CN110885067A - Tin selenide based thermoelectric material and preparation method thereof - Google Patents
Tin selenide based thermoelectric material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a tin selenide-based thermoelectric material and a preparation method thereof, wherein the tin selenide-based thermoelectric material comprises the following components: selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid; the molar ratio of selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid is 1: 1-5: 1-3: 8-10. The invention also provides a preparation method of the tin selenide-based thermoelectric material. According to the invention, the tin selenide-based thermoelectric material is prepared by a hydrothermal method, the preparation process is simple and easy to repeat, toxic substances are not used, the problems of long preparation time, high cost and environmental pollution are effectively solved, and the tin selenide-based thermoelectric material with high purity is prepared.
Description
Technical Field
The invention relates to the technical field of thermoelectric material preparation, in particular to a tin selenide-based thermoelectric material and a preparation method thereof.
Background
The SnSe is a narrow-band-gap semiconductor material, belongs to an orthorhombic system, has a crystal with a layered structure, has a band gap of 1.0-1.5 eV, and has important application prospects in near-infrared photoelectric detection and photovoltaic cells due to the advantages of excellent photoelectric performance, nontoxicity, cheap raw materials and relatively rich reserves. In addition, SnSe is also a very promising thermoelectric material due to its ultra-low thermal conductivity and excellent electrical properties. At present, liquid phase methods, precipitation methods and the like are adopted as the synthesis methods, but most of the methods need special instruments, the difficulty of preparation operation is increased, the preparation process is complex and difficult to control, the required time is long, the cost is high, toxic substances such as hydrazine hydrate and the like can be used in some preparation processes, the physical and mental damage to experimenters can be caused, and the environment can be polluted.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the tin selenide-based thermoelectric material and the preparation method thereof, the tin selenide-based thermoelectric material is prepared by a hydrothermal method, the preparation process is simple and easy to repeat, toxic substances are not used, the problems of complex preparation process, difficulty in control, high cost and environmental pollution are effectively solved, and the tin selenide-based thermoelectric material with high purity is prepared.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the tin selenide-based thermoelectric material comprises the following components: selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid;
the molar ratio of selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid is 1: 1-5: 1-3: 8-10.
Further, the molar ratio of selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid is 1: 1-3: 1-2: 8-9.
Further, the molar ratio of selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid is 1:2:1: 9.
The preparation method of the tin selenide-based thermoelectric material is characterized by comprising the following steps:
(1) dissolving selenium dioxide and ascorbic acid in an alkaline solution, and stirring until the selenium dioxide and the ascorbic acid are dissolved to obtain a solution I;
(2) adding tartaric acid or citric acid into distilled water, stirring uniformly, then adding stannous chloride, and stirring until the mixture is dissolved to obtain a solution II;
(3) slowly adding the solution I obtained in the step (1) into the solution II obtained in the step (2), stirring for 30-60 min, pouring into a reaction kettle, heating to 180-240 ℃, preserving heat for 10-16 h, and cooling to room temperature to obtain a reaction product;
(4) and (4) washing the reaction product obtained in the step (3) with distilled water and absolute ethyl alcohol for 2-4 times respectively, and then centrifuging and drying to obtain the tin selenide-based thermoelectric material.
Further, in the step (1), the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
Further, in the step (1), the molar ratio of the tin dioxide to the alkaline solution is 1: 18-22.
Further, in the step (2), the concentration of the tartaric acid or citric acid added with distilled water is 1-1.3 g/mL.
Further, magnetic stirring is adopted in the step (3), and the lining of the reaction kettle is made of polytetrafluoroethylene.
Further, in the step (4), centrifuging for 10-15 min at the rotating speed of 900-1100 rpm.
Further, in the step (4), vacuum drying is carried out for 2-4 hours at the temperature of 70-90 ℃.
In summary, the invention has the following advantages:
1. according to the invention, the tin selenide-based thermoelectric material is prepared by a hydrothermal method, and the components such as selenium dioxide, ascorbic acid and stannous chloride have low cost and no toxicity, so that the experimental personnel cannot be harmed and the environment cannot be polluted; the preparation process is simple and easy to repeat, no special instrument is needed during the preparation by a hydrothermal method, the preparation process is simple and effective, the tin selenide-based thermoelectric material can be quickly prepared, the problems of complex preparation process, difficult control, high cost and environmental pollution are effectively solved, and the tin selenide-based thermoelectric material with high purity is prepared.
2. In the preparation process, selenium dioxide and ascorbic acid are subjected to reduction reaction under alkaline condition to generate Se2-Dissolving stannous chloride in water to obtain Sn2+，Se2-And Sn2+Reacting to obtain tin selenide; ascorbic acid for reducing tin dioxide to quickly generate Se2-Tartaric acid or citric acid is used as a catalyst; the preparation process has simple engineering, can effectively shorten the preparation time, quickly prepare the tin selenide, has less impurities prepared by a hydrothermal method, and obtains the tin selenide-based thermoelectric material with higher purity.
Drawings
FIG. 1 is a schematic diagram showing the X-ray diffraction results of a tin selenide-based thermoelectric material;
fig. 2 is a schematic view of the scanning result of the tin selenide-based thermoelectric material by an electron microscope.
Detailed Description
Example 1
A tin selenide-based thermoelectric material comprising the following components: selenium dioxide, ascorbic acid, stannous chloride and tartaric acid; the molar ratio of the selenium dioxide to the ascorbic acid to the stannous chloride to the tartaric acid is 1:1:1: 8.
The preparation method of the tin selenide-based thermoelectric material is characterized by comprising the following steps:
(1) dissolving selenium dioxide and ascorbic acid in a sodium hydroxide solution, wherein the molar ratio of tin dioxide to the sodium hydroxide solution is 1:18, and stirring until the solution is dissolved to obtain a solution I;
(2) adding tartaric acid into distilled water, uniformly stirring, adding tartaric acid into distilled water to obtain a solution II with the concentration of 1g/mL, then adding stannous chloride, and stirring until the tartaric acid is dissolved to obtain a solution II;
(3) slowly adding the solution I obtained in the step (1) into the solution II obtained in the step (2), magnetically stirring for 30min, pouring into a reaction kettle, heating to 180 ℃, preserving heat for 10h, and cooling to room temperature to obtain a reaction product;
(4) and (4) respectively washing the reaction product obtained in the step (3) with distilled water and absolute ethyl alcohol for 3 times, then centrifuging at the rotating speed of 900rpm for 10min, and carrying out vacuum drying at the temperature of 70 ℃ for 2h to obtain the tin selenide-based thermoelectric material.
Example 2
A tin selenide-based thermoelectric material comprising the following components: selenium dioxide, ascorbic acid, stannous chloride and tartaric acid; the molar ratio of the selenium dioxide to the ascorbic acid to the stannous chloride to the tartaric acid is 1:2:2: 8.
The preparation method of the tin selenide-based thermoelectric material is characterized by comprising the following steps:
(1) dissolving selenium dioxide and ascorbic acid in a sodium hydroxide solution, wherein the molar ratio of tin dioxide to the sodium hydroxide solution is 1:19, and stirring until the solution is dissolved to obtain a solution I;
(2) adding tartaric acid into distilled water, uniformly stirring, adding tartaric acid into distilled water to obtain a solution II with the concentration of 1.1g/mL, then adding stannous chloride, and stirring until the tartaric acid is dissolved to obtain a solution II;
(3) slowly adding the solution I obtained in the step (1) into the solution II obtained in the step (2), magnetically stirring for 40min, pouring into a reaction kettle, heating to 200 ℃, preserving heat for 13h, and cooling to room temperature to obtain a reaction product;
(4) and (4) respectively washing the reaction product obtained in the step (3) with distilled water and absolute ethyl alcohol for 3 times, then centrifuging for 12min at the rotating speed of 1000rpm, and carrying out vacuum drying for 3h at the temperature of 80 ℃ to obtain the tin selenide-based thermoelectric material.
Example 3
A tin selenide-based thermoelectric material comprising the following components: selenium dioxide, ascorbic acid, stannous chloride and citric acid; the molar ratio of selenium dioxide, ascorbic acid, stannous chloride and citric acid is 1:2:1: 9.
The preparation method of the tin selenide-based thermoelectric material is characterized by comprising the following steps:
(1) dissolving selenium dioxide and ascorbic acid in a potassium hydroxide solution, wherein the molar ratio of tin dioxide to potassium hydroxide solution is 1:20, and stirring until the solution is dissolved to obtain a solution I;
(2) adding citric acid into distilled water, uniformly stirring, adding citric acid into distilled water to obtain a solution II with the concentration of 1.2g/mL, adding stannous chloride, and stirring until the citric acid is dissolved to obtain a solution II;
(3) slowly adding the solution I obtained in the step (1) into the solution II obtained in the step (2), magnetically stirring for 45min, pouring into a reaction kettle, heating to 210 ℃, preserving heat for 14h, and cooling to room temperature to obtain a reaction product;
(4) and (4) respectively cleaning the reaction product obtained in the step (3) with distilled water and absolute ethyl alcohol for 3 times, centrifuging at the rotating speed of 1000rpm for 13min, and drying in vacuum at the temperature of 70-90 ℃ for 3h to obtain the tin selenide-based thermoelectric material.
Example 4
A tin selenide-based thermoelectric material comprising the following components: selenium dioxide, ascorbic acid, stannous chloride and citric acid; the molar ratio of the selenium dioxide to the ascorbic acid to the stannous chloride to the citric acid is 1:5:3: 10.
The preparation method of the tin selenide-based thermoelectric material is characterized by comprising the following steps:
(1) dissolving selenium dioxide and ascorbic acid in a potassium hydroxide solution, wherein the molar ratio of tin dioxide to potassium hydroxide solution is 1:22, and stirring until the solution is dissolved to obtain a solution I;
(2) adding citric acid into distilled water, uniformly stirring, adding citric acid into distilled water to obtain a solution II with the concentration of 1.3g/mL, adding stannous chloride, and stirring until the citric acid is dissolved to obtain a solution II;
(3) slowly adding the solution I obtained in the step (1) into the solution II obtained in the step (2), magnetically stirring for 60min, pouring into a reaction kettle, heating to 240 ℃, preserving heat for 16h, and cooling to room temperature to obtain a reaction product;
(4) and (4) respectively washing the reaction product obtained in the step (3) with distilled water and absolute ethyl alcohol for 3 times, then centrifuging at the rotating speed of 1100rpm for 15min, and carrying out vacuum drying at the temperature of 90 ℃ for 4h to obtain the tin selenide-based thermoelectric material.
The tin selenide-based thermoelectric materials obtained in examples 1 to 4 were subjected to X-ray diffraction and electron microscope scanning, and the results are shown in fig. 1 to 2, respectively.
As can be seen from fig. 1, the diffraction peaks of other impurities are not present in the figure, and are more consistent with the standard spectrum, which indicates that the obtained tin selenide-based thermoelectric material has high purity and does not contain other impurities; from fig. 2, it can be seen that the morphology of the tin selenide-based thermoelectric material is relatively complete, which indicates that the tin selenide-based thermoelectric material obtained by the preparation method has higher quality.
Comparative example
A method for preparing tin selenide nanowires comprises the following steps: firstly, cleaning a silicon wafer, putting tin selenide powder into a central temperature area of a high-temperature tube furnace, placing the cleaned silicon wafer at the downstream of airflow as a silicon substrate, vacuumizing, restoring the temperature to normal pressure by using argon airflow, keeping a certain argon flow, heating the central temperature area of the high-temperature tube furnace to 700-1000 ℃, keeping the reaction for 0.5-5 hours, and then naturally cooling to obtain a product tin selenide nanowire; wherein, the inside of the reaction growth system is at atmospheric pressure; the argon flow is 30-70 sccm; the tin selenide powder has the purity of more than 99.8 percent; the silicon substrate is placed at a position 5-25 cm away from the central temperature zone in the downstream of the air flow.
When the method of the comparative example is adopted for preparing the tin selenide, vacuumizing is needed, the normal pressure is recovered by using argon, the silicon wafer needs to be heated to 700-1000 ℃ for reaction, the process flow is complex, the operation is not easy to control, meanwhile, the silicon wafer which needs to be cleaned generally needs to be sequentially polished by using abrasive paper with different meshes and then cleaned for standby, and once impurities are left on the surface of the silicon wafer, the obtained tin selenide nanowire contains impurities. The preparation method provided by the invention has relatively simple process flow, only needs to heat to 180-240 ℃ at most, and obtains the tin selenide-based thermoelectric material by centrifugal drying after cleaning with distilled water and absolute ethyl alcohol; meanwhile, the used raw materials are low in cost and free of toxicity, do not cause harm to the body and mind of experimenters, and do not cause environmental pollution.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (10)
1. A tin selenide-based thermoelectric material is characterized by comprising the following components: selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid;
the molar ratio of the selenium dioxide to the ascorbic acid to the stannous chloride to the tartaric acid or the citric acid is 1: 1-5: 1-3: 8-10.
2. The tin selenide-based thermoelectric material according to claim 1, wherein the molar ratio of selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid is 1: 1-3: 1-2: 8-9.
3. The tin selenide-based thermoelectric material according to claim 1, wherein the molar ratio of selenium dioxide, ascorbic acid, stannous chloride, tartaric acid or citric acid is 1:2:1: 9.
4. A method of producing a tin selenide-based thermoelectric material according to any one of claims 1 to 3, comprising the steps of:
(1) dissolving selenium dioxide and ascorbic acid in an alkaline solution, and stirring until the selenium dioxide and the ascorbic acid are dissolved to obtain a solution I;
(2) adding tartaric acid or citric acid into distilled water, stirring uniformly, then adding stannous chloride, and stirring until the mixture is dissolved to obtain a solution II;
(3) slowly adding the solution I obtained in the step (1) into the solution II obtained in the step (2), stirring for 30-60 min, pouring into a reaction kettle, heating to 180-240 ℃, preserving heat for 10-16 h, and cooling to room temperature to obtain a reaction product;
(4) and (4) washing the reaction product obtained in the step (3) with distilled water and absolute ethyl alcohol for 2-4 times respectively, and then centrifuging and drying to obtain the tin selenide-based thermoelectric material.
5. The method of preparing a tin selenide-based thermoelectric material according to claim 4, wherein in the step (1), the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
6. The method for preparing a tin selenide-based thermoelectric material as claimed in claim 4, wherein in the step (1), the molar ratio of the tin dioxide to the alkaline solution is 1: 18-22.
7. The method for preparing a tin selenide-based thermoelectric material as claimed in claim 4, wherein in the step (2), the concentration of the tartaric acid or citric acid added with distilled water is 1-1.3 g/mL.
8. The method for preparing a tin selenide-based thermoelectric material as claimed in claim 4, wherein magnetic stirring is adopted in the step (3), and the lining material of the reaction kettle is polytetrafluoroethylene.
9. The method for preparing a tin selenide-based thermoelectric material as claimed in claim 4, wherein the centrifugation in the step (4) is carried out at 900-1100 rpm for 10-15 min.
10. The method for preparing a tin selenide-based thermoelectric material as claimed in claim 4, wherein in the step (4), the tin selenide-based thermoelectric material is dried in vacuum at a temperature of 70-90 ℃ for 2-4 h.
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| US20110052918A1 (en) * | 2008-03-24 | 2011-03-03 | Krauss Todd D | Magic Size Nanoclusters and Methods of Preparing Same |
| CN107601441A (en) * | 2017-10-10 | 2018-01-19 | 陕西科技大学 | A kind of method of hydro-thermal method synthesis stannic selenide micron crystalline flour body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110052918A1 (en) * | 2008-03-24 | 2011-03-03 | Krauss Todd D | Magic Size Nanoclusters and Methods of Preparing Same |
| CN107601441A (en) * | 2017-10-10 | 2018-01-19 | 陕西科技大学 | A kind of method of hydro-thermal method synthesis stannic selenide micron crystalline flour body |
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