CN114380325A - Ultra-thin SnS2Nanosheet and SnS2Film, preparation and application thereof - Google Patents

Ultra-thin SnS2Nanosheet and SnS2Film, preparation and application thereof Download PDF

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CN114380325A
CN114380325A CN202111511019.9A CN202111511019A CN114380325A CN 114380325 A CN114380325 A CN 114380325A CN 202111511019 A CN202111511019 A CN 202111511019A CN 114380325 A CN114380325 A CN 114380325A
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芮一川
徐雨田
金作明
王晓洁
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Shanghai University of Engineering Science
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Abstract

The invention relates to the technical field of preparation of n-type semiconductor nano materials, in particular to ultrathin SnS2Nanosheet and SnS2Film and preparation and application thereof. The invention adopts cheap tin tetrachloride as a tin source and L-glutathione as a sulfur source to form a precursor solution (a first mixed solution) under an acidic condition, and then the ultrathin SnS with controllable size can be obtained by a low-temperature hydrothermal reaction at the temperature of 120-2Nanoplatelets having a particle size of at least about 5 nm; then using ultra-thin SnS2SnS prepared by nanosheet2Film and SnS2The film is used as an inorganic electron transport layer of the perovskite solar cell for preparing the perovskite solar cell. Compared with the prior art, the invention can reduce the manufacturing cost of materials, and has the advantages of short reaction time, simple preparation process, good conductivity and the like.

Description

Ultra-thin SnS2Nanosheet and SnS2Film, preparation and application thereof
Technical Field
The invention relates to the technical field of preparation of n-type semiconductor nano materials, in particular to ultrathin SnS2Nanosheet and SnS2Film and preparation and application thereof.
Background
SnS2Consists of nontoxic tin and oxygen elements which are abundant in the earth, and is environment-friendly CdI2The n-type narrow band gap semiconductor material with the crystal structure has the forbidden band width of 2.21-2.25eV, has good carrier mobility, optical transparency, mechanical performance and the like, and is widely applied to the fields of photocatalysis, diodes, solar cells and the like. However, there are problems that: (1) SnS is prepared by physical methods such as magnetron sputtering or vapor deposition2The nano material has higher requirement on equipment and high cost; (2) the conventional method is difficult to obtain the SnS with small size and large specific surface area2The material has poor dispersibility, and the solution processing application of the material is limited. Therefore, the solution method is adopted to prepare the size-controllable superfine SnS2The colloid nano-sheet has important significance.
Huang et al (Yuan Huang, et al. ACS Nano.2014,8,10,10743-10755) grow layered SnS by the vertical Bridgman method2The layered bulk crystal is peeled into thinner slices comprising a small number of monolayers and a monolayer SnS2But the size of the material reaches 1 μm. Sun et al (Wenping Sun, et al ACS Nano.2015,9,11, 11371-11381) by refluxing SnCl in a mixed solution of Ethylene Glycol (EG) and 1-Octadecene (ODE)2And 1,3, 4-thiadiazole-2, 5-Dithiol (DMCT) to give a thinner two-dimensional SnS2Nanosheets, having a lateral dimension of about 3nm, and an overall particle size of 2 μm. Chu et al (Weijing Chu, ACS appl. energy Mater.2019,2,1, 382. snake 388.) prepare n-type SnS at room temperature by vacuum deposition2And the semiconductor thin film is used as an electron transport layer of the perovskite type flexible solar cell. But the electron transport and device conversion efficiency is poor due to the size being difficult to control and large. These methods prepare SnS2The material has the problems of complex operation, large and uncontrollable size, environment-friendliness and the like, and is not suitable for large-scale production. From this it can be found that hydrothermal treatment with the precursorMethod for preparing small-particle-size and high-dispersion SnS2The nano-sheet is still a technical problem, and SnS is regulated and controlled by controlling the concentration of a precursor and the reaction temperature2The size of the nano-sheet is more difficult, so that the ultra-thin SnS with controllable structure can be realized2The large-scale production of the nano-sheets can obtain greater benefit return and simultaneously can add SnS2The promotion of the material in the fields of catalysis, solar cells and the like is greatly beneficial.
Disclosure of Invention
To solve the above problems, it is an object of the present invention to provide an ultra-thin SnS2Nanosheet and SnS2Film and preparation and application thereof. The invention adopts cheap tin tetrachloride as a tin source and L-glutathione as a sulfur source to form a precursor solution (a first mixed solution) under an acidic condition, and then the ultrathin SnS with controllable size can be obtained by a low-temperature hydrothermal reaction at the temperature of 120-2Nanoplatelets having a particle size of at least about 5 nm; then using ultra-thin SnS2SnS prepared by nanosheet2Film and SnS2The film is used as an inorganic electron transport layer of the perovskite solar cell for preparing the perovskite solar cell. Compared with the prior art, the invention can reduce the manufacturing cost of materials, and has the advantages of short reaction time, simple preparation process, good conductivity and the like.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to provide an ultrathin SnS2A method of making nanoplatelets comprising the steps of:
(1) adding concentrated hydrochloric acid into a tin tetrachloride aqueous solution, and then uniformly mixing the concentrated hydrochloric acid with a sulfur source to obtain a first mixed solution;
(2) transferring the first mixed solution obtained in the step (1) to a reaction kettle for hydrothermal reaction to obtain wet precipitate after the reaction is finished;
(3) washing the wet precipitate obtained in the step (2) by deionized water and ethanol, and centrifuging to obtain ultrathin SnS2Nanosheets.
In one embodiment of the present invention, in step (1), the tin tetrachloride is selected from anhydrous tin tetrachloride or tin tetrachloride pentahydrate;
the sulfur source is selected from L-glutathione and CH4N2S、(NH4)2S or CH3CSNH2One of (1); preferably, the sulphur source is selected from L-glutathione.
In one embodiment of the present invention, in the step (1), the concentration of the aqueous solution of tin tetrachloride is 0.05 to 0.2 mol/L; preferably, the concentration of the aqueous solution of tin tetrachloride is 0.05 mol/L;
the volume ratio of the stannic chloride aqueous solution to the concentrated hydrochloric acid is 30-120: 1; preferably, the volume ratio of the tin tetrachloride aqueous solution to the concentrated hydrochloric acid is 60: 1;
the molar ratio of tin tetrachloride to sulfur source is 1: 2-4; preferably, the molar ratio of tin tetrachloride to sulfur source is 1: 3.
in one embodiment of the present invention, in the step (2), the filling rate in the reaction kettle is 50-80%; preferably, the filling rate of the reaction kettle is 70%.
In one embodiment of the invention, in the step (2), in the hydrothermal reaction process, the reaction temperature is 120-;
preferably, in the hydrothermal reaction process, the reaction temperature is 120 ℃ and the reaction time is 12 h.
In the present invention, based on the above-mentioned preparation conditions, the lower the reaction temperature (120-2The smaller the size of the nanoplatelets.
The second purpose of the invention is to provide the ultrathin SnS prepared by the method2Nanosheets.
The third purpose of the invention is to provide the ultrathin SnS2Preparation of SnS by nano sheet2Application in thin films.
The fourth purpose of the invention is to provide an SnS2A preparation method of the film, the ultrathin SnS is prepared2Dissolving the nano-sheet in ethanol to obtain ultrathin SnS2Sol of the nanosheets; then the ultrathin SnS2Coating the nano-sheet sol on a conductive substrate, and annealing to obtain SnS2A film.
First aspect of the inventionFive aims are to provide the SnS prepared by the method2A film.
It is a sixth object of the present invention to provide the above-mentioned SnS2The thin film is applied to the preparation of perovskite solar cells, and SnS is prepared2The film is used as an inorganic electron transport layer of the perovskite solar cell, a perovskite active layer and a hole transport layer are sequentially coated in a spinning mode, and finally, a silver electrode is plated on the top of the hole transport layer through vacuum evaporation; and finishing the preparation of the perovskite solar cell.
The ultrathin SnS prepared by the invention2The nano-sheet has controllable size, the minimum size can reach 5nm, and the nano-sheet is an excellent n-type hole transport material and can be used for perovskite solar cells and organic solar cells. In the prior art, thioacetamide, thiourea and the like are used as sulfur sources; the invention adopts L-glutathione as a sulfur source for the first time and prepares the ultrathin SnS at low temperature2Nanosheets; SnS with pure amorphous structure generated by tetravalent tin ions and sulfide ions2Avoid the occurrence of SnO2Or SnS, etc., to slow the crystallization rate. The invention utilizes ultrathin SnS2SnS prepared from nanosheets2The thin film is used as an inorganic electron transmission layer in perovskite solar cells and organic solar cells.
In solution, SnCl4Hydrolyzing to break bonds into Sn under high-pressure environment4+And Cl-L-glutathione is readily soluble in acidic solutions and hydrolyzes to give off hydrogen sulfide, wherein tetravalent tin ions react with hydrogen sulfide to form amorphous SnS2(ii) a A part of the sulfur ions are reduced to sulfur, and then the reaction with unreacted Sn is continued4+Reacting to generate ultrathin SnS2Nanosheets, avoiding the formation of SnO2And the crystallization rate is slowed, which is beneficial to obtaining smaller nano materials. In the present invention, the acidic conditions provided by the concentrated hydrochloric acid not only aid in the hydrolysis of the sulfur source, but also aid in the formation of amorphous SnS2Better crystallization, so that the prepared SnS2The phases are purer and the reaction time is shorter. In addition, the raw materials adopted by the invention are low in price and are suitable for commercial popularization.
Compared with the prior art, the invention has the following beneficial effects:
(1) the size can be controlled: the invention can control the grain size of the nano-sheet by adjusting the temperature and the sulfur source concentration of the reaction system, thereby flexibly adjusting the size of the prepared nano-sheet, wherein the transverse size is 5-50nm, and the thickness is 2-5 nm;
(2) the cost of the raw materials is low: the price of the ammonium sulfide adopted by the invention is low, and meanwhile, the sulfur source and the tin source adopted by the invention are stable, so that the cost is greatly reduced;
(3) the preparation process is simple: the invention adopts a simple and high-efficiency hydrothermal synthesis method to prepare the ultrathin SnS2The nano-sheet has simple and convenient process route, low energy consumption, short time consumption and high yield, and can realize the ultra-thin SnS with controllable size and high crystallinity2Preparing a nano sheet;
(4) the product performance is excellent: the ultrathin SnS prepared by the invention2The nano-sheet has good dispersibility and crystallinity and excellent photoelectric property, and the photoelectric conversion efficiency can exceed 17 percent after the nano-sheet is used for the perovskite solar cell.
Drawings
FIG. 1 is an ultra-thin SnS prepared in example 12A field emission scanning electron microscope image of the nanosheets;
FIG. 2 is an ultra-thin SnS prepared in example 12An X-ray diffraction pattern of the nanosheets;
FIG. 3 is an ultra-thin SnS prepared in example 12Transmission electron microscopy images of the nanosheets;
FIG. 4 is an ultra-thin SnS prepared in example 22A field emission scanning electron microscope image of the nanosheets;
FIG. 5 is an ultra-thin SnS prepared in example 32A field emission scanning electron microscope image of the nanosheets;
FIG. 6 is a sectional view of a field emission scanning electron microscope of the perovskite solar cell prepared in example 15;
fig. 7 is a photocurrent voltage curve of the perovskite solar cell prepared in example 15.
Detailed Description
The invention provides an ultrathin SnS2A process for the preparation of nanoplatelets comprisingThe method comprises the following steps:
(1) adding concentrated hydrochloric acid into a tin tetrachloride aqueous solution, and then uniformly mixing the concentrated hydrochloric acid with a sulfur source to obtain a first mixed solution;
(2) transferring the first mixed solution obtained in the step (1) to a reaction kettle for hydrothermal reaction to obtain wet precipitate after the reaction is finished;
(3) washing the wet precipitate obtained in the step (2) by deionized water and ethanol, and centrifuging to obtain ultrathin SnS2Nanosheets.
In one embodiment of the present invention, in step (1), the tin tetrachloride is selected from anhydrous tin tetrachloride or tin tetrachloride pentahydrate;
the sulfur source is selected from L-glutathione and CH4N2S、(NH4)2S or CH3CSNH2One of (1); preferably, the sulphur source is selected from L-glutathione.
In one embodiment of the present invention, in the step (1), the concentration of the aqueous solution of tin tetrachloride is 0.05 to 0.2 mol/L; preferably, the concentration of the aqueous solution of tin tetrachloride is 0.05 mol/L;
the volume ratio of the stannic chloride aqueous solution to the concentrated hydrochloric acid is 30-120: 1; preferably, the volume ratio of the tin tetrachloride aqueous solution to the concentrated hydrochloric acid is 60: 1;
the molar ratio of tin tetrachloride to sulfur source is 1: 2-4; preferably, the molar ratio of tin tetrachloride to sulfur source is 1: 3.
in one embodiment of the present invention, in the step (2), the filling rate in the reaction kettle is 50-80%; preferably, the filling rate of the reaction kettle is 70%.
In one embodiment of the invention, in the step (2), in the hydrothermal reaction process, the reaction temperature is 120-;
preferably, in the hydrothermal reaction process, the reaction temperature is 120 ℃ and the reaction time is 12 h.
In the present invention, based on the above-mentioned preparation conditions, the lower the reaction temperature (120-2The smaller the size of the nanoplatelets.
The invention provides a preparation method of the compoundTo ultra-thin SnS2Nanosheets.
The invention provides the ultrathin SnS2Preparation of SnS by nano sheet2Application in thin films.
The invention provides SnS2A preparation method of the film, the ultrathin SnS is prepared2Dissolving the nano-sheet in ethanol to obtain ultrathin SnS2Sol of the nanosheets; then the ultrathin SnS2Coating the nano-sheet sol on a conductive substrate, and annealing to obtain SnS2A film.
The invention provides SnS prepared by the method2A film.
The invention provides the SnS2The thin film is applied to the preparation of perovskite solar cells, and SnS is prepared2The film is used as an inorganic electron transport layer of the perovskite solar cell, a perovskite active layer and a hole transport layer are sequentially coated in a spinning mode, and finally, a silver electrode is plated on the top of the hole transport layer through vacuum evaporation; and finishing the preparation of the perovskite solar cell.
The invention is described in detail below with reference to the figures and specific embodiments.
In the following examples, the starting materials and the treatment steps used are conventional commercial products and conventional techniques, unless otherwise specified.
Example 1
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2O; taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; wet precipitate is obtained after the reaction is finished, and the wet precipitate is taken out for useRepeatedly washing with deionized water and ethanol and centrifugally separating to obtain ultrathin SnS2Nanosheets.
FIG. 1 shows the ultra-thin SnS prepared by this example2The field emission scanning electron microscope image of the nano sheet shows that the ultrathin SnS can be seen2The size of the nanosheets is about 5-10 nm.
FIG. 2 shows the ultra-thin SnS prepared by this example2The X-ray diffraction spectrum of the nanosheet can find that the ultrathin SnS prepared by the embodiment2The nanosheets being pure SnS2Phase, no impurities. (001) Stronger diffraction peaks indicate SnS2The crystallinity of the material is better.
FIG. 3 is a prepared ultrathin SnS2Transmission electron microscopy of nanoplatelets. SnS can be seen from the figure2The nano-sheet has good dispersibility, and is beneficial to ultrathin SnS2Preparation of thin films, further facilitating SnS2The film is used as an inorganic electron transport layer of the perovskite solar cell to transport electrons of the perovskite solar cell prepared.
Example 2
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2O; taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 160 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
FIG. 4 shows the ultra-thin SnS prepared by this example2The field emission scanning electron microscope image of the nano sheet shows that the ultrathin SnS can be seen2The size of the nanosheets is about 20-30 nm.
Example 3
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to form a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 200 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
FIG. 5 shows the ultra-thin SnS prepared by this example2The field emission scanning electron microscope image of the nano sheet shows that the ultrathin SnS can be seen2The size of the nanosheets is about 30-50 nm.
By mixing the ultra-thin SnS obtained in examples 1-32The nano-sheets are compared, and the ultra-thin SnS can be effectively reduced by reducing the reaction temperature2The size of the nanoplatelets.
Example 4
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 2 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 6mmol of L-glutathione into the stannic chloride aqueous solution to form a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; wet precipitate is obtained after the reaction is finished,taking out, repeatedly washing with deionized water and ethanol, and centrifuging to obtain ultrathin SnS2Nanosheets.
Example 5
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 4 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 12mmol of L-glutathione into the stannic chloride aqueous solution to form a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 6
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 0.5ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione to the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 7
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2O, taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 2ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 8
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 50%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 9
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2O, taking 60 ml of deionized water, and sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain stannic chloride aqueous solution (with the concentration of 0.05 mo)L/L), then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into tin tetrachloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 80%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 10
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 6 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 11
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 3mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.05mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 9mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 3 hours; knot to be reactedAfter finishing, wet precipitation is obtained, the solution is taken out and repeatedly washed by deionized water and ethanol and centrifugally separated to obtain the ultrathin SnS2Nanosheets.
Example 12
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2Taking 60 ml of deionized water, sequentially adding 6mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.1mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 18mmol of L-glutathione into the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 13
This embodiment provides a superfine SnS2Nanosheets and a method for preparing the same.
At room temperature according to Sn: the molar ratio of S is 1: 3 weigh C10H17N3O6S and SnCl4·5H2O, taking 60 ml of deionized water, sequentially adding 12mmol of stannic chloride pentahydrate under the condition of magnetic stirring to obtain a stannic chloride aqueous solution (the concentration is 0.2mol/L), and then adding 1ml of concentrated hydrochloric acid solution and 36mmol of L-glutathione to the stannic chloride aqueous solution to obtain a first mixed solution; transferring the obtained first mixed solution into a reaction kettle for hydrothermal reaction, wherein the filling rate of the reaction kettle is 70%, the reaction temperature is controlled at 120 ℃, and the reaction time is 12 hours; obtaining wet precipitate after the reaction is finished, repeatedly washing the wet precipitate with deionized water and ethanol after the wet precipitate is taken out, and centrifugally separating the washed precipitate to obtain the ultrathin SnS2Nanosheets.
Example 14
The embodiment provides an SnS2A film and a preparation method thereof.
The ultra-thin SnS prepared in example 12Dissolving the nano-sheet in ethanol to obtain ultrathin SnS2Sol of nanoplatelets (2 mg/mL); then the ultrathin SnS2Coating the nano-sheet sol on a conductive substrate, and annealing at 200 ℃ for 30min to obtain ultrathin SnS2A film.
Example 15
The embodiment provides an SnS2The thin film is applied to the preparation of perovskite solar cells.
SnS obtained in example 142The film is used as an inorganic electron transport layer of the perovskite solar cell, a perovskite active layer and a hole transport layer are sequentially coated in a spinning mode, and finally, an 80nm silver electrode is plated on the top of the hole transport layer through vacuum evaporation; and finishing the preparation of the perovskite solar cell.
Fig. 6 is a sectional view of a field emission scanning electron microscope of the perovskite solar cell prepared in the embodiment. As can be seen, SnS having a thickness of about 30nm to 40nm is obtained by the spin coating method2A film; SnS2The film is used as an inorganic electron transport layer of the perovskite solar cell and is closely contacted with a perovskite active layer, and perovskite crystal grains in the obtained perovskite solar cell are large.
FIG. 7 is a photocurrent voltage curve of a perovskite solar cell prepared in this example, wherein the open circuit voltage (V)OC) 1.17V, current density (J)SC) Is 20.53mA/cm2The Fill Factor (FF) is 71.11%, and the efficiency of the perovskite solar cell can reach 17.12%. Due to ultra-thin SnS2The nano sheet is an ultrathin two-dimensional material, so that the nano sheet has good contact, and a larger open-circuit voltage is obtained.
In the above embodiments, the sulfur source used may be replaced by CH while maintaining the total molar amount of the sulfur source added4N2S、(NH4)2S or CH3CSNH2Any one of them.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. Ultra-thin SnS2The preparation method of the nanosheet is characterized by comprising the following steps:
(1) adding concentrated hydrochloric acid into a tin tetrachloride aqueous solution, and then uniformly mixing the concentrated hydrochloric acid with a sulfur source to obtain a first mixed solution;
(2) transferring the first mixed solution obtained in the step (1) to a reaction kettle for hydrothermal reaction to obtain wet precipitate after the reaction is finished;
(3) washing the wet precipitate obtained in the step (2) by deionized water and ethanol, and centrifuging to obtain ultrathin SnS2Nanosheets.
2. Ultra-thin SnS according to claim 12The preparation method of the nanosheet is characterized in that in the step (1), the stannic chloride is selected from anhydrous stannic chloride or stannic chloride pentahydrate;
the sulfur source is selected from L-glutathione and CH4N2S、(NH4)2S or CH3CSNH2One of (1); preferably, the sulphur source is selected from L-glutathione.
3. Ultra-thin SnS according to claim 12The preparation method of the nano-sheet is characterized in that in the step (1), the concentration of the stannic chloride aqueous solution is 0.05-0.2 mol/L; preferably, the concentration of the aqueous solution of tin tetrachloride is 0.05 mol/L;
the volume ratio of the stannic chloride aqueous solution to the concentrated hydrochloric acid is 30-120: 1; preferably, the volume ratio of the tin tetrachloride aqueous solution to the concentrated hydrochloric acid is 60: 1;
the molar ratio of tin tetrachloride to sulfur source is 1: 2-4; preferably, the molar ratio of tin tetrachloride to sulfur source is 1: 3.
4. ultra-thin SnS according to claim 12The preparation method of the nanosheet is characterized in that in the step (2), the filling rate in the reaction kettle is 50-80%; preferably, the filling rate of the reaction kettle is 70%.
5. Ultra-thin SnS according to claim 12The preparation method of the nano-sheet is characterized in that in the step (2), in the hydrothermal reaction process, the reaction temperature is 120-200 ℃, and the reaction time is 3-12 h;
preferably, in the hydrothermal reaction process, the reaction temperature is 120 ℃ and the reaction time is 12 h.
6. Ultra-thin SnS prepared by the method of any one of claims 1-52Nanosheets.
7. The ultra-thin SnS of claim 62Preparation of SnS by nano sheet2Application in thin films.
8. SnS2A method for producing a thin film, characterized in that the ultra-thin SnS of claim 6 is used2Dissolving the nano-sheet in ethanol to obtain ultrathin SnS2Sol of the nanosheets; then the ultrathin SnS2Coating the nano-sheet sol on a conductive substrate, and annealing to obtain SnS2A film.
9. SnS prepared by the method of claim 82A film.
10. An SnS according to claim 92The application of the thin film in the preparation of perovskite solar cells is characterized in that SnS is added2The film is used as an inorganic electron transport layer of the perovskite solar cell, a perovskite active layer and a hole transport layer are sequentially coated in a spinning mode, and finally, a silver electrode is plated on the top of the hole transport layer through vacuum evaporation; and finishing the preparation of the perovskite solar cell.
CN202111511019.9A 2021-12-11 2021-12-11 Ultra-thin SnS2Nanosheet and SnS2Film, preparation and application thereof Pending CN114380325A (en)

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