CN108565330A - A kind of preparation method of the silicide of the calcium as thermoelectric material - Google Patents
A kind of preparation method of the silicide of the calcium as thermoelectric material Download PDFInfo
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- CN108565330A CN108565330A CN201810396426.1A CN201810396426A CN108565330A CN 108565330 A CN108565330 A CN 108565330A CN 201810396426 A CN201810396426 A CN 201810396426A CN 108565330 A CN108565330 A CN 108565330A
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- calcium
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
Abstract
The invention discloses a kind of preparation methods of the silicide of the calcium as thermoelectric material, it is in nitrogen atmosphere, prodan and calcium chloride are put into stainless steel autoclave, metal k particle is put into after being mixed uniformly, it is washed with hydrochloric acid, dilute alkaline soln, distilled water and absolute ethyl alcohol respectively to remove impurity after 10 ~ 12 hours through 600 ~ 900 DEG C of heating, then vacuum dried obtains the silicide of the calcium.The silicide for the calcium that the present invention obtains is a kind of nano material, and preparation method is simple, is suitble to large-scale production, and it is used as thermoelectric material.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of preparation side of the silicide of the calcium as thermoelectric material
Method.
Background technology
Metal silicide has many advantages, such as when cheap, high temperature that antioxygenic property is good and stable chemical performance, therefore
Quite favored by researchers.Alkaline earth metal silicide is a kind of mostly important metal silicide, is widely used in heat
In electric material, photoelectric material and novel electron equipment.Mg2Si is a kind of excellent warm thermoelectric material.Experimental report at present,
Mg2Si1-xSnxThe thermoelectric figure of merit of solid solution can reach 1.4.Certain Sr2Si and BaSi2Also have with valence in hot fields
Value.
The silicide of calcium is a kind of silicide common in alkaline earth metal silicide, the successful synthesis calcium of experiment at present
Silicide has 8 kinds, respectively Ca2Si、Ca5Si3、CaSi、Ca3Si4、Ca14Si19、CaSi2、CaSi3And CaSi6.Wherein Ca2Si
And Ca3Si4It is semi-conducting material, their band gap magnitude is respectively 0.61eV and 0.34eV；Ca5Si3Under being likely to be with CaSi
The hydrogen storage material of a generation；And CaSi6And CaSi2It is a kind of superconductor under high pressure.Therefore, the silicide of calcium thermoelectricity field,
Possess huge applying value in photoelectronic device and superconductor.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation sides of the silicide of the calcium as thermoelectric material
The silicide purity of method, the powdered calcium of gained is higher, and preparation method is simple, is suitble to large-scale production.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of the silicide of the calcium as thermoelectric material, it is characterised in that：Include the following steps：
（1）In nitrogen atmosphere, into stainless steel autoclave be added 0.005 ~ 0.02mol prodans, then be added 0.01 ~
The calcium chloride of 0.02mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 1.6 ~ 5g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, heats 10 ~ 12 hours, then cools to room temperature in 600 ~ 900 DEG C in stove；
（4）It is washed respectively with hydrochloric acid, dilute alkaline soln, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance in 50 ~ 60 DEG C be dried in vacuo 10 ~ 12 hours to get.
The grain size of the metal k particle is 0.05 ~ 0.1 cm.
The dilute alkaline soln is the sodium hydroxide solution of a concentration of 0.1mol/L.
The silicide of the calcium is specially Ca2Si, CaSi or CaSi2。
The beneficial effects of the present invention are：
（1）Ca-Si bianry alloys are there are a variety of phases, the product purity of the silicide for the single calcium that existing preparation method is prepared
It is relatively low, often along with Ca5Si3The silicide by-product of equal calcium generates.The present invention is by strictly controlling ratio and the reaction of reactant
Condition keeps the purity of the silicide for the calcium being prepared higher, and its particle can reach Nano grade.
（2）In the present invention using fine particle shape metallic potassium as reducing agent, be to make it be come into full contact with reactant, and
It reacts fully.
（3）Preparation process of the present invention is simple, operation is easy, is at low cost, and product component is easy to control, the powdered calcium of gained
Silicide purity is higher, is expected to be applied to every field.
Description of the drawings
Fig. 1 is 1 gained Ca of embodiment2The XRD diagram of Si；
Fig. 2 is 1 gained Ca of embodiment2The conductivity variation with temperature situation map of Si；
Fig. 3 is the XRD diagram of 2 gained CaSi of embodiment；
Fig. 4 is the conductivity variation with temperature situation map of 2 gained CaSi of embodiment；
Fig. 5 is 3 gained CaSi of embodiment2XRD diagram；
Fig. 6 is 3 gained CaSi of embodiment2Conductivity variation with temperature situation map.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
（1）Stainless steel autoclave is put into the glove box full of nitrogen, 0.005mol fluorine silicon is added into stainless steel autoclave
Then sour sodium is added the calcium chloride of 0.01mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 1.6g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, 700 DEG C of heating in stove is placed on and heats 10 hours, then cool to room temperature；
（4）It is washed respectively with 0.1M hydrochloric acid, 0.1M sodium hydroxides, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance obtains Ca in drying 12 hours in 50 DEG C of vacuum drying2The powder sample of Si,
Grain size is 50 ~ 300nm.
The XRD diagram of powder sample is as shown in Figure 1, its conductivity variation with temperature situation is as shown in Figure 2 obtained by the example.
Embodiment 2
（1）Stainless steel autoclave is put into the glove box full of nitrogen, 0.01mol fluosilicic acid is added into stainless steel autoclave
Then sodium is added the calcium chloride of 0.01mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 2.5g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, 600 DEG C of heating in stove is placed on and heats 11 hours, then cool to room temperature；
（4）It is washed respectively with 0.1M hydrochloric acid, 0.1M sodium hydroxides, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance obtains the powder sample of CaSi, grain in drying 10 hours in 60 DEG C of vacuum drying
Diameter is 50 ~ 200nm.
The XRD diagram of powder sample is as shown in figure 3, its conductivity variation with temperature situation is as shown in Figure 4 obtained by the example.
Embodiment 3
（1）Stainless steel autoclave is put into the glove box full of nitrogen, 0.02mol fluosilicic acid is added into stainless steel autoclave
Then sodium is added the calcium chloride of 0.01mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 4g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, 800 DEG C of heating in stove is placed on and heats 10 hours, then cool to room temperature；
（4）It is washed respectively with 0.1M hydrochloric acid, 0.1M sodium hydroxides, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance obtains CaSi in drying 10 hours in 60 DEG C of vacuum drying2Powder sample,
Grain size is 50 ~ 300nm.
The XRD diagram of powder sample is as shown in figure 5, its conductivity variation with temperature situation is as shown in Figure 6 obtained by the example.
Embodiment 4
（1）Stainless steel autoclave is put into the glove box full of nitrogen, 0.01mol fluosilicic acid is added into stainless steel autoclave
Then sodium is added the calcium chloride of 0.02mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 3.5g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, 900 DEG C of heating in stove is placed on and heats 12 hours, then cool to room temperature；
（4）It is washed respectively with 0.1M hydrochloric acid, 0.1M sodium hydroxides, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance obtains CaSi in drying 12 hours in 50 DEG C of vacuum drying2Powder sample,
Grain size is 50 ~ 300nm.
Embodiment 5
（1）Stainless steel autoclave is put into the glove box full of nitrogen, 0.02mol fluosilicic acid is added into stainless steel autoclave
Then sodium is added the calcium chloride of 0.02mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 5g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, 600 DEG C of heating in stove is placed on and heats 11 hours, then cool to room temperature；
（4）It is washed respectively with 0.1M hydrochloric acid, 0.1M sodium hydroxides, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance obtains the powder sample of CaSi, grain in drying 11 hours in 55 DEG C of vacuum drying
Diameter is 50 ~ 200nm.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (4)
1. a kind of preparation method of the silicide of the calcium as thermoelectric material, it is characterised in that：Include the following steps：
（1）In nitrogen atmosphere, into stainless steel autoclave be added 0.005 ~ 0.02mol prodans, then be added 0.01 ~
The calcium chloride of 0.02mol, the two is uniformly mixed；
（2）In step（1）The metal k particle of 1.6 ~ 5g is put into obtained uniform mixed-powder；
（3）Autoclave is sealed, heats 10 ~ 12 hours, then cools to room temperature in 600 ~ 900 DEG C in stove；
（4）It is washed respectively with hydrochloric acid, dilute alkaline soln, distilled water and absolute ethyl alcohol, to remove impurity；
（5）By step（4）Obtained substance is dried in vacuo 10 ~ 12 hours silicides to get the calcium in 50 ~ 60 DEG C.
2. the preparation method of the silicide of calcium according to claim 1, it is characterised in that：The grain size of the metal k particle
For 0.05 ~ 0.1 cm.
3. the preparation method of the silicide of calcium according to claim 1, it is characterised in that：The dilute alkaline soln is a concentration of
The sodium hydroxide solution of 0.1mol/L.
4. the preparation method of the silicide of calcium according to claim 1, it is characterised in that：The silicide of the calcium is specially
Ca2Si, CaSi or CaSi2。
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| CN201810396426.1A CN108565330A (en) | 2018-04-28 | 2018-04-28 | A kind of preparation method of the silicide of the calcium as thermoelectric material |
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| CN201810396426.1A CN108565330A (en) | 2018-04-28 | 2018-04-28 | A kind of preparation method of the silicide of the calcium as thermoelectric material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186300A (en) * | 2007-12-17 | 2008-05-28 | 湖南大学 | Method for preparing titanium-silicon compound and doping material thereof by microwave irradiation |
| CN103771420A (en) * | 2014-01-14 | 2014-05-07 | 南昌大学 | Chloride-induced controllable method for preparing transition-metal silicide material with specific crystal phase |
| CN106116587A (en) * | 2016-06-22 | 2016-11-16 | 福州大学 | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof |
-
2018
- 2018-04-28 CN CN201810396426.1A patent/CN108565330A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186300A (en) * | 2007-12-17 | 2008-05-28 | 湖南大学 | Method for preparing titanium-silicon compound and doping material thereof by microwave irradiation |
| CN103771420A (en) * | 2014-01-14 | 2014-05-07 | 南昌大学 | Chloride-induced controllable method for preparing transition-metal silicide material with specific crystal phase |
| CN106116587A (en) * | 2016-06-22 | 2016-11-16 | 福州大学 | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冯志青 等: "以氟硅酸钠为硅源合成二硅化钒纳米晶的研究", 《浙江树人大学学报》 * |
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Application publication date: 20180921 |