CN108172680B - Cubic phase Ca2Ge thermoelectric material and preparation method thereof - Google Patents

Cubic phase Ca2Ge thermoelectric material and preparation method thereof Download PDF

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CN108172680B
CN108172680B CN201810065984.XA CN201810065984A CN108172680B CN 108172680 B CN108172680 B CN 108172680B CN 201810065984 A CN201810065984 A CN 201810065984A CN 108172680 B CN108172680 B CN 108172680B
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powder
cubic phase
thermoelectric material
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preparation
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CN108172680A (en
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温翠莲
谢秋罕
张炜坚
萨百晟
叶健霞
熊锐
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Fuzhou University
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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
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/10—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Abstract

The invention discloses a cubic phase Ca2A Ge thermoelectric material is prepared through such steps as mixing Ca powder and Ge powder under protection of Ar gas, heating to 940 ~ 1100 deg.C for a certain time, putting the molten liquid in vacuum quenching furnace, filling high-purity Ar gas for remelting alloy, throwing out the molten liquid at 25 ~ 50 m/s by water-cooled Mo wheel to obtain acicular quick-setting powder, grinding, sieving, heating to 200 ~ 400 deg.C, holding the temp for a certain time, hot pressing to obtain sample, heating to 400 ~ 700 deg.C, holding the temp for a certain time, and cooling to obtain Ca cubic phase2And Ge. Cubic phase Ca obtained by the invention2The Ge material has uniform alloy components and tissues and compact structure.

Description

Cubic phase Ca2Ge thermoelectric material and preparation method thereof
Technical Field
The invention belongs to the field of thermoelectric functional materials, and particularly relates to cubic phase Ca2Ge thermoelectric material and a preparation method thereof.
Background
With the consumption of non-renewable energy and the increasing severity of environmental pollution, finding a high-efficiency pollution-free energy conversion mode has become an urgent problem to be solved today. The thermoelectric material is an environment-friendly semiconductor functional material which realizes the interconversion between heat energy and electric energy through the charge carrier pre-migration in the solid. The equipment made of thermoelectric material has many advantages, small volume, no noise and no pollution, and can be applied to various fields such as thermal power generation, semiconductor refrigeration equipment and the like. Dimensionless figure of merit ZT = S for standard evaluation of thermoelectric material performance2σ T/κ denotes where S is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the absolute temperature, so materials with both higher electrical conductivity and Seebeck coefficient, and lower thermal conductivity, have higher thermoelectric conversion efficiency.
Ge is a semiconductor element, is relatively abundant in the earth crust, and is found relatively late in chemical history because few ores contain Ge. Ge is a semiconductor material with a direct band gap, has good photoelectric property, has good compatibility with the existing Si technology, and is expected to become a high-efficiency solar cell. Ca2Ge is a novel semiconductor material which is friendly to the environment and can be used for electronic devices and solar cells. For germanide Ca2Ge, which is composed of two elements of Ca and Ge with extremely long service life, can be recycled, and has no pollution to environment.
The preparation of Ca is troublesome due to the volatility of Ca. 6 intermediate phases appear in the reaction process of Ca and Ge, and Ca is simultaneously generated due to the preparation technology5Ge3、CaGe2And the purity of the compound such as CaGe is not high. The method adopts a rapid solidification method, and adopts the processes of suspension smelting, rapid solidification, nitriding treatment, annealing treatment and the like under a vacuum environment to synthesize single-phase cubic phase Ca2The Ge wafer sample becomes a desired thermoelectric material. At present, Ca for cubic phase2The preparation process of Ge is less studied.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a single-phase, fine and uniform-grain cubic phase Ca2Ge thermoelectric material and a preparation method thereof.
In order to solve the problems, the invention provides cubic phase Ca2The Ge thermoelectric material and the preparation method thereof comprise the following steps:
1. cubic phase Ca2The preparation method of the Ge material comprises the following steps:
(1) uniformly mixing Ca powder and Ge powder according to the molar ratio of Ca to Ge = (2.0 ~ 2.8) to 1 under the protection of argon;
(2) vacuumizing the vacuum magnetic induction suspension smelting furnace, filling argon for protection, placing the mixture obtained in the step (1) into a water-cooled crucible of the vacuum magnetic induction suspension smelting furnace, heating to 940 ~ 1100 ℃ to enable Ca and Ge in the crucible to be in a molten state, smelting for 15 ~ 45 min, and removing surface impurities after smelting, wherein the smelting and impurity removal process is repeated for 1 ~ 5 times;
(3) putting the molten liquid obtained in the step (2) into a vacuum rapid quenching furnace, recharging high-purity argon gas, remelting the alloy, throwing the molten liquid out by a water-cooled molybdenum wheel at the linear speed of 25 ~ 50 m/s, wherein the cooling speed is within the range of 104~109K/s, obtaining needle-shaped quick-setting powder;
(4) manually grinding the powder obtained in the step (3), sieving the powder by a sieve of 80 ~ 160 mu m, heating to 200 ~ 400 ℃, preserving the heat for 1 ~ 12 h under the vacuum condition, applying mechanical pressure of 10 ~ 15 MPa to remove gas among the powder as much as possible, heating to 400 ~ 700 ℃ and 700 ℃ under the condition of 30 ~ 60 MPa, and carrying out hot pressing for 15 ~ 90 min to prepare a block sample;
(5) putting the block sample obtained in the step (4) into a vacuum tube furnace, heating to 400 ~ 700 ℃, preserving heat for 5 ~ 40 h, and then cooling along with the furnace to obtain cubic phase Ca2A Ge thermoelectric material.
The purity of Ca powder in the step (1) is 99% ~ 99.9.9%, and the purity of Ge powder is 99% ~ 99.9.9%;
before the crucible is used in the step (2), sequentially adopting deionized water, alcohol and acetone to carry out ultrasonic cleaning, wherein the total ultrasonic cleaning time is 10 ~ 40 min, the heating power range of the vacuum magnetic induction suspension smelting is 10 ~ 45 kW, and the heating speed is 20 ~ 80 ℃/min;
the purity of the argon in the step (1) ~ (3) is 99-99.99%;
the vacuum degree in the step (2) ~ (5) is 10-2~10-4 Pa。
Compared with the prior art, the invention has the following advantages:
1) the magnetic induction suspension smelting utilizes the induction behavior of the material in a high-frequency magnetic field to heat and melt the material so as to achieve the smelting purpose. Under the action of the magnetic field, the material is in a suspension state after being melted, so that the pollution caused by contact reaction of the experimental material in a molten state and the crucible is reduced, and the homogenization of components is facilitated;
2) the rapid solidification process has a considerable cooling rate, and since the cooling rate is extremely high, other phases cannot be generated in time, and Ca is preferentially formed2Ge, thus obtaining single-phase Ca2Ge, no other impurity phase exists, and the long-range diffusion of atoms is inhibited, so that not only are crystal grains fine, but also the annealing time is greatly shortened; the hot pressing technology can reduce the sintering temperature on the premise of ensuring the density of the material, shorten the sintering time and is beneficial to inhibiting the grain growth of the material in the hot processing process;
3) can bear higher hot-pressing pressure at lower temperature and can well control the volatilization of Ca, so that the components of the product are fixed to obtain single-phase Ca2Ge；
4) The preparation process combining the rapid solidification method with the hot pressing is simple and convenient to operate, the reaction temperature is low, the atomic ratio and the components of Ca and Ge can be accurately controlled, the requirement of large-scale production is met, and the cost is reduced;
5) XRD diffraction analysis of the material of the invention shows that the phase is cubic phase Ca2Ge (see fig. 1); cubic phase Ca obtained by analysis of SEM photograph2The Ge material has fine grains, uniform alloy composition and structure and compact structure (see figure 3).
Drawings
FIG. 1 shows a bulk cubic phase Ca according to example 1 of the present invention2XRD spectra of Ge thermoelectric materials;
FIG. 2 shows a cubic phase Ca of the present invention2A structural schematic diagram of Ge;
fig. 3 is a scanning electron microscope morphology of a bulk thermoelectric material corresponding to embodiment 1 of the present invention.
Detailed description of the invention
The technical solution of the present invention will be described in detail by examples, but the present invention is not limited thereto.
Example 1
Cubic phase Ca2The preparation method of the Ge thermoelectric material comprises the following steps:
(1) uniformly mixing Ca powder and Ge powder according to the molar ratio of Ca to Ge = 2.3 to 1 under the protection of argon;
(2) and vacuumizing the vacuum magnetic induction suspension smelting furnace, and then filling argon for protection. Placing the mixture obtained in the step (1) in a water-cooled crucible of the vacuum magnetic induction suspension smelting furnace, heating to 1100 ℃, and enabling Ca and Ge in the crucible to be in a molten state, wherein the smelting time is 30 min; and removing surface impurities after smelting. The smelting and impurity removing processes are repeated for 3 times;
(3) putting the molten liquid obtained in the step (2) into a vacuum rapid quenching furnace, and recharging high-purity argon for alloy remelting; then the melt is thrown out by a water-cooled molybdenum wheel at a linear speed of 25 m/s, and the cooling speed is within 104~109K/s, obtaining needle-shaped quick-setting powder;
(4) manually grinding the powder obtained in the step (3), sieving the powder by a 110-micron sieve, heating to 200 ℃ under a vacuum condition, preserving heat for 2 h, applying a mechanical pressure of 12 MPa to remove gas among the powder as much as possible, and then heating to 700 ℃ and 50 MPa for hot pressing for 30 min to prepare a block-shaped sample;
(5) putting the block sample obtained in the step (4) into a vacuum tube furnace, heating to 400 ℃, preserving heat for 20 hours, and then cooling along with the furnace to obtain cubic phase Ca2And (4) Ge samples.
The purity of Ca powder in the step (1) is 99 percent, and the purity of Ge powder is 99 percent;
before the crucible in the step (2) is used, sequentially adopting deionized water, alcohol and acetone for ultrasonic cleaning, wherein the total ultrasonic cleaning time is 30 min; the heating power range of the vacuum magnetic induction suspension smelting is 15 kW, and the temperature rising speed is 25 ℃/min;
the purity of argon in the step (1) ~ (3) is 99%, and the vacuum degree in the step (2) ~ (5) is 10-3 Pa。
Example 2
Cubic phase Ca2The preparation method of the Ge thermoelectric material comprises the following steps:
(1) uniformly mixing Ca powder and Ge powder according to the molar ratio of Ca to Ge = 2.5 to 1 under the protection of argon;
(2) and vacuumizing the vacuum magnetic induction suspension smelting furnace, and then filling argon for protection. Placing the mixture obtained in the step (1) in a water-cooled crucible of the vacuum magnetic induction suspension smelting furnace, heating to 950 ℃, and enabling Ca and Ge in the crucible to be in a molten state, wherein the smelting time is 45 min; and removing surface impurities after smelting. The smelting and impurity removing processes are repeated for 4 times;
(3) putting the molten liquid obtained in the step (2) into a vacuum rapid quenching furnace, and recharging high-purity argon for alloy remelting; then the melt is thrown out by a water-cooled molybdenum wheel at a linear speed of 45 m/s, and the cooling speed is within 104~109K/s, obtaining needle-shaped quick-setting powder;
(4) manually grinding the powder obtained in the step (3), sieving the powder by a 80-micron sieve, heating to 300 ℃ under a vacuum condition, preserving heat for 5 hours, applying a mechanical pressure of 10 MPa to remove gas among the powder as much as possible, heating to 600 ℃ and 60 MPa, and carrying out hot pressing for 90 min to prepare a block-shaped sample;
(5) putting the block sample obtained in the step (4) into a vacuum tube furnace, heating to 600 ℃, preserving heat for 8 hours, and then cooling along with the furnace to obtain cubic phase Ca2And (4) Ge samples.
The purity of the Ca powder in the step (1) is 99.5 percent, and the purity of the Ge powder is 99.5 percent;
before the crucible in the step (2) is used, sequentially adopting deionized water, alcohol and acetone for ultrasonic cleaning, wherein the total ultrasonic cleaning time is 15 min; the heating power range of the vacuum magnetic induction suspension smelting is 30 kW, and the heating speed is 75 ℃/min;
the purity of argon in the step (1) ~ (3) is 99.5%, and the vacuum degree in the step (2) ~ (5) is 10-4 Pa。
Example 3
Cubic phase Ca2The preparation method of the Ge thermoelectric material comprises the following steps:
(1) uniformly mixing Ca powder and Ge powder according to the molar ratio of Ca to Ge = 2.8 to 1 under the protection of argon;
(2) and vacuumizing the vacuum magnetic induction suspension smelting furnace, and then filling argon for protection. Placing the mixture obtained in the step (1) in a water-cooled crucible of the vacuum magnetic induction suspension smelting furnace, heating to 1000 ℃, and enabling Ca and Ge in the crucible to be in a molten state, wherein the smelting time is 15 min; and removing surface impurities after smelting. The smelting and impurity removing processes are repeated for 5 times;
(3) putting the molten liquid obtained in the step (2) into a vacuum rapid quenching furnace, and recharging high-purity argon for alloy remelting; then the melt is thrown out by a water-cooled molybdenum wheel at a linear speed of 30 m/s, and the cooling speed is within 104~109K/s, obtaining needle-shaped quick-setting powder;
(4) manually grinding the powder obtained in the step (3), sieving the powder by a 160-micron sieve, heating to 400 ℃ under a vacuum condition, preserving heat for 11 hours, applying a mechanical pressure of 15 MPa to remove gas among the powder as much as possible, and then heating to 500 ℃ and 30 MPa for hot pressing for 60 min to prepare a block-shaped sample;
(5) putting the block sample obtained in the step (4) into a vacuum tube furnace, heating to 700 ℃, preserving heat for 40 h, and then cooling along with the furnace to obtain cubic phase Ca2And (4) Ge samples.
The purity of the Ca powder in the step (1) is 99.9 percent, and the purity of the Ge powder is 99.9 percent;
before the crucible in the step (2) is used, sequentially adopting deionized water, alcohol and acetone for ultrasonic cleaning, wherein the total ultrasonic cleaning time is 40 min; the heating power range of the vacuum magnetic induction suspension smelting is 30 kW, and the temperature rising speed is 50 ℃/min;
the purity of argon in the step (1) ~ (3) is 99.9%, and the vacuum degree in the step (2) ~ (5) is 10-2 Pa。
TABLE 1 cubic phase Ca2Atomic position of Ge
Table 2 cubic phase Ca prepared in example 12Compositional analysis of Ge
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (6)

1. Cubic phase Ca2The preparation method of the Ge thermoelectric material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing Ca powder and Ge powder according to the molar ratio of Ca to Ge = 2.0 ~ 2.8 to 1 under the protection of argon;
(2) vacuumizing the vacuum magnetic induction suspension smelting furnace, filling argon for protection, placing the mixture obtained in the step (1) into a water-cooled crucible of the vacuum magnetic induction suspension smelting furnace, heating to 940 ~ 1100 ℃ to enable Ca and Ge in the crucible to be in a molten state, smelting for 15 ~ 45 min, and removing surface impurities after smelting, wherein the smelting and impurity removal process is repeated for 1 ~ 5 times;
(3) putting the molten liquid obtained in the step (2) into a vacuum rapid quenching furnace, recharging high-purity argon gas, remelting the alloy, throwing the molten liquid out by a water-cooled molybdenum wheel at the linear speed of 25 ~ 50 m/s, wherein the cooling speed is within the range of 104~109K/s, obtaining needle-shaped quick-setting powder;
(4) manually grinding the powder obtained in the step (3), sieving the powder by a sieve of 80 ~ 160 mu m, heating to 200 ~ 400 ℃, preserving the heat for 1 ~ 12 h under the vacuum condition, applying mechanical pressure of 10 ~ 15 MPa to remove gas among the powder, and then hot-pressing for 15 ~ 90 min under the conditions of 400 ~ 700 ℃ and 30 ~ 60 MPa to prepare a block sample;
(5) putting the block sample obtained in the step (4) into a vacuum tube furnace, heating to 400 ~ 700 ℃, preserving heat for 5 ~ 40 h, and then cooling along with the furnace to finally obtain cubic phase Ca2A Ge thermoelectric material;
the vacuum degree in the step (2) ~ (5) is 10-2~10-4 Pa。
2. A cubic phase Ca according to claim 12The preparation method of the Ge thermoelectric material is characterized in that the purity of Ca powder in the step (1) is 99% ~ 99.9.9%, and the purity of Ge powder is 99% ~ 99.9.9%.
3. A cubic phase Ca according to claim 12The preparation method of the Ge thermoelectric material is characterized in that the crucible in the step (2) is sequentially subjected to ultrasonic cleaning by using deionized water, alcohol and acetone, and the total ultrasonic cleaning time is 10 ~ 40 min.
4. A cubic phase Ca according to claim 12The preparation method of the Ge thermoelectric material is characterized in that the heating power range of vacuum magnetic induction suspension smelting in the step (2) is 10 ~ 45 kW, and the temperature rise speed is 20 ~ 80 ℃/min.
5. A cubic phase Ca according to claim 12The preparation method of the Ge thermoelectric material is characterized in that the purity of argon in the step (1) ~ (3) is 99-99.99%.
6. Cubic phase Ca produced by the production method according to any one of claims 1 to 52A Ge thermoelectric material.
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