CN113013314A - 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
- Publication number
- CN113013314A CN113013314A CN201911328324.7A CN201911328324A CN113013314A CN 113013314 A CN113013314 A CN 113013314A CN 201911328324 A CN201911328324 A CN 201911328324A CN 113013314 A CN113013314 A CN 113013314A
- Authority
- CN
- China
- Prior art keywords
- diamond
- thermoelectric material
- sintering
- performance
- thermoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims description 47
- 238000005245 sintering Methods 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 238000009461 vacuum packaging Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 11
- 238000002490 spark plasma sintering Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001513 hot isostatic pressing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 38
- 238000000137 annealing Methods 0.000 description 19
- 239000010453 quartz Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 18
- 238000005259 measurement Methods 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- -1 CuCl compound Chemical class 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开一种p型高性能Cu‑Sn‑S类金刚石结构热电材料及其制备方法。所述Cu‑Sn‑S类金刚石结构热电材料的化学组成为Cu7Sn3S10‑ x M x ，其中M选自卤族元素F、Cl、Br、I中的至少一种，0≤x≤2。
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 Cu-Sn-S diamond-like 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 0≤x ≤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. With the rapid economic growth of various countries and the continuous improvement of the living standard of people, together with the increasing exhaustion of the traditional energy, the environmental pollution is more and more serious, and various countries in the world are urgent for developing rich raw materials, protecting environment, cleaning and novel 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, waste 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 figure of merit zT determined by the material itself, and the larger the value of zT, the higher the energy conversion efficiency. zT can be expressed by the following formula zT ═ S2σT/(κe+κL) Wherein S is Seebeck coefficient, sigma is conductivity, and kappaeAs carrier thermal conductivity, κLIs 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 structure compound has a Cu-X framework 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. Therefore, the compound with the diamond-like structure 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 Cu7Sn3S10-xMxWherein 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-1Preferably 50000-150000S m-1。
Preferably, the Seebeck coefficient of the Cu-Sn-S diamond-like structure thermoelectric material is 35-300 mu V K-1Preferably 70 to 200 μ V K-1。
Preferably, the thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.5-4.0W m-1K-1Preferably 0.7 to 2W m-1K-1。
Preferably, the lattice thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material is 0.2-1.6W m-1K-1Preferably 0.5 to 1.5W m-1K-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, carrying out 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 temperature rising rate is 1 to 100 ℃/hour, and the temperature lowering rate is 1 to 50 ℃/hour.
Preferably, the sintering atmosphere is argon atmosphere, and the pressure is 0.001 to 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-1K-1The 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-1K-1In the meantime. The thermoelectric material compound provided by the invention has the advantages that the thermal property and the electrical property 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 17Sn3S10Graph of thermoelectric performance versus temperature;
FIG. 3 shows a thermoelectric material Cu of example 27Sn3S9.9Cl0.1Graph of thermoelectric performance versus temperature;
FIG. 4 shows a thermoelectric material Cu of example 37Sn3S9.5Cl0.5Graph of thermoelectric performance versus temperature;
FIG. 5 shows the thermoelectric material Cu of example 47Sn3S9.1Cl0.9Graph of thermoelectric performance versus temperature;
FIG. 6 shows a thermoelectric material Cu of example 57Sn3S8Cl2Graph of thermoelectric performance versus temperature;
FIG. 7 shows a thermoelectric material Cu of example 67Sn3S9.7F0.3Graph of thermoelectric performance versus temperature;
FIG. 8 shows a thermoelectric material Cu of example 77Sn3S9.5Br0.5The thermoelectric property of the alloy is changed along with the temperature;
FIG. 9 shows a thermoelectric material Cu of example 87Sn3S9.5I0.5Graph of thermoelectric performance versus temperature;
in the above fig. 2-9, (a) a graph of conductivity versus temperature; (b) a curve chart of the Seebeck coefficient changing with the temperature is shown; (c) is a graph of thermal conductivity and lattice thermal conductivity as a function of temperature; (d) is a graph of thermoelectric figure of merit zT versus temperature.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
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 present inventionThe high-performance p-type Cu-Sn-S diamond-like structure thermoelectric material has the chemical composition of Cu7Sn3S10-xMx(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 Cu7Sn3S10Or partial doping can be carried out on the S bit.
The crystal structure of ternary chalcogenides is generally such that anions constitute the structural framework of the polyhedron, while cations fill the interstitial sites of the framework. 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 coordination rules of tetrahedrons, other irregular coordination structural units may appear, increasing the complexity and distortion of the structure. Compared with the chemical composition of Cu of the high-temperature thermoelectric semiconductor in the Chinese patent CN 105970060A2Sn3S7The 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 Cu7Sn3S10-xMxWherein 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 thermal and electrical properties of the Cu-Sn-S diamond-like structure thermoelectric material can be regulated and controlled in a wide range, and the electric conductivity of the Cu-Sn-S diamond-like structure thermoelectric material can be 15000-350000S m-1To (c) to (d); the Seebeck coefficient of the Cu-Sn-S diamond-like structure thermoelectric material can be 35-300 mu V K-1To (c) to (d); the thermal conductivity of the Cu-Sn-S diamond-like structure thermoelectric material can be 0.5-4W m-1K-1To (c) to (d); the lattice thermal conductivity of the compound is far lower than that of other diamond-like structural compounds reported at present, and can be 0.2-1.6W m-1K-1To (c) to (d); the ZT value of the Cu-Sn-S diamond-like structure thermoelectric material is between 0.5 and 1.5 when the ZT value is 750K.
The thermal conductivity of a material is composed of the lattice thermal conductivity and the carrier thermal conductivity of the material (κ＝κL+κe). 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)eL 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 105970060A2Sn3S7Has an intrinsically complex distorted crystal structure and thus has a very low lattice thermal conductivity and also a very low electrical conductivity, so that its overall thermal conductivity is relatively low. Cu in the invention7Sn3S10The 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，CuGaTe2Etc.) 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 carbon compound A of Chinese patent 102194989A2BX3(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 all p-type semiconductors, and carriers participating in conductive transport are holes. The conductivity of the system is low (e.g. Cu)2SnSe3Room temperature conductivity 14500S m-1) Therefore, it is necessary to increase the concentration of holes in the material to increase the conductivity. Usually by incorporating a low valent cation at the cation site (e.g., at Sn)4+Doped with Zn2+Or In3+Etc.) or incorporate higher anions at the anion sites to create excess holes (e.g.: at S2-Doping with P3-Etc.). Ternary diamond-like carbon compound C in the inventionu7Sn3S10Also a p-type semiconductor, but this material has a very high conductivity of 350000S m-1(room temperature value), it is necessary to reduce the hole concentration inside the material. Usually, higher cations are incorporated at the cation sites (e.g., in Cu)+Doped with Zn2+Etc.) or by incorporating a lower anion at the anion site (e.g.: at S2-Doping with Cl-Etc.).
The following is an exemplary description of the preparation method of the high-performance Cu-Sn-S diamond-like structure thermoelectric material provided by the invention, as shown in FIG. 1.
Mixing a Cu simple substance, a Sn simple substance, a S simple substance and CuMn(M is at least one of halogen elements F, Cl, Br and I, and n is 1 or 2) the compound is weighed according to the molar ratio of (7-x):3, (10-x): x (n is 1) or (7-x):3, (10-2x): x (n is 2) and is packaged in vacuum. Selecting CuMnThe 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 mixedn(M is at least one of halogen elements F, Cl, Br and I, and n is 1 or 2) is packaged in a quartz tube according to a stoichiometric ratio, and is subjected to vacuum packaging in an argon atmosphere glove box by adopting plasma or a flame gun, 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 ℃/h, the temperature is maintained for 0.5-20 h, then the temperature is raised to 800-1100 ℃, and the quartz tube is melted at constant temperature for 1-100 h.
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 cooling rate is 1-50 ℃/h, the annealing temperature is 300-600 ℃, and the annealing time is 1-150 h.
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, and the pressure is 0.001-0.09 MPa. 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 annealed polycrystalline ingots are 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.
According to the invention, at least one of halogen elements (F, Cl, Br and I) is doped at the S position to adjust the thermal property and the electrical property of the Cu-Sn-S diamond-like structure thermoelectric material, and the thermal property and the electrical property can be adjusted and controlled in a wide range.
Measuring thermal diffusion coefficient lambda of the thermoelectric material by using a laser thermal conductivity meter, and estimating specific heat C of the material by utilizing Neumann-Kopp rulepThe density D of the material is tested by the Archimedes principle, and the formula kappa ═ lambda C is utilizedpAnd D, calculating the thermal conductivity of the material. The sample is then diamond cut to the desired shape (e.g., a long strip), the conductivity σ of the sample is measured 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 κL＝κ-κe，κeL σ T. Using the formula zT ═ S2And 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-1To (c) to (d); the Seebeck coefficient of the semiconductor material provided by the invention can be 35-300 mu V K-1To (c) to (d); the thermal conductivity of the semiconductor material provided by the invention can be 0.5-4W m-1K-1The 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-1K-1To (c) to (d); the zT value of the semiconductor material provided by the invention is between 0.5 and 1.5 at 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 the appropriate ranges through the description herein, and are not limited to the specific values of the following examples.
Example 1: cu7Sn3S10Polycrystalline bulk of semiconductor material
The method comprises the 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 7:3:10, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/hour, preserving heat for 2 hours, then continuously heating to 950 ℃, and melting at constant temperature for 12 hours. 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. 2, the resulting Cu7Sn3S10Thermoelectric property measurement of the polycrystalline block shows that the material has higher conductivity (the conductivity is 150000-350000S m) within a measured temperature range (300-750K)-1) And a moderate Seebeck coefficient (the Seebeck coefficient is 40-100 mu V K-1In (d) of (a); while the material exhibits moderate thermal conductivity (whichThe thermal conductivity is 2.0-4.0W m-1K-1And (C) has a lattice thermal conductivity of 0.2 to 1.6W m-1K-1In the meantime. The zT value of the material calculated from the performance measurements can reach 0.5 at 750K.
Example 2: cu7Sn3S9.9Cl0.1Polycrystalline bulk of semiconductor material
Mixing the raw materials of the Cu simple substance, the Sn simple substance, the S simple substance and the CuCl compound according to a molar ratio of 6.9:3:9.9:0.1, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/h, preserving heat for 2 hours, then continuing heating to 950 ℃, and melting at constant temperature for 12 hours. 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 Cu7Sn3S9.9Cl0.1Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 75000-200000S m within a measured temperature range (300-750K)-1The Seebeck coefficient is 49-130 mu V K-1The thermal conductivity of the material is 1.5-3.3W m-1K-1In the meantime. The zT value of the material calculated from the performance measurements can reach 0.64 at 750K.
Example 3: cu7Sn3S9.5Cl0.5Polycrystalline bulk of semiconductor material
Mixing the raw materials of the Cu simple substance, the Sn simple substance, the S simple substance and the CuCl compound according to a molar ratio of 6.5:3:9.5:0.5, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/h, preserving heat for 2 hours, then continuing heating to 950 ℃, and melting at constant temperature for 12 hours. 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. 4, the resulting Cu7Sn3S9.5Cl0.5Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 40000-114000S m within a measured temperature range (300-750K)-1The Seebeck coefficient (in the range of 69-162 mu V K)-1The thermal conductivity of the material is 1.0-2.3W m-1K-1In the meantime. The zT value of the material calculated from the performance measurements can reach 0.66 at 750K.
Example 4: cu7Sn3S9.1Cl0.9Polycrystalline bulk of semiconductor material
Mixing the raw materials of the Cu simple substance, the Sn simple substance, the S simple substance and the CuCl compound according to a molar ratio of 6.1:3:9.1:0.9, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/h, preserving heat for 2 hours, then continuing heating to 950 ℃, and melting at constant temperature for 12 hours. 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 resulting Cu7Sn3S9.1Cl0.9Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 15800-46000S m within a measured temperature range (300-750K)-1The Seebeck coefficient is 97-213 mu V K-1The thermal conductivity of the material is 0.7-1.5W m-1K-1The lattice thermal conductivity is 0.5-1.3W m-1K-1In the meantime. The zT value of the material calculated from the performance measurements can reach 0.8 at 750K.
Example 5: cu7Sn3S8Cl2Polycrystalline bulk of semiconductor material
The method comprises the 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 5:3:8:2, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/h, preserving heat for 2 hours, then continuing heating to 950 ℃, and melting at constant temperature for 12 hours. 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. 6, the obtained Cu7Sn3S8Cl2Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 17000-44800S m within a measured temperature range (300-750K)-1The Seebeck coefficient is 95-208 mu V K-1The thermal conductivity of the material is 0.7-1.4W m-1K-1In the meantime. The zT value of the material calculated from the performance measurements can reach 0.77 at 750K.
Example 6: cu7Sn3S9.7F0.3Polycrystalline bulk of semiconductor material
Raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and CuF2The compound is prepared according to the mol ratio of 6.85:3:9.7:0.15, then is packaged in a quartz tube in vacuum, is heated to 450 ℃ at the heating rate of 100 ℃/hour, is kept warm for 2 hours, is continuously heated to 950 ℃, and 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 Cu7Sn3S9.7F0.3Thermoelectric performance measurement of the polycrystalline block shows that the material has moderate conductivity (the conductivity is 63000-174000S m) within a measured temperature range (300-750K)-1) And a moderate Seebeck coefficient (the Seebeck coefficient is 52-135 mu V K-1In the middle) and the material shows lower thermal conductivity (the thermal conductivity is 1.3-2.8W m)-1K-1In between). The zT value of the material calculated from the performance measurements can reach 0.66 at 750K.
Example 7 Cu7Sn3S0.5Br0.5Polycrystalline bulk of semiconductor material
Mixing raw materials of a Cu simple substance, a Sn simple substance, an S simple substance and a CuBr compound according to a molar ratio of 6.5:3:9.5:0.5, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/h, preserving heat for 2 hours, then continuing heating to 950 ℃, and melting at constant temperature for 12 hours. 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 Cu7Sn3S0.5Br0.5Thermoelectric performance 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-1In the middle) and the material shows lower thermal conductivity (the thermal conductivity is 1.1-2.3W m)-1K-1In between). The zT value of the material calculated from the performance measurements can reach 0.78 at 750K.
Example 8: cu7Sn3S0.5I0.5Polycrystalline bulk of semiconductor material
Mixing the raw materials of the Cu simple substance, the Sn simple substance, the S simple substance and the CuI compound according to a molar ratio of 6.5:3:9.5:0.5, then packaging in a quartz tube in vacuum, heating to 450 ℃ at a heating rate of 100 ℃/h, preserving heat for 2 hours, then continuing heating to 950 ℃, and melting at constant temperature for 12 hours. 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 Cu7Sn3S0.5I0.5Thermoelectric property measurement of the polycrystalline block shows that the conductivity of the material is 48000-140000S m within a measured temperature range (300-750K)-1The Seebeck coefficient is 61-156 mu V K-1The thermal conductivity of the material is 1.1-2.4W m-1K-1In the meantime. The zT value of the material calculated from the performance measurements can reach 0.8 at 750K.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911328324.7A CN113013314B (en) | 2019-12-20 | 2019-12-20 | A p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911328324.7A CN113013314B (en) | 2019-12-20 | 2019-12-20 | A p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113013314A true CN113013314A (en) | 2021-06-22 |
| CN113013314B CN113013314B (en) | 2022-12-13 |
Family
ID=76382777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911328324.7A Active CN113013314B (en) | 2019-12-20 | 2019-12-20 | A p-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113013314B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117385473A (en) * | 2023-12-13 | 2024-01-12 | 乌镇实验室 | Preparation method of quaternary copper-based diamond-like semiconductor crystal |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0878733A (en) * | 1994-09-01 | 1996-03-22 | Mitsubishi Heavy Ind Ltd | Cusns group thermoeletric conversion semiconductor material and its manufacturing method |
| WO2011066205A1 (en) * | 2009-11-25 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
| CN102194989A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Method for preparing thermoelectric material of ternary diamond structure |
| EP2497588A1 (en) * | 2011-03-10 | 2012-09-12 | Universidad de Barcelona | Continuous flow process for the preparation of colloidal solutions of nanoparticles, colloidal solutions and uses thereof |
| CN102867905A (en) * | 2012-07-27 | 2013-01-09 | 清华大学 | Sn-S-based thermoelectric compound and preparation method thereof |
| JP2014138125A (en) * | 2013-01-17 | 2014-07-28 | Toyota Central R&D Labs Inc | Thermoelectric material and method for producing the same |
| CN105502479A (en) * | 2015-11-04 | 2016-04-20 | 南京工业大学 | Improved Cu2SnS3Method of synthesis of |
| CN105679928A (en) * | 2016-01-28 | 2016-06-15 | 济南大学 | A kind of alloy electrode suitable for Cu2SnSe3 based thermoelectric element and the preparation process of the thermoelectric element |
| WO2017203938A1 (en) * | 2016-05-25 | 2017-11-30 | 株式会社日本触媒 | Thermoelectric conversion material, thermoelectric conversion element, powder for thermoelectric conversion material, and method for producing thermoelectric conversion material |
-
2019
- 2019-12-20 CN CN201911328324.7A patent/CN113013314B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0878733A (en) * | 1994-09-01 | 1996-03-22 | Mitsubishi Heavy Ind Ltd | Cusns group thermoeletric conversion semiconductor material and its manufacturing method |
| WO2011066205A1 (en) * | 2009-11-25 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
| CN102194989A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Method for preparing thermoelectric material of ternary diamond structure |
| EP2497588A1 (en) * | 2011-03-10 | 2012-09-12 | Universidad de Barcelona | Continuous flow process for the preparation of colloidal solutions of nanoparticles, colloidal solutions and uses thereof |
| CN102867905A (en) * | 2012-07-27 | 2013-01-09 | 清华大学 | Sn-S-based thermoelectric compound and preparation method thereof |
| JP2014138125A (en) * | 2013-01-17 | 2014-07-28 | Toyota Central R&D Labs Inc | Thermoelectric material and method for producing the same |
| CN105502479A (en) * | 2015-11-04 | 2016-04-20 | 南京工业大学 | Improved Cu2SnS3Method of synthesis of |
| CN105679928A (en) * | 2016-01-28 | 2016-06-15 | 济南大学 | A kind of alloy electrode suitable for Cu2SnSe3 based thermoelectric element and the preparation process of the thermoelectric element |
| WO2017203938A1 (en) * | 2016-05-25 | 2017-11-30 | 株式会社日本触媒 | Thermoelectric conversion material, thermoelectric conversion element, powder for thermoelectric conversion material, and method for producing thermoelectric conversion material |
Non-Patent Citations (2)
| Title |
|---|
| YAWEI SHEN等: ""Eco-friendly P-type CusSnS3 thermoelectric material:crystal structure and transport properties"", 《SCIENTIFIC REPORTS》 * |
| 何彤彤等: ""Cu4Sn7S16基半导体化合物结构及热电性能研究"", 《万方数据》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117385473A (en) * | 2023-12-13 | 2024-01-12 | 乌镇实验室 | Preparation method of quaternary copper-based diamond-like semiconductor crystal |
| CN117385473B (en) * | 2023-12-13 | 2024-04-16 | 乌镇实验室 | Preparation method of quaternary copper-based diamond-like semiconductor crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113013314B (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102194989B (en) | Method for preparing thermoelectric material of ternary diamond structure | |
| JP6266099B2 (en) | High performance P-type thermoelectric material having reversible phase transition and method for producing the same | |
| CN104555950B (en) | Bismuth telluride material with excellent thermoelectric properties at medium temperature zone and method for preparing bismuth telluride material with excellent thermoelectric properties at medium temperature zone | |
| CN108238796B (en) | Copper-selenide based solid solution thermoelectric material and preparation method thereof | |
| CN103872237A (en) | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof | |
| CN108447972B (en) | SnTe-based high-performance thermoelectric material and preparation method thereof | |
| CN107235477A (en) | A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof | |
| CN104851967B (en) | A kind of c-axis orientation bismuth copper selenolite base oxide thermal electric film and preparation method thereof | |
| CN113421959B (en) | A kind of n-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof | |
| CN106986315B (en) | A kind of p-type bismuth telluride thermoelectric material and preparation method suitable for low-temperature electricity-generating | |
| CN110350074A (en) | A kind of high-performance BiCuSeO base thermoelectricity material and preparation method thereof | |
| CN111490148A (en) | A kind of preparation method of polycrystalline SnSe-based thermoelectric material | |
| CN113013314A (en) | P-type high-performance Cu-Sn-S diamond-like structure thermoelectric material and preparation method thereof | |
| CN105990510B (en) | A kind of copper seleno high performance thermoelectric material and preparation method thereof | |
| CN108516526A (en) | A kind of high-performance PbTe based solid solution thermoelectric materials and preparation method thereof | |
| CN111048658A (en) | A kind of SnI2-doped CsGeI3 perovskite thermoelectric material and preparation method thereof | |
| CN109022863A (en) | A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga | |
| CN113292342A (en) | Copper-silver based chalcogenide thermoelectric material and preparation and application thereof | |
| CN111276597B (en) | Ag doped Cu 2 SnSe 4 Thermoelectric material and method for reducing thermal conductivity of Cu-based thermoelectric material | |
| JPWO2018123899A1 (en) | Thermoelectric conversion material and thermoelectric conversion element | |
| JP2808580B2 (en) | Thermoelectric semiconductor materials | |
| KR102612880B1 (en) | Preparation method of P-type Ag-Bi-Se based thermoelectric material using selenium steam heat treatment and P-type Ag-Bi-Se based thermoelectric material and thermoelectric device | |
| CN114551706B (en) | P-type bismuth antimony selenide thermoelectric material and preparation method thereof | |
| CN114477104B (en) | (Sb 2 Te 3 ) n (GeTe) m Thermoelectric material and method for producing same | |
| CN116903370B (en) | SnTe-based thermoelectric material with multi-scale nano composite structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |