CN101327518A - Method for preparing CoSb3 thermoelectric compound nano powder - Google Patents

Abstract

The invention relates to a preparation method of CoSb3 thermoelectric compound nano-powder. The preparation method of CoSb3 thermoelectric compound nano-powder includes the following steps: 1). Preparation of A solution, that is, mixture of cobalt chloride and antimony chloride, with ethanol as solvent; 2). Preparation of B solution, that is, mixture of sodium hydroxide and sodium borohydride, with ethanol as solvent; 3) Slowly dripping the A solution into the B solution under ultrasound conditions; 4). Centrifugation and drying of the products after ultrasonic processing in step 3) to produce amorphous precursor powder; 5). Reaction of the amorphous precursor powder in tubular atmosphere furnace under H2 atmosphere conditions at 370 to 400 degrees centigrade for 5 to 60 minutes, thus producing CoSb 3 thermoelectric compound nano-powders with particle size of 30 to 50 nanometers. The process of the method is simple and is easily controllable, the reaction time is short, the energy consumption is low, the method is safe and environment-friendly, the repeatability is high, and the CoSb3 thermoelectric compound nano-powders prepared in the method are characterized by small and uniform particle size and high purity.

Description

CoSb 3The preparation method of thermoelectric compound nano powder

Technical field

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

Background technology

Utilize the Seebeck effect (Seebeck Effect) of thermoelectric material directly heat energy to be converted into electric energy.To and solve environmental pollution for alleviating energy crisis as a kind of novel, eco-friendly clear energy sources switch technology an important channel will be provided.

CoSb ₃Compound is a kind of novel thermoelectric material, and theory and practice shows, by mixing and structure nanoization can increase substantially the thermoelectricity capability of material, in the thermoelectric power generation field wide application prospect is arranged.Because the higher thermoelectricity capability that has influence on material of thermal conductivity of this material, when the structure nano of material, its thermal conductivity can be reduced greatly, be expected to increase substantially the thermoelectricity capability index ZT value of material.Thereby adopt different preparation methods can obtain the thermoelectricity capability that different micro-structurals is expected controlled material.At present, for CoSb ₃The preparation method of polycrystalline compounds has solid reaction process (Solid state reaction, SSR), the method for getting rid of (Melt-Spinning is revolved in fusion, MS), coprecipitation (Cross-Coprecipitation, CC), sol-gal process (Sol-Gel method, SG).The CoSb that different preparation methods obtains ₃Its micro-structural of polycrystalline material is different with performance, and its pluses and minuses are respectively arranged, but all difficult CoSb that obtains particle size less than 50nm, size homogeneous, good reproducibility ₃Compound nano powder.

Summary of the invention

The object of the present invention is to provide a kind of CoSb ₃The preparation method of thermoelectric compound nano powder, this method good process repeatability, the CoSb of preparation ₃The particle diameter of thermoelectric compound nano powder is tiny, even, purity is high.

To achieve these goals, technical scheme of the present invention is: a kind of CoSb ₃The preparation method of thermoelectric compound nano powder is characterized in that it comprises the steps:

1). with ethanol is solvent, and the mixed solution of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.05mol/L-0.1mol/L in the A solution, and the concentration of antimony chloride is 0.15mol/L-0.3mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.1mol/L-0.2mol/L in the B solution, and the concentration of sodium borohydride is 0.1mol/L-0.2mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 1-1: 4, choose A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 2-16h; The product after the ultrasonic processing;

4). the product after the ultrasonic processing of step 3) is carried out centrifugal, dry, obtain the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 5min-60min in the tubular type atmosphere furnace in 370-400 ℃ of reaction time under the atmospheric condition, promptly obtain the CoSb that particle diameter is 30-50nm ₃Thermoelectric compound nano powder.

Centrifugation time in the described step 4) is that 5min-10min, rotating speed are 10000rpm-12000rpm.

The CoSb that the present invention obtains ₃Thermoelectric compound nano powder can be used for preparing CoSb ₃Thermoelectric material.

The present invention is by the adjusting to the reaction raw materials concentration proportioning, prepare two kinds of solution, carry out ultrasonic reaction after two kinds of solution are mixed, centrifugal, drying obtains the amorphous state precursor powder, place the tubular type atmosphere furnace to carry out reaction heat treatment resulting amorphous state precursor powder, get CoSb ₃Thermoelectric compound nano powder.

The invention has the beneficial effects as follows: adopt sonochemical method, this method raw material adopts chloride to compare cheap and easy to get as raw material than the used metal simple-substance of methods such as solid reaction process or fusion method; This method only needs ultrasonic 2h-16h, and heat treatment 5min-60min is simple and easy to control than solid reaction process long term annealing technology, the reaction time is short, energy consumption is low, safety non-pollution; This method good reproducibility; The CoSb of preparation ₃The particle diameter of thermoelectric compound nano powder tiny (particle diameter is 30-50nm), evenly, purity is high.

Description of drawings

Fig. 1 is a process chart of the present invention.

Fig. 2 is the XRD figure spectrum of the embodiment of the invention 1.

Fig. 3 is the SEM shape appearance figure of the embodiment of the invention 1.

Fig. 4 is the XRD figure spectrum of the embodiment of the invention 2.

Fig. 5 is the SEM shape appearance figure of the embodiment of the invention 2.

The specific embodiment

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

Embodiment 1:

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

1). with ethanol is solvent, and the mixed solution 100ml of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.05mol/L in the A solution, and the concentration of antimony chloride is 0.15mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution 200ml of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.1mol/L in the B solution, and the concentration of sodium borohydride is 0.1mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 2, chooses A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 16h; Ultrasonic device is a KQ-50DB type numerical control supersonic washer;

4). with the product after the ultrasonic processing of step 3) carry out centrifugal, in vacuum drying chamber, carry out drying, centrifugation time is that 5min, rotating speed are 10000rpm, obtains the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 5min in the tubular type atmosphere furnace in 370 ℃ of reaction time under the atmospheric condition, promptly obtain CoSb ₃Thermoelectric compound nano powder (end product).

Resulting CoSb ₃The XRD figure spectrum of thermoelectric compound nano powder is seen Fig. 2, CoSb ₃The SEM pattern of thermoelectric compound nano powder is seen Fig. 3.As shown in Figure 2, detecting powder through X ray is CoSb ₃The phase of compound does not have other dephasign (being the purity height).Morphology microstructure shown in Fig. 3 stereoscan photograph, CoSb ₃Compound is graininess, and average grain diameter is 30nm, is evenly distributed.

Embodiment 2:

A kind of CoSb ₃The preparation method of thermoelectric compound nano powder, it comprises the steps:

1). with ethanol is solvent, and the mixed solution 100ml of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.05mol/L in the A solution, and the concentration of antimony chloride is 0.15mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution 200ml of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.1mol/L in the B solution, and the concentration of sodium borohydride is 0.1mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 2, chooses A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 2h; Ultrasonic device is a KQ-50DB type numerical control supersonic washer;

4). with the product after the ultrasonic processing of step 3) carry out centrifugal, in vacuum drying chamber, carry out drying, centrifugation time is that 5min, rotating speed are 10000rpm, obtains the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 5min in the tubular type atmosphere furnace in 380 ℃ of reaction time under the atmospheric condition, promptly obtain CoSb ₃Thermoelectric compound nano powder.

Resulting CoSb ₃The XRD figure spectrum of thermoelectric compound nano powder is seen Fig. 4, CoSb ₃The SEM pattern of thermoelectric compound nano powder is seen Fig. 5.As shown in Figure 4, detecting powder through X ray is CoSb ₃The phase of compound does not have other dephasign (being the purity height).Morphology microstructure shown in Fig. 5 stereoscan photograph, CoSb ₃Compound is graininess, and average grain diameter is 50nm, is evenly distributed.

Embodiment 3:

A kind of CoSb ₃The preparation method of thermoelectric compound nano powder, it comprises the steps:

1). with ethanol is solvent, and the mixed solution of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.1mol/L in the A solution, and the concentration of antimony chloride is 0.3mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.2mol/L in the B solution, and the concentration of sodium borohydride is 0.2mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 2, chooses A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 16h; Ultrasonic device is a KQ-50DB type numerical control supersonic washer;

4). the product after the ultrasonic processing of step 3) is carried out centrifugal, dry, centrifugation time is that 10min, rotating speed are 12000rpm; Obtain the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 60min in the tubular type atmosphere furnace in 400 ℃ of reaction time under the atmospheric condition, promptly obtain the CoSb that particle diameter is 30-50nm ₃Thermoelectric compound nano powder.

Embodiment 4:

A kind of CoSb ₃The preparation method of thermoelectric compound nano powder, it comprises the steps:

1). with ethanol is solvent, and the mixed solution of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.1mol/L in the A solution, and the concentration of antimony chloride is 0.3mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.1mol/L in the B solution, and the concentration of sodium borohydride is 0.1mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 4, chooses A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 2h; The product after the ultrasonic processing; Ultrasonic device is a KQ-50DB type numerical control supersonic washer;

4). the product after the ultrasonic processing of step 3) is carried out centrifugal, dry, centrifugation time is that 5min, rotating speed are 10000rpm, obtains the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 5min in the tubular type atmosphere furnace in 370 ℃ of reaction time under the atmospheric condition, promptly obtain the CoSb that particle diameter is 30-50nm ₃Thermoelectric compound nano powder.

Embodiment 5:

A kind of CoSb ₃The preparation method of thermoelectric compound nano powder, it comprises the steps:

1). with ethanol is solvent, and the mixed solution of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.05mol/L in the A solution, and the concentration of antimony chloride is 0.15mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.2mol/L in the B solution, and the concentration of sodium borohydride is 0.2mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 1, chooses A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 16h; The product after the ultrasonic processing; Ultrasonic device is a KQ-50DB type numerical control supersonic washer;

4). the product after the ultrasonic processing of step 3) is carried out centrifugal, dry, centrifugation time is that 10min, rotating speed are 12000rpm, obtains the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 60min in the tubular type atmosphere furnace in 400 ℃ of reaction time under the atmospheric condition, promptly obtain the CoSb that particle diameter is 30-50nm ₃Thermoelectric compound nano powder.

Claims (2)

1. CoSb ₃The preparation method of thermoelectric compound nano powder is characterized in that it comprises the steps:

1). with ethanol is solvent, and the mixed solution of preparation cobalt chloride and antimony chloride is A solution; The concentration of cobalt chloride is 0.05mol/L-0.1mol/L in the A solution, and the concentration of antimony chloride is 0.15mol/L-0.3mol/L in the A solution;

2). with ethanol is solvent, and the mixed solution of preparation NaOH and sodium borohydride is B solution; Concentration sodium hydroxide is 0.1mol/L-0.2mol/L in the B solution, and the concentration of sodium borohydride is 0.1mol/L-0.2mol/L in the B solution;

3). the volume ratio by A solution and B solution is 1: 1-1: 4, choose A solution and B solution; Under ultrasound condition A solution is slowly splashed in the B solution, ultrasonic time is 2-16h; The product after the ultrasonic processing;

4). the product after the ultrasonic processing of step 3) is carried out centrifugal, dry, obtain the amorphous state precursor powder of Co and Sb;

5). Co that step 4) is obtained and the amorphous state precursor powder of Sb place H ₂Be 5min-60min in the tubular type atmosphere furnace in 370-400 ℃ of reaction time under the atmospheric condition, promptly obtain the CoSb that particle diameter is 30-50nm ₃Thermoelectric compound nano powder.

2. a kind of CoSb according to claim 1 ₃The preparation method of thermoelectric compound nano powder is characterized in that: the centrifugation time in the described step 4) is that 5min-10min, rotating speed are 10000rpm-12000rpm.

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