene lining of a reaction vessel, adding deionized water, wherein the proportion of the deionized water to the solid raw material is 2.2505-11.2525g per 50mL of the deionized water, stirring, and adding a reducing agent N2H4·H2O, the proportion of the solid raw material is 1-8mL per 2.2505g of the reducing agent N2H4·H2Continuously stirring and fully mixing, sleeving a polytetrafluoroethylene inner lining on a stainless steel high-pressure reaction kettle, sealing, and then heating to 120-200 ℃ for reaction for 6-24 hours; cooling to room temperature after the reaction is finished, washing the obtained precipitate nano powder with distilled water, performing suction filtration, soaking the precipitate nano powder in absolute ethyl alcohol for not less than 1 hour, and drying the precipitate nano powder in a vacuum drying oven at the temperature of between 60 and 80 ℃ for 12 to 24 hours to obtain silver-selenium ternary compound nano powder;
(2) cold-pressing the silver-selenium ternary compound nano powder obtained in the step (1) into a block, and then performing heat treatment in an atmosphere tube furnace at the temperature of 400-800 ℃ for 2-16 hours, wherein the pressure of cold pressing is not lower than 318 kilo-gram force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1-8%, the block obtained by heat treatment is ground into powder, then mixed with a solid raw material selected by doping halogen atoms, and finally packaged in vacuum stone by a quartz tube packaging technologyHeating to 500-700 deg.C in quartz tube for doping halogen atoms, wherein the dosage of the solid raw material is nHalogen atom/(nHalogen atom+nSe) The halogen atom is selected from Cl or Br, then sintering is carried out in a hot pressing furnace at the temperature of 300-600 ℃ for 30-360 minutes under the pressure of 30-50MPa, and finally the silver-selenium ternary compound Ag with high thermoelectric performance is obtainedxMSeyA polycrystalline bulk material.
When M is selected from Sn, the precursor of Sn in the step (1) contains stannic chloride selected from SnCl2·2H2O、SnCl2、SnCl4·5H2Any one of O, the raw material selected in the step (2) for doping the halogen atoms Cl or Br is SnCl2Or SnBr2。
When M is selected from Cr, the precursor of M in the step (1) is CrCl3·6H2O, the raw material selected for doping the halogen atoms Cl in the step (2) is CrCl3。
When M is selected from Bi, the precursor of M in the step (1) is BiCl3(ii) a The raw materials selected in the step (2) for doping the halogen atoms Cl or Br are respectively BiCl3Or BiBr3。
When M is selected from Ga, the precursor of M in the step (1) is GaCl3(ii) a The raw materials selected in the step (2) for doping the halogen atoms Cl or Br are respectively GaCl3Or GaBr3。
When M is selected from Al, the precursor of M in the step (1) is AlCl3(ii) a The raw materials selected in the step (2) for doping the halogen atoms Cl or Br are respectively AlCl3Or AlBr3。
Preferably, the heat treatment in step (2) is raised to 600-800 ℃ at a temperature rise rate of not less than 5 ℃/min.
The gas flow rate through the sample in step (2) may be between 0.01L/min and 1L/min.
Compared with the prior art, the invention has the following advantages:
1) the invention creatively adopts a synthesis method of crystal growth by hydrothermal reaction, in a closed system, under a certain temperature and the autogenous pressure of a solvent, reaction raw materials react progressively to synthesize a target product, the size, the shape, the composition and the phase structure of the target product are effectively regulated and controlled deeply by changing the reaction temperature and the reaction time, then the precursor is further thermally treated, foreign atoms are introduced to replace Se, the defects are regulated and controlled, the carrier concentration is improved, the electric conductivity is improved, the thermoelectric figure of merit is further optimized, and the mechanical property of ZT is enhanced by a hot-pressing sintering process, so that the silver-selenium ternary compound polycrystalline block material with high density, good mechanical strength, low thermal conductivity and high thermoelectric property of high power factors is prepared.
2) The invention has simple synthesis process, abundant raw material resources and low synthesis temperature, does not adopt a surfactant and an organic auxiliary agent in the preparation process, has clean surfaces of the silver-selenium ternary compound polycrystalline nano-material cleaned by deionized water, can exert the corresponding functions to the maximum extent, is energy-saving and environment-friendly, has low cost, stable high-temperature performance in the product, and has high power factor and low thermal conductivity.
Description of the drawings:
FIG. 1 shows a hydrothermal reaction method of Ag according to example 1 of the present invention8SnSe6X-ray diffraction picture of nano powder;
FIG. 2 shows Ag synthesized by hydrothermal reaction in example 1 of the present invention8SnSe6The change curve of the resistivity, the Seebeck coefficient and the power factor of the polycrystalline nano-bulk along with the temperature is along with the change curve of the temperature.
Detailed Description
The following is a further description of the invention and is not intended to be limiting.
Example 1
Per Ag8SnSe60.4513g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、2.7179gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 4.5007g), and 50mL of deionized water was added to the reaction vessel. Measuring 6mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, vacuum drying at 80 deg.C for 12 hr to obtain Ag8SnSe6XRD of the black nanopowder is shown in FIG. 1. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 16h at the heat treatment temperature of 400 ℃, wherein the cold-pressing pressure is 318 kilogram-force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the block obtained by heat treatment is ground into powder and then is subjected to heat treatment with SnCl2A solid raw material is as followsCl/(nCl+nSe) Mixing the components in the ratio of 3%, packaging in a vacuum quartz tube by a quartz tube packaging technology, heating to 500 ℃ for doping with halogen atoms Cl, and sintering in a hot pressing furnace at 600 ℃ for 30 minutes under the pressure of 30 MPa. Namely, the Ag with high density (relative density of 98%) and high thermoelectric property is obtained8SnSe6The resistivity, seebeck coefficient and power factor of the polycrystalline bulk material are shown in fig. 2.
Example 2
Per Ag8SnSe60.3792g SnCl is weighed according to the molar ratio of each element in the chemical formula2、2.7179gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (SnCl)2、AgNO3And SeO2The total amount of powder was 4.4286g), and 50mL of deionized water was added to the reaction vessel. Measuring 6mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. Sealing obtained in the above stepAnd putting the reaction container into heating equipment, heating to 120 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, vacuum drying at 80 deg.C for 12 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 2h at the heat treatment temperature of 400 ℃, wherein the cold-pressing pressure is 318 kilogram-force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 8%, and the block obtained by heat treatment is ground into powder and then is mixed with SnBr2A solid raw material is as followsBr/(nBr+nSe) Mixing the components according to the ratio of 1%, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the vacuum quartz tube to 700 ℃, doping halogen atoms Br, and sintering the mixture in a hot pressing furnace at 500 ℃ for 30 minutes, wherein the pressure is 40 MPa. Namely, Ag having thermoelectric properties equivalent to those of example one was obtained8SnSe6A polycrystalline bulk material.
Example 3
Per Ag8SnSe60.7012g SnCl is weighed according to the molar ratio of each element in the chemical formula4·5H2O、2.7179gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (SnCl)4·5H2O、AgNO3And SeO2The total amount of powder was 4.7506g), and 50mL of deionized water was added to the reaction vessel. Measuring 6mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. By using anhydrousSoaking in ethanol for 4 hr, vacuum drying at 60 deg.C for 24 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 2h, wherein the heat treatment temperature is 800 ℃, the cold-pressing pressure is 350 kilo-gram force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 8%, and the block obtained by heat treatment is ground into powder and then is subjected to SnCl treatment2A solid raw material is as followsCl/(nCl+nSe) Mixing the components in the ratio of 4%, packaging in a vacuum quartz tube by a quartz tube packaging technology, heating to 600 ℃ for doping with halogen atoms Cl, and sintering in a hot pressing furnace at 600 ℃ for 30 minutes, wherein the pressure is 30 MPa. Namely, Ag having thermoelectric properties equivalent to those of example one was obtained8SnSe6A polycrystalline bulk material.
Example 4
Per Ag8SnSe60.9026g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、5.4358gAgNO3And 2.6630g SeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 9.0014g), and 50mL of deionized water was added to the reaction vessel. Measuring 4mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 200 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 2 hr, vacuum drying at 80 deg.C for 12 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6The nano powder is cold-pressed into a block and then is heat-treated in an atmosphere tube furnace for 2 hours, the heat treatment temperature is 800 ℃, the pressure of cold pressing is 318 kilogram force/square centimeter,the atmosphere used by the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 8%, the block obtained by heat treatment is ground into powder and then mixed with SnCl2A solid raw material is as followsCl/(nCl+nSe) Mixing the components according to the ratio of 1 percent, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 500 ℃ for doping halogen atoms Cl, and sintering the mixture in a hot pressing furnace at 300 ℃ for 360 minutes, wherein the pressure is 40MPa, so that the Ag with equivalent thermoelectric property to that of the Ag in the example I is obtained8SnSe6A polycrystalline bulk material.
Example 5
According to AgBiSe23.1535gBiCl is weighed according to the corresponding molar ratio of each element in the chemical formula3、3.3974gAgNO3And 2.2192g SeO2Adding into polytetrafluoroethylene lining (BiCl)3、AgNO3And SeO2The total amount of powder was 8.7701g), and 50mL of deionized water was added to the reaction vessel. Measuring 6mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 200 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 4 hr, and vacuum drying at 80 deg.C for 12 hr to obtain AgBiSe2Black nano-powder. AgBiSe2Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 16h at the heat treatment temperature of 400 ℃, wherein the cold-pressing pressure is 320 kilograms force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 8%, and the block obtained by heat treatment is ground into powder and then mixed with BiCl3A solid raw material is as followsCl/(nCl+nSe) Mixing the above components at a ratio of 3%, packaging in a vacuum quartz tube by quartz tube packaging technology, and heating to 500 deg.C for doping with halogen atom ClSintering the mixture in a hot pressing furnace at 300 ℃ for 360 minutes, wherein the pressure is 30MPa, and obtaining AgBiSe with thermoelectric performance equivalent to that of the example2A polycrystalline bulk material.
Example 6
According to AgBiSe23.1535gBiCl is weighed according to the corresponding molar ratio of each element in the chemical formula3、3.3974gAgNO3And 2.2192g SeO2Adding into polytetrafluoroethylene lining (BiCl)3、AgNO3And SeO2The total amount of powder was 8.7701g), and 50mL of deionized water was added to the reaction vessel. Measuring 6mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 200 ℃, reacting for 24 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 4 hr, and vacuum drying at 80 deg.C for 12 hr to obtain AgBiSe2Black nano-powder. AgBiSe2Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 16h at 700 ℃, wherein the cold-pressing pressure is 320 kgf/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 8%, and the block obtained by heat treatment is ground into powder and then mixed with BiBr3A solid raw material is as followsBr/(nBr+nSe) Mixing the components with the ratio of 4 percent, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 600 ℃ for doping halogen atoms Br, and sintering the mixture in a hot pressing furnace at 300 ℃ for 360 minutes, wherein the pressure is 30MPa, so that AgBiSe with thermoelectric performance equivalent to that of the embodiment can be obtained2A polycrystalline bulk material.
Example 7
Per Ag9GaSe60.3521gGaCl is weighed according to the corresponding molar ratio of each element in the chemical formula3、3.0577gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (GaCl)3、AgNO3And SeO2The total amount of powder was 4.7413g), and 50mL of deionized water was added to the reaction vessel. Measuring 16ml LN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 18h under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, vacuum drying at 80 deg.C for 2 hr to obtain Ag9GaSe6Black nano-powder. Ag9GaSe6Cold-pressing the nano powder into blocks, and then carrying out heat treatment in an atmosphere tube furnace for 12h at the heat treatment temperature of 400 ℃, wherein the cold-pressing pressure is 318 kilogram force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the blocks obtained by heat treatment are ground into powder and then are mixed with GaCl3A solid raw material is as followsCl/(nCl+nSe) Mixing the components in a ratio of 4%, packaging in a vacuum quartz tube by a quartz tube packaging technology, heating to 700 ℃ for doping with halogen atoms Cl, and sintering in a hot pressing furnace at 600 ℃ for 30 minutes under a pressure of 50MPa to obtain Ag with thermoelectric properties equivalent to those of the first embodiment9GaSe6A polycrystalline bulk material.
Example 8
Per Ag9GaSe60.3521gGaCl is weighed according to the corresponding molar ratio of each element in the chemical formula3、3.0577gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (GaCl)3、AgNO3And SeO2The total amount of powder was 4.7413g), and 50mL of deionized water was added to the reaction vessel. Measuring 16ml LN2H4·H2Slowly adding O into the polytetrafluoroethylene lining, and stirringStirring for ten minutes to fully mix the solution and the reactants, sleeving a stainless steel high-pressure reaction kettle on the polytetrafluoroethylene inner lining, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 18h under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, vacuum drying at 80 deg.C for 2 hr to obtain Ag9GaSe6Black nano-powder. Ag9GaSe6Cold-pressing the nano powder into blocks, and then performing heat treatment in an atmosphere tube furnace for 12h at the heat treatment temperature of 400 ℃, wherein the cold-pressing pressure is 318 kilogram-force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the blocks obtained by heat treatment are ground into powder and then are mixed with GaBr3A solid raw material is as followsBr/(nBr+nSe) Mixing the components according to the ratio of 1%, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 700 ℃ for doping halogen atoms Br, and sintering the mixture in a hot pressing furnace at 400 ℃ for 30 minutes, wherein the pressure is 50MPa, so that Ag with thermoelectric property equivalent to that of the Ag in the example I is obtained9GaSe6A polycrystalline bulk material.
Example 9
Per Ag9AlSe6Weighing 0.2667g AlCl according to the molar ratio of each element in the chemical formula3、5.0961gAgNO3And 2.2192g SeO2Adding into polytetrafluoroethylene lining (AlCl)3、AgNO3And SeO2The total amount of powder was 7.582g), and 50mL of deionized water was added to the reaction vessel. Measuring 10ml of LN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. Putting the sealed reaction container obtained in the step into heating equipment, heating to 120 ℃, reacting for 24 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into the heating equipmentAnd standing in a beaker. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 2 hr, vacuum drying at 80 deg.C for 12 hr to obtain Ag9AlSe6Black nano-powder. Ag9AlSe6Cold-pressing the nano powder into blocks, and then performing heat treatment in an atmosphere tube furnace for 12h at the heat treatment temperature of 600 ℃, wherein the cold-pressing pressure is 400 kgf/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the blocks obtained by heat treatment are ground into powder and then are mixed with AlCl3A solid raw material is as followsCl/(nCl+nSe) Mixing the components according to the ratio of 1%, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 500 ℃ for doping with halogen atoms Cl, and sintering the mixture in a hot pressing furnace at 500 ℃ for 60 minutes under the pressure of 30MPa to obtain Ag with thermoelectric properties equivalent to those of the Ag in the example9AlSe6A polycrystalline bulk material.
Example 10
Per Ag9AlSe6Weighing 0.2667g AlCl according to the molar ratio of each element in the chemical formula3、5.0961gAgNO3And 2.2192g SeO2Adding into polytetrafluoroethylene lining (AlCl)3、AgNO3And SeO2The total amount of powder was 7.582g), and 50mL of deionized water was added to the reaction vessel. Measuring 10ml of LN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 120 ℃, reacting for 24 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 2 hr, vacuum drying at 80 deg.C for 12 hr to obtain Ag9AlSe6Black nano-powder. Ag9AlSe6Cold pressing nanometer powder into blocksHeat treating the block in an atmosphere tube furnace for 12h at 600 deg.C under the pressure of 400 kgf/cm, in which the mixture of argon and hydrogen is used as the atmosphere of the atmosphere tube furnace, the volume ratio of hydrogen is 8%, grinding the block obtained by heat treatment into powder, and mixing with AlBr3A solid raw material is as followsBr/(nBr+nSe) Mixing the components in a ratio of 4%, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 500 ℃ for doping halogen atoms Br, and sintering the mixture in a hot pressing furnace at 600 ℃ for 60 minutes, wherein the pressure is 50MPa, so that the Ag with thermoelectric property equivalent to that of the Ag in the example9AlSe6A polycrystalline bulk material.
Example 11
According to AgCrSe23.167g of CrCl is weighed according to the molar ratio of each element in the chemical formula3、3.3974gAgNO3And 4.4384g SeO2Adding into polytetrafluoroethylene lining (CrCl)3、AgNO3And SeO2The total amount of powder was 11.0028g), and 50mL of deionized water was added to the reaction vessel. Measuring 20ml LN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, and vacuum drying at 80 deg.C for 12 hr to obtain AgCrSe2Black nano-powder. AgCrSe2The nano powder is cold-pressed into a block and then is thermally treated in an atmosphere tube furnace for 12 hours at the thermal treatment temperature of 400 ℃, wherein the cold pressing pressure is 318 kilogram force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1-8 percent, the block obtained by thermal treatment is ground into powder and then is mixed with CrCl3A solid raw material is as followsCl/(nCl+nSe) Mixing the components according to the ratio of 1 percent, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 600 ℃ for doping halogen atoms Cl, sintering the mixture in a hot pressing furnace at 600 ℃ for 30 minutes, wherein the pressure is 30MPa, and obtaining AgCrSe with the thermoelectric property equivalent to that of the example I2A polycrystalline bulk material.
Example 12
Per Ag8SnSe60.4513g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、2.7179gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 4.5007g), and 50mL of deionized water was added to the reaction vessel. Measuring 10ml of LN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, vacuum drying at 80 deg.C for 12 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 16h at the heat treatment temperature of 600 ℃, wherein the cold-pressing pressure is 318 kilogram-force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the block obtained by heat treatment is ground into powder and then is subjected to heat treatment with SnCl2A solid raw material is as followsCl/(nCl+nSe) Mixing the components according to the ratio of 1 percent, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 500 ℃ for doping halogen atoms Cl, and sintering the mixture in a hot pressing furnace at 600 ℃ for 30 minutes, wherein the pressure is 30MPa, so that the Ag with thermoelectric property equivalent to that of the Ag in the embodiment I is obtained8SnSe6A polycrystalline bulk material.
Example 13
Per Ag8SnSe60.4513g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、2.7179gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 4.5007g), and 50mL of deionized water was added to the reaction vessel. Measuring 16ml LN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 120 ℃, reacting for 16h under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 2 hr, vacuum drying at 60 deg.C for 12 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 16h at the heat treatment temperature of 600 ℃, wherein the cold-pressing pressure is 318 kilogram-force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the block obtained by heat treatment is ground into powder and then is subjected to heat treatment with SnCl2A solid raw material is as followsCl/(nCl+nSe) Mixing the components in the ratio of 4%, packaging in a vacuum quartz tube by a quartz tube packaging technology, heating to 500 ℃ for doping with halogen atoms Cl, and sintering in a hot pressing furnace at 500 ℃ for 30 minutes under the pressure of 30MPa to obtain Ag with thermoelectric properties equivalent to those of the first embodiment8SnSe6A polycrystalline bulk material.
Example 14
Per Ag8SnSe60.4513g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、2.7179gAgNO3And 1.3315g SeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 4.5007g), and 50mL of deionized water was added to the reaction vessel. Measuring 8mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 120 ℃, reacting for 24 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 5 hr, vacuum drying at 80 deg.C for 14 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 16h at the heat treatment temperature of 800 ℃, wherein the cold-pressing pressure is 318 kilogram-force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 8%, and the block obtained by heat treatment is ground into powder and then is subjected to heat treatment with SnBr2A solid raw material is as followsBr/(nBr+nSe) Mixing the components according to the ratio of 1 percent, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 700 ℃ for doping halogen atoms Br, and sintering the mixture in a hot pressing furnace at 400 ℃ for 90 minutes, wherein the pressure is 30MPa, so that the Ag with the thermoelectric property equivalent to that of the Ag in the embodiment I is obtained8SnSe6A polycrystalline bulk material.
Example 15
Per Ag8SnSe61.1285g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、6.795gAgNO3And 3.329g SeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 11.2525g), and 50mL of deionized water was added to the reaction vessel. Measuring 40mLN2H4·H2Slowly adding O into the polytetrafluoroethylene liningStirring for ten minutes to fully mix the solution and the reactants, sleeving a stainless steel high-pressure reaction kettle on the polytetrafluoroethylene inner lining, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 24 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. The hydrothermal reaction precipitate obtained in the above step was then washed three times with 500mL of deionized water each time, and then filtered with suction. Soaking in anhydrous ethanol for 1 hr, vacuum drying at 80 deg.C for 24 hr to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold pressing the nanometer powder into block, heat treating in an atmosphere tube furnace at 800 deg.c for 2 hr to obtain block, grinding the block into powder, and mixing with SnCl2A solid raw material is as followsCl/(nCl+nSe) Mixing the components in the ratio of 4%, packaging in a vacuum quartz tube by a quartz tube packaging technology, heating to 600 ℃ for doping with halogen atoms Cl, and sintering in a hot pressing furnace at 600 ℃ for 60 minutes under the pressure of 30MPa to obtain Ag with thermoelectric properties equivalent to those of the first embodiment8SnSe6A polycrystalline bulk material.
Example 16
Per Ag8SnSe60.2257g SnCl is weighed according to the molar ratio of each element in the chemical formula2·2H2O、1.3590gAgNO3And 0.6658gSeO2Adding into polytetrafluoroethylene lining (SnCl)2·2H2O、AgNO3And SeO2The total amount of powder was 2.2505g), and 50mL of deionized water was added to the reaction vessel. Measuring 1mLN2H4·H2And slowly adding the O into the polytetrafluoroethylene lining, stirring for ten minutes to fully mix the solution and the reactants, sleeving the polytetrafluoroethylene lining on a stainless steel high-pressure reaction kettle, and sealing. And (3) putting the sealed reaction container obtained in the step into heating equipment, heating to 150 ℃, reacting for 6 hours under the constant temperature condition, naturally cooling to room temperature, pouring the obtained nano powder into a beaker, and standing. Then washing the hydrothermal reaction precipitate obtained in the previous step with 500mL of deionized water each time, and repeating the washing three timesAnd then suction filtration is carried out. Soaking the Ag powder in absolute ethyl alcohol for 2 to 4 hours, and then drying the soaked Ag powder in vacuum at the temperature of 80 ℃ for 12 hours to obtain Ag8SnSe6Black nano-powder. Ag8SnSe6Cold-pressing the nano powder into a block, and then carrying out heat treatment in an atmosphere tube furnace for 2h at the heat treatment temperature of 400 ℃, wherein the cold-pressing pressure is not lower than 318 kgf/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1%, and the block obtained by heat treatment is ground into powder and then is subjected to SnBr treatment2A solid raw material is as followsBr/(nBr+nSe) Mixing the components in a ratio of 3%, packaging the mixture in a vacuum quartz tube by a quartz tube packaging technology, heating the mixture to 500 ℃ for doping halogen atoms Br, and sintering the mixture in a hot pressing furnace at 600 ℃ for 30 minutes, wherein the pressure is 30MPa, so that the Ag with thermoelectric property equivalent to that of the Ag in the embodiment I is obtained8SnSe6A polycrystalline bulk material.

Claims (8)

1. A chemical formula of Ag with high thermoelectric performancexMSeyThe method for preparing the silver-selenium ternary compound polycrystalline bulk material is characterized in that M is selected from any one of Sn, Cr, Bi, Ga and Al, x and y are positive integers, when M is Sn, x is 8, and y is 6; when M is Cr and Bi, x is 1, y is 2; when M is Ga and Al, x is 9 and y is 6; the method comprises the following steps:
(1) per AgxMSeyThe molar ratio of each element in the chemical formula is that Ag precursor AgNO3Precursor SeO of Se2Adding a solid raw material consisting of precursor of M and chloride salt containing M into a polytetrafluoroethylene lining of a reaction vessel, adding deionized water, wherein the proportion of the deionized water to the solid raw material is 2.2505-11.2525g per 50mL of the deionized water, stirring, and adding a reducing agent N2H4·H2O, the proportion of the solid raw material is 1-8mL per 2.2505g of the reducing agent N2H4·H2Continuously stirring and fully mixing, sleeving a polytetrafluoroethylene inner lining on a stainless steel high-pressure reaction kettle, sealing, and then heating to 120-200 ℃ for reaction for 6-24 hours; cooling to room temperature after the reaction is finished, washing the obtained precipitate nano powder with distilled water, performing suction filtration, and then soaking the precipitate nano powder in absolute ethyl alcohol to be not less thanDrying for 1 hour in a vacuum drying oven at 60-80 ℃ for 12-24 hours to obtain silver-selenium ternary compound nano powder;
(2) cold-pressing the silver-selenium ternary compound nano powder obtained in the step (1) into a block, and then carrying out heat treatment for 2-16 hours in an atmosphere tube furnace at the temperature of 400-800 ℃, wherein the pressure intensity of cold pressing is not lower than 318 kilo-gram force/square centimeter, the atmosphere used in the atmosphere tube furnace is a mixed gas of argon and hydrogen, the volume ratio of the hydrogen is 1-8%, the block obtained by heat treatment is ground into powder and then mixed with solid raw materials selected by halogen atom doping, then the powder is packaged in a vacuum quartz tube by a quartz tube packaging technology, and then the vacuum quartz tube is heated to the temperature of 500-700 ℃ for halogen atom doping, and the dosage of the solid raw materials selected by halogen atom doping is nHalogen atom/(nHalogen atom+nSe) The halogen atom is selected from Cl or Br, then sintering is carried out in a hot pressing furnace at the temperature of 300 to 600 ℃ for 30 to 360 minutes, wherein the pressure is 30 to 50MPa, and finally the silver-selenium ternary compound Ag with high thermoelectric performance is obtainedxMSeyA polycrystalline bulk material.
2. The high thermoelectric performance chemical formula of claim 1 being AgxMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that when M is selected from Sn, the chloride salt containing tin of the Sn precursor in the step (1) is selected from SnCl2·2H2O、SnCl2、SnCl4·5H2Any one of O, the raw material selected in the step (2) for doping the halogen atoms Cl or Br is SnCl2Or SnBr2。
3. A thermoelectric property of chemical formula Ag according to claim 1 or 2xMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that when M is selected from Cr, the precursor of M in the step (1) is CrCl3·6H2O; the raw material used for doping the halogen atoms Cl in the step (2) is CrCl3。
4. According to claim 1 or2 the chemical formula of the high thermoelectric property is AgxMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that when M is selected from Bi, the precursor of M in the step (1) is BiCl3(ii) a The raw materials selected in the step (2) for doping the halogen atoms Cl or Br are respectively BiCl3Or BiBr3。
5. A thermoelectric property of chemical formula Ag according to claim 1 or 2xMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that when M is selected from Ga, the precursor of M in the step (1) is GaCl3The raw materials selected in the step (2) for doping the halogen atoms Cl or Br are respectively GaCl3Or GaBr3。
6. A thermoelectric property of chemical formula Ag according to claim 1 or 2xMSeyThe preparation method of the silver-selenium ternary compound polycrystalline bulk material is characterized in that when M is selected from Al, the precursor of M in the step (1) is AlCl3The raw materials selected in the step (2) for doping the halogen atoms Cl or Br are respectively AlCl3Or AlBr3。
7. A thermoelectric property of chemical formula Ag according to claim 1 or 2xMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that the temperature rise rate of the heat treatment in the step (2) is not lower than 5 ℃/min and is increased to 600-800 ℃.
8. A thermoelectric property of chemical formula Ag according to claim 1 or 2xMSeyThe preparation method of the silver-selenium ternary compound polycrystalline block material is characterized in that the air flow rate of the sample passing through the step (2) can be between 0.01L/min and 1L/min.
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