CN113004045A - High-content heavy element doped beta-FeSi2Base thermoelectric material and preparation method thereof - Google Patents

High-content heavy element doped beta-FeSi2Base thermoelectric material and preparation method thereof Download PDF

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CN113004045A
CN113004045A CN201911309148.2A CN201911309148A CN113004045A CN 113004045 A CN113004045 A CN 113004045A CN 201911309148 A CN201911309148 A CN 201911309148A CN 113004045 A CN113004045 A CN 113004045A
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fesi
thermoelectric material
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sintering
base thermoelectric
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史迅
杜小龙
仇鹏飞
陈立东
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a method for doping heavy elements with high contentβ‑FeSi2Based thermoelectric material and method for producing the sameβ‑FeSi2The chemical composition of the base thermoelectric material is Fe x1‑M x Si2M is at least one of Ta, W, Re, Os, Ir and Pt, 0 < (R) >x≤0.50。

Description

High-content heavy element doped beta-FeSi2Base thermoelectric material and preparation method thereof
Technical Field
The invention relates to high-content heavy element doped beta-FeSi2A base thermoelectric material and a preparation method thereof belong to the field of thermoelectric materials.
Background
At present, the human society is developing rapidly, along with the increasing flourishing of economy and culture, the demand and consumption of people for resources such as natural gas, petroleum and the like are increasing, and the problems of energy and environment are highlighted day by day. During the use of a wide variety of energy sources, a significant proportion of the energy is not efficiently utilized and is released to the atmosphere as waste heat. The energy is collected and fully used, the energy utilization efficiency is improved, and an important way for solving the energy crisis is provided. In such a large background, the thermoelectric material has received much attention because it can directly realize interconversion between thermal energy and electric energy. The system has the characteristics of no pollution, no mechanical transmission, no noise, high stability and the like, and has unique advantages in the fields of industrial waste heat recovery, deep space exploration power supply, special electronic refrigeration and the like.
Thermoelectric materials achieve the interconversion of thermal and electrical energy based on two effects: the Seebeck effect and the Peltier effect. The Seebeck effect means that if a temperature difference exists between two ends of a conductor, a potential difference is generated inside the conductor, and the potential difference forms the theoretical basis of thermoelectric power generation. The Peltier effect is a phenomenon that when current is applied to a loop composed of different conductors, heat absorption occurs at one end and heat release occurs at the other end of the loop, which also forms the theoretical basis of thermoelectric refrigeration. The energy conversion efficiency of a thermoelectric material depends on the high and low end temperatures at which the material operates and the properties of the material itself. High and low end temperatures are generally determined for a particular use environment, and therefore, increasing the energy conversion efficiency of thermoelectric materials is often achieved by increasing material performance. The performance of thermoelectric materials is often described by a dimensionless figure of merit, zT, where zT ═ S2σT/(κe+κL) In the formula, S, sigma, T, kappae,κLThe Seebeck coefficient, the electrical conductivity, the absolute temperature, the electron thermal conductivity and the lattice thermal conductivity are respectively expressed. Typical thermoelectric materials such as Bi2Te3、PbTe、CoSb3、La3T4And Half-hesler alloy and the like, have a series of problems such as toxic composition elements, poor material thermal stability and easy oxidation while having high performance, and are difficult to effectively realize from materials to devicesAnd (6) transition. On the premise of high-temperature application, the material is required to be green, nontoxic and good in stability.
β-FeSi2The base thermoelectric material has great potential in the field of thermoelectric power generation. Firstly, the components are green and nontoxic, and are very environment-friendly. Second, beta-FeSi2The high-temperature-resistant thermoelectric material has excellent thermal stability and oxidation resistance, and can realize thermoelectric conversion in a wide temperature range of 300-1200K. More importantly, N and P type materials are easily obtained through doping of neighbor elements, and the homologous N and P thermoelectric legs bring great convenience to the manufacture of thermoelectric devices and lay a solid foundation for industrial application of materials.
β-FeSi2The compound has the characteristics of environmental friendliness, outstanding thermal stability and oxidation resistance and the like, and has a wide application basis. However, the electrical conductivity of the material is very low, and at the same time, the material has high lattice thermal conductivity, so that the thermoelectric figure of merit zT of the material is very low, and is generally only 10-5～10-3. Although external element doping is a common means of improving the thermoelectric properties of materials. Some documents also disclose that the electrical and thermal properties of the material can be improved by doping, but are limited by the low doping type and amount of the element, and the obtained beta-FeSi2The range over which the thermoelectric figure of merit zT of the base compound can be optimized is very limited. Thus, even after many years of research, β -FeSi2The thermoelectric performance of the material has no major breakthrough.
Disclosure of Invention
In view of the above problems, the present invention is directed to provide a high heavy-doped β -FeSi2A base thermoelectric material and a method for producing the same.
In one aspect, the present invention provides a high heavy element doped beta-FeSi2Based on a thermoelectric material, said beta-FeSi2The chemical composition of the base thermoelectric material is Fe1-xMxSi2M is at least one of Ta, W, Re, Os, Ir and Pt, and x is more than 0 and less than or equal to 0.50.
In this disclosure, beta-FeSi2The chemical composition of the base thermoelectric material is Fe1-xMxSi2. Wherein Ta, W, Re can be doped at the Fe position,At least one element or the combination of more than two elements of Os, Ir and Pt, wherein the doping amount is more than 0 and less than or equal to 0.50. Within the doping range, the orthorhombic phase beta-FeSi can be obtained2The compounds, while the carrier concentration and conductivity of the material can be optimized in a very wide range. Secondly, the doping element M belongs to heavy elements and has two periods different from Fe elements on the periodic table. Because the difference between the atomic mass and the radius of the object M element and the host Fe element is large, a strong mass field and stress field fluctuation can be induced in the crystal lattice, the scattering of phonons is obviously enhanced, the crystal lattice thermal conductivity of the material is reduced, the thermal property of the material is optimized, and the thermoelectric figure of merit (zT) of the material is further improved.
Preferably, the beta-FeSi2The base thermoelectric material has a ZT of 0.001 to 1.5 at 1000K.
Preferably, x is more than or equal to 0.05 and less than or equal to 0.35; preferably 0.10. ltoreq. x.ltoreq.0.25.
Also, preferably, the beta-FeSi2The base thermoelectric material has a ZT of 0.1 to 1.5, preferably 0.35 to 1.2 at 1000K.
On the other hand, the invention also provides the high-content heavy element doped beta-FeSi2A method of making a base thermoelectric material, comprising:
(1) selecting a simple substance Fe, a simple substance Si and a simple substance M as initial raw materials, smelting, condensing and grinding to obtain raw material powder;
(2) the obtained raw material powder is subjected to pressure sintering to obtain a compact block;
(3) the obtained compact block is packaged in vacuum and then is annealed to obtain the beta-FeSi doped with the high content of heavy elements2A base thermoelectric material.
Preferably, the smelting temperature is 500-3500 ℃.
Preferably, the cooling rate of the condensation is 10-106DEG C/sec.
Preferably, the pressure sintering mode is spark plasma sintering and hot isostatic pressing sintering; the temperature of the spark plasma sintering is 500-1100 ℃, the sintering pressure is 10-500 MPa, and the time is 5-200 minutes; the hot isostatic pressing sintering temperature is 500-1100 ℃, the sintering pressure is 10-500 MPa, and the time is 5-200 minutes.
Preferably, the annealing temperature is 400-1300 ℃, and the total time is 2-600 hours.
Further, it is preferable that the annealing treatment is performed in a stepwise manner, and in the n-th annealing treatment, T is controlledn＜Tn-1Stage, n is an integer and is not less than 2; the time of the annealing treatment of each stage is at least 1 hour.
Has the advantages that:
(1) in the present invention, the thermoelectric material Fe1-xMxSi2The content x of the doping element can be properly adjusted between 0 and 0.50;
(2) in the invention, the lattice heat rate of the thermoelectric material is 0.5-25W m-1K-1To (c) to (d);
(3) in the invention, the electric conductivity of the thermoelectric material is 10-300000 omega-1m-1To (c) to (d);
(4) in the invention, the zT value of the thermoelectric material is controllable between 0.001 and 1.5 when 1000K;
(5) in the invention, the doping amount, the electric conductivity, the lattice thermal conductivity and the thermoelectric figure of merit zT of the thermoelectric material can be regulated and controlled in a wide range;
(6) in the invention, the high-content heavy-element-doped beta-FeSi is provided2The base thermoelectric material is environment-friendly, has outstanding thermal stability and oxidation resistance, and has wide application prospect in the field of thermoelectric power generation.
Drawings
FIG. 1 shows high content heavy element doped beta-FeSi in the present invention2A schematic flow chart of the preparation of the base thermoelectric material;
FIG. 2 shows beta-Fe prepared in the present invention0.96Ir0.04Si2Materials, beta-FeSi prepared in comparative examples 1, 2 and 3, respectively2、β-Fe0.96Co0.04Si2And beta-Fe0.96Mn0.04Si2The thermoelectric properties of (a);
FIG. 3 shows beta-Fe prepared in the present invention0.88Ir0.12Si2The thermoelectric properties of the material;
FIG. 4 shows beta-Fe prepared in the present invention0.80Ir0.20Si2The thermoelectric properties of the material;
FIG. 5 shows beta-Fe prepared in the present invention0.75Os0.15Ir0.10Si2Thermoelectric properties of the material.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, in a single compound, β -FeSi2On the basis of the method, at least one element or more than two elements of Ta, W, Re, Os, Ir and Pt are doped at the Fe position to prepare the high-content heavy-element doped beta-FeSi2A base thermoelectric material. The high-content heavy element doped beta-FeSi2The thermoelectric material can be represented by the general formula Fe1-xMxSi2Wherein x is the doping content of M at the Fe site, and can be in the range of 0 < x ≦ 0.50. x is preferably 0.05 to 0.35, more preferably 0.10 to 0.25. The semiconductor material provided by the invention has wide application prospect in the field of thermoelectric power generation by combining the characteristics of environment friendliness, outstanding thermal stability and oxidation resistance and the like.
In an alternative embodiment, β -FeSi2The thermal and electrical properties of the base thermoelectric material can be regulated and controlled in a wide range. beta-FeSi2The lattice thermal conductivity of the base thermoelectric material can be distributed in the range of 0.5-25W m-1K-1In the meantime. beta-FeSi2The electric conductivity of the base thermoelectric material can be distributed between 10 and 300000 omega-1m-1In the meantime. beta-FeSi2The zT value of the base thermoelectric material is 0.001 to 1.5 at 1000K.
When x is preferably 0.05-0.35, the beta-FeSi doped with high-content heavy elements2The lattice thermal conductivity of the base thermoelectric material can be distributed in the range of 0.5-12W m-1K-1In the meantime. High content heavy element doped beta-FeSi2The electric conductivity of the base thermoelectric material can be distributed between 1000-250000 omega-1m-1In the meantime. beta-FeSi2The zT value of the base thermoelectric material is between 0.1 and 1.5 at 1000K.
When x is preferably 0.10-0.25, the beta-FeSi is doped with high-content heavy elements2The lattice thermal conductivity of the base thermoelectric material can be distributed in the range of 0.5-6W m-1K-1In the meantime. High content heavy element doped beta-FeSi2The electric conductivity of the base thermoelectric material can be distributed in 10000-200000 omega-1m-1In the meantime. beta-FeSi2The zT value of the base thermoelectric material is between 0.35 and 1.2 at 1000K.
In one embodiment of the invention, the high-content heavy-element-doped beta-FeSi is obtained by smelting simple substances of Fe, Si and M with high purity in an inert protective atmosphere and combining with pressure sintering and at least two-step annealing process2A base thermoelectric material. The method has the advantages of simple process operation, short period, high controllability and low production cost, and can obtain the beta-FeSi doped with high content of heavy elements2Based on a single phase compound. The high content heavy element doped beta-FeSi provided by the present invention is exemplarily illustrated as follows2The preparation method of the base thermoelectric material is shown in figure 1.
High-purity Fe, M (M can be at least one element or the combination of more than two elements of Ta, W, Re, Os, Ir and Pt) and Si are weighed according to the molar ratio of (1-x) x:2 as initial raw materials. The initial raw materials are placed in a cavity of smelting equipment, and inert protective gas is filled in the cavity. And controlling the internal pressure of the inert protective atmosphere to be 0.1-40000 Pa. The periphery of the cavity is connected with cooling water pipelines, and the water flow is 1-200L/min. It should be noted that the smelting mode in the invention includes, but is not limited to, smelting the raw materials by using technologies such as arc smelting, suspension smelting, laser smelting or induction heating, and only needs to achieve complete melting at 500-3500 ℃ (preferably 1000-2500 ℃). The initial raw materials are completely melted to obtain liquid melt. And solidifying the obtained liquid melt into a cast ingot under high-speed circulating cooling water. It should be noted that the condensing manner in the present invention includes but is not limited to the manner of cooling by circulating water, and is only required to be 10-10%6The condensation can be carried out at a cooling rate of 10 to 500 ℃/sec.
And grinding the smelted cast ingot into powder as raw material powder. And (3) performing pressure sintering on the raw material powder to obtain a compact block. The pressure sintering can be hot isostatic pressing sintering and spark plasma sintering. The sintering temperature of the pressure sintering is 500-1100 ℃, the sintering pressure is 10-500 MPa, and the sintering time is 5-200 minutes. Preferably, the sintering atmosphere of the pressure sintering is a low-pressure argon atmosphere, and the pressure is 0.001-0.09 MPa. As an example, the compact block can be obtained by spark plasma sintering, the sintering method is to sinter the powder under pressure, the sintering temperature is 500-1100 ℃, the sintering pressure is 10-500 MPa, the sintering time is 5-200 minutes, the sintering atmosphere is low-pressure argon atmosphere, and the pressure is 0.001-0.09 MPa.
And carrying out vacuum packaging on the compact block after pressure sintering. Wherein the vacuum packaging is performed under the protection of inert gas. During packaging, the inside of the container is vacuumized, and the internal pressure is 0.1-40000 Pa. The vacuum packaging adopts a plasma or flame gun packaging mode. As an example, the block body is placed in a quartz tube, and vacuum packaging is carried out in an argon atmosphere glove box by adopting plasma or a flame gun, wherein the internal pressure is 0.1-40000 Pa.
And putting the vacuum-packaged block together with the quartz tube into an annealing furnace for annealing (or heat treatment). Preferably, the annealing treatment is performed in a stepwise manner, and T is controlled in the n-th annealing treatmentn＜Tn-1Stage, n is an integer and is not less than 2; the annealing treatment time of each stage is at least 1 hour, which aims to eliminate different M-Si compound mixed phases at high temperature in a segmented mode and ensure the formation of beta-FeSi through subsequent inclusion reaction2The process of (3) is smoothly carried out. For example, the procedure of the annealing treatment includes two stages. Wherein the annealing temperature T of the first stage annealing process1The temperature is 600-1300 ℃, and the annealing time is 1-300 hours; annealing temperature T of the second stage annealing process2At 400-1000 deg.C, annealing time of 1-300 hours, and T2＜T1. Annealing the compact block, and cooling to room temperature to obtain the beta-FeSi2A base thermoelectric material.
In the invention, the obtained beta-FeSi is adjusted by doping M (M is at least one element or the combination of more than two elements of Ta, W, Re, Os, Ir and Pt) element at the Fe position2The thermal property and the electrical property of the base thermoelectric material, the electrical conductivity, the thermal conductivity and the thermoelectric figure of merit ZT can be adjusted and controlled in a wide range. The beta-FeSi provided by the invention2The base thermoelectric material is a semiconductor material, the lattice thermal conductivity of the base thermoelectric material can be regulated and controlled in a wide range, and the value at room temperature can be 0.5-25W m-1K-1In the meantime. The conductivity of the semiconductor material can be regulated and controlled within a wide range and can be 10-300000 omega-1m-1In the meantime. The thermoelectric figure of merit of the semiconductor material, zT, is between 0.001 and 1.5 at 1000K.
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
β-Fe0.96Ir0.04Si2(M is Ir and x is 0.04) a polycrystalline bulk of semiconductor material:
mixing the elementary substances of Fe, Ir and Si according to the molar ratio of 0.96:0.04:2, smelting at 1750 ℃ to obtain a liquid melt, and condensing at the cooling rate of 20 ℃/s to obtain an ingot sample;
grinding the cast ingot into powder, and performing spark plasma sintering at the sintering temperature of 900 ℃, the sintering pressure of 65MPa and the sintering time of 10 minutes, wherein the sintering atmosphere is a low-pressure argon atmosphere and the pressure is 0.07MPa to obtain a compact block;
and (3) packaging the compact block in a quartz tube in vacuum, and placing the quartz tube and the compact block in an annealing furnace for heat treatment. The method comprises the following specific steps: at 100 deg.C/hourHeating to 1150 deg.C at a heating rate, maintaining the temperature for 24 hr, cooling to 900 deg.C at a cooling rate of 100 deg.C/hr, maintaining the temperature for 120 hr, and cooling to room temperature to obtain beta-Fe0.96Ir0.04Si2A compound is provided.
Comparative example 1
beta-FeSi in comparative example 12The preparation process of the base thermoelectric material is basically the same as that of example 1, except that: x is 0; and because M-Si compound impurity phase does not exist in the high-temperature phase after smelting and condensation, sectional annealing is not needed, and the annealing mode is that annealing treatment is carried out for 120 hours at 900 ℃.
Comparative example 2
beta-FeSi in comparative example 22The preparation process of the base thermoelectric material is basically the same as that of example 1, except that: m is Co; because M-Si compound impurity phase does not exist in the high-temperature phase after smelting and condensation, sectional annealing is not needed, and the annealing mode is that annealing treatment is carried out for 120 hours at 900 ℃.
Comparative example 3
beta-FeSi in comparative example 32The preparation process of the base thermoelectric material is basically the same as that of example 1, except that: m is Mn; because M-Si compound impurity phase does not exist in the high-temperature phase after smelting and condensation, sectional annealing is not needed, and the annealing mode is that annealing treatment is carried out for 120 hours at 900 ℃.
As shown in FIG. 2, the resulting beta-Fe0.96Ir0.04Si2Thermoelectric performance measurement of the polycrystalline block shows that the material has moderate conductivity (the conductivity is 20000-45000 omega) within a measured temperature range (300-1000K)-1m-1In the middle) and the Seebeck coefficient (the absolute value of the Seebeck coefficient value is 140-200 mu V K-1In between). Meanwhile, the material has lower lattice thermal conductivity (the lattice thermal conductivity is 3.0-6.0W m)-1K-1In between). The zT value of this material, calculated from the performance measurements, is close to 0.22 at 1000K. beta-Fe can inhibit the lattice thermal conductivity more obviously due to heavy element doping0.96Ir0.04Si2zT of (A) is less doped than beta-FeSi2Is increased by orders of magnitude and is higher than the beta-Fe doped with the adjacent elements of Co and Mn under the same doping ratio0.96Co0.04Si2And beta-Fe0.96Mn0.04Si2。
Example 2
beta-FeSi in example 22The preparation process of the base thermoelectric material is substantially the same as that of example 1, except that: x is 0.12.
As shown in FIG. 3, the resulting beta-Fe0.88Ir0.12Si2Thermoelectric property measurement of the polycrystalline block shows that the material has moderate conductivity (the conductivity is 50000-85000 omega) within a measured temperature range (300-1000K)-1m-1In the middle) and the Seebeck coefficient (the absolute value of the Seebeck coefficient value is 100-180 mu V K-1In between). Meanwhile, the material has lower lattice thermal conductivity (the lattice thermal conductivity is 2.0-3.5W m)-1K-1In between). The zT value of this material, calculated from the performance measurements, is close to 0.42 at 1000K.
Example 3
beta-FeSi in example 32The preparation process of the base thermoelectric material is basically the same as that of example 1, except that: x is 0.20.
As shown in FIG. 4, the obtained beta-Fe0.80Ir0.20Si2Thermoelectric property measurement of the polycrystalline block shows that the material has moderate conductivity (the conductivity is 75000-120000 omega) in a measured temperature range (300-1000K)-1m-1In the interval) and the Seebe coefficient (the absolute value of the Seebeck coefficient value is between 90 and 160 mu V K-1In between). Meanwhile, the material has lower lattice thermal conductivity (the lattice thermal conductivity is 1.5-2.5W m)-1K-1In between). The zT value of this material, calculated from the performance measurements, is close to 0.62 at 1000K.
Example 4
beta-FeSi in example 42The preparation process of the base thermoelectric material is substantially the same as that of example 1 except that: m is Os and Ir, and the specific component is beta-Fe0.75Os0.15Ir0.10Si2。
As shown in FIG. 5, the obtained beta-Fe0.75Os0.15Ir0.10Si2Thermoelectric property measurements of polycrystalline masses indicate that the temperature region is measuredWithin (300-1000K), the material has moderate conductivity (the conductivity is 55000-70000 omega)-1m-1In the middle) and the Seebeck coefficient (the absolute value of the Seebeck coefficient value is 90-170 mu V K-1In between). Meanwhile, the material has lower lattice thermal conductivity (the lattice thermal conductivity is 1.0-1.5W m)-1K-1In between). The zT value of this material, calculated from the performance measurements, is close to 0.83 at 1000K.
Example 5
beta-FeSi in example 52The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: m is Ta.
Example 6
beta-FeSi in example 62The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: m is W.
Example 7
beta-FeSi in example 72The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: m is Re.
Example 8
beta-FeSi in example 82The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: m is Pt.
Example 9
beta-FeSi in example 92The preparation process of the base thermoelectric material is basically the same as that of example 1, except that: the annealing mode is annealing treatment at 900 ℃ for 120 hours.
Example 10
beta-FeSi in example 102The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: the annealing mode is annealing treatment at 900 ℃ for 120 hours.
Comparative example 4
beta-FeSi in comparative example 42The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: m is Co; because M-Si compound impurity phase does not exist in the high-temperature phase after smelting and condensation, sectional annealing is not needed, and the annealing mode is that annealing treatment is carried out for 120 hours at 900 ℃.
Comparative example 5
beta-FeSi in comparative example 52The preparation process of the base thermoelectric material is basically the same as that of example 2, except that: m is Mn; because M-Si compound impurity phase does not exist in the high-temperature phase after smelting and condensation, sectional annealing is not needed, and the annealing mode is that annealing treatment is carried out for 120 hours at 900 ℃.
Table 1 shows the beta-FeSi prepared according to the invention2Composition of the base thermoelectric material and its performance parameters:
Figure BDA0002324025180000081

Claims (10)

1. high content heavy element dopedβ-FeSi2A base thermoelectric material, characterized in thatβ-FeSi2The chemical composition of the base thermoelectric material is Fe x1-M x Si2M is at least one of Ta, W, Re, Os, Ir and Pt, 0 < (R) >x≤0.50。
2. The method of claim 1β-FeSi2The base thermoelectric material is characterized in that the content of the base thermoelectric material is not more than 0.05 ≤x0.35 or less, preferably 0.10 or lessx≤0.25。
3. The method of claim 1β-FeSi2A base thermoelectric material, characterized in thatβ-FeSi2Base thermoelectric material at 1000KzT0.001 to 1.5.
4. The method of claim 2β-FeSi2A base thermoelectric material, characterized in thatβ-FeSi2Base thermoelectric material at 1000KzT0.1 to 1.5, preferably 0.35 to 1.2.
5. High heavy doped according to any one of claims 1 to 4β-FeSi2The preparation method of the base thermoelectric material is characterized by comprising the following steps:
(1) selecting a simple substance Fe, a simple substance Si and a simple substance M as initial raw materials, smelting, condensing and grinding to obtain raw material powder;
(2) the obtained raw material powder is subjected to pressure sintering to obtain a compact block;
(3) the obtained compact block is packaged in vacuum and then is annealed to obtain the high-content heavy element doped materialβ-FeSi2A base thermoelectric material.
6. The preparation method according to claim 5, wherein the temperature of the smelting is 500-3500 ℃.
7. The preparation method according to claim 5 or 6, wherein the cooling rate of the condensation is 10-10%6 DEG C/sec.
8. The production method according to any one of claims 5 to 7, wherein the pressure sintering is by spark plasma sintering and hot isostatic pressing sintering; the temperature of the spark plasma sintering is 500-1100 ℃, the sintering pressure is 10-500 MPa, and the time is 5-200 minutes; the hot isostatic pressing sintering temperature is 500-1100 ℃, the sintering pressure is 10-500 MPa, and the time is 5-200 minutes.
9. The method according to any one of claims 5 to 8, wherein the annealing is performed at a temperature of 400 to 1300 ℃ for a total time of 2 to 600 hours.
10. The method of claim 9, wherein the annealing is performed in a stepwise manner, and T is controlled during the n-th annealingn＜Tn-1Stage, n is an integer and is not less than 2; the time of the annealing treatment of each stage is at least 1 hour.
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