CN109402434B - Method for preparing ZnSb compound ultra-rapidly - Google Patents

Method for preparing ZnSb compound ultra-rapidly Download PDF

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CN109402434B
CN109402434B CN201811257110.0A CN201811257110A CN109402434B CN 109402434 B CN109402434 B CN 109402434B CN 201811257110 A CN201811257110 A CN 201811257110A CN 109402434 B CN109402434 B CN 109402434B
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znsb
raw materials
powder
direct current
compound
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CN109402434A (en
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唐新峰
杨东旺
黎俊
程睿
杨龙
唐昊
柳伟
鄢永高
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/007—Preparing arsenides or antimonides, especially of the III-VI-compound type, e.g. aluminium or gallium arsenide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth

Abstract

The invention firstly develops an ultra-fast solid-phase synthesis method of ZnSb compound, which takes Zn powder and Sb powder as main raw materials, firstly, the raw materials are uniformly mixed and then compacted, then, direct current is directly introduced into the mixed raw materials, and under the action of current, the ZnSb single-phase compound can be prepared in a short time. The method has the advantages of ultra-simple process, ultra-short preparation time, mild reaction conditions and easy and accurate control of components, and can lay a good foundation for large-scale preparation and large-scale application of ZnSb compounds.

Description

Method for preparing ZnSb compound ultra-rapidly
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a method for preparing a ZnSb compound ultra-rapidly.
Background
The ZnSb material, as one of binary antimonides, has lower thermal conductivity, higher electrical conductivity and stronger thermal stability, and draws great attention to the fields of thermoelectricity, lithium ion battery anodes, phase change storages and the like.
At present, the synthesis of ZnSb materials mainly comprises a high-temperature vacuum melting method, a solid-phase reaction method, a wet chemical method, an electrochemical method and the like; wherein the high-temperature treatment is easy to accelerate the volatilization of Zn, so that the control of the components is difficult; impurities are easily introduced by a wet chemical method, so that pollution is caused, and the process is complicated, time-consuming and energy-consuming; the electrochemical method usually needs to use an organic solvent, has high dependence on reaction equipment, and has high requirements on electrochemical measurement and electrodeposition experimental conditions (electrolyte, pH conditions and the like need to be regulated). Therefore, it is urgent to find a synthesis technology that is simple, energy-saving, green and environment-friendly and can avoid long-time high-temperature treatment.
Disclosure of Invention
The invention mainly aims to provide a method for preparing ZnSb compound at ultra-fast speed aiming at the defects in the prior art, the related process is simple and easy to implement, the preparation time is ultra-short, the components are easy to accurately control, and a good foundation can be laid for the large-scale preparation and large-scale application of the ZnSb compound.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for ultrafast preparing ZnSb compound comprising the steps of: zn powder and Sb powder are used as raw materials, the raw materials are firstly mixed uniformly, the obtained mixed raw materials are filled into a die to be compacted, direct current is directly introduced into the compacted mixed raw materials, and the ZnSb single-phase compound is prepared by reaction under the action of current.
In the scheme, the molar ratio of the Zn powder to the Sb powder is 1: 1.
In the above scheme, the direct current includes a constant direct current or a pulsed direct current.
In the scheme, the current density of the direct current is 1.5A/cm2The above.
Preferably, the current density of the direct current is 1.5-20A/cm2。
In the scheme, the direct current is switched on for within 60 s.
The ZnSb compound synthesized according to the above scheme had good single-phase properties.
The principle of the invention is as follows:
the invention adopts a solid-phase synthesis process, takes Zn powder and Sb powder as raw materials, uniformly mixes the raw materials, and introduces direct current to form Zn on the interface of Zn particles and Sb particles4Sb3The compound is a fast ion conductor, Zn in crystal lattices can migrate under the action of current, Sb in the raw materials can further react with the migrated Zn to form a ZnSb compound, and Zn in the raw materials is continuously supplemented into Zn4Sb3Carrying out cyclic iteration on the crystal lattices, and finally quickly forming a target product ZnSb in a short time; in this process, Zn is an intermediate product4Sb3The ultrafast ion channel formed under the current is the reason for the rapid reaction, which is obviously different from the gain and loss under the action of the current in the traditional electrochemical processAn electronic behavior.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention discloses an ultrafast solid-phase synthesis process of ZnSb compound for the first time, aiming at Zn powder and Sb powder solid raw materials, a target product with good single-phase property can be obtained by directly utilizing small direct current within 60s, the complex preparation process of the traditional method is avoided, the related process is ultra-simple, the preparation time is ultra-short, and the energy consumption can be obviously reduced; and the method does not need to depend on specific reaction equipment, and has wide applicability.
2) The reaction conditions involved in the invention are mild, and the stoichiometric ratio of the obtained product to the target design product (ZnSb) is consistent; the raw material proportion is simple and easy to control, the stoichiometric ratio does not need to be additionally adjusted, and the components are easy to accurately control.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 1.
FIG. 2 shows the product A obtained in example 11Field emission scanning electron micrographs of fresh sections.
Figure 3 is the XRD pattern of the product obtained in example 2.
FIG. 4 shows the product A obtained in example 22Field emission scanning electron micrographs of fresh sections.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the Zn powder and the Sb powder used were commercially available products, and the purity was 4N.
Example 1
A method for preparing ZnSb compound by constant direct current ultrafast speed comprises the following steps:
1) weighing Zn powder and Sb powder according to a molar ratio of 1:1, wherein 4 groups are provided, and each group is 4g and is respectively numbered as A1、B1、C1And D1；
2) Putting each group of raw materials into an agate mortar respectively, and grinding for 20min to obtain uniform mixed powder (mixed raw materials);
3) respectively filling each group of mixed powder into a BN mold with the diameter of phi 16mm, compacting the upper end and the lower end by using a graphite pressure head with good conductivity, and respectively reacting under the action of different currents to prepare a ZnSb single-phase compound; wherein A is1、B1、C1And D1The conditions are respectively as follows: 3A/60s, 10A/48s, 20A/40s and 30A/25s, respectively, corresponding to a current density of 1.5A/cm2，5A/cm2，10A/cm2，15A/cm2。
After the completion of the energization reaction, the resultant products were subjected to phase analysis (XRD analysis), respectively, and as shown in FIG. 1, the resultant product A was obtained1、B1、C1And D1All were single phase ZnSb compounds, indicating that a modest constant direct current can promote the synthesis of ZnSb in a very short time.
FIG. 2 is A1The field emission scanning electron microscope image of the fresh section of the product has large grains, which indicates that the crystallinity of the material is good.
Example 2
A method for preparing ZnSb compound by pulse direct current ultrafast speed comprises the following steps:
1) weighing Zn powder and Sb powder according to a molar ratio of 1:1, wherein 4 groups are provided, and each group is 4g and is respectively numbered as A2、B2、C2And D2；
2) Putting each group of raw materials into an agate mortar respectively, and grinding for 20min to obtain uniform mixed powder (mixed raw materials);
3) respectively filling each group of mixed powder into a BN mold with the diameter of phi 16mm, compacting the upper end and the lower end by using a graphite pressure head with good conductivity, and respectively reacting under the action of different currents to prepare a ZnSb single-phase compound; in which the ON/OFF pulse time is set to 30ms, A2、B2、C2And D2The other conditions are respectively as follows: 3A/60s, 10A/45s, 20A/38s and 30A/28s, respectively, corresponding to a current density of 1.5A/cm2，5A/cm2，10A/cm2，15A/cm2。
After the completion of the energization reaction, the resultant products were subjected to phase analysis (XRD analysis), respectively, and as shown in FIG. 3, the resultant product A was obtained2、B2、C2And D2Are all single-phase ZnSb compounds. Similar to the constant dc effect, the small pulsed dc can promote ZnSb synthesis in a very short time.
FIG. 4 is A2The field emission scanning electron microscope image of the fresh section of the product has large grains, which indicates that the crystallinity of the material is good.
Comparative example
A method for preparing ZnSb compounds by applying a pulse electrochemical technology (refer to the literature: preparation of Liudan and Zn-Sb nano-film thermoelectric materials by a pulse electrochemical method and performance research [ D ], Changsha university, 2009) specifically comprises the following steps:
1) by using ZnCl2、SbCl3Primary salt, pulsed electrochemical electrodeposition experiments were performed in electrochemical workstation CHI 602B;
2) controlling conditions: pH value of 1.0-3.0, temperature of 25-40 deg.C, duty ratio of 5-10%, and molar concentration ratio of main salt concentration (n)Zn2+/(nZn2++nSb3+) 0.3 to 0.6 and a current density of 1 to 7A/dm2；
3) Obtaining the ZnSb nano film after 30 min.
It can be seen that the electrochemical method for synthesizing the ZnSb compound has higher requirements on the electrodeposition equipment and the electrolyte system, and the concentration, the pH condition and the like of the electrolyte need to be regulated and controlled; and the waste electrolyte has great pollution to the environment and is not beneficial to popularization and application.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.

Claims (2)

1. A method for ultrafast preparing ZnSb compound comprising the steps of: taking Zn powder and Sb powder as raw materials, firstly, uniformly mixing the raw materials, then, putting the obtained mixed raw materials into a mold for compaction, introducing direct current into the compacted mixed raw materials, and reacting under the action of current to prepare a ZnSb single-phase compound;
the current density of the direct current is 1.5-20A/cm2；
The molar ratio of the Zn powder to the Sb powder is 1: 1;
the direct current comprises constant direct current or pulsed direct current;
the direct current power-on time is within 60 s.
2. A ZnSb compound prepared by the process of claim 1.
CN201811257110.0A 2018-10-26 2018-10-26 Method for preparing ZnSb compound ultra-rapidly Active CN109402434B (en)

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EP1728880A1 (en) * 2005-05-31 2006-12-06 Aarhus Universitet Improved p-type thermoelectric materials, a process for their manufacture and uses thereof
KR101530376B1 (en) * 2008-10-23 2015-06-26 한국교통대학교산학협력단 Bulk thermoelectric material and thermoelectric device comprising same
CN101723669A (en) * 2008-10-31 2010-06-09 中国科学院上海硅酸盐研究所 Compound capable of being used for thermoelectric material and preparation method thereof
CN101857928A (en) * 2010-04-06 2010-10-13 武汉理工大学 P-type Zn4Sb3 based thermoelectric material and preparation method thereof
KR20140051302A (en) * 2011-07-15 2014-04-30 오르후스 우니베르시테트 Method for producing a thermoelectric solid element
CN107794387B (en) * 2016-09-07 2019-11-26 武汉理工大学 A kind of supper-fast preparation β-Zn4Sb3The method of base block thermoelectric material

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