CN111139519A - Preparation method of flaky SnSe monocrystal - Google Patents
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- CN111139519A CN111139519A CN202010002921.7A CN202010002921A CN111139519A CN 111139519 A CN111139519 A CN 111139519A CN 202010002921 A CN202010002921 A CN 202010002921A CN 111139519 A CN111139519 A CN 111139519A
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention provides a preparation method of a flaky SnSe monocrystal, which comprises the following preparation processes: dispersing Se powder in ethanolamine solvent to obtain selenium source precursor solution A, and then weighing a certain amount of SnCl2·2H2Dissolving O in distilled water, and stirring until the O is completely dissolved to obtain a tin source solution B; dripping the solution B into the solution A to form a mixed solution C, and adding NaOH to adjust the pH value of the solution C; and finally, transferring the uniformly stirred solution C into a hydrothermal reaction kettle, preserving the heat at 200-230 ℃ for at least 6 hours, naturally cooling to room temperature, and carrying out suction filtration, washing and vacuum drying to obtain the silvery white flaky SnSe material. The invention adopts solvent thermal growth SnSe material to obtain large-size high-quality flaky single crystal>1mm) is adopted, a new way is provided for the preparation of high-performance thermoelectric materials, and the two-dimensional scale of the thermoelectric materials can be directly researched by various stripping meansThe method has the advantages of simple preparation method, low cost, high repeatability, short crystal growth period, high yield and suitability for large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation of van der Waals layered single crystals, and particularly relates to a preparation method of a flaky SnSe single crystal.
Background
Stannous selenide, with the chemical formula of SnSe, belongs to a typical layered non-transition metal chalcogenide compound, has an indirect band gap of 0.90eV and a direct band gap of 1.30eV, and is an important IV-VI semiconductor material. At room temperature, SnSe has a black-scale-like orthorhombic (Pnma) structure, and as the temperature increases, a structural phase transition from orthorhombic to tetragonal (Ccm) occurs around 800K. Furthermore, SnSe exhibits a very strong anisotropy, resulting in specificity in physical properties such as high carrier mobility along the in-layer direction and low thermal conductivity perpendicular to the layer direction, single-layer or odd-number less piezoelectric effect. These basic properties allow SnSe to exhibit superior electrical, optical, thermoelectric, etc. performance. Meanwhile, the method has the characteristics of environmental friendliness, stable chemical properties, low raw material price, abundant crustal reserves and the like. Therefore, the SnSe material has great commercial prospect in various fields.
The preparation of high-quality SnSe single crystals is important for improving the performance of the SnSe single crystals, for example, the SnSe material shows excellent thermoelectric performance, and the single crystal thermoelectric performance (ZT-2.6) of the SnSe single crystals is far superior to the polycrystalline SnSe thermoelectric performance (ZT-0.6-0.8). Moreover, the interlayer spacing of SnSe is small
The interlayer acting force is large, a single-layer or few-layer structure is difficult to prepare through mechanical stripping, and the preparation of the high-quality bulk single crystal is beneficial to obtaining a SnSe two-dimensional layered structure, so that experimental research on two-dimensional photoelectric, piezoelectric and auxetic properties of the SnSe two-dimensional layered structure is realized. At present, the bulk single crystal SnSe material is mainly prepared by solid phase synthesis methods, such as gas phase transport method (Mater.Lett.,2007,61(30): 5188-. The methods have harsh growth conditions, difficult control of the preparation process, expensive equipment and long time, are not beneficial to large-scale industrial production, and most of the bulk SnSe single crystals cannot be directly stripped to obtain the low-dimensional structure of the bulk SnSe single crystals. Another commonly used method for preparing SnSe single crystal is wet chemical method, including hydrothermal method (Inorg. chem.2000,39:4237-4239), solvothermal method (CrystEngComm,2015,17: 807-813; NanoEnergy 2017,38569-. At present, the maximum single crystal size synthesized by a wet chemical method is in the micron order, and the two-dimension synthesis of the single crystal by a stripping technology is difficult to adopt.
Therefore, the existing SnSe single crystal preparation technology is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for producing a flaky SnSe single crystal. In the method, water and ethanolamine are used as solvents, and a Se simple substance and SnCl in a reaction kettle are utilized under an alkaline condition2·2H2The method has the advantages of simple preparation, low cost, short time, good repeatability, mass production and convenient industrial popularization.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a flaky SnSe single crystal comprises the following steps:
dispersing selenium powder in an organic solvent to obtain a selenium source precursor solution, and adding a tin salt solution into the selenium source precursor solution to obtain a mixed solution;
and adjusting the pH value of the mixed solution, reacting under a preset reaction condition, and then sequentially filtering and drying to obtain the flaky SnSe monocrystal.
Optionally, the preparation method of the flaky SnSe single crystal comprises a step of adding an organic solvent to the flaky SnSe single crystal, wherein the organic solvent is one or more of ethanolamine, diethanolamine and triethanolamine.
Optionally, the preparation method of the flaky SnSe single crystal comprises the step of preparing a flaky SnSe single crystal, wherein a tin salt in the tin salt solution is SnCl2·2H2O。
Optionally, in the preparation method of the flaky SnSe single crystal, the molar ratio of the selenium powder to the tin salt is 1: 2-2: 1.
Optionally, the pH value of the flaky SnSe single crystal is not less than 13.
Optionally, in the method for preparing the flaky SnSe single crystal, the predetermined reaction condition is a reaction temperature of 200-230 ℃.
Optionally, in the method for preparing the flaky SnSe single crystal, the predetermined reaction condition is a reaction time of 6 to 144 hours.
Optionally, the method for preparing the flaky SnSe single crystal comprises the step of drying in vacuum at 50-90 ℃.
Optionally, the flaky SnSe single crystal preparation method is characterized in that the drying time is 1-5 hours.
Alternatively, the production method may be one in which the length of the flaky SnSe single crystal is not less than 1 mm.
Has the advantages that: the preparation method of the flaky SnSe single crystal has the following effects:
1. the method for preparing the large-size bulk SnSe single crystal by utilizing solvothermal is provided, XRD diffraction results prove that the obtained flaky single crystal has an orthogonal structure pure phase, and the method provides a new way for growing the bulk high-quality single crystal material; 2. the preparation method is simple, low in cost, high in repeatability, short in crystal growth period and high in yield, and is suitable for large-scale production; 3. the method for synthesizing the flaky SnSe single crystal can be applied to the research in the thermoelectric field, directly test the thermoelectric property of the flaky SnSe single crystal, and also provide raw materials for preparing the high thermoelectric property single crystal by means of discharge plasma sintering and the like; 4. with the change of the conditions such as the molar ratio of the precursor, the ratio of water and the organic solvent, the solvothermal reaction temperature, the solvothermal reaction time and the like, the high-quality flaky SnSe single crystal synthesized by the method has adjustable size and thickness, can be used for mechanical and electrochemical stripping, and is beneficial to the research of obtaining a two-dimensional layered structure and intrinsic performance thereof.
Drawings
Fig. 1 is a flow chart of a method for preparing a flaky SnSe single crystal according to a preferred embodiment of the present invention.
FIG. 2 is a photograph and a Scanning Electron Microscope (SEM) image of a flaky SnSe single crystal prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction (XRD) pattern and SnSe standard PDF card (#89-0236) of the product prepared in example 1 of the present invention;
FIG. 4 is a Raman spectrum of a product prepared in example 1 of the present invention;
FIG. 5 is an XRD pattern of flaky SnSe single crystals prepared in examples 2, 3, 4, 5, 6 and 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, reaction vessels, etc. used in the following examples are commercially available unless otherwise specified.
As shown in fig. 1, the method for preparing a flaky SnSe single crystal provided by the invention comprises the following steps:
s10, dispersing selenium powder in an organic solvent to obtain a selenium source precursor solution, and adding a tin salt solution into the selenium source precursor solution to obtain a mixed solution.
Specifically, under the condition of room temperature, Se powder is dispersed in an ethanolamine solvent to obtain a selenium source precursor solution A, then a certain amount of inorganic tin salt is weighed and dissolved in distilled water, and the solution is stirred until the inorganic tin salt is completely dissolved to obtain a tin source solution B; pouring the solution B into the solution A to form a mixed solution, wherein the organic solvent comprises but is not limited to ethanolamine, diethanolamine and triethanolamine, and the inorganic tin salt is SnCl2·2H2And O. The molar ratio interval of the Se powder to the inorganic tin salt is 1: 2-2: 1, and 1: 1. and magnetically stirring the solution C at 200-800 r/min for 10-30 mins.
And S20, adjusting the pH value of the mixed solution, reacting under a preset reaction condition, and sequentially filtering and drying to obtain the flaky SnSe monocrystal.
Specifically, NaOH is added into the mixed solution to adjust the pH value, and solution C is obtained after magnetic stirring; and transferring the uniformly stirred solution C into a hydrothermal reaction kettle, preserving heat at 200-230 ℃ for 6-144 hours, naturally cooling to room temperature, and performing suction filtration, washing and vacuum drying to obtain the silvery white flaky SnSe material.
In the present invention, SnSe is produced by an ionic reaction under an alkaline condition, and the ease of producing a bulk single crystal of flaky SnSe depends on the concentrations of two ions in a solution. Sn (tin)2+Sn is easily generated by a complex formed by the N-containing ligand (ethanolamine) and NaOH at low temperature2+The content and the reducing capability are reduced, and Se and Sn are prevented2+Reaction to form Se2-And Sn4+Reaction of Se with NaOH to provide Se as the temperature increases2-And SeO3 2-While the Sn complex is destroyed to release Sn2+Thus the first stage is a large amount of Se2-And Sn2+The ions will grow into a large size single crystal along the most energetically preferred orientation. However, when Se is in solution2-At too low a content, SeO3 2-Can react with ethanolamine to generate a simple substance Se, and the simple substance Se and Sn2+Further reaction to obtain Se2-And Sn4+Due to Sn in this second stage2+And Se2-The concentration is low, so that the SnSe growth process is slow, single crystals with different appearances appear, and elementary substances such as Se, Sn and the like are generated. The above brief description of the reaction process is for understanding the mechanism of growing large-sized single crystals, in which complicated reaction processes and intermediates are involved. Based on the above reaction process, it can be known that the molar ratio of Sn to Se, which are different reaction precursors, has a great influence on the reaction product, but the SnSe single crystal growth mainly depends on the first stage, which causes the SnSe single crystal to have a significant size difference with other products, and the larger the size, the higher the quality of the SnSe single crystal. The molar ratio of Sn to Se of the precursor is close to 1: 1, a large amount of high-quality flaky SnSe single crystal can be obtained, and if the deviation is too large, 1: 1 can cause the simple substances of Sn and Se to be separated out, and a small amount of SnSe can be accompanied2The formation of impurity phases, which affect the purity and performance of the single crystal; the higher the growth temperature is, the higher the pressure in the container is, the two factors are favorable for improving the ion concentration of the solution reactant, thereby being favorable for the growth of SnSe single crystal, the higher the temperature is, the higher the requirement on the inner lining of the hydrothermal reaction kettle is, the corresponding cost is higher, but the temperature is as followsIf the temperature is lower than 200 ℃, a large-size bulk SnSe single crystal can be difficult to obtain; it should be noted that under the same other experimental conditions, the volume of the reaction kettle also has influence on the size of the flaky SnSe single crystal, and the large-volume reaction kettle is beneficial to the growth of the single crystal.
The following provides a further explanation of the method for producing a flaky SnSe single crystal provided by the present invention, by way of specific examples.
High purity SnCl was used in the examples described below2·2H2O (alatin, 99.999%) and Se powder (alatin, 99.999%) are used as raw materials, and the used solvents are ethanolamine (alatin, 99%) and distilled water, and NaOH (alatin, 99.9%) is used for adjusting the pH value of the solution.
Example 1
Weighing 2mmol Se powder (0.1579g) and dispersing in 15ml ethanolamine solvent to obtain selenium source precursor solution A, then weighing 2mmol SnCl2·2H2O (0.4513g) was dissolved in 15ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
The solution B was poured into the solution A to form a mixed solution, 1.2g NaOH was added to adjust the pH to 14, and the solution C was magnetically stirred at 400r/min for 30 mins.
And finally, stirring, transferring the solution C into a 50ml hydrothermal reaction kettle, preserving the heat at 230 ℃ for 144 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 1 hour to obtain the silvery white flaky SnSe material.
And performing characterization test on the obtained silvery white flaky SnSe material. First, FIG. 2 is a photograph showing the cross-sectional size of the flaky SnSe single crystal prepared in example 1, and the comparative graph paper shows that three single crystals having aspect ratios of about 2X 6, 3X 5 and 3X 3mm are observed2. Using Phenom ProX scanning electron microscope to measure 3X 3mm2The thickness of the flaky SnSe single crystal was measured, and it was shown that the thickness of the single crystal was 8 μm and a distinct layered structure was observed.
The structure was analyzed using a Bruker D8 Advance X-ray diffractometer (XRD) with X-rays incident on a sheet-like SnSe cross-section as shown in FIG. 3. Diffraction peaks of (200)/(400)/(600)/(800) crystal planes appear in an XRD pattern, and angles of the diffraction peaks correspond to diffraction peaks in a card of an SnSe orthorhombic system PDF #89-0236, so that the high-quality orthorhombic flaky SnSe single crystal is prepared in example 1.
The prepared silver white flaky SnSe material is characterized by adopting a HORIBA LabRAM HR Evolution laser micro-confocal Raman spectrometer, the excitation wavelength is 514nm, and the test result is shown in figure 4. The spectrum is 105.6, 128.8 and 148.5cm-1Respectively appear B3g、A2 g、A3 gThe Raman peaks of the three modes are consistent with the reported SnSe Raman spectrum, and further prove that the method in the example 1 prepares pure phase flaky SnSe single crystal.
Example 2
Weighing 2mmol of Se powder (0.1579g) and dispersing in 15ml of ethanolamine solvent at room temperature to obtain a selenium source precursor solution A, then weighing 1mmol of SnCl2·2H2O (0.2257g) was dissolved in 15ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
The solution B was poured into the solution A to form a mixed solution, 1g of NaOH was added to adjust the pH to 14, and the solution C was magnetically stirred at 600r/min for 30 mins.
And finally, stirring, transferring the solution C into a 50ml hydrothermal reaction kettle, preserving the heat at 230 ℃ for 144 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 3 hours to obtain the silvery white flaky SnSe material.
Example 3
Under the condition of room temperature, 1mmol of Se powder (0.0790g) is weighed and dispersed in 15ml of ethanolamine solvent to obtain a selenium source precursor solution A, and then 2mmol of SnCl is weighed2·2H2O (0.4513g) was dissolved in 15ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
The solution B was poured into the solution A to form a mixed solution, 1.3g NaOH was added to adjust the pH to 14, and the solution C was magnetically stirred at 400r/min for 30 mins.
And finally, stirring, transferring the solution C into a 50ml hydrothermal reaction kettle, preserving the heat at 230 ℃ for 144 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 5 hours to obtain the silvery white flaky SnSe material.
Example 4
Weighing 2mmol Se powder (0.1579g) and dispersing in 15ml ethanolamine solvent to obtain selenium source precursor solution A, then weighing 2mmol SnCl2·2H2O (0.4513g) was dissolved in 15ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
The solution B was poured into the solution A to form a mixed solution, 1.5g NaOH was added to adjust the pH to 14, and the solution C was magnetically stirred at 800r/min for 10 mins.
And finally, stirring, transferring the solution C into a 50ml hydrothermal reaction kettle, preserving the heat at 200 ℃ for 144 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 1 hour to obtain the silvery white flaky SnSe material.
Example 5
At room temperature, 0.5mmol Se powder (0.0395g) is weighed and dispersed in 3ml ethanolamine solvent to obtain selenium source precursor solution A, and then 0.5mmol SnCl is weighed2·2H2O (0.1128g) was dissolved in 3ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
The solution B was poured into the solution A to form a mixed solution, 0.24g NaOH was added to adjust the pH to 14, and the solution C was magnetically stirred at 400r/min for 30 mins.
And finally, stirring, transferring the solution C into a 50ml hydrothermal reaction kettle, preserving heat at 230 ℃ for 6 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 1 hour to obtain the silvery white flaky SnSe material.
Example 6
At room temperature, 0.5mmol Se powder (0.0395g) is weighed and dispersed in 2ml ethanolamine solvent to obtain selenium source precursor solution A, and then 0.5mmol SnCl is weighed2·2H2O (0.1128g) was dissolved in 4ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
The solution B was poured into the solution A to form a mixed solution, 0.24g NaOH was added to adjust the pH to 14, and the solution C was magnetically stirred at 400r/min for 30 mins.
And finally, stirring, transferring the solution C into a 10ml hydrothermal reaction kettle, preserving heat at 230 ℃ for 24 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 2 hours to obtain the silvery white flaky SnSe material.
Example 7
At room temperature, 0.5mmol Se powder (0.0395g) is weighed and dispersed in 4ml ethanolamine solvent to obtain selenium source precursor solution A, and then 0.5mmol SnCl is weighed2·2H2O (0.1128g) was dissolved in 2ml of distilled water, and the solution was stirred until it was completely dissolved, thereby obtaining a tin source solution B.
And pouring the solution B into the solution A to form a mixed solution, adding a small amount of NaOH to adjust the pH value of the solution to be 13, and magnetically stirring the solution C at 400r/min for 30 mins.
And finally, stirring, transferring the solution C into a 10ml hydrothermal reaction kettle, preserving the heat at 230 ℃ for 48 hours, naturally cooling to room temperature, washing with distilled water and alcohol for multiple times in the suction filtration process, and drying in vacuum at 50 ℃ for 2 hours to obtain the silvery white flaky SnSe material.
XRD tests of the flaky SnSe crystals prepared in examples 2, 3, 4, 5, 6 and 7 showed that the XRD pattern of the flaky SnSe crystals prepared in examples 5 has diffraction peaks consistent with those of XRD crystals prepared in example 1, and thus it was confirmed that large-sized flaky SnSe single crystals can be obtained using examples 2, 3, 4, 5, 6 and 7.
In summary, the invention provides a preparation method of a flaky SnSe single crystal, which comprises the steps of dispersing selenium powder in an organic solvent to obtain a selenium source precursor solution, and adding a tin salt solution into the selenium source precursor solution to obtain a mixed solution; and adjusting the pH value of the mixed solution, reacting under a preset reaction condition, and then sequentially filtering and drying to obtain the flaky SnSe monocrystal. In the method, water and ethanolamine are used as solvents, and a Se simple substance and SnCl in a reaction kettle are utilized under an alkaline condition2·2H2The method has the advantages of simple preparation, low cost, short time, good repeatability, mass production and convenient industrial popularization. The method for synthesizing the flaky SnSe monocrystal can be applied to the research in the field of thermoelectricity and can be directly used forThe thermoelectric property of the material is tested, and raw materials can be provided for preparing high thermoelectric property single crystals by means of spark plasma sintering and the like; with the change of the conditions such as the molar ratio of the precursor, the ratio of water and the organic solvent, the solvothermal reaction temperature, the solvothermal reaction time and the like, the high-quality flaky SnSe single crystal synthesized by the method has adjustable size and thickness, can be used for mechanical and electrochemical stripping, and is beneficial to the research of obtaining a two-dimensional layered structure and intrinsic performance thereof.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing a flaky SnSe single crystal is characterized by comprising the following steps:
dispersing selenium powder in an organic solvent to obtain a selenium source precursor solution, and adding a tin salt solution into the selenium source precursor solution to obtain a mixed solution;
and adjusting the pH value of the mixed solution, reacting under a preset reaction condition, and then sequentially filtering and drying to obtain the flaky SnSe monocrystal.
2. The method for producing a flaky SnSe single crystal according to claim 1, wherein the organic solvent is one or more of ethanolamine, diethanolamine and triethanolamine.
3. The method for producing a flaky SnSe single crystal according to claim 1, wherein the tin salt in the tin salt solution is SnCl2·2H2O。
4. The method for preparing the flaky SnSe single crystal according to claim 3, wherein the molar ratio of the selenium powder to the tin salt is 1: 2-2: 1.
5. The method for producing a flaky SnSe single crystal according to claim 1, wherein the pH is not less than 13.
6. The method for producing a flaky SnSe single crystal according to claim 1, wherein the predetermined reaction conditions are a reaction temperature of 200 to 230 ℃.
7. The method for producing a flaky SnSe single crystal according to claim 6, wherein the predetermined reaction condition is a reaction time of 6 to 144 hours.
8. The method for producing a flaky SnSe single crystal according to claim 1, wherein the drying is performed in vacuum drying at a temperature of 50 to 90 ℃.
9. The method for producing a flaky SnSe single crystal according to claim 8, wherein the drying time is 1 to 5 hours.
10. The method for producing a flaky SnSe single crystal according to any one of claims 1 to 9, wherein the length of the flaky SnSe single crystal is not less than 1 mm.
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| CN113101949A (en) * | 2021-04-08 | 2021-07-13 | 深圳大学 | Transition metal selenide heterostructure material and preparation method thereof |
| CN113604877A (en) * | 2021-07-22 | 2021-11-05 | 深圳大学 | Method for preparing polycrystalline SnSe by solvothermal method |
| CN113937210A (en) * | 2021-10-12 | 2022-01-14 | 河北大学 | Preparation of SnSe/SnSe by selenization2Method for compounding thermoelectric film |
| CN114686986A (en) * | 2022-04-02 | 2022-07-01 | 齐齐哈尔大学 | SnSe2Method for producing single crystal |
| CN115259157A (en) * | 2022-08-23 | 2022-11-01 | 重庆大学 | SnSe/Ti 3 C 2 T x Thermoelectric composite material and preparation method thereof |
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| CN113101949A (en) * | 2021-04-08 | 2021-07-13 | 深圳大学 | Transition metal selenide heterostructure material and preparation method thereof |
| CN113604877A (en) * | 2021-07-22 | 2021-11-05 | 深圳大学 | Method for preparing polycrystalline SnSe by solvothermal method |
| CN113937210A (en) * | 2021-10-12 | 2022-01-14 | 河北大学 | Preparation of SnSe/SnSe by selenization2Method for compounding thermoelectric film |
| CN113937210B (en) * | 2021-10-12 | 2024-05-10 | 河北大学 | Preparation of SnSe/SnSe by selenization2Method for compounding thermoelectric film |
| CN114686986A (en) * | 2022-04-02 | 2022-07-01 | 齐齐哈尔大学 | SnSe2Method for producing single crystal |
| CN115259157A (en) * | 2022-08-23 | 2022-11-01 | 重庆大学 | SnSe/Ti 3 C 2 T x Thermoelectric composite material and preparation method thereof |
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