CN101913575B

CN101913575B - Method for preparing In4Se3 thermoelectric compound powder

Info

Publication number: CN101913575B
Application number: CN2010102712197A
Authority: CN
Inventors: 唐新峰; 刘丹丹; 李涵; 张清杰
Original assignee: Wuhan University of Technology WUT
Current assignee: Wuhan University of Technology WUT
Priority date: 2010-08-31
Filing date: 2010-08-31
Publication date: 2012-05-30
Anticipated expiration: 2030-08-31
Also published as: CN101913575A

Abstract

The invention belongs to the field of new energy materials, and relates to a method for preparing In4Se3 thermoelectric compound powder. The method is characterized by comprising the following steps of: 1) preparing mixed solution A of an indium hydrated soluble salt and sodium selenite in a molar ratio of a selenium element to an indium element in the sodium selenite and the indium hydrated soluble salt of 3:4-3.1-4; 2) adding reducing agent hydrazine hydrate into the mixed solution A, controlling the reaction temperature to be between 50 and 80 DEG C and reacting for 3 to 12 hours to obtain a product B; 3) centrifuging the product B and performing freeze drying on sediment obtained by centrifuging to obtain dark red powder; and 4) reducing the dark red powder for 1 to 3 hours in the hydrogen atmosphere at the temperature of between 450 and 525 DEG C to obtain the In4Se3 thermoelectric compound powder. The method has the advantages of cheap and readily available raw materials, simple and easily controlled process, short reaction time, low power consumption, light pollution, high repeatability and suitability for large-scale preparation.

Description

A kind of In 4Se 3The preparation method of thermoelectric compound powder

Technical field

The invention belongs to the new energy materials field, be specifically related to a kind of In ₄Se ₃The preparation method of thermoelectric compound powder.

Background technology

Thermoelectric material is a kind of environmentally friendly functional materials, is replacing traditional fossil fuel, is improving aspect such as environment great potential is arranged.The technology that Seebeck effect and the peltier effect that thermoelectric generation technology is utilized semi-conductor thermoelectric material just directly changed heat energy and electric energy.Because it does not contain the needed huge transmission rig of other generation technology; Have that volume is little, the life-span is long, safety is high, ME is simple, manufacturing and characteristics such as running cost is low, wide application and receive scientific worker's attention, at numerous areas vast potential for future development is arranged.

In ₄Se ₃Compound is a kind of n type thermoelectric material of reporting recently, makes this material have the ZT value high than other traditional materials in room temperature to the extremely low thermal conductivity in middle temperature field.At present, the In that has reported ₄Se ₃The preparation method of polycrystalline compounds be generally solid reaction process (Solid state reaction, SSR), scorification (Melt reaction, MR) etc., but the aforesaid method ubiquity that repeatability is poor, temperature of reaction is high, the cycle is long, and energy consumption is big etc. problem.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of In ₄Se ₃The preparation method of thermoelectric compound powder, this method low in raw material cost is easy to get, technology is simple and easy to control, the reaction times is short.

In order to solve the problems of the technologies described above, technical scheme of the present invention is:

A kind of In ₄Se ₃The preparation method of thermoelectric compound powder is characterized in that it comprises the steps:

1) the amount of substance ratio according to selenium element and phosphide element in the hydration soluble salt of Sodium Selenite and indium is 3: 4～3.1: 4, takes by weighing the hydration soluble salt and the Sodium Selenite raw material of indium,, mixes as solvent with deionized water, obtains mixed solution A;

2) in mixed solution A, add the reductive agent Hydrazine Hydrate 80, control reaction temperature is 50～80 ℃, reacts 3～12 hours, obtains product B, and the purpose that adds the reductive agent Hydrazine Hydrate 80 here is the selenium in the Sodium Selenite is reduced to simple substance selenium;

3) product B is carried out centrifugal, the centrifugal deposition that obtains is carried out lyophilize, obtain the garnet powder;

4) the garnet powder that step 3) is obtained in 450～525 ℃ of reduction 1～3 hour, obtains In under hydrogen atmosphere ₄Se ₃Thermoelectric compound powder.

Press such scheme, the hydration soluble salt of the described indium of step 1) is the chloride monohydrate of indium or the nitric hydrate salt of indium.

Press such scheme, step 2) described reaction is to react under the ultrasonic reaction condition or under the whipped state.

Press such scheme, step 2) proportioning of the amount of substance of described reductive agent Hydrazine Hydrate 80 and Sodium Selenite was at least 10: 1.

Press such scheme, the described centrifugation time of step 3) is 3～5min, and centrifugal rotational speed is 8000～12000r/min.

In the such scheme, be in theory according to the synthetic In of institute ₄Se ₃Hydration soluble salt and Sodium Selenite raw material that the stoichiometric ratio of thermoelectric compound powder takes by weighing indium get final product; And in actual procedure; Consider that there is small loss in the selenium element because of volatilization in entire reaction course; Can suitably improve the proportioning of Sodium Selenite, the amount of substance ratio that is about to phosphide element in the hydration soluble salt of selenium element and indium in the Sodium Selenite is adjusted into 3: 4～and 3.1: 4.

The In that the present invention obtains ₄Se ₃Thermoelectric compound powder can be applied to prepare In ₄Se ₃Block thermoelectric material.

Beneficial effect of the present invention: compare In provided by the invention with solid reaction process or high-temperature melting method ₄Se ₃The preparation method of thermoelectric compound powder, the low in raw material cost that is adopted is easy to get, technology is simple and easy to control, the reaction times is short, energy consumption is low, pollute little, good reproducibility, and be applicable to mass preparation.

Description of drawings

Fig. 1 is preparation technology's schema of the present invention.

Fig. 2 is the In of the embodiment of the invention 1 preparation ₄Se ₃The XRD figure spectrum of thermoelectric compound powder.

Fig. 3 is the In of the embodiment of the invention 1 preparation ₄Se ₃The SEM shape appearance figure of thermoelectric compound powder.

Embodiment

In order to understand the present invention better, further illustrate content of the present invention below in conjunction with instance, but content of the present invention not only is confined to following embodiment.

Embodiment 1:

As shown in Figure 1, a kind of In ₄Se ₃The preparation method of thermoelectric compound powder, it comprises the steps:

1) gets 400 ml beakers, take by weighing 0.5865 gram analytical pure, four hydration indium chlorides, 0.2681 gram Sodium Selenite successively, take 200 ml deionized water, mix, obtain mixed solution A;

2) hydrazine hydrate solution that in step 1) gained mixed solution A, adds 1mL commercially available 85% is as reductive agent, and control reaction temperature is 60 ℃, and ultrasonic reaction 3 hours obtains product B, and said ultrasonic frequency is 42KHz, and power is 100-400W;

3) with step 2) product B that obtains carries out centrifugally, and centrifugation rate is 8000r/min, and the time is 3min, and centrifugal being deposited in of obtaining carried out lyophilize in the freeze drying equipment, and the lyophilize temperature is-80 ℃, be 2h time of drying, obtains the garnet powder;

4) the garnet powder that step 3) is obtained in 450 ℃ of reduction 1 hour, obtains In under hydrogen atmosphere in atmosphere furnace ₄Se ₃Thermoelectric compound powder.

The In that step 4) is obtained ₄Se ₃Product carries out XRD and SEM test, sees Fig. 2 and Fig. 3 respectively, among Fig. 2: the In of the present invention's preparation ₄Se ₃The diffraction peak of thermoelectric compound powder and In ₄Se ₃Diffraction peak in the standard spectrogram is consistent, and this explanation gained final product is single-phase In ₄Se ₃Thermoelectric compound; Fig. 3 explains gained In ₄Se ₃The about 200nm of the particle diameter of thermoelectric compound.

Embodiment 2:

1) gets 500 ml beakers, take by weighing 1.5276 gram analytical pure, four five nitric hydrate indiums, 0.5188 gram Sodium Selenite successively, take 400 ml deionized water, mix, obtain mixed solution A;

2) hydrazine hydrate solution that in step 1) gained mixed solution A, adds 10mL commercially available 85% is as reductive agent, and control reaction temperature is 80 ℃, and ultrasonic reaction 12 hours obtains product B, and said ultrasonic frequency is that 42KHz, power are 100-400W;

3) with step 2) product B that obtains carries out centrifugally, centrifugation rate is 10000r/min, the time is 5min, with centrifugal obtain be deposited in lyophilize in the freeze drying equipment, the lyophilize temperature is-85 ℃, be 6h time of drying, obtains the garnet powder;

4) powder that step 3) is obtained places atmosphere furnace, under hydrogen atmosphere, in 525 ℃ of reduction 3 hours, obtains In ₄Se ₃Thermoelectric compound powder.

The In that step 4) is obtained ₄Se ₃Product carries out XRD and SEM test, and presentation of results: the gained final product is single-phase In ₄Se ₃Thermoelectric compound, the about 200nm of particle diameter.

Embodiment 3:

1) gets 400 ml beakers, take by weighing 0.5865 gram analytical pure, four hydration indium chlorides, 0.2594 gram Sodium Selenite successively, take 200 ml deionized water, mix, obtain mixed solution A;

2) hydrazine hydrate solution that in step 1) gained mixed solution A, adds 3mL commercially available 85% is as reductive agent, and control reaction temperature is 50 ℃, and reaction is 10 hours under whipped state, obtains product B;

3) with step 2) product B that obtains carries out centrifugally, and centrifugation rate is 12000r/min, and the time is 3min, and centrifugal being deposited in of obtaining carried out lyophilize in the freeze drying equipment, and the lyophilize temperature is-75 ℃, be 2h time of drying, obtains the garnet powder;

4) the garnet powder that step 3) is obtained in 475 ℃ of reductase 12s hour, obtains In under hydrogen atmosphere in atmosphere furnace ₄Se ₃Thermoelectric compound powder.

Each concrete raw material that the present invention is cited, and the bound of each raw material, interval value, and the bound of processing parameter (like temperature, time etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.

Claims

1. In ₄Se ₃The preparation method of thermoelectric compound powder is characterized in that: it comprises the steps:

2) in mixed solution A, add the reductive agent Hydrazine Hydrate 80, the proportioning of the amount of substance of described reductive agent Hydrazine Hydrate 80 and Sodium Selenite was at least 10: 1, and control reaction temperature is 50～80 ℃, reacts 3～12 hours, obtains product B;

2. In according to claim 1 ₄Se ₃The preparation method of thermoelectric compound powder is characterized in that: the hydration soluble salt of the described indium of step 1) is the chloride monohydrate of indium or the nitric hydrate salt of indium.

3. In according to claim 1 ₄Se ₃The preparation method of thermoelectric compound powder is characterized in that: step 2) described reaction is to react under the ultrasonic reaction condition or under the whipped state.

4. In according to claim 1 ₄Se ₃The preparation method of thermoelectric compound powder is characterized in that: the described centrifugation time of step 3) is 3～5min, and centrifugal rotational speed is 8000～12000r/min.