CN113013314B - P-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and preparation method thereof - Google Patents
P-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and a preparation method thereof. The chemical composition of the thermoelectric material with the Cu-Sn-S diamond-like structure is Cu 7 Sn 3 S 10‑ x M x Wherein M is at least one of halogen elements F, cl, br and I, and is not less than 0x≤2。
Description
Technical Field
The invention relates to a p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and a preparation method thereof, belonging to the field of thermoelectric materials.
Background
Energy has been the material basis on which humans rely for survival. Along with the rapid increase of economy of each country and the continuous improvement of living standard of people, the traditional energy is increasingly exhausted, the environmental pollution is more and more serious, and the countries in the world are urgent to develop abundant raw materials, protect the environment and clean, and novel and efficient available energy. In addition, a large amount of energy is lost in human activities, and especially, the loss is the most serious in a heat energy mode, such as industrial waste heat, automobile exhaust waste heat, garbage incineration heat and the like, which are lost by heat emission. In this context, thermoelectric conversion materials have come into play. The thermoelectric material can realize direct interconversion between heat energy and electric energy, has the characteristics of no noise, no pollution, no mechanical transmission and high reliability, and draws much attention in recent decades.
Thermoelectric conversion technology is based on the Seebeck effect and the Peltier effect of thermoelectric materials to realize thermoelectric power generation and refrigeration. Thermoelectric devices are generally single pi pairs composed of p-type and n-type semiconductor materials, and several pi pairs are connected in series to form a device module, so as to realize application. However, the conversion efficiency of the thermoelectric material is still low (< 10%), and large-scale commercial use is not realized. The thermoelectric conversion efficiency of the thermoelectric material depends on the environmental temperature difference and a dimensionless optimal value zT determined by the material, and the larger the value zT is, the higher the energy conversion efficiency is. zT can be represented by the following formula zT = S 2 σT/(κ e +κ L ) Wherein S is Seebeck coefficient, sigma is conductivity, and kappa e As carrier thermal conductivity, κ L Is the lattice thermal conductivity and T is the absolute temperature. The development of high zT thermoelectric semiconductor materials is therefore a key scientific problem in the field of thermoelectric research.
The copper-based diamond-like structure compound has a structure/functional unit which is favorable for realizing the synergistic regulation and control of electrical property and thermal property. On one hand, the diamond-like compound has a Cu-X frame structure, a three-dimensional conductive network channel is formed, and good electric transport performance is ensured; in addition, the twisted crystal structure forms additional scattering to phonons, which is beneficial to obtaining intrinsic low lattice thermal conductivity. Thus, the diamond-like structure compound is a thermoelectric material system with great potential. The Cu-Sn-S system has the characteristics of abundant reserves in the earth crust, low cost, environmental friendliness and the like, but the currently reported Cu-Sn-S system thermoelectric material cannot meet the application requirements of thermoelectric conversion materials and devices due to the low thermoelectric figure of merit, so that the development of the Cu-Sn-S system thermoelectric material in the thermoelectric field is limited.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and a method for preparing the same.
The chemical composition of the p-type Cu-Sn-S diamond-like structure thermoelectric material is Cu 7 Sn 3 S 10-x M x Wherein M is selected from at least one of halogen elements F, cl, br and I, and x is more than or equal to 0 and less than or equal to 2.
The Cu-Sn-S diamond-like structure thermoelectric material can be doped with halogen elements (such as F, cl, br and I) at the S position, the doping amount is 0-2, x is more than or equal to 0, and the carrier concentration of the material is effectively reduced along with the increase of the doping amount, so that the electrical conductivity of the material is obviously reduced, and the carrier thermal conductivity of the material is greatly reduced; meanwhile, a large number of point defects are introduced into the material by doping, so that strong scattering is generated on phonons, and the lattice thermal conductivity of the material is reduced, thereby optimizing the thermal property of the material and improving the thermoelectric figure of merit (ZT) of the material.
Preferably, x is more than or equal to 0.5 and less than or equal to 0.9, and the Cu-Sn-S diamond-like structure thermoelectric material obtained in the range has better electrical property (power factor) and lower thermal conductivity.
Preferably, the electric conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 15000 to 350000S m -1 Preferably 50000-150000S m -1 。
Preferably, the Seebeck coefficient of the Cu-Sn-S diamond-like structure thermoelectric material is 35-300 mu V K -1 Preferably 70 to 200. Mu.V K -1 。
Preferably, the thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.5-4.0W m -1 K -1 Preferably 0.7 to 2W m -1 K -1 。
Preferably, the thermal conductivity of the crystal lattice of the Cu-Sn-S diamond-like structure thermoelectric material is 0.2-1.6W m -1 K -1 Preferably 0.5 to 1.5W m -1 K -1 。
Preferably, the thermoelectric figure of merit zT of the Cu-Sn-S diamond-like structure thermoelectric material is 0.5 to 1.5, preferably 0.5 to 1.0 at 750K.
In another aspect, the invention further provides a preparation method of the above Cu-Sn-S diamond-like structure thermoelectric material, which comprises:
(1) Weighing compound raw materials according to chemical compositions, vacuum packaging, heating to 300-600 ℃, preserving heat for 0.5-20 hours, then continuously heating to 800-1100 ℃, and melting at constant temperature for 1-100 hours to obtain a liquid mixture;
(2) Cooling the liquid mixture to 300-600 ℃, preserving heat for 1-150 hours, cooling to room temperature, and grinding into powder to obtain sintered powder;
(3) And pressurizing and sintering the obtained sintering powder to obtain the thermoelectric material with the Cu-Sn-S diamond-like structure.
Preferably, the vacuum packaging mode is plasma or flame gun packaging.
Preferably, the heating rate is 1-100 ℃/hour, and the cooling rate is 1-50 ℃/hour.
Preferably, the sintering atmosphere is argon atmosphere, and the pressure is 0.001-0.09 MPa.
Preferably, the pressure sintering mode is hot isostatic pressing sintering and/or spark plasma sintering, and preferably, the sintering temperature is 300-800 ℃, the sintering pressure is 10-65 Mpa, and the sintering time is 5-200 minutes.
The thermal conductivity of the semiconductor material provided by the invention is 0.5-4W m -1 K -1 The lattice thermal conductivity of the compound is far lower than that of other diamond-like structure compounds reported at present, and can be 0.2-1.6W m -1 K -1 In the meantime. The thermoelectric material compound provided by the invention has the advantages that the thermal and electrical properties can be regulated and controlled in a wide range, the thermoelectric figure of merit zT is excellent in a Cu-Sn-S system, and the storage amount of the constituent elements is rich, the cost is low, and the environment is friendly, so that the thermoelectric material compound is a novel thermoelectric material with potential.
Drawings
FIG. 1 shows a schematic flow diagram for the preparation of an exemplary thermoelectric material of the present invention;
FIG. 2 shows a thermoelectric material Cu of example 1 7 Sn 3 S 10 Graph of thermoelectric performance versus temperature;
FIG. 3 shows a thermoelectric material Cu of example 2 7 Sn 3 S 9.9 Cl 0.1 Graph of thermoelectric performance versus temperature;
FIG. 4 shows a thermoelectric material Cu of example 3 7 Sn 3 S 9.5 Cl 0.5 Graph of thermoelectric performance as a function of temperature;
FIG. 5 shows the thermoelectric material Cu of example 4 7 Sn 3 S 9.1 Cl 0.9 Graph of thermoelectric performance versus temperature;
FIG. 6 shows a thermoelectric material Cu of example 5 7 Sn 3 S 8 Cl 2 Graph of thermoelectric performance versus temperature;
FIG. 7 shows Cu as a thermoelectric material in example 6 7 Sn 3 S 9.7 F 0.3 Graph of thermoelectric performance versus temperature;
FIG. 8 shows a thermoelectric material Cu of example 7 7 Sn 3 S 9.5 Br 0.5 The thermoelectric property of the alloy is changed along with the temperature;
FIG. 9 shows a thermoelectric material Cu of example 8 7 Sn 3 S 9.5 I 0.5 Graph of thermoelectric performance versus temperature;
in the above fig. 2-9, (a) a graph of conductivity versus temperature; (b) is a graph of the Seebeck coefficient varying with temperature; (c) Is a graph of thermal conductivity and lattice thermal conductivity as a function of temperature; and (d) is a graph of thermoelectric figure of merit zT as a function of temperature.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention.
The Cu-Sn-S ternary diamond-like structure compound system has the characteristics of rich raw material reserves, low cost, environmental friendliness and the like, and has a wide application basis. But its application in the thermoelectric field is limited due to its lower thermoelectric figure of merit. Therefore, the invention provides a high-performance p-type Cu-Sn-S diamond-like structure thermoelectric material, and the chemical composition of the material is Cu 7 Sn 3 S 10-x M x (M is at least one of halogen elements F, cl, br and I), wherein x is more than or equal to 0 and less than or equal to 2. That is, the Cu-Sn-S diamond-like structure thermoelectric material may be a single compound Cu 7 Sn 3 S 10 Or partial doping can be carried out on the S bit.
The crystal structure of ternary chalcogenides is generally such that the anions constitute the structural framework of a polyhedron, while the cations constituteThe sub-filling is at the gap position of the frame. Diamond-like structures generally refer to a structural framework of regular tetrahedra formed by anions, with cations filling interstitial sites of the tetrahedra. When the number of anions and cations does not match the tetrahedral coordination rules, other irregular coordination structural units may appear, increasing the complexity and the degree of distortion of the structure. Compared with the chemical composition of the high-temperature thermoelectric semiconductor of Chinese patent CN 105970060A as Cu 2 Sn 3 S 7 The mismatching of the numbers of anions and cations in the chemical components may be the manifestation of the complexity of the crystal structure, and the material has extremely low lattice thermal conductivity and a complex energy band structure.
General formula Cu 7 Sn 3 S 10-x M x Wherein x is the doping content of M at the S site, and can be adjusted within the range of x being more than or equal to 0 and less than or equal to 2. The thermoelectric material with the Cu-Sn-S diamond-like structure can regulate and control the thermal and electrical properties in a wide range, and the electric conductivity of the thermoelectric material with the Cu-Sn-S diamond-like structure can be 15000 to 350000S m -1 In the middle of; the Seebeck coefficient of the thermoelectric material with the Cu-Sn-S diamond-like structure can be 35-300 mu V K -1 To (c) to (d); the thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material can be 0.5-4W m -1 K -1 In the middle of; the lattice thermal conductivity of the compound is far lower than that of other diamond-like structure compounds reported at present and can be between 0.2 and 1.6W m -1 K -1 To (c) to (d); the ZT value of the Cu-Sn-S diamond-like structure thermoelectric material is between 0.5 and 1.5 when being 750K.
The thermal conductivity of a material is composed of the lattice thermal conductivity and the carrier thermal conductivity of the material (k = k) L +κ e ). The lattice thermal conductivity of the material is related to the distortion degree or the irregularity degree of the lattice, and the structural distortion degree can be increased and the lattice thermal conductivity of the material can be reduced by means of element doping, solid solution and the like; while the carrier thermal conductance (κ) e = L σ T) is directly related to the electrical conductivity of the material, so reducing electrical conductivity (i.e. reducing carrier concentration) can effectively reduce carrier thermal conductivity. Compound Cu in Chinese patent CN 105970060A 2 Sn 3 S 7 Has a crystal structure with intrinsic complex distortion, so that the thermal conductivity of the crystal lattice is extremely lowAnd its electrical conductivity is also very low, so its overall thermal conductivity is relatively low. Cu in the invention 7 Sn 3 S 10 The matching of chemical components leads the diamond-like material to have a regular tetragonal diamond-like structure, but weak chemical bonds and point defects exist in the crystal structure due to the fact that the crystal structure is microscopically occupied by the intrinsically diversified cations, and the diamond-like material further shows the defect ratio than other diamond-like materials (CuInS) 2 ，CuGaTe 2 Etc.) have lower lattice thermal conductivity. Doping of elements will generally greatly adjust the carrier thermal conductivity of the material while somewhat reducing the lattice thermal conductivity.
The electrical conductivity of a thermoelectric material is a crucial performance parameter, and too high or too low can affect the thermoelectric performance of the material. Experimentally, the method of adjusting the carrier concentration inside the material is usually adopted to reach an optimal interval, so as to obtain the optimal thermoelectric performance. Ternary diamond-like compound A of Chinese patent 102194989A 2 BX 3 (A is selected from one of Cu and Ag; B is selected from one of Ge and Sn; and X is selected from one of S, se and Te) are p-type semiconductors, and carriers participating in conductive transport are holes. The conductivity of the system is relatively low (e.g. Cu) 2 SnSe 3 The room temperature conductivity is 14500S m -1 ) Therefore, it is necessary to increase the concentration of holes in the material to increase the conductivity. The incorporation of a low-valent cation (e.g. in Sn) is generally carried out at the cation site 4+ Doped with Zn 2+ Or In 3+ Etc.) or incorporate higher anions at the anion sites to create excess holes (e.g.: at S 2- Doping with P 3- Etc.). Ternary diamond-like compound Cu in the invention 7 Sn 3 S 10 Also a p-type semiconductor, but the material has very high conductivity of 350000S m -1 (room temperature value), the hole concentration inside the material needs to be reduced. Usually, higher cations are incorporated at the cation sites (e.g., in Cu) + Doped with Zn 2+ Etc.) or by incorporating a lower anion at the anion site (e.g.: at S 2- Doping with Cl - Etc.).
The following is an exemplary description of the preparation method of the high-performance thermoelectric material with a Cu-Sn-S diamond-like structure provided by the invention, as shown in FIG. 1.
Mixing a Cu simple substance, a Sn simple substance, a S simple substance and CuM n (M is at least one of halogen elements F, cl, br and I, and n =1 or 2) the compound is weighed according to the molar ratio of (7-x): 3 (10-x): x (n = 1) or (7-x): 3 (10-2 x): x (n = 2) and is packaged in vacuum. Selecting CuM n The compound (M is at least one of halogen elements F, cl, br and I) is mainly solid powder at room temperature, is easy to operate and is safer. Wherein the vacuum packaging is performed under the protection of inert gas. When packaging, the container is vacuumized, and the internal pressure is 0.1-40000 Pa. The vacuum packaging adopts a plasma or flame gun packaging mode. Wherein, the adopted raw materials are preferably high-purity elements and compounds. As an example, the elementary Cu, the elementary Sn, the elementary S and the CuM are mixed n (M is at least one of halogen elements F, cl, br and I, and n =1 or 2) is encapsulated in a quartz tube according to a stoichiometric ratio, and is encapsulated in a vacuum manner by adopting plasma or a flame gun in an argon atmosphere glove box, wherein the internal pressure of the glove box is 0.1-40000 Pa.
Then, the vacuum-packed raw materials are melted to form a liquid mixture. As an example, the temperature of the packaged quartz tube is raised to 300-600 ℃ at the heating rate of 1-100 ℃/hour, the temperature is maintained for 0.5-20 hours, and then the temperature is raised to 800-1100 ℃ continuously, and the quartz tube is melted for 1-100 hours at constant temperature.
And cooling the liquid mixture to a certain temperature, annealing, cooling to room temperature, and grinding into powder to obtain sintered powder. As an example, the temperature reduction rate is 1 to 50 ℃/hour, the annealing temperature is 300 to 600 ℃, and the annealing time is 1 to 150 hours.
And pressurizing and sintering the obtained sintering powder to obtain the Cu-Sn-S diamond-like structure thermoelectric material. Wherein, the sintering mode is hot isostatic pressing sintering and/or spark plasma sintering. The sintering temperature is 300-800 ℃, the sintering heat preservation time is 5-200 minutes, and the sintering pressure is 10-65 Mpa. The sintering atmosphere is a low-pressure argon atmosphere with a pressure of 0.001 to 0.09MPa. Specifically, the formed compact polycrystalline block (the thermoelectric material with the Cu-Sn-S diamond-like structure) can be obtained by hot isostatic pressing sintering or discharge plasma sintering, the sintering method is that the annealed polycrystalline ingot is ground into powder, the obtained powder is subjected to pressure sintering, the sintering temperature is 300-800 ℃, the sintering heat preservation time is 5-200 minutes, the sintering pressure is 10-65 MPa, the sintering atmosphere is a low-pressure argon atmosphere, and the pressure is 0.001-0.09 MPa.
The thermal property and the electrical property of the thermoelectric material with the Cu-Sn-S diamond-like structure are adjusted by doping at least one halogen element (F, cl, br, I) in the S position, and the thermal property and the electrical property can be adjusted and controlled in a wide range.
Measuring the thermal diffusion coefficient lambda of the thermoelectric material by using a laser thermal conductivity meter, and estimating the specific heat C of the material by utilizing Neumann-Kopp rule p The density D of the material is measured by the Archimedes principle, and the formula kappa = lambda C is utilized p And D, calculating the thermal conductivity of the material. The sample is then diamond cut into the desired shape (e.g., a long strip), tested for conductivity σ using the classical four-terminal method, and the seebeck coefficient S is measured as the ratio of the potential difference across the sample to the temperature difference. Lattice thermal conductivity κ L ＝κ-κ e ，κ e = L σ T. Using the formula zT = S 2 And calculating the thermoelectric figure of merit of the measured material by the sigma T/kappa.
The conductivity of the semiconductor material provided by the invention can be 15000-350000S m -1 To (c) to (d); the Seebeck coefficient of the semiconductor material provided by the invention can be 35-300 mu V K -1 To (c) to (d); the thermal conductivity of the semiconductor material provided by the invention can be 0.5-4W m -1 K -1 The lattice thermal conductivity of the compound is far lower than that of other diamond-like structure compounds reported at present, and can be 0.2-1.6W m -1 K -1 To (c) to (d); the zT value of the semiconductor material provided by the invention is between 0.5 and 1.5 when the zT value is 750K.
The present invention will be described in detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select them within suitable ranges through the description herein, and are not limited to the specific values of the following examples.
Example 1: cu 7 Sn 3 S 10 Polycrystalline block of semiconductor material
The method comprises the following steps of mixing raw materials of a Cu simple substance, a Sn simple substance and an S simple substance according to a molar ratio of 7. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving heat for 72 hours, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at 650 ℃ for 12 minutes under the conditions of sintering pressure of 65MPa, low-pressure argon atmosphere and pressure of 0.07MPa to obtain the compact block material.
As shown in FIG. 2, the resulting Cu 7 Sn 3 S 10 Thermoelectric property measurement of the polycrystalline block shows that the material has higher conductivity (the conductivity is between 150000 and 350000S m) in a temperature range (between 300 and 750K) -1 ) And a moderate Seebeck coefficient (the Seebeck coefficient is 40-100 mu V K) -1 In (d) of (a); meanwhile, the material shows moderate thermal conductivity (the thermal conductivity is between 2.0 and 4.0W m) -1 K -1 Between) with a lattice thermal conductivity of 0.2 to 1.6W m -1 K -1 In between. The zT value of the material calculated from the performance measurements can reach 0.5 at 750K.
Example 2: cu (copper) 7 Sn 3 S 9.9 Cl 0.1 Polycrystalline bulk of semiconductor material
The preparation method comprises the following steps of mixing raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and a CuCl compound according to a molar ratio of 6.9. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving heat for 72 hours, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at the sintering temperature of 650 ℃ for 12 minutes under the sintering pressure of 65MPa and the pressure of 0.07MPa under the low-pressure argon atmosphere to finally obtain the compact block material.
As shown in FIG. 3, the resulting Cu 7 Sn 3 S 9.9 Cl 0.1 Thermoelectric property measurement of the polycrystalline block body shows that the conductivity of the material is 75000-200000S m within a measured temperature range (300-750K) -1 The Seebeck coefficient is 49-130 mu V K -1 The thermal conductivity of the material is between 1.5 and 3.3W m -1 K -1 In the meantime. The zT value of the material calculated from the performance measurements can reach 0.64 at 750K.
Example 3: cu 7 Sn 3 S 9.5 Cl 0.5 Polycrystalline block of semiconductor material
Mixing raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and a CuCl compound according to a molar ratio of 6.5. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving the heat for 72 hours for pre-annealing, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at the sintering temperature of 650 ℃ for 12 minutes under the sintering pressure of 65MPa and the pressure of 0.07MPa under the low-pressure argon atmosphere to finally obtain the compact block material.
As shown in FIG. 4, the obtained Cu 7 Sn 3 S 9.5 Cl 0.5 Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 40000-114000S m within a measured temperature range (300-750K) -1 Seebeck coefficient (between 69 and 162 mu V K) -1 The thermal conductivity of the material is between 1.0 and 2.3W m -1 K -1 In the meantime. The zT value of the material calculated from the performance measurements can reach 0.66 at 750K.
Example 4: cu (copper) 7 Sn 3 S 9.1 Cl 0.9 Polycrystalline block of semiconductor material
Mixing raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and a CuCl compound according to a molar ratio of 6.1. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving heat for 72 hours, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at the sintering temperature of 650 ℃ for 12 minutes under the sintering pressure of 65MPa and the pressure of 0.07MPa under the low-pressure argon atmosphere to finally obtain the compact block material.
As shown in FIG. 5, the obtained Cu 7 Sn 3 S 9.1 Cl 0.9 Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 15800 to 46000S m within a measured temperature range (300 to 750K) -1 The Seebeck coefficient is 97-213 mu V K -1 The thermal conductivity of the material is 0.7-1.5W m -1 K -1 The lattice thermal conductivity is between 0.5 and 1.3W m -1 K -1 In the meantime. The zT value of the material calculated from the performance measurements can reach 0.8 at 750K.
Example 5: cu 7 Sn 3 S 8 Cl 2 Polycrystalline bulk of semiconductor material
The preparation method comprises the following steps of mixing raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and a CuCl compound according to a molar ratio of 5. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving the heat for 72 hours for pre-annealing, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at 650 ℃ for 12 minutes under the conditions of sintering pressure of 65MPa, low-pressure argon atmosphere and pressure of 0.07MPa to obtain the compact block material.
As shown in FIG. 6, the obtained Cu 7 Sn 3 S 8 Cl 2 Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 17000-44800S m within a measured temperature range (300-750K) -1 The Seebeck coefficient is 95-208 mu V K -1 The thermal conductivity of the material is between 0.7 and 1.4W m -1 K -1 In the meantime. The zT value of the material calculated from the performance measurements can reach 0.77 at 750K.
Example 6: cu 7 Sn 3 S 9.7 F 0.3 Polycrystalline block of semiconductor material
Raw materials of a Cu simple substance, a Sn simple substance, a S simple substance and CuF 2 The compound is prepared according to the mol ratio of 6.85The temperature is increased to 950 ℃ for 2 hours, and the mixture is melted for 12 hours at constant temperature. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving heat for 72 hours, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at the sintering temperature of 650 ℃ for 12 minutes under the sintering pressure of 65MPa and the pressure of 0.07MPa under the low-pressure argon atmosphere to finally obtain the compact block material.
As shown in FIG. 7, the resulting Cu 7 Sn 3 S 9.7 F 0.3 Thermoelectric property measurement of the polycrystalline block body shows that the material has moderate conductivity (the conductivity is 63000-174000S m) in a measured temperature range (300-750K) -1 ) And moderate Seebeck coefficient (the Seebeck coefficient is 52-135 muV K) -1 In between) while the material exhibits a low thermal conductivity (thermal conductivity in the range of 1.3 to 2.8W m) -1 K -1 In between). The zT value of the material calculated from the performance measurements can reach 0.66 at 750K.
Example 7 7 Sn 3 S 0.5 Br 0.5 Polycrystalline block of semiconductor material
The preparation method comprises the following steps of mixing raw materials of a Cu simple substance, a Sn simple substance, a S simple substance and a CuBr compound according to a molar ratio of 6.5. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving heat for 72 hours, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at the sintering temperature of 650 ℃ for 12 minutes under the sintering pressure of 65MPa and the pressure of 0.07MPa under the low-pressure argon atmosphere to finally obtain the compact block material.
As shown in FIG. 8, the obtained Cu 7 Sn 3 S 0.5 Br 0.5 Thermoelectric property measurement of the polycrystalline block shows that the material has moderate conductivity (the conductivity is 45000-130000S m) in a measured temperature range (300-750K) -1 ) And a moderate Seebeck coefficient (the Seebeck coefficient is 65-158 mu V K) -1 In between) while the material exhibits a low thermal conductivity (its thermal conductivity is between 1.1 and 2.3W m -1 K -1 In between). The zT value of the material calculated from the performance measurements can reach 0.78 at 750K.
Example 8: cu 7 Sn 3 S 0.5 I 0.5 Polycrystalline bulk of semiconductor material
Mixing raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and a CuI compound according to a molar ratio of 6.5. Then cooling to 420 ℃ at a cooling rate of 50 ℃/hour for pre-annealing, preserving heat for 72 hours, and cooling to room temperature to obtain an ingot sample;
grinding the obtained cast ingot sample, tabletting, carrying out vacuum packaging in a quartz tube again, heating to 420 ℃ at the heating rate of 100 ℃/hour, annealing for 72 hours, and cooling to room temperature at the cooling rate of 50 ℃/hour;
grinding the obtained product into powder, and performing spark plasma sintering at the sintering temperature of 650 ℃ for 12 minutes under the sintering pressure of 65MPa and the pressure of 0.07MPa under the low-pressure argon atmosphere to finally obtain the compact block material.
As shown in FIG. 9, the obtained Cu 7 Sn 3 S 0.5 I 0.5 Thermoelectric property measurement of the polycrystalline block shows that the electricity of the material is within a measured temperature range (300-750K)The conductivity is 48000-140000 Sm -1 The Seebeck coefficient is between 61 and 156 mu V K -1 The thermal conductivity of the material is between 1.1 and 2.4W m -1 K -1 In between. The zT value of the material calculated from the performance measurements can reach 0.8 at 750K.
Claims (15)
1. The p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material is characterized in that the chemical composition of the Cu-Sn-S diamond-like structure thermoelectric material is Cu 7 Sn 3 S x10- M x Wherein M is at least one of halogen elements F, cl, br and I, and is not more than 0.5x≤0.9。
2. The p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material as claimed in claim 1, wherein the electrical conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 15000 to 350000S m -1 。
3. The p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material as claimed in claim 2, wherein the electrical conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 50000-150000S m -1 。
4. The p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material as claimed in claim 1, wherein Seebeck coefficient of the Cu-Sn-S diamond-like structure thermoelectric material is 35-300 μ V K -1 。
5. The p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material according to claim 4, wherein the Seebeck coefficient of the Cu-Sn-S diamond-like structure thermoelectric material is 70 to 200 μ V K -1 。
6. The p-type high performance Cu-Sn-S diamond-like structure thermoelectric material according to claim 1, wherein the thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.5 to 4.0W m -1 K -1 。
7. The p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material as claimed in claim 6, wherein the thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.7-2W m -1 K -1 。
8. The p-type high performance Cu-Sn-S diamond-like structure thermoelectric material according to claim 1, wherein the lattice thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.2 to 1.6W m -1 K -1 。
9. The p-type high performance Cu-Sn-S diamond-like structure thermoelectric material of claim 8, wherein the lattice thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.5 to 1.5W m -1 K -1 。
10. The p-type high performance Cu-Sn-S diamond-like structure thermoelectric material of claim 1, wherein the thermoelectric figure of merit of the Cu-Sn-S diamond-like structure thermoelectric materialzT0.5 to 1.5 at 750K.
11. The p-type high performance Cu-Sn-S diamond-like structure thermoelectric material of claim 10, wherein the thermoelectric figure of merit of the Cu-Sn-S diamond-like structure thermoelectric materialzT0.5 to 1.0 at 750K.
12. The method for preparing a p-type high performance Cu-Sn-S diamond-like structure thermoelectric material according to any one of claims 1 to 11, comprising:
(1) Weighing compound raw materials according to chemical compositions, vacuum packaging, heating to 300-600 ℃, keeping the temperature for 0.5-20 hours, then continuously heating to 800-1100 ℃, and melting at constant temperature for 1-100 hours to obtain a liquid mixture;
(2) Cooling the liquid mixture to 300-600 ℃, preserving heat for 1-150 hours, cooling to room temperature, and grinding into powder to obtain sintered powder;
(3) And pressurizing and sintering the obtained sintering powder to obtain the thermoelectric material with the Cu-Sn-S diamond-like structure.
13. The method for preparing a composite material according to claim 12, wherein the vacuum packaging mode is plasma or flame gun packaging.
14. The method of claim 12, wherein the pressure sintering is hot isostatic pressing sintering and/or spark plasma sintering.
15. The method according to claim 14, wherein the sintering temperature is 300 to 800 ℃, the sintering pressure is 10 to 65Mpa, and the sintering time is 5 to 200 minutes.
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