CN108242500B - Copper-selenium-based nano composite thermoelectric material and preparation method thereof - Google Patents

Copper-selenium-based nano composite thermoelectric material and preparation method thereof Download PDF

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CN108242500B
CN108242500B CN201611218178.9A CN201611218178A CN108242500B CN 108242500 B CN108242500 B CN 108242500B CN 201611218178 A CN201611218178 A CN 201611218178A CN 108242500 B CN108242500 B CN 108242500B
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CN108242500A (en
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史迅
赵琨鹏
陈立东
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Shanghai Institute of Ceramics of CAS
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen

Abstract

The invention relates to a copper-selenium-based nano composite thermoelectric material and a preparation method thereof, wherein the p-type nano composite thermoelectric material comprises Cu2‑xSe1‑y‑zSyTezAnd distributed in the Cu2‑xSe1‑y‑ zSyTezWherein x is more than or equal to 0 and less than or equal to 0.15, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, y + z is less than or equal to 1, and the mass percent of the carbon nano tube is less than or equal to 2%. The preparation method has the advantages of rich sources of raw materials, low cost, simple production process and production equipment, and good controllability and repeatability.

Description

Copper-selenium-based nano composite thermoelectric material and preparation method thereof
Technical Field
The invention relates to a copper-selenium-based nano composite thermoelectric material and a preparation method thereof, in particular provides a novel p-type nano composite thermoelectric material and a preparation method thereof, and belongs to the field of thermoelectric materials.
Background
The thermoelectric conversion material is a clean energy material which directly realizes the interconversion between thermal energy and electric energy by utilizing the Seebeck effect and the Peltier effect of the material. It can use the temperature difference of nature, industrial waste heat and afterheat to generate electricity, and can be made into refrigerator without noise and drive device and with high reliability. The transduction efficiency of a thermoelectric material is determined by the high and low end temperatures at which the material operates and the intrinsic properties of the material. For certain use environments, the high and low end temperatures are usually determined, so that only optimization of the material itself can be used for improving the transduction efficiency. The nondimensional thermoelectric figure of merit ZT is generally used to evaluate the energy conversion efficiency of thermoelectric materials, and is defined by the following formula: ZT ═ S2T σ/κ, where S is the thermoelectric potential (seebeck coefficient), T is the absolute temperature, σ is the electrical conductivity, and κ is the thermal conductivity. In order to obtain high thermoelectric conversion efficiency, the material must have a high thermoelectric figure of merit. The thermoelectric materials that have been used up to now are mostly metal compounds and their solid solutions, such as Bi2Te3SiGe, PbTe and the like, but the preparation conditions of the thermoelectric materials are high, the thermoelectric materials need to be prepared under certain protective gas, heavy metals harmful to human bodies are contained, and the ZT value is about 1.0, so that the energy conversion efficiency is not high, and the like. In recent decades, researchers have realized a great improvement in thermoelectric performance of thermoelectric materials through various means, such as doping, compounding, nanocrystallization, and searching for new compounds.
Copper selenium based compound Cu2-xM (M ═ S, Se or Te) is a novel thermoelectric material, and has the advantages of simple composition, low raw material price, higher Seebeck coefficient, lower thermal conductivity and excellent thermoelectric performance. Cu2-xM (M ═ S, Se, or Te) shows p-type conductivity behavior due to Cu vacancies, and the conductivity increases with increasing x value. Due to its moderate forbidden band width (Cu)2Se and Cu2S is about 1.2eV, Cu2Te is about 1.1eV), so the material is an ideal material for solar cells, the research on the material is mostly focused on the aspect of the cells, only a few documents report that the material has larger thermoelectric potential and lower thermal conductivity, and the research on the thermoelectric property of a solid solution formed between the compounds is little.
In recent years, processes such as vacuum melting, high-temperature self-propagating synthesis, hydrothermal synthesis and spark plasma sintering are used for preparing the copper-selenium-based bulk thermoelectric material in sequence. Among them, vacuum melting combined with spark plasma sintering is the manufacturing process of most copper-selenium based bulk thermoelectric materials. But Cu2Se and Cu2In the preparation process, copper is easily separated out, so that the carrier concentration is increased, the thermal conductivity of the material is greatly increased, and the thermoelectric property of the material is reduced. On the other hand, the material prepared by the method has larger crystal grains and weaker scattering to short-wave phonons.
Disclosure of Invention
Therefore, the invention provides a copper-selenium-based nano composite thermoelectric material and a preparation method thereof.
In one aspect, the present invention provides a p-type nanocomposite thermoelectric material (copper-selenium-based nanocomposite thermoelectric material) comprising Cu2-xSe1-y-zSyTezAnd distributed in the Cu2-xSe1-y-zSyTezWherein x is more than or equal to 0 and less than or equal to 0.15, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, y + z is less than or equal to 1, and the mass percent of the carbon nano tube is less than or equal to 2%.
Preferably, the diameter of the carbon nanotube is 10 to 20 nanometers, and the length is more than 3 μm.
In another aspect, the present invention further provides a method for preparing a p-type nanocomposite thermoelectric material, comprising:
in the general formula Cu2-xSe1-y-zSyTezThe elementary substance powder and the carbon nano tube in the alloy are used as initial raw materials according to Cu2- xSe1-y-zSyTezStoichiometric ratio of (C) and Cu2-xSe1-y-zSyTezWeighing the carbon nano tubes according to the mass ratio, and then ball-milling for 5-48 hours at the ball-milling rotating speed of 450-500 r/min;
and (3) after the ball-milled mixed powder is prepared and molded, the mixture is subjected to pressure sintering at the temperature of 450-600 ℃ and the pressure of 60-65MPa, and the p-type nano composite thermoelectric material is obtained.
The invention is represented by the general formula Cu2-xSe1-y-zSyTezThe elemental powder and the carbon nano tube in the nano composite material are used as initial raw materials, after mixing, the mechanical energy generated by ball milling (high-energy ball milling: ball milling is carried out for 5-48 hours at the ball milling rotating speed of 450-500 r/min) is utilized to induce the change of the organization, structure and performance of the material and chemical reaction, and the material particles are induced to generate lattice defects and dislocation, generate plastic deformation and are cold welded, so that the nano composite material with the uniformly distributed carbon nano tubes is obtained. The reaction process is approximately as follows: (2-x) Cu + (1-y-z) Se + yS + zTe + n% CNT → Cu2-xSe1-y-zSyTezN% CNT). Then the raw materials are combined with pressure sintering to obtain the block material. The method of the invention can adjust the carrier concentration of the copper selenium-based compound on one hand, and can nanocrystallize crystal grains, enhance phonon scattering and reduce thermal conductivity on the other hand, thereby improving thermoelectric performance.
Preferably, the purity of the carbon nano tube is more than 96 percent,conductivity > 104S/m。
Preferably, the particle size of the elementary substance powder is less than or equal to 100 meshes.
Moreover, the purity of the elementary substance powder of each element is preferably more than 99.9%.
Preferably, the initial raw materials and the tungsten carbide balls are put into a ball milling pot made of tungsten carbide in an argon atmosphere glove box and ball milling is carried out.
Preferably, the mass ratio of the tungsten carbide ball to the starting material is 5:1 to 20: 1.
Preferably, the pressure sintering is discharge plasma sintering, and the time of the discharge plasma sintering is 5-10 minutes.
In yet another aspect, the present invention provides the use of a p-type nanocomposite thermoelectric material of the present invention in a thermoelectric device. The thermoelectric device comprises a thermoelectric power generation or thermoelectric refrigeration device in a medium-high temperature region, such as a thermoelectric power generation or thermoelectric refrigeration device in automobile exhaust and industrial production, particularly in a medium-high temperature region in the metallurgical industry.
In the invention, the p-type nano composite thermoelectric material is suitable for thermoelectric power generation or thermoelectric refrigeration in medium and high temperature regions, such as in automobile exhaust and industrial production, especially in the metallurgical industry, the power generation is carried out by utilizing high-temperature waste heat and waste heat thereof, the effective utilization of a low-density heat source can be realized, and the purposes of energy conservation and emission reduction can be achieved to a certain extent.
The Seebeck coefficient of the material of the invention gradually increases with the rise of temperature, the conductivity changes non-monotonously with the rise of temperature, and the change trend of the conductivity changes near the solid phase transition temperature. Meanwhile, the carrier concentration decreases with the increase of the carbon nanotube content, and the thermal conductivity decreases with the increase of the carbon nanotube content. So that the thermoelectric figure of merit can reach about 1.0 at 750K, and the thermoelectric performance is better.
In addition, the preparation method has the advantages of rich raw material sources, low cost, simple production process and production equipment, and good controllability and repeatability. The carbon nano-tubes in the p-type nano-composite thermoelectric material are uniformly distributed, and the p-type nano-composite thermoelectric material has better thermoelectric performance.
Drawings
FIG. 1 is a schematic flow diagram of a production process of the present invention;
FIG. 2 is a nanocomposite thermoelectric material (Cu) according to one embodiment of the present invention2Se/0.25% CNTs), wherein (a) is the electrical resistivity of the nanocomposite, (b) is the seebeck coefficient of the nanocomposite, (c) is the thermal conductivity of the nanocomposite, and (d) is the thermoelectric figure of merit ZT of the nanocomposite;
FIG. 3 is a nanocomposite thermoelectric material (Cu) according to one embodiment of the present invention2Se/0.5% CNTs), wherein (a) is the electrical resistivity of the nanocomposite, (b) is the seebeck coefficient of the nanocomposite, (c) is the thermal conductivity of the nanocomposite, and (d) is the thermoelectric figure of merit ZT of the nanocomposite;
FIG. 4 is a nanocomposite thermoelectric material (Cu) according to one embodiment of the invention2Se0.5Te0.50.5% CNTs), wherein the upper left graph is the electrical resistivity of the nanocomposite, the upper right graph is the seebeck coefficient of the nanocomposite, the lower left graph is the thermal conductivity of the nanocomposite, and the lower right graph is the thermoelectric figure of merit ZT of the nanocomposite;
FIG. 5 is a nanocomposite thermoelectric material (Cu) according to an embodiment of the present invention2Se/0.5% CNTs).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The general formula of the material synthesized by the invention is Cu2-xSe1-y-zSyTezThe CNTs (wherein the CNTs are carbon nano tubes, m% is mass percent), wherein the value of x is 0-0.15, the value of y is 0-1, the value of z is 0-1, y + z is less than or equal to 1, and the mass percent of the carbon nano tubes is more than 0 and less than or equal to 2 percent.
The preparation process of the invention is realized by the processes of material preparation, ball milling (high energy ball milling) and spark plasma sintering, and fig. 1 shows a process flow chart of the material preparation, which specifically comprises the following steps: to be provided withGeneral formula Cu2-xSe1-y-zSyTezThe stoichiometric ratio of the CNTs is respectively weighed high-purity powder of each element simple substance and the carbon nano tube with the mass percent of m percent as initial raw materials. Weighing, charging and high-energy ball milling to obtain the nano composite thermoelectric material powder. And performing SPS sintering on the obtained nano composite thermoelectric material powder to obtain a compact wafer, and finally performing performance tests such as thermal conductivity, electric conductivity, Seebeck and the like. The following is an exemplary description of the method of preparing the novel p-type nanocomposite thermoelectric material provided by the present invention.
In the general formula Cu2-xSe1-y-zSyTezThe elementary substance powder and the carbon nano tube in the alloy are used as initial raw materials according to Cu2- xSe1-y-zSyTezStoichiometric ratio of (C) and Cu2-xSe1-y-zSyTezAnd weighing the carbon nano tube according to the mass ratio. The diameter of the carbon nano tube can be 10-20 nanometers, and the length is more than 3 mu m. The particle size of each element simple substance powder is less than or equal to 100 meshes, and the purity of each element simple substance powder is more than 99.9%. The present invention adopts high-purity powder of each element simple substance and carbon nanotubes as initial raw materials, such as copper powder (about 100 mesh) with a purity of 99.95%, selenium powder (about 100 mesh) with a purity of 99.9%, sulfur powder (about 100 mesh) with a purity of 99.9% and tellurium powder (about 100 mesh) with a purity of 99.9%, respectively. The carbon nanotube is multi-wall carbon nanotube with purity of more than 96%, diameter of 10-20 nm, length of more than 3mm, and electrical conductivity of more than 104And (5) S/m. Starting material Cu2-xSe1-y-zSyTezThe nominal stoichiometric ratio in the m% CNTs was weighed.
And (3) after the weighed initial raw materials are subjected to high-energy ball milling for 5-48 hours at the ball milling rotating speed of 450-500 r/min. The initial raw materials are loaded into a tungsten carbide ball milling tank under inert atmosphere. The ball-to-material ratio of the high-energy ball mill can be 5:1-20: 1. As an example, the charging process is to charge initial raw material powder (each element simple substance high-purity powder and carbon nano tubes) and tungsten carbide balls into a ball milling tank made of tungsten carbide in a glove box in an inert atmosphere (such as argon atmosphere) and then start high-energy ball milling, wherein the mass ratio of the tungsten carbide balls to the initial raw materials can be 5:1-20: 1.
And sintering and molding the nano composite material obtained by ball milling. As an example, the p-type nanocomposite thermoelectric material is obtained by preparing and molding the mixed powder after the high-energy ball milling, and then performing pressure sintering at 450-600 ℃ and 60-65 MPa. The sintering mode can be spark plasma sintering.
The molding may be performed by using a sintering mold (e.g., a graphite mold), and Boron Nitride (BN) is sprayed inside the mold and at the upper and lower indenters for insulation. Wherein the sintering temperature is 450-600 ℃, the pressure is 60-65MPa, and the sintering time is 5-10 minutes.
The invention carries out high-energy ball milling on high-purity copper powder, selenium powder (sulfur powder or tellurium powder) and carbon nano tubes in inert atmosphere to obtain nano composite material powder, and then sintering is carried out by discharge plasma (SPS) to obtain the block material. The method is simple and reliable, the grain size of the obtained material is nano-scale, the carbon nano tubes are uniformly distributed, the lattice thermal conductivity can be obviously reduced, and the thermoelectric performance is improved.
In the invention, the nano composite Cu with part regulated by carrier concentration2-xSe1-y-zSyTezThe thermoelectric figure of merit ZT of the/m% CNTs can reach 1.0 and above at 750K, and the method is suitable for application in medium and high temperature regions. And, the Cu2- xSe1-y-zSyTezThe/m% CNTs nano composite thermoelectric material has higher Seebeck coefficient and lower thermal conductivity.
The present invention will be described in detail by way of 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 exemplified below.
Example 1: cu2Se/0.25％CNTs(x＝0,y＝0，z＝0，m＝0.25)
Weighing high-purity powder raw materials Cu powder and Se powder according to a molar ratio of 2:1, and adding 0.25 mass percent of carbon nano tubes. Then, the powder raw materials, the carbon nano tubes and the tungsten carbide balls are put into a ball milling tank made of tungsten carbide in an argon atmosphere glove box. Wherein the ball-to-material ratio is 10: 1. Then high-energy ball milling is carried out at the rotating speed of 500 revolutions per minute, and the ball milling time is 48 hours;
and (3) performing discharge plasma sintering (SPS sintering) on the nano composite material obtained by ball milling, wherein the sintering temperature is 480 ℃, the pressure is 65MPa, and the sintering time is 5 minutes, so as to finally obtain the compact block material.
As shown in FIG. 2, the resulting Cu2Thermoelectric property measurements of Se/0.25% CNTs bulk material show that the material has a higher Seebeck coefficient and a lower resistivity in the measured temperature region (300-750K). At the same time, has very low thermal conductivity: within the temperature range of 300-750K, the value is less than 0.8Wm-1K-1. The ZT value of the material calculated according to the performance measurement value can reach 1.05 at 750K.
Example 2: cu2Se/0.5％CNTs(x＝0,y＝0，z＝0，m＝0.5)
Weighing high-purity powder raw materials Cu powder and Se powder according to a molar ratio of 2:1, and adding 0.5 mass percent of carbon nano tubes. Then, the powder raw materials, the carbon nano tubes and the tungsten carbide balls are put into a ball milling tank made of tungsten carbide in an argon atmosphere glove box. Wherein the ball-to-material ratio is 10: 1. Then high-energy ball milling is carried out at the rotating speed of 500 revolutions per minute, and the ball milling time is 48 hours;
and (3) performing discharge plasma sintering (SPS sintering) on the nano composite material obtained by ball milling, wherein the sintering temperature is 480 ℃, the pressure is 65MPa, and the sintering time is 5 minutes, so as to finally obtain the compact block material.
As shown in FIG. 3, the resulting Cu2Thermoelectric property measurements of Se/0.5% CNTs bulk material show that the material has a higher Seebeck coefficient and a lower resistivity in the measured temperature region (300-750K). At the same time, has very low thermal conductivity: within the temperature range of 300-750K, the value is less than 0.7Wm-1K-1. According to performance measuresThe ZT value of the material can reach 1.25 at 750K.
Example 3: cu2Se0.5Te0.5/0.5％CNTs(x＝0,y＝0，z＝0.5，m＝0.5)
Weighing high-purity powder raw materials of Cu powder, Se powder and Te powder according to the molar ratio of 2:0.5:0.5, and adding carbon nano tubes with the mass fraction of 0.5%. Then, the powder raw materials, the carbon nano tubes and the tungsten carbide balls are put into a ball milling tank made of tungsten carbide in an argon atmosphere glove box. Wherein the ball-to-material ratio is 10: 1. Then high-energy ball milling is carried out at the rotating speed of 500 revolutions per minute, and the ball milling time is 24 hours;
and (3) performing discharge plasma sintering (SPS sintering) on the nano composite material obtained by ball milling, wherein the sintering temperature is 600 ℃, the pressure is 65MPa, and the sintering time is 5 minutes, so as to finally obtain the compact block material.
As shown in FIG. 4, the resulting Cu2Se0.5Te0.5Thermoelectric property measurements of a 0.5% CNTs bulk material show that the material has a higher Seebeck coefficient, lower electrical resistivity and lower thermal conductivity within the measured temperature region (300-. The ZT value of the material calculated according to the performance measurement value can reach 0.7 at 750K.
FIG. 5 is a nanocomposite thermoelectric material (Cu) according to an embodiment of the present invention2Se/0.5% CNTs) and the grain size is about several tens of nanometers.

Claims (8)

1. A p-type nanocomposite thermoelectric material, characterized in that the p-type nanocomposite thermoelectric material comprises Cu2-xSe1- zTezAnd distributed in the Cu2-xSe1-zTezWherein x is more than or equal to 0 and less than or equal to 0.15, z is more than or equal to 0 and less than or equal to 1, and the mass percent of the carbon nano tube is less than or equal to 2 percent;
the preparation method of the p-type nanocomposite thermoelectric material comprises the following steps:
in the general formula Cu2-xSe1-zTezThe elementary substance powder and the carbon nano tube in the alloy are used as initial raw materials according to Cu2-xSe1-zTezStoichiometric ratio ofAnd Cu2-xSe1-zTezWeighing the carbon nano tube according to the mass ratio, and ball-milling for 5-48 hours in an inert atmosphere at a ball-milling rotating speed of 450-500 r/min to obtain Cu2-xSe1-zTeza/CNT nanocomposite;
ball-milled Cu2-xSe1-zTezAnd after the/CNT nano composite material is prepared and molded, carrying out pressure sintering at 450-600 ℃ and 60-65MPa to obtain the p-type nano composite thermoelectric material.
2. The p-type nanocomposite thermoelectric material according to claim 1, wherein the carbon nanotubes have a diameter of 10 to 20 nm and a length of > 3 μm.
3. The p-type nanocomposite thermoelectric material according to claim 1, wherein the carbon nanotubes have a purity of > 96% and an electrical conductivity of > 104S/m。
4. The p-type nanocomposite thermoelectric material as claimed in claim 1, wherein the particle size of the elemental powder of each element is 100 mesh or less.
5. The p-type nanocomposite thermoelectric material as claimed in claim 4, wherein the purity of the elemental powder of each element is > 99.9%.
6. The p-type nanocomposite thermoelectric material according to claim 1, wherein the starting materials and the tungsten carbide balls are ball-milled in a ball-milling pot made of tungsten carbide in an argon atmosphere glove box.
7. The p-type nanocomposite thermoelectric material according to claim 6, wherein the mass ratio of the tungsten carbide spheres to the starting raw material is 5:1 to 20: 1.
8. The p-type nanocomposite thermoelectric material according to any one of claims 1 to 7, wherein the pressure sintering is spark plasma sintering, and the time of the spark plasma sintering is 5 to 10 minutes.
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