CN108511587B - P-type Cu with excessive copper3.9Ga4.2Te8Medium-temperature thermoelectric material and preparation process thereof - Google Patents
P-type Cu with excessive copper3.9Ga4.2Te8Medium-temperature thermoelectric material and preparation process thereof Download PDFInfo
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Abstract
The invention relates to P-type Cu with excessive copper3.9Ga4.2Te8The design key point of the medium-temperature thermoelectric material is that Cu is used as a base material and a medium-temperature thermoelectric material is prepared by a preparation process3.8Ga4.2Te8The mol fraction of Cu in the solid solution is increased from 0.2375 to 0.2422, and the chemical formula is Cu3.9Ga4.2Te8The thermoelectric material of (1); the preparation process comprises the following steps: weighing corresponding amounts of three elements of Cu, Ga and Te according to a chemical formula, carrying out vacuum melting for 24 hours at 950 ℃, cooling to 523 ℃ for annealing for 72 hours after melting synthesis, cooling the annealed ingot to room temperature, taking out the ingot, crushing and ball-milling, carrying out spark plasma spark sintering on the ball-milled powder for short time to form, wherein the sintering time is 8 minutes, the sintering temperature is 750 ℃, and the sintering pressure is 65Mpa, thus obtaining the Cu by preparation3.9Ga4.2Te8A thermoelectric material. The thermoelectric material has the advantages that the thermoelectric material is 775.82K, the Seebeck coefficient alpha is 227.53 (mu V/K), and the electric conductivity sigma is 6.25 multiplied by 103Ω‑ 1.m‑1Thermal conductivity k is 0.16 (W.K)‑1.m‑1) The maximum thermoelectric figure of merit ZT was 1.57. The material has no pollution and no noise, and has the advantages of reliable operation, long service life and simple preparation process.
Description
Technical Field
The invention relates to the field of new materials, is suitable for a key component material for medium-high temperature power generation with direct conversion of heat energy and electric energy, and is P-type Cu with excessive copper3.9Ga4.2Te8A medium-temperature thermoelectric material and a preparation process thereof.
Background
The thermoelectric semiconductor material is a novel semiconductor functional material which realizes direct interconversion of electric energy and heat energy through movement of carriers including electrons or holes. The power generation and refrigeration device made of thermoelectric material has the advantages of small volume, no pollution, no noise, no abrasion, good reliability, long service life and the like. In the civil field, the potential range of applications is: domestic refrigerators, freezers, superconducting electronic device cooling and waste heat power generation, waste heat utilization power supply, small-sized power supply devices in remote areas and the like.
The overall performance of thermoelectric materials is described by the dimensionless thermoelectric figure of merit ZT ═ T σ α2And/κ, where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the absolute temperature. Therefore, the performance of the thermoelectric material has a close relationship with the temperature, and the maximum thermoelectric figure of merit (ZT) of the material is maximum only at a certain temperature value. At present, thermoelectric power generation materials for medium-temperature power generation, which have been applied to a small extent, are mainly series alloys such as Pb — Te-based, metal silicide, and the like, developed in the 50 s. The maximum thermoelectric figure of merit of the two is about 1.5, but Pb has great environmental pollution and is harmful to human bodies. The optimum use temperature for these materials is generally below 550 ℃. As for the wide-bandgap Cu-Ga-Te ternary semiconductor material, under the intrinsic condition, the resistance is generally larger, so that the thermoelectric conversion efficiency is not high, and the thermoelectric device for medium-temperature power generation is difficult to manufacture. The main reasons for this are that the carrier concentration inside such materials is not high and the conductivity of the materials is low. However, some semiconductor materials with ternary chalcopyrite structures have special composition and structural characteristics, and the semiconductor materials are not formed according to a normal proportion, namely the Cu content in the materials is excessive. Due to the excessive content of Cu, the conductivity of the material is improved. Meanwhile, the semiconductor material with excessive Cu has higher use temperature and higher Seebeck coefficient. The thermal conductivity can be greatly reduced by proper element impurities, so that the thermoelectric performance is greatly improved.
Disclosure of Invention
In order to overcome the problem of insufficient performance of a wide bandgap Cu-Ga-Te ternary semiconductor, the invention aims to provide a P-type Cu with higher performance and excessive copper3.9Ga4.2Te8The medium-temperature thermoelectric material and the preparation process thereof solve the technical problem that the thermoelectric performance of the existing similar material is poor. The purpose is realized by the following technical scheme.
P-type Cu with excessive copper3.9Ga4.2Te8Medium-temperature thermoelectric material and preparation thereofThe process is to use Cu3.8Ga4.2Te8Increasing the mole fraction of Cu in solid solution from 0.2375 to 0.2422, i.e. the excess Cu in the solution3.9Ga4.2Te8A thermoelectric material. The thermoelectric material is prepared by adopting a conventional powder metallurgy method, and the preparation process comprises the following steps: according to the chemical formula Cu3.9Ga4.2Te8Three elements of Cu, Ga and Te are proportioned and then directly placed in a quartz tube for vacuum melting synthesis, wherein the melting synthesis temperature is 900-1000 ℃, and the synthesis time is 20-28 hours. Cooling to 523 ℃ after smelting synthesis for annealing for 72 hours, cooling the annealed ingot to room temperature, taking out the ingot, crushing and ball milling for 5 hours, sintering and forming the powder subjected to ball milling drying in a short time by spark discharge plasma spark, wherein the sintering time is 5-10 minutes, the sintering temperature is 700-800 ℃, and the sintering pressure is 60-70 MPa, and the Cu is obtained by preparation3.9Ga4.2Te8A thermoelectric material.
In the above preparation process, the Cu3.9Ga4.2Te8The preferred smelting synthesis temperature of the thermoelectric material is 950 ℃, the sintering temperature is 750 ℃, the sintering pressure is 65MPa, and the sintering time is 8 minutes.
The invention has the advantages that: p-type Cu obtained by adopting the preparation process3.9Ga4.2Te8When the medium-temperature thermoelectric material is at 775.82K, the Seebeck coefficient alpha of the material is 227.50 (mu V/K), and the electric conductivity sigma is 6.25 multiplied by 103Ω-1.m-1Thermal conductivity k is 0.16 (W.K)-1.m-1) The maximum thermoelectric figure of merit ZT is 1.57, which is a material with better performance in the Cu-Ga-Te ternary medium temperature thermoelectric material reported at present. The material adopts a conventional preparation process, has low cost, can be applied to the manufacture of medium-temperature power generation components, and the manufactured thermoelectric conversion device has the characteristics of no noise, no pollution, reliable operation and long service life. Is suitable for being used as an environment-friendly thermoelectric material.
Drawings
FIG. 1 is a schematic representation of thermoelectric performance of the present invention compared to other materials.
The ordinate in the above figures is the thermoelectric figure of merit ZT; the abscissa is the temperature T/K; and the chemical compositions are indicated in relation to the examples by different labels.
Detailed Description
The invention will be further described in the following with reference to specific embodiments thereof, in conjunction with the accompanying drawings.
Cu3.9Ga4.2Te8Absolute Seebeck coefficient of (a) from 265.91(μ V.K) around room temperature-1) Increase to 311.53(μ V.K) at 575.6K-1) Then gradually decreases to 213.52(μ V.K) at 822.94K-1). Conductivity of 7.07X 10 from the vicinity of room temperature2Ω-1.m-1Increased to 6.25X 10 at 775.82K3Ω-1.m-1Then 6.0X 10 at 822.94K with temperature drop3Ω-1.m-1. Total thermal conductivity from 0.55 at room temperature (WK)-1m-1) 0.16 (WK) at 775.82K-1m-1) Then increased to 0.29 at 822.94K (WK)-1m-1). The comprehensive thermoelectric performance of the medium-temperature thermoelectric material is maximum when T is 822.94K, and the maximum thermoelectric figure of merit is ZT 1.57.
Example 1:
according to the chemical formula Cu3.8Ga4.2Te8Weighing ternary element particles of Cu, Ga and Te with the purity of more than 99.999 wt.% and directly placing the ternary element particles in a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 950 ℃, directly cooling to 523 ℃ by water cooling and annealing for 72 hours after smelting and synthesizing, and cooling the annealed ingot from 523 ℃ to room temperature. Crushing and ball-milling the cast ingot cooled to room temperature, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by discharge plasma spark sintering, wherein the sintering time is 8 minutes, the sintering temperature is 750 ℃, and the sintering pressure is 65MPa, and preparing the Cu3.8Ga4.2Te8A thermoelectric material.
Example 2:
according to the chemical formula Cu3.9Ga4.2Te8Weighing ternary element particles of Cu, Ga and Te with the purity of more than 99.999 wt.% and directly placing the ternary element particles in a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 950 ℃, and directly cooling by water cooling after smelting and synthesizingAnnealing is carried out for 72 hours at the temperature of 523 ℃, and the annealed ingot is cooled from the temperature of 523 ℃ to the room temperature. Crushing and ball-milling the cast ingot cooled to room temperature, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by discharge plasma spark sintering, wherein the sintering time is 8 minutes, the sintering temperature is 750 ℃, and the sintering pressure is 65MPa, and preparing the Cu3.9Ga4.2Te8A thermoelectric material.
Example 3:
according to the chemical formula Cu4.0Ga4.2Te8Weighing ternary element particles of Cu, Ga and Te with the purity of more than 99.999 wt.% and directly placing the ternary element particles in a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 950 ℃, directly cooling to 523 ℃ by water cooling and annealing for 72 hours after smelting and synthesizing, and cooling the annealed ingot from 523 ℃ to room temperature. Crushing and ball-milling the cast ingot cooled to room temperature, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by discharge plasma spark sintering, wherein the sintering time is 8 minutes, the sintering temperature is 750 ℃, and the sintering pressure is 65MPa, and preparing the Cu4.8Ga4.0Te8A thermoelectric material.
Example 4:
according to the chemical formula Cu4.1Ga4.2Te8Weighing ternary element particles of Cu, Ga and Te with the purity of more than 99.999 wt.% and directly placing the ternary element particles in a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 950 ℃, directly cooling to 523 ℃ by water cooling and annealing for 72 hours after smelting and synthesizing, and cooling the annealed ingot from 523 ℃ to room temperature. Crushing and ball-milling the cast ingot cooled to room temperature, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by discharge plasma spark sintering, wherein the sintering time is 8 minutes, the sintering temperature is 750 ℃, and the sintering pressure is 65MPa, and preparing the Cu4.1Ga4.2Te8A thermoelectric material.
Example 5:
according to the chemical formula Cu4.3Ga4.2Te8Weighing ternary element particles of Cu, Ga and Te with the purity of more than 99.999 wt.% and directly placing the ternary element particles in a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 950 ℃, and smeltingDirectly cooling to 523 ℃ by water after smelting synthesis for annealing for 72 hours, and cooling the annealed ingot from 523 ℃ to room temperature. Crushing and ball-milling the cast ingot cooled to room temperature, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by discharge plasma spark sintering, wherein the sintering time is 8 minutes, the sintering temperature is 750 ℃, and the sintering pressure is 65MPa, and preparing the Cu4.3Ga4.2Te8A thermoelectric material.
Seebeck coefficient (. mu. V.K) of the material obtained in each of the above examples-1) Conductivity (omega)-1m-1) Thermal conductivity (WK)-1m-1) Thermoelectric figure of merit (ZT) is shown in table one below:
watch 1
As is clear from the above Table I, the thermoelectric material (Cu) produced in example 2 of the present invention3.9Ga4.2Te8) The medium-temperature thermoelectric material has the best thermoelectric performance, adopts the conventional powder metallurgy preparation process, has low cost and has practical application value.
Claims (3)
1. P-type Cu with excessive copper3.9Ga4.2Te8A medium-temperature thermoelectric material, characterized in that Cu is used as a material for a thermoelectric element3.8Ga4.2Te8The molar fraction of Cu in the solid solution is increased from 0.2375 to 0.2422, which constitutes Cu in excess of Cu3.9Ga4.2Te8A thermoelectric material.
2. P-type Cu with excessive copper3.9Ga4.2Te8The preparation process of medium-temperature thermoelectric material is characterized by that said preparation process is according to chemical formula Cu3.9Ga4.2Te8Proportioning three elements of Cu, Ga and Te, directly placing the mixture in a quartz tube for vacuum melting synthesis, wherein the melting synthesis temperature is 900-1000 ℃, the synthesis time is 20-28 hours, and cooling to 523 ℃ after melting synthesis for annealing for 72 hoursCooling the annealed cast ingot to room temperature, taking out the cast ingot, crushing and ball milling for 5 hours, sintering and forming the powder subjected to ball milling drying in a short time by spark discharge plasma spark for 5-10 minutes at the sintering temperature of 700-800 ℃ and the sintering pressure of 60-70 MPa, and preparing the Cu3.9Ga4.2Te8A thermoelectric material.
3. The P-type Cu of claim 2 in excess of copper3.9Ga4.2Te8The preparation process of the medium-temperature thermoelectric material is characterized in that the Cu3.9Ga4.2Te8The smelting synthesis temperature of the thermoelectric material is 950 ℃, the sintering temperature is 750 ℃, the sintering pressure is 65MPa, and the sintering time is 8 minutes.
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| KR101626933B1 (en) * | 2013-11-29 | 2016-06-02 | 주식회사 엘지화학 | New compound semiconductors and their application |
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