CN103042232B - Method for preparing zinc-stibium alloy nano material by using one-step solvothermal method - Google Patents
Method for preparing zinc-stibium alloy nano material by using one-step solvothermal method Download PDFInfo
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- CN103042232B CN103042232B CN201310033916.2A CN201310033916A CN103042232B CN 103042232 B CN103042232 B CN 103042232B CN 201310033916 A CN201310033916 A CN 201310033916A CN 103042232 B CN103042232 B CN 103042232B
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- nano material
- zinc
- alloy nano
- antimony alloy
- zncl
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Abstract
The invention discloses a method for preparing a zinc-stibium alloy nano material by using a one-step solvothermal method and using ZnCl2 as zinc source, relates to a method for preparing a zinc-stibium alloy nano material using ZnCl2 as zinc source and aims at overcoming the defects of many impurities, high toxicity and poor controllability in grain size existing in the method for preparing the zinc-stibium alloy nano material. The method comprises the following steps of: 1, preparing a reaction raw material; 2, preparing a pre-product; and 3, cleaning and drying the pre-product to obtain the zinc-stibium alloy nano material. The method is low in cost, simple in required reaction equipment, good in controllability and repeatability, capable of reducing the reaction temperature for preparing the zinc-stibium alloy nano material, saving energy sources and realizing one-step obtaining of the zinc-stibium alloy nano material, simple in step and convenient to operate. The method is used for preparing the zinc-stibium alloy nano material.
Description
Technical field
The present invention relates to the method preparing zinc antimony alloy nano material.
Background technology
Along with the continuous aggravation of environmental problem and energy problem, in order to economize energy, people have started the recycling turning one's attention to used heat, and as by vehicle exhaust, power plant, the used heat in boiler factory is converted to electric energy and is used.The functional material that heat energy and electric energy directly change can be realized and be called thermoelectric material.Zn
4sb
3with the thermoelectric material most at middle warm area with practical application potentiality that ZnSb is generally acknowledged both at home and abroad at present, Zn
4sb
3monocrystalline under 670K its thermoelectric figure of merit (zT) value up to 1.3, ZnSb monocrystalline zT value of its monocrystalline under 500K also reaches 0.6, and Zn, the cost of the elements such as Sb is lower, toxicity is less, reserves are large, and Zn-Sb alloy thermoelectric material to become the focus of thermoelectric material research field research in recent years.And progress in the last few years has shown that nano material has lower lattice thermal conductivity relative to body material, thus there is the thermoelectricity capability more excellent than body material.So the preparation realizing Zn-Sb alloy nano-material is for promotion Zn
4sb
3significant in the commercial application in thermoelectricity field with ZnSb.
Tradition preparation Zn
4sb
3two kinds are mainly contained: 1, synthesize Zn by high temperature heat treatment Zn powder and Sb powder fusion-crystallization under the protection of inert gas with the method for ZnSb
4sb
3with ZnSb, the method needs to consume a large amount of energy, and equipment and technology is more complicated, and the poor heat stability of the Zn-Sb alloy prepared.2, the solvent-thermal method of substep is adopted; first utilize solvent-thermal method under the help of reducing agent, restore Zn powder and Sb powder in the solution; then by the collection step Zn such as centrifugal, to dry under argon shield; Sb powder; transfer to (as trioctylamine) in another kind of solvent subsequently again, then be heated to 250 ~ 300 DEG C of preparation Zn
4sb
3with ZnSb, need subsequently to collect, centrifugal, the steps such as oven dry, the method step is comparatively complicated, and the reaction temperature of needs is higher, and the chemical raw material of needs is also more, and cost compare is expensive again.
In the research of this area, application number is 201210374580.1, name is called that " a kind of preparation method of zinc-base antimonide nanostructured " discloses a kind of preparation method of zinc antimony alloy material.But this preparation method exists, and impurity is many, toxicity large, the defect of the size controlling difference of zinc-base antimonide nanostructured.
Summary of the invention
The present invention is that will to solve with zinc powder be that the zinc antimony alloy preparation method of nano material in zinc source exists that impurity is many, toxicity large, the defect of size tunable difference, and the one provided is with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material.
A kind of with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, specifically prepare according to following steps:
One, under argon shield condition by ZnCl
2and SbCl
3put into the reducing solution that concentration is (1 ~ 8) mol/L, obtain reaction raw materials, wherein ZnCl
2with SbCl
3the ratio of amount of substance be 0.5 ~ 10:1;
Two, the reaction raw materials that step one obtains is put into reactor from room temperature to 65 DEG C ~ 100 DEG C, keep 1h ~ 1.5h, then be warming up to 150 DEG C ~ 250 DEG C, keep 1h ~ 240h; Or to control heating rate be 1 DEG C/reaction raw materials that min ~ 3 DEG C/step one obtains by min puts into reactor from room temperature to 150 DEG C ~ 250 DEG C, keeps 1h ~ 240h, obtain pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2 ~ 3 times, be the acetic acid solution centrifuge washing 2 ~ 3 times of 2% ~ 5% again by volumetric concentration, get solid, use deionized water centrifuge washing again 3 ~ 4 times, then absolute ethyl alcohol centrifuge washing is used 1 ~ 2 time, dry 1h ~ 12h under temperature is 40 DEG C ~ 90 DEG C conditions, obtains zinc antimony alloy nano material again.
The chemical equation that the present invention uses is as follows:
Zn+Sb → ZnSb or Zn+Sb → Zn
4sb
3
Wherein, in product, the crystal type of zinc antimonide depends on reaction raw materials ZnCl
2with SbCl
3amount of substance ratio and the experiment parameter of reaction condition.
The invention has the beneficial effects as follows:
(1) one-step method realizing zinc antimony alloy nano material obtains, and step is simple, easy to operate, controlling and reproducible.
(2) reduce the reaction temperature to 150 DEG C of preparing zinc antimony alloy nano material ~ 250 DEG C, saved the energy, reduced the impact in the life-span on equipment and instrument.
(3) raw material is with low cost, and the consersion unit of needs is simple.
The present invention is for the preparation of zinc antimony alloy nano material.
Accompanying drawing explanation
Fig. 1 is Zn prepared by embodiment one
4sb
3zinc antimony alloy nano material and Zn
4sb
3the XRD curve map of nano material, the wherein Zn for preparing for embodiment one of curve " a "
4sb
3the XRD curve of zinc antimony alloy nano material, " b " is Zn
4sb
3the XRD curve of nano material;
Fig. 2 is Zn prepared by embodiment one
4sb
3the scanning electron microscope (SEM) photograph of zinc antimony alloy nano material;
Fig. 3 is Zn prepared by embodiment one
4sb
3the X-ray electronic diffraction energy spectrogram of zinc antimony alloy nano material, wherein " a " peak and " c " peak represent Zn, and " b " peak represents Sb;
Fig. 4 is the ZnSb zinc antimony alloy nano material prepared of embodiment two and the XRD curve map of ZnSb nano material, wherein the XRD curve of ZnSb zinc antimony alloy nano material prepared for embodiment two of curve " a ", the XRD curve that " b " is ZnSb nano material;
Fig. 5 is the scanning electron microscope (SEM) photograph of ZnSb zinc antimony alloy nano material prepared by embodiment two;
Fig. 6 is the X-ray electronic diffraction energy spectrogram of ZnSb zinc antimony alloy nano material prepared by embodiment two, and wherein " a " peak and " c " peak represent Zn, and " b " peak represents Sb.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: present embodiment is a kind of with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, specifically prepare according to following steps:
One, under argon shield condition by ZnCl
2and SbCl
3put into the reducing solution that concentration is (1 ~ 8) mol/L, obtain reaction raw materials, wherein ZnCl
2with SbCl
3the ratio of amount of substance be 0.5 ~ 10:1;
Two, the reaction raw materials that step one obtains is put into reactor from room temperature to 65 DEG C ~ 100 DEG C, keep 1h ~ 1.5h, then be warming up to 150 DEG C ~ 250 DEG C, keep 1h ~ 240h; Or to control heating rate be 1 DEG C/reaction raw materials that min ~ 3 DEG C/step one obtains by min puts into reactor from room temperature to 150 DEG C ~ 250 DEG C, keeps 1h ~ 240h, obtain pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2 ~ 3 times, be the acetic acid solution centrifuge washing 2 ~ 3 times of 2% ~ 5% again by volumetric concentration, get solid, use deionized water centrifuge washing again 3 ~ 4 times, then absolute ethyl alcohol centrifuge washing is used 1 ~ 2 time, again under temperature is 40 DEG C ~ 90 DEG C conditions, dry 1h ~ 12h, obtains zinc antimony alloy nano material.
The beneficial effect of present embodiment is:
(1) raw material is with low cost, and the consersion unit of needs is simple, controlling and reproducible.
(2) reduce the reaction temperature to 150 DEG C of preparing zinc antimony alloy nano material ~ 250 DEG C, saved the energy, reduced the impact in the life-span on equipment and instrument.
(3) one-step method realizing zinc antimony alloy nano material obtains, and step is simple, easy to operate.
Detailed description of the invention two: present embodiment and detailed description of the invention one are unlike ZnCl in step one
2with SbCl
3the ratio of amount of substance be 4:3, obtained is ZnSb zinc antimony alloy nano material.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two are unlike ZnCl in step one
2with SbCl
3the ratio of amount of substance be 2:1, that obtained is Zn
4sb
3zinc antimony alloy nano material.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: in step one, reducing solution is lithium triethylborohydride/tetrahydrofuran solution.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: be warming up to 65 DEG C ~ 70 DEG C in step 2 in still, keep 1.2h, then be warming up to 180 DEG C ~ 240 DEG C, keep 2h ~ 72h; Or controlling heating rate is that reaction raw materials that step one obtains by 2 DEG C/min puts into reactor from room temperature to 180 DEG C ~ 240 DEG C, keeps 2h ~ 72h.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: dry under temperature is 45 DEG C ~ 85 DEG C conditions in step 3.Other is identical with one of detailed description of the invention one to five.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
A kind of method taking ZnCl2 as zinc source one step solvent-thermal method and prepare zinc antimony alloy nano material of the present embodiment, specifically prepare according to following steps:
One, under argon shield condition by 0.273g ZnCl
2with 0.228g SbCl
3put into the tetrahydrofuran solution (lithium triethylborohydride concentration is 1mol/L) that 10.5mL is dissolved with lithium triethylborohydride, fully dissolve and obtain reaction raw materials;
Two, the reaction raw materials that step one obtains is put into reactor and be warming up to 65 DEG C, keep 1h, then be warming up to 200 DEG C, keep 72h, obtain pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2, then is the acetic acid solution centrifuge washing 2 times of 2% by volumetric concentration, gets solid, use deionized water centrifuge washing again 3 times, then use absolute ethyl alcohol centrifuge washing 1 time, then under temperature is 40 DEG C of conditions, dry 12h, obtains Zn
4sb
3zinc antimony alloy nano material.
Zn prepared by the present embodiment
4sb
3zinc antimony alloy nano material and Zn
4sb
3the XRD curve map of nano material, as shown in Figure 1, the wherein Zn for preparing for the present embodiment of curve " a "
4sb
3the XRD curve of zinc antimony alloy nano material, " b " is Zn
4sb
3the XRD curve of nano material, as seen from the figure, Zn prepared by the present embodiment
4sb
3zinc antimony alloy nano material is pure Zn
4sb
3.
Zn prepared by the present embodiment
4sb
3as shown in Figure 2, its particle diameter is in nanometer scale as can be seen from Figure for the scanning electron microscope (SEM) photograph of zinc antimony alloy nano material.
Zn prepared by the present embodiment
4sb
3the X-ray electronic diffraction energy spectrogram of zinc antimony alloy nano material, as shown in Figure 3, wherein " a " peak and " c " peak represent Zn, and " b " peak represents Sb, can analyze Zn prepared by the present embodiment by figure
4sb
3in zinc antimony alloy nano material, the percentage of Zn atom and Sb atomic quantity is 58.3%:41.7%, substantially meets 4:3.
Embodiment two:
A kind of method taking ZnCl2 as zinc source one step solvent-thermal method and prepare zinc antimony alloy nano material of the present embodiment, specifically prepare according to following steps:
One, under argon shield condition by 0.187g ZnCl
2with 0.228g SbCl
3put into the tetrahydrofuran solution (lithium triethylborohydride concentration is 1mol/L) that 8.5mL is dissolved with lithium triethylborohydride, fully dissolve and obtain reaction raw materials;
Two, the reaction raw materials that step one obtains is put into reactor and be warming up to 65 DEG C, keep 1h, then be warming up to 250 DEG C, keep 72h, obtain pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2, be the acetic acid solution centrifuge washing 2 times of 2% again by volumetric concentration, get solid, use deionized water centrifuge washing again 3 times, then absolute ethyl alcohol centrifuge washing is used 1 time, again under temperature is 40 DEG C of conditions, dry 12h, obtains ZnSb zinc antimony alloy nano material.
The XRD curve map of ZnSb zinc antimony alloy nano material prepared by the present embodiment, as shown in Figure 4, the wherein XRD curve of ZnSb zinc antimony alloy nano material prepared for the present embodiment of curve " a ", the XRD curve that " b " is ZnSb nano material, as seen from the figure, the ZnSb zinc antimony alloy nano material that prepared by the present embodiment is purer ZnSb.
As shown in Figure 5, its particle diameter is in nanometer scale as can be seen from Figure for the scanning electron microscope (SEM) photograph of ZnSb zinc antimony alloy nano material prepared by the present embodiment.
The X-ray electronic diffraction energy spectrogram of ZnSb zinc antimony alloy nano material prepared by the present embodiment, as shown in Figure 6, wherein " a " peak and " c " peak represent Zn, " b " peak represents Sb, the percentage that can be analyzed Zn atom and Sb atomic quantity in ZnSb zinc antimony alloy nano material prepared by the present embodiment by figure is 52.8%:47.2%, substantially meets 1:1.
Embodiment three:
A kind of method taking ZnCl2 as zinc source one step solvent-thermal method and prepare zinc antimony alloy nano material of the present embodiment, specifically prepare according to following steps:
One, under argon shield condition by 0.273g ZnCl
2with 0.228g SbCl
3put into the tetrahydrofuran solution (lithium triethylborohydride concentration is 1mol/L) that 10.5mL is dissolved with lithium triethylborohydride, fully dissolve and obtain reaction raw materials;
Two, controlling heating rate is that the reaction raw materials that step one obtains by 2 DEG C/min puts into reactor from room temperature to 200 DEG C, keeps 72h, obtains pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2, then is the acetic acid solution centrifuge washing 2 times of 2% by volumetric concentration, gets solid, use deionized water centrifuge washing again 3 times, then use absolute ethyl alcohol centrifuge washing 1 time, then under temperature is 40 DEG C of conditions, dry 12h, obtains Zn
4sb
3zinc antimony alloy nano material.
Embodiment four:
A kind of method taking ZnCl2 as zinc source one step solvent-thermal method and prepare zinc antimony alloy nano material of the present embodiment, specifically prepare according to following steps:
One, under argon shield condition by 0.187g ZnCl
2with 0.228g SbCl
3put into the tetrahydrofuran solution (lithium triethylborohydride concentration is 1mol/L) that 8.5mL is dissolved with lithium triethylborohydride, fully dissolve and obtain reaction raw materials;
Two, controlling heating rate is that the reaction raw materials that step one obtains by 2 DEG C/min puts into reactor from room temperature to 250 DEG C, keeps 72h, obtains pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2, be the acetic acid solution centrifuge washing 2 times of 2% again by volumetric concentration, get solid, use deionized water centrifuge washing again 3 times, then absolute ethyl alcohol centrifuge washing is used 1 time, again under temperature is 40 DEG C of conditions, dry 12h, obtains ZnSb zinc antimony alloy nano material.
Claims (5)
1. one kind with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, it is characterized in that a kind of with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, specifically prepare according to following steps:
One, under argon shield condition by ZnCl
2and SbCl
3put into the reducing solution that concentration is 1mol/L ~ 8mol/L, obtain reaction raw materials, wherein ZnCl
2with SbCl
3the ratio of amount of substance be 0.5 ~ 10:1;
Two, the reaction raw materials that step one obtains is put into reactor from room temperature to 65 DEG C ~ 100 DEG C, keep 1h ~ 1.5h, then be warming up to 150 DEG C ~ 250 DEG C, keep 1h ~ 240h; Or to control heating rate be 1 DEG C/reaction raw materials that min ~ 3 DEG C/step one obtains by min puts into reactor from room temperature to 150 DEG C ~ 250 DEG C, keeps 1h ~ 240h, obtain pre-product;
Three, pre-product step 2 obtained first uses absolute ethyl alcohol centrifuge washing 2 ~ 3 times, be the acetic acid solution centrifuge washing 2 ~ 3 times of 2% ~ 5% again by volumetric concentration, get solid, use deionized water centrifuge washing again 3 ~ 4 times, then absolute ethyl alcohol centrifuge washing is used 1 ~ 2 time, dry 1h ~ 12h under temperature is 40 DEG C ~ 90 DEG C conditions, obtains zinc antimony alloy nano material again;
Wherein, in step one, reducing solution is lithium triethylborohydride/tetrahydrofuran solution.
2. one according to claim 1 is with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, it is characterized in that ZnCl in step one
2with SbCl
3the ratio of amount of substance be 4:3, obtained is ZnSb zinc antimony alloy nano material.
3. one according to claim 1 is with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, it is characterized in that ZnCl in step one
2with SbCl
3the ratio of amount of substance be 2:1, that obtained is Zn
4sb
3zinc antimony alloy nano material.
4. one according to claim 1 is with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, it is characterized in that in step 2, in still, being warming up to 65 DEG C ~ 70 DEG C, keep 1.2h, then be warming up to 180 DEG C ~ 240 DEG C, keep 2h ~ 72h; Or controlling heating rate is that reaction raw materials that step one obtains by 2 DEG C/min puts into reactor from room temperature to 180 DEG C ~ 240 DEG C, keeps 2h ~ 72h.
5. one according to claim 4 is with ZnCl
2for zinc source one step solvent-thermal method prepares the method for zinc antimony alloy nano material, it is characterized in that in step 3 dry under temperature is 45 DEG C ~ 85 DEG C conditions.
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|---|---|---|---|
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|---|---|---|---|
| CN201310033916.2A CN103042232B (en) | 2013-01-29 | 2013-01-29 | Method for preparing zinc-stibium alloy nano material by using one-step solvothermal method |
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| EP2959989B1 (en) * | 2014-06-23 | 2017-08-02 | Belenos Clean Power Holding AG | Sb nanocrystals or Sb-alloy nanocrystals for fast charge/discharge Li- and Na-ion battery anodes |
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|---|---|---|---|---|
| CN101302358B (en) * | 2007-05-09 | 2011-12-14 | 北京有色金属研究总院 | Waterless nano-znic antimonite sol and preparation thereof |
| CN100491025C (en) * | 2007-07-03 | 2009-05-27 | 杭州电子科技大学 | Process for producing zinc antimonide powder at low temperature |
| CN101275192B (en) * | 2008-05-09 | 2013-01-30 | 湖南晟通科技集团有限公司 | Composite nanometer ZnSb-based thermoelectric material and preparation thereof |
| KR101103104B1 (en) * | 2008-12-23 | 2012-01-04 | 서울대학교산학협력단 | Preparation Method of ZnSb-C Composite and Anode Materials for Secondary Batteries Containing the Same Composite |
| CN102863017B (en) * | 2012-09-29 | 2014-06-04 | 浙江东晶光电科技有限公司 | Method for preparing zinc-based antimonide Kano-structure |
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