阅读说明：本技术 一种ZrNiSn基Half-Heusler热电材料及其制备和调控反位缺陷的方法 (ZrNiSn-based Half-Heusler thermoelectric material and preparation method thereof and method for regulating and controlling inversion defects ) 是由 康慧君 王同敏 杨雄 郭恩宇 陈宗宁 李廷举 曹志强 卢一平 接金川 张宇博 于 2019-09-11 设计创作，主要内容包括：本发明提供一种ZrNiSn基Half-Heusler热电材料及其制备和调控反位缺陷的方法,ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法包括以下步骤：在氩气氛围或者密闭无氧环境中按照原子比1：1：1将Zr、Ni、Sn混合,将混合物料置于磁悬浮熔炼炉中熔炼得到铸锭,将铸锭研磨后干燥获得粉体,采用放电等离子体烧结技术将粉体烧结后至于真空容器中,热处理后淬火得到ZrNiSn基Half-Heusler热电材料。本发明所述方法流程短、步骤少、易控制,能成功的制备出具有反位缺陷的ZrNiSn单相Half-Heusler热电材料。(The invention provides a ZrNiSn-based Half-Heusler thermoelectric material and a preparation method and a method for regulating and controlling a flip defect thereof, wherein the preparation method and the method for regulating and controlling the flip defect of the ZrNiSn-based Half-Heusler thermoelectric material comprise the following steps: in an argon atmosphere or a closed oxygen-free environment, according to the atomic ratio of 1: 1: 1, mixing Zr, Ni and Sn, putting the mixture into a magnetic suspension smelting furnace to be smelted to obtain an ingot, grinding the ingot, drying to obtain powder, sintering the powder by adopting a discharge plasma sintering technology, putting the powder into a vacuum container, and quenching after heat treatment to obtain the ZrNiSn-based Half-Heusler thermoelectric material. The method has the advantages of short flow, few steps and easy control, and can successfully prepare the ZrNiSn single-phase Half-Heusler thermoelectric material with the inversion defect.)

1. A method for preparing ZrNiSn-based Half-Heusler thermoelectric material and regulating and controlling inversion defects is characterized by comprising the following steps:

according to the atomic ratio of 1: 1: 1, mixing Zr, Ni and Sn, putting the mixture into a magnetic suspension smelting furnace to be smelted to obtain an ingot, grinding the ingot, drying to obtain powder, sintering the powder by adopting a discharge plasma sintering technology, putting the powder into a vacuum container, and quenching after heat treatment to obtain the ZrNiSn-based Half-Heusler thermoelectric material.

2. The method for preparing ZrNiSn based Half-Heusler thermoelectric material and regulating inversion defect according to claim 1, which comprises the following steps:

(1) according to the atomic ratio of 1: 1: 1 mixing Zr, Ni and Sn;

(2) placing the mixed material into a magnetic suspension smelting furnace for smelting, wherein the smelting is carried out under the argon protection atmosphere, heating the mixed material to 1600-1800 ℃, and then preserving heat for 1-5 min to obtain an ingot;

(3) ball-milling the cast ingot to 0.5-2 μm, and naturally drying to obtain powder;

(4) sintering the powder by adopting a discharge plasma sintering technology, wherein the sintering temperature is 900-;

(5) placing the sintered powder into a vacuum container;

(6) placing the vacuum container filled with the powder in a box type high-temperature sintering furnace for long-time diffusion annealing treatment; the annealing temperature is 800-;

(7) and carrying out rapid quenching treatment on the heat-insulated sample to obtain the ZrNiSn-based Half-Heusler thermoelectric material.

3. The method for preparing and regulating the inversion defect of the ZrNiSn based Half-Heusler thermoelectric material as claimed in claim 1 or 2, wherein the purity of the Zr, Ni and Sn is more than or equal to 99.9%.

4. The method for preparing and regulating the dislocation defect of the ZrNiSn based Half-Heusler thermoelectric material as claimed in claim 2, wherein the melting in the step (2) is performed 3-6 times.

5. The method for preparing ZrNiSn based Half-Heusler thermoelectric material and regulating inversion defects according to claim 2, wherein the nitrogen atmosphere pressure in the step (2) is 10⁴-10⁵Pa。

6. The method for preparing and regulating the inversion defect of the ZrNiSn based Half-Heusler thermoelectric material as claimed in claim 2, wherein the ball milling in the step (3): firstly, roughly grinding cast ingots into powder with the particle size of 0.1-1mm by using a mortar; then carrying out wet ball milling in an argon atmosphere; the ball milling medium is absolute ethyl alcohol, the ball-material ratio is 10:1-20:1, and the rotating speed is as follows: 200 and 600r/min, and the ball milling time is 5-20 h.

7. The method for preparing and controlling the dislocation defect of the ZrNiSn based Half-Heusler thermoelectric material as claimed in claim 2, wherein the drying in the step (3): and naturally drying the powder subjected to suction filtration for 12-48h in an argon atmosphere or a sealed oxygen-free environment.

8. The method for preparing ZrNiSn based Half-Heusler thermoelectric material and regulating inversion defects according to claim 2, wherein the vacuum degree of the vacuum container in the step (5) is less than or equal to 5 x 10^-3Pa。

9. The method for preparing and controlling the dislocation defect of the ZrNiSn based Half-Heusler thermoelectric material as claimed in claim 2, wherein the quenching medium for quenching in the step (7) is water.

10. A ZrNiSn-based Half-Heusler thermoelectric material, prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to a thermoelectric material technology, in particular to a ZrNiSn-based Half-Heusler thermoelectric material and a preparation method thereof as well as a method for regulating and controlling a flip defect.

Background

The thermoelectric power generation technology has important application value in the fields of special power supplies, green energy, environmental energy collection, industrial waste heat power generation and the like. In recent years, the thermoelectric figure of merit ZT of thermoelectric materials is continuously getting breakthrough, and the corresponding thermoelectric device application technology is also greatly developed. The thermoelectric material is an effective energy material capable of directly converting thermal energy into electric energy, has the characteristics of high stability, simple structure and the like, but the application of the thermoelectric material is limited due to low energy efficiency. Therefore, how to effectively improve the efficiency of the thermoelectric material is the next research focus. In recent years, Half Heusler alloys with semiconductor characteristics or the seebeck effect have good application prospects in the field of thermoelectric power generation, and can be used as a typical medium-high temperature thermoelectric material.

The performance of the thermoelectric material is mainly determined by the thermoelectric figure of merit ZT, and the larger the ZT value is, the higher the thermoelectric conversion efficiency is. Thermoelectric figure of merit is defined as ZT ═ alpha²Sigma T/kappa, wherein alpha is Seebeck (Seebeck)) Coefficient, σ, conductivity, α²σ can also be defined as the power factor PF, T is the absolute temperature, and κ is the total thermal conductivity, including the lattice (phonon) thermal conductivity κ_lAnd electron thermal conductivity κ_e(κ＝κ_l+κ_e). However, due to these thermoelectric parameters (Seebeck coefficient α, electrical conductivity σ, and electron thermal conductivity κ_e) Has strong dependence on the carrier concentration n and is mutually coupled, namely, the high electrical conductivity sigma obtained by adjusting the carrier concentration n can lead to low Seebeck coefficient alpha and high electronic thermal conductivity kappa_e. Therefore, how to effectively improve the ZT value is always a difficult problem which besets the academic world.

The Half-Heusler compounds are considered to be potential thermoelectric materials with large-scale commercial production and application due to their good high-temperature chemical and thermal stability, excellent mechanical properties, and higher high-temperature thermoelectric figure-of-merit. However, the thermoelectric property of the ZrNiSn-based Half-Heusler compound is sensitive to the preparation process, and different preparation processes are easy to cause the difference of the microstructure and the atomic disorder degree of the material. Since the atomic radii of Zr and Sn are similar, the defect is easily generated in situ during the high temperature manufacturing process and recovered by annealing. When the content of Zr/Sn inversion defects is higher, the ZrNiSn thermoelectric material is converted from the semiconductor characteristic to the semimetal characteristic. However, early preparation conditions made it difficult to obtain single phase samples by direct smelting and structural defects made it difficult to obtain reliable results.

Disclosure of Invention

The invention aims to provide a method for preparing a ZrNiSn-based Half-Heusler thermoelectric material and regulating and controlling a flip defect aiming at the problem that the ZT value of the conventional thermoelectric material cannot be effectively improved.

In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing ZrNiSn based Half-Heusler thermoelectric material and regulating and controlling inversion defects comprises the following steps:

in an argon atmosphere or a closed oxygen-free environment, according to the atomic ratio of 1: 1: 1, mixing Zr, Ni and Sn, putting the mixture into a magnetic suspension smelting furnace to be smelted to obtain an ingot, grinding the ingot, drying to obtain powder, sintering the powder by adopting a discharge plasma sintering technology, putting the powder into a vacuum container, and quenching after heat treatment to obtain the ZrNiSn-based Half-Heusler thermoelectric material.

Further, the method for preparing the ZrNiSn based Half-Heusler thermoelectric material and regulating and controlling the inversion defect comprises the following steps:

(1) in order to prevent oxidation, the reaction solution is prepared in an argon atmosphere or a sealed oxygen-free environment according to the atomic ratio of 1: 1: 1 mixing Zr, Ni and Sn;

(2) placing the mixed material into a magnetic suspension smelting furnace for smelting, wherein the smelting is carried out under the argon protection atmosphere, heating the mixed material to 1600-1800 ℃, then preserving heat for 1-5 min to obtain an ingot, preferably heating to 1650-1750 ℃, and preserving heat for 3-5 min to obtain an ingot;

(3) ball-milling the cast ingot to 0.5-2 μm, and naturally drying to obtain powder;

(4) sintering the powder by adopting a discharge plasma sintering technology, wherein the sintering temperature is 800-; the preferable sintering temperature is 900-;

(5) placing the sintered powder into a vacuum container;

(6) placing the vacuum container filled with the powder in a box type high-temperature sintering furnace for long-time diffusion annealing treatment; the annealing temperature is 800-; the preferred annealing temperature is 900-

(7) And (3) carrying out rapid quenching treatment on the vacuum container filled with the sample after heat preservation to obtain the ZrNiSn-based Half-Heusler thermoelectric material, wherein the cooling rate is 200-.

Furthermore, the purities of the Zr, the Ni and the Sn are more than or equal to 99.9 percent.

Further, the Zr, Ni and Sn are selected from small particles with the diameter multiplied by the length of 1 multiplied by 2mm to 2 multiplied by 5 mm.

Further, the smelting in the step (2) is carried out for 3-6 times so as to ensure the uniformity of the smelted structure.

Further, the pressure of the nitrogen protective atmosphere in the step (2) is 10⁴-10⁵Pa。

Further, the ball milling in the step (3): firstly, roughly grinding cast ingots into powder with the particle size of 0.1-1mm by using a mortar; and then performing wet ball milling under an argon atmosphere. The ball milling medium is absolute ethyl alcohol, the ball-material ratio is 10:1-20:1, and the rotating speed is as follows: 200 and 600r/min, and the ball milling time is 5-20 h.

Further, the drying in the step (3): and naturally drying the powder subjected to suction filtration for 12-48h in an argon atmosphere or a sealed oxygen-free environment.

Further, the vacuum degree of the vacuum container in the step (5) is less than or equal to 5 multiplied by 10^-3Pa. The vacuum vessel includes, but is not limited to, a quartz glass tube having a diameter of 15-30 mm.

Further, the quenching medium for quenching in the step (7) is water.

The invention also discloses a ZrNiSn-based Half-Heusler thermoelectric material which is prepared by adopting the method.

Compared with the prior art, the ZrNiSn-based Half-Heusler thermoelectric material and the preparation method thereof and the method for regulating and controlling the inversion defect have the following advantages that:

the invention takes ZrNiSn alloy as a research target, prepares a single-phase ZrNiSn-based Half-Heusler thermoelectric material by combining magnetic suspension smelting with a discharge plasma sintering process, and adjusts the concentration of the inversion defect through different heat treatment processes. The composition of the samples was characterized using XRD and tested for the relevant thermoelectric properties. The result shows that the ZrNiSn-based Half-Heusler reverse defect thermoelectric material prepared by the method has the advantages of short flow, few steps, easiness in control and the like. By regulating the concentration of the inversion defects, relevant thermoelectric parameters caused by the change of the inversion defects can be effectively regulated, so that the thermoelectric figure of merit (ZT) of the material is improved. The results show that the single-phase ZrNiSn-based Half-Heusler thermoelectric material can be effectively prepared by adopting the magnetic suspension smelting combined with the discharge plasma sintering process, and the concentration of the inversion defects can be effectively regulated and controlled by different heat treatment processes.

By applying the method, the ZrNiSn thermoelectric materials with different heat treatment processes are all single-phase through XRD detection, the conductivity of the material is directly measured by adopting a four-probe method through a laser thermal conductivity meter, and the result shows that the inversion defects of the sample are gradually reduced and the conductivity is gradually reduced along with the increase of the diffusion annealing temperature. And when the inversion defects are found to be reduced through calculation, the power factor of the sample is correspondingly reduced. The final calculation result shows that the increase of the inversion defects can effectively improve the thermoelectric figure of merit (ZT) of the material. The invention obtains a method for successfully preparing the ZrNiSn single-phase Half-Heusler thermoelectric material with the inversion defect and discloses the influence of the inversion defect on the thermoelectric property of the Half-Heusler thermoelectric material with the ZrNiSn component.

Drawings

FIG. 1 shows XRD of samples after spark plasma sintering of different compositions.

FIG. 2 shows the electrical conductivity of a ZrNiSn component Half-Heusler thermoelectric material with different heat treatment processes.

FIG. 3 shows power factors of the ZrNiSn component Half-Heusler thermoelectric material of different heat treatment processes.

FIG. 4 shows thermoelectric figure of merit of the ZrNiSn component Half-Heusler thermoelectric material of different heat treatment processes.

Detailed Description

The invention is further illustrated by the following examples: