CN103341641A - Preparing method for CoSb3 thermoelectric nanometer powder materials - Google Patents
Preparing method for CoSb3 thermoelectric nanometer powder materials Download PDFInfo
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- CN103341641A CN103341641A CN2013103145722A CN201310314572A CN103341641A CN 103341641 A CN103341641 A CN 103341641A CN 2013103145722 A CN2013103145722 A CN 2013103145722A CN 201310314572 A CN201310314572 A CN 201310314572A CN 103341641 A CN103341641 A CN 103341641A
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Abstract
A preparing method for CoSb3 thermoelectric nanometer powder materials relates to thermoelectric materials. The preparing method for the CoSb3 thermoelectric nanometer powder materials is good in process repeatability, and the CoSb3 thermoelectric nanometer particles prepared by the preparing method are small and even in particle size and high in purity. The preparing method comprises the steps of 1, using solvent to prepare mixed solution A of cobalt chloride and antimony chloride, 2, adding NaOH into the mixed solution A to obtain solution B, adding a reductive agent of NaBH4 into the solution B after the solution B cools down to enable cobalt ions and antimony ions in the solution B to be completely reduced, moving the solution B into a reaction kettle, and placing the solution B into a drying box to react to obtain block precipitate after being sealed, and 3, sequentially centrifuging and drying the black precipitate reacted and obtained from the step 2 to obtain the CoSb3 thermoelectric nanometer powder materials. The preparing method is simple in process, easy to control, short in reaction time, safe, free of pollution and good in repeatability. Prepared CoSb3 nanometer powder is small and even in particle size and high in purity.
Description
Technical field
The present invention relates to thermoelectric material, especially relate to a kind of CoSb
3The preparation method of thermoelectric nano-powder material.
Background technology
Thermoelectric material be a kind of can be with the direct functional material of conversion mutually of heat energy and electric energy.The device made from thermoelectric material has little, in light weight, the no drive disk assembly of volume, accurate advantage such as reliable, is having broad application prospects aspect thermo-electric generation and the thermoelectric cooling.Thermoelectric conversion as a kind of novel, eco-friendly energy-conservation switch technology for alleviating energy crisis with solve environmental pollution an important channel is provided.
CoSb
3Skutterudite thermoelectric material is a kind of novel thermoelectric material, and theory and practice proves, reduces CoSb
3The dimension of thermoelectric material can effectively improve the thermoelectricity capability of material, in the thermoelectric power generation field wide application prospect is arranged.This material itself has good electrical conductivity and Seebeck coefficient, but thermal conductivity than higher, after the material low-dimensionalization, the thermal conductivity of material can reduce greatly, is expected to increase substantially the thermoelectric figure of merit of material.Adopt different preparation methods can obtain different micro-structurals, thereby be expected the thermoelectricity capability of controlled material.
Chinese patent CN1594623A discloses a kind of with cobalt powder and the antimony powder CoSb that has been feedstock production
3Nano-sized powder by solid-state reaction method, Chinese patent CN101327518A have reported preparation CoSb
3The chemical alloying method (Chemical alloying) of thermoelectric nano-powder.The CoSb that above-mentioned preparation method obtains
3The micro-structural of material is different with performance, and its pluses and minuses are respectively arranged, but all is difficult to obtain the CoSb that the particle size particle diameter is tiny, even, purity is high
3Compound nano powder.
Summary of the invention
The object of the present invention is to provide a kind of good process repeatability, the CoSb of preparation
3The CoSb that the nanoparticle size particle diameter is tiny, even, purity is high
3The preparation method of thermoelectric nano-powder material.
The present invention includes following steps:
1) with solvent preparation cobalt chloride and antimony chloride mixed solution A;
2) in mixed solution A, add NaOH, get solution B, treat solution B cooling after, in solution B, add reducing agent NaBH
4, cobalt ions and antimony ion in the solution B are reduced fully, move into again in the reactor, put into drying box after the sealing and react, get black precipitate;
3) with step 2) black precipitate that obtains of reaction successively in deionized water and ethanol centrifugal back dry, namely get CoSb
3Thermoelectric nano-powder material.
In step 1), the solvent of described preparation cobalt chloride and antimony chloride mixed solution A can adopt deionized water etc., and the mol ratio of described cobalt chloride and antimony chloride can be 1: 3; The concentration of cobalt chloride can be 0.05～0.1mol/L in the described mixed solution A, and the concentration of antimony chloride can be 0.15～0.3mol/L.
In step 2) in, the addition of described NaOH and the proportioning of mixed solution A can be 1.2g: (20～25) mL, and wherein, NaOH calculates in mass, and the mixed solution A by volume is calculated; The temperature of described reaction can be 220～280 ℃, and the time of reaction can be 8～24h.
In step 3), described centrifugal number of times can be 3 times, and the centrifugal time can be 5min, and centrifugal rotation speed can be 5000rpm; The condition of described drying can be at 80 ℃ of following dry 5h; Resultant CoSb
3The particle diameter of thermoelectric nano-powder material is about 50nm.
The CoSb that the present invention obtains
3Thermoelectric compound nano powder can be used for preparing CoSb
3Block materials.
The present invention at first contains the precursor solution of cobalt and antimony with the certain proportion preparation, sealing changes in the reactor, and by the adjusting to reaction temperature and temperature retention time, final centrifugal drying obtains CoSb
3The thermoelectric compound nanometer powder.
The invention has the beneficial effects as follows: adopt hydro-thermal method, the chloride that the raw material of this method adopts cobalt and the antimony metal simple-substance used than solid reaction method or fusion method is cheap and easy to get; Synthesis temperature is 220～280 ℃, and temperature retention time is 8～24h, and is long with the high temperature of solid reaction process and fusion method, reaction time, need heat treatment comparatively speaking, and this method technology is simple and easy to control, reaction time weak point, safety non-pollution, good reproducibility; The CoSb of preparation
3The particle diameter of nano-powder is tiny, even, purity is high.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of the embodiment of the invention 1.In Fig. 1, abscissa be the angle of diffraction (°), ordinate is intensity.
Fig. 2 is the SEM shape appearance figure of the embodiment of the invention 1.In Fig. 2, scale is 200nm.
Fig. 3 is the XRD collection of illustrative plates of the embodiment of the invention 2.In Fig. 3, abscissa be the angle of diffraction (°), ordinate is intensity.
Fig. 4 is the SEM shape appearance figure of the embodiment of the invention 2.In Fig. 4, scale is 200nm.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment and accompanying drawing, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of CoSb
3The preparation method of thermoelectric compound nano powder, it comprises the steps:
1). be solvent with the deionized water, with 1: 3 ratio preparation cobalt chloride and the mixed solution A of antimony chloride, the concentration of cobalt chloride is 0.06mol/L in the mixed solution A, and the concentration of antimony chloride is 0.18mol/L, and constantly stirs.
2). slowly add NaOH and get solution B in the 20mL mixed solution A: the addition of NaOH is 1.2g, stirs 10min, treats the solution cooling.
3). in solution B, add the reducing agent NaBH of capacity
4, cobalt ions and antimony ion in the solution B are reduced fully, move in the reactor (25ml) behind the stirring 1min, put into drying box after the sealing and react.Reaction temperature is 270 ℃, and temperature retention time is 24h.
4). the black precipitate that obtains of reaction in deionized water and ethanol centrifugal three times successively, centrifugation time is that 5min, rotating speed are 5000rpm, at 80 ℃ of dry 5h down, obtains the CoSb that particle diameter is about 50nm at last
3Thermoelectric nano-powder material.
Resulting CoSb
3The XRD collection of illustrative plates of thermoelectric nano-powder is seen Fig. 1, CoSb
3The SEM pattern of thermoelectric nano-powder is seen Fig. 2.As shown in Figure 1, gained CoSb
3Thermoelectric nano-powder is CoSb
3The phase of compound does not have other dephasigns.CoSb
3The stereoscan photograph of thermoelectric nano-powder shows CoSb
3Compound is graininess, and average grain diameter is about 50nm, is evenly distributed.
Embodiment 2
A kind of CoSb
3The preparation method of thermoelectric compound nano powder, it comprises the steps:
1). be solvent with the deionized water, with 1: 3 ratio preparation cobalt chloride and the mixed solution A of antimony chloride, the concentration of cobalt chloride is 0.06mol/L in the mixed solution A, and the concentration of antimony chloride is 0.18mol/L, and constantly stirs.
2). slowly add NaOH and get solution B in the 25mL mixed solution A, the addition of NaOH is 1.2g, stirs 10min, treats the solution cooling.
3). in solution B, add the reducing agent NaBH of capacity
4, cobalt ions and antimony ion in the solution B are reduced fully, move in the reactor (25ml) behind the stirring 1min, put into drying box after the sealing and react.Reaction temperature is 280 ℃, and temperature retention time is 24h.
4). the black precipitate that obtains of reaction in deionized water and ethanol centrifugal three times successively, centrifugation time is that 5min, rotating speed are 5000rpm, at 80 ℃ of dry 5h down, obtains the CoSb that particle diameter is about 50nm at last
3Thermoelectric nano-powder material.
Resulting CoSb
3The XRD collection of illustrative plates of thermoelectric nano-powder is seen Fig. 3, CoSb
3The SEM pattern of thermoelectric nano-powder is seen Fig. 4.As shown in Figure 3, gained CoSb
3Thermoelectric nano-powder is CoSb
3The phase of compound does not have other dephasigns.CoSb
3The stereoscan photograph of thermoelectric nano-powder shows CoSb
3Compound is graininess, and average grain diameter is about 50nm, is evenly distributed.
Embodiment 3
A kind of CoSb
3The preparation method of thermoelectric compound nano powder, it comprises the steps:
1). be solvent with the deionized water, with 1: 3 ratio preparation cobalt chloride and the mixed solution A of antimony chloride, the concentration of cobalt chloride is 0.08mol/L in the mixed solution A, and the concentration of antimony chloride is 0.24mol/L, and constantly stirs.
2). slowly add NaOH and get solution B in the 22mL mixed solution A, the addition of NaOH is 1.2g, stirs 10min, treats the solution cooling.
3). in solution B, add the reducing agent NaBH of capacity
4, cobalt ions and antimony ion in the solution B are reduced fully, move in the reactor (25ml) behind the stirring 1min, put into drying box after the sealing and react.Reaction temperature is 220 ℃, and temperature retention time is 24h.
4). the black precipitate that obtains of reaction in deionized water and ethanol centrifugal three times successively, centrifugation time is that 5min, rotating speed are 5000rpm, at 80 ℃ of dry 5h down, obtains CoSb at last
3Thermoelectric nano-powder.
Embodiment 4
A kind of CoSb
3The preparation method of thermoelectric compound nano powder, it comprises the steps:
1). be solvent with the deionized water, with 1: 3 ratio preparation cobalt chloride and the mixed solution A of antimony chloride, the concentration of cobalt chloride is 0.08mol/L in the mixed solution A, and the concentration of antimony chloride is 0.24mol/L, and constantly stirs.
2). slowly add NaOH and get solution B in the 23mL mixed solution A, the addition of NaOH is 1.2g, stirs 10min, treats the solution cooling.
3). in solution B, add the reducing agent NaBH of capacity
4, cobalt ions and antimony ion in the solution B are reduced fully, move in the reactor (25ml) behind the stirring 1min, put into drying box after the sealing and react.Reaction temperature is 250 ℃, and temperature retention time is 24h.
4). the black precipitate that obtains of reaction in deionized water and ethanol centrifugal three times successively, centrifugation time is that 5min, rotating speed are 5000rpm, at 80 ℃ of dry 5h down, obtains CoSb at last
3Thermoelectric nano-powder.
Embodiment 5
A kind of CoSb
3The preparation method of thermoelectric compound nano powder, it comprises the steps:
1). be solvent with the deionized water, with 1: 3 ratio preparation cobalt chloride and the mixed solution A of antimony chloride, the concentration of cobalt chloride is 0.1mol/L in the mixed solution A, and the concentration of antimony chloride is 0.3mol/L, and constantly stirs.
2). slowly add NaOH and get solution B in the 22mL mixed solution A, the addition of NaOH is 1.2g, stirs 10min, treats the solution cooling.
3). in solution B, add the reducing agent NaBH of capacity
4, cobalt ions and antimony ion in the solution B are reduced fully, move in the reactor (25ml) behind the stirring 1min, put into drying box after the sealing and react.Reaction temperature is 270 ℃, and temperature retention time is 8h.
4). the black precipitate that obtains of reaction in deionized water and ethanol centrifugal three times successively, centrifugation time is that 5min, rotating speed are 5000rpm, at 80 ℃ of dry 5h down, obtains CoSb at last
3Thermoelectric nano-powder.
Embodiment 6
A kind of CoSb
3The preparation method of thermoelectric compound nano powder, it comprises the steps:
1). be solvent with the deionized water, with 1: 3 ratio preparation cobalt chloride and the mixed solution A of antimony chloride, the concentration of cobalt chloride is 0.1mol/L in the mixed solution A, and the concentration of antimony chloride is 0.3mol/L, and constantly stirs.
2). slowly add NaOH and get solution B in the 20mL mixed solution A, the addition of NaOH is 1.2g, stirs 10min, treats the solution cooling.
3). in solution B, add the reducing agent NaBH of capacity
4, cobalt ions and antimony ion in the solution B are reduced fully, move in the reactor (25ml) behind the stirring 1min, put into drying box after the sealing and react.Reaction temperature is 270 ℃, and temperature retention time is 16h.
4). the black precipitate that obtains of reaction in deionized water and ethanol centrifugal three times successively, centrifugation time is that 5min, rotating speed are 5000rpm, at 80 ℃ of dry 5h down, obtains CoSb at last
3Thermoelectric nano-powder.
Claims (9)
1.CoSb
3The preparation method of thermoelectric nano-powder material is characterized in that comprising the steps:
1) with solvent preparation cobalt chloride and antimony chloride mixed solution A;
2) in mixed solution A, add NaOH, get solution B, treat solution B cooling after, in solution B, add reducing agent NaBH
4, cobalt ions and antimony ion in the solution B are reduced fully, move into again in the reactor, put into drying box after the sealing and react, get black precipitate;
3) with step 2) black precipitate that obtains of reaction successively in deionized water and ethanol centrifugal back dry, namely get CoSb
3Thermoelectric nano-powder material.
2. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 1), and the solvent of described preparation cobalt chloride and antimony chloride mixed solution A adopts deionized water.
3. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 1) the mol ratio of described cobalt chloride and antimony chloride is 1: 3.
4. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 1) the concentration of cobalt chloride is 0.05～0.1mol/L in the described mixed solution A, and the concentration of antimony chloride is 0.15～0.3mol/L.
5. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 2) in, the addition of described NaOH and the proportioning of mixed solution A are 1.2g: (20～25) mL, and wherein, NaOH calculates in mass, and the mixed solution A by volume is calculated.
6. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 2) in, the temperature of described reaction is 220～280 ℃, the time of reaction is 8～24h.
7. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 3) described centrifugal number of times is 3 times.
8. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 3) the described centrifugal time is 5min, and centrifugal rotation speed is 5000rpm.
9. CoSb according to claim 1
3The preparation method of thermoelectric nano-powder material is characterized in that in step 3), and the condition of described drying is dry 5h under 80 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195757A (en) * | 2014-06-23 | 2015-12-30 | 巴莱诺斯清洁能源控股公司 | Sb nanocrystals or Sb-alloy nanocrystals for fast charge/discharge Li- and Na-ion battery anodes |
| CN108296492A (en) * | 2017-01-12 | 2018-07-20 | 丰田自动车株式会社 | The manufacturing method of alloy nano particle |
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| US20090263496A1 (en) * | 2006-04-15 | 2009-10-22 | Bayer Technology Services Gmbh | Method for producing metal particles, metal particles produced thereby, and the use thereof |
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| US20090263496A1 (en) * | 2006-04-15 | 2009-10-22 | Bayer Technology Services Gmbh | Method for producing metal particles, metal particles produced thereby, and the use thereof |
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| CN101559494A (en) * | 2009-06-02 | 2009-10-21 | 四川大学 | Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof |
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| CN105195757A (en) * | 2014-06-23 | 2015-12-30 | 巴莱诺斯清洁能源控股公司 | Sb nanocrystals or Sb-alloy nanocrystals for fast charge/discharge Li- and Na-ion battery anodes |
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| CN108296492A (en) * | 2017-01-12 | 2018-07-20 | 丰田自动车株式会社 | The manufacturing method of alloy nano particle |
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Application publication date: 20131009 |