CN108448091B - MoO (MoO)2/SnS2Nanocomposite and method for preparing same - Google Patents

MoO (MoO)2/SnS2Nanocomposite and method for preparing same Download PDF

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CN108448091B
CN108448091B CN201810227164.6A CN201810227164A CN108448091B CN 108448091 B CN108448091 B CN 108448091B CN 201810227164 A CN201810227164 A CN 201810227164A CN 108448091 B CN108448091 B CN 108448091B
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sns
hexagonal
moo
sns2
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CN108448091A (en
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王俊鹏
王刚
车全德
杨萍
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University of Jinan
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a MoO2/SnS2The nanometer composite material and the preparation method thereof, the method is as follows: mixing and stirring a sulfur source, a tin source and water uniformly to obtain a precursor solution, and carrying out hydrothermal reaction on the precursor solution to obtain SnS2Hexagonal tablets; SnS2Dispersing the hexagonal tablets into a mixed aqueous solution of ammonium heptamolybdate and EDTA-2Na, adjusting the pH value, and carrying out secondary hydrothermal treatment to obtain the product. The preparation method has the advantages of simple preparation process, good repeatability, good controllability, low cost, strong operability and practicability, and suitability for industrial production. The product composition is not reported, the product has novel and single appearance, good repeatability of microscopic appearance, good dispersibility, good stability, adjustable size and component proportion and narrow particle size distribution range, and MoO2 is used as a metallic semiconductor, can obviously improve the conductivity of SnS2 and has important significance for improving the capacity and the cycling stability of the lithium ion battery cathode.

Description

MoO (MoO)2/SnS2Nanocomposite and method for preparing same
Technical Field
The invention relates to a composite material composed of MoO2And SnS2Composite MoO2/SnS2A nano composite material and a preparation method thereof, in particular to a surface loaded MoO2SnS of nanoparticles2Hexagonal tablets and a preparation method thereof.
Background
With the rapid development of social economy and society, the demand and damage of human life and industrial development to the nature are increased, and the global energy shortage and environmental pollution problems are increasingly severe. In order to replace increasingly exhausted fossil energy and slow down the damage of energy demand to the environment, human beings continuously search various renewable energy sources and expand the use ratio of new energy sources. The lithium ion battery is considered as a high-performance battery which can best meet the sustainable development requirement of the future society, and the application of the lithium ion battery covers various fields of our lives at present, and the position of the lithium ion battery is more and more important. In order to pursue higher battery performance, researchers are continuously designing, searching and developing new electrode materials, and improving the capacity and cycle performance of lithium ion batteries.
SnS2The semiconductor material with the band gap of about 2.35eV has excellent optical performance and electrical performance, and is widely applied to the field of photocatalysis. In the field of cathode materials for lithium ion batteries, SnS2The theoretical specific capacity of the anode is 645mAh g < -1 > which is far greater than that of a carbon anode material, however, in practical application, SnS2The volume expansion and pulverization are easy to occur in the circulation process to influence the circulation performance; while being semiconductor material, SnS2The electron conductivity is poor. Researchers have therefore improved SnS through various modifications2The electrochemical performance of (2). The problem of volume pulverization expansion is generally achieved by the nano-poling of materials, such as the documents "Liu S A, Yin X M, Chen L B, et al]Solid State sci, 2010, 12 (5): 712-2The capacity is kept at 502mAh g after 50 weeks of circulation-. The document "ZHai C X, Du N, ZHang H, et al, MultiwalledCarbon Nanotubes absorbed with SnS2 Nanosheets as High-Performance oriented materials of Lithium-Ion Batteries [ J]Appl. mater. interfaces, 2011, 3 (10): 4067-2The carbon material is loaded on the carbon nano tube, the conductivity of the system is improved, although the carbon material has good conductivity, the improvement of the whole capacity of the system is not greatly facilitated due to the lower theoretical capacity, and therefore a material with good conductivity and high theoretical capacity and SnS are searched2Compounding to increase SnS2Has important significance on the electrochemical performance.
Nano MoO2The theoretical specific capacity of the nano-silver can reach 838mAhg-1Simultaneous MoO2Has low resistance (good electronic conductivity) and high electrochemical reversibility, and is a research hotspot in the field of electrochemical energy storage. Preparation of MoO2And SnS2The nano composite material has important significance for improving the capacity and the cycling stability of the lithium ion battery cathode, but reports are not found at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a MoO2/SnS2A nano composite material, which is prepared by compounding molybdenum oxide and tin sulfide and has a special shape, MoO2The load improves the electrochemical performance of the tin sulfide, and has important application significance.
The invention also provides the MoO2/SnS2The preparation method of the nano composite material has the advantages of simple operation process, adjustable tin-molybdenum ratio, strong controllability of product appearance and high yield.
The specific technical scheme of the invention is as follows:
the invention firstly proposes that molybdenum oxide and tin sulfide are compounded, and MoO is successfully obtained2/SnS2Nanocomposite material made of MoO2Nanoparticles and SnS2Hexagonal plates, the MoO2Nano particles loaded in SnS2The surface of hexagonal piece.
Further, MoO2Nanoparticles in SnS2The surfaces of the hexagonal tablets are uniformly dispersed, and no agglomeration phenomenon exists. MoO2The nanoparticles are irregular in shape. SnS2The hexagonal plate is hexagonal.
Further, the MoO2The size of the nanoparticles is 20-80 nm. The SnS2The thickness of the hexagonal plate is 40-60nm, and the size is 500 nm-1 μm. Due to SnS2The thickness of the hexagonal plate is nano-scale, so the hexagonal plate can also be called SnS2The hexagonal piece is SnS2Hexagonal nano-sheet.
The invention also provides the MoO2/SnS2A method of preparing a nanocomposite, the method comprising the steps of:
(1) mixing and stirring a sulfur source, a tin source and water uniformly to obtain a precursor solution;
(2) heating the precursor solution for hydrothermal reaction to obtain SnS2Hexagonal tablets;
(3) SnS2Dispersing hexagonal tablets into an aqueous solution of ammonium heptamolybdate and EDTA-2Na, adjusting the pH value of the solution to 2-3, and performing hydrothermal treatmentReacting to obtain MoO2/SnS2A nanocomposite material.
In the above preparation method, the sulfur source is thiourea or thioacetamide.
In the preparation method, the tin source is tin tetrachloride.
In the step (1), the sulfur source and the water are uniformly mixed, and then the mixture is mixed with the tin source or the tin source water solution to obtain the precursor solution.
According to the invention, water is used as a solvent, a sulfur source and a tin source are prepared into SnS2 hexagonal nanosheets with uniform size and good dispersibility by a hydrothermal method, then EDTA-2Na is used as a complexing agent, the SnS2 hexagonal nanosheets are dispersed in an ammonium heptamolybdate aqueous solution, and MoO2 nanoparticles are formed on the surfaces of the SnSO2 hexagonal nanosheets by secondary hydrothermal. EDTA-2Na has the function of complexing ions in SnS2On the surface of the hexagonal plate, EDTA-2Na can complex ammonium heptamolybdate, can play a role in connecting molybdenum and sulfur, and the complexing ability of EDTA-2Na is controlled by the pH value, so that molybdenum dioxide is smoothly loaded on the surface of the SnSO2 hexagonal plate, otherwise MoO is difficult to realize2The load of (2).
In the preparation method, the product with adjustable size and good appearance can be obtained by adjusting the hydrothermal reaction condition, the concentration of the tin source and the sulfur source, the dosage of EDTA-2Na, the acid, the pH value and the like. By controlling the concentration of ammonium heptamolybdate, the loading of molybdenum oxide can be adjusted.
Preferably, the molar ratio of the sulfur source to the tin source in the precursor solution is 6: 1.
Preferably, the concentration of the tin source in the precursor solution is 0.05-0.15 mol/L.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 120-160 ℃. The time of the hydrothermal reaction is 6-24 h.
Preferably, in the step (2), the hydrothermal reaction is performed in a closed environment.
Preferably, in the step (3), the concentration of ammonium heptamolybdate in the aqueous solution is 0.005-0.02mol/L, the molar ratio of EDTA-2Na to Mo is 1:0.8-1.5, and the molar ratio of Mo to Sn is 0.05-0.3: 1.
preferably, in the step (3), the hydrothermal temperature is 180-.
Preferably, in the step (3), the hydrothermal reaction is performed in a closed environment.
Furthermore, in the step (3), citric acid and tartaric acid are used for adjusting the pH value, and the citric acid and the tartaric acid are used as a pH regulator and an auxiliary complexing agent, so that the loading amount of the molybdenum dioxide is increased. Preferably, the mass ratio of citric acid to tartaric acid is 2-5: 1.
The preparation method has the advantages of simple preparation process, easy control of synthesis conditions, low price of used raw materials, good repeatability of the preparation method, good controllability, low cost, strong operability and practicability, and suitability for industrial production. MoO product of the invention2/SnS2The nano composite material consists of MoO2Nanoparticles and SnS2The hexagonal tablets are compounded, and the composition is not reported. The product has novel and single appearance, good repeatability of microscopic appearance, good dispersibility, good stability, adjustable size and component ratio, narrow particle size distribution range, and MoO2Good electronic conductivity, high electrochemical reversibility and high theoretical specific capacity2The electrochemical performance of the lithium ion battery has important significance for improving the capacity and the cycling stability of the lithium ion battery cathode.
Drawings
Figure 1X-ray diffraction (XRD) pattern of hexagonal SnS2 tablets synthesized in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of hexagonal SnS2 tablets synthesized in example 1 of the present invention.
Figure 3X-ray diffraction (XRD) pattern of hexagonal plate-like SnS2 loaded with MoO2 nanoparticles prepared in example 1 of the present invention.
Fig. 4 Scanning Electron Microscope (SEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized in example 1 of the present invention.
Fig. 5 Transmission Electron Microscope (TEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized in example 1 of the present invention.
Fig. 6 is a Scanning Electron Microscope (SEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized in example 2 of the present invention.
Fig. 7 is a Scanning Electron Microscope (SEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized in example 3 of the present invention.
Fig. 8 Scanning Electron Microscope (SEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized in example 4 of the present invention.
Fig. 9 Scanning Electron Microscope (SEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized by comparative example 1 of the present invention.
Fig. 10 Scanning Electron Microscope (SEM) photograph of hexagonal flaky SnS2 supporting MoO2 nanoparticles synthesized by comparative example 3 of the present invention.
Detailed description of the invention
The present invention is further illustrated by the following examples, which should be understood as being merely illustrative and not limiting.
Example 1
1.1 dissolve 0.912 g of thiourea in 30mL of deionized water and stir at room temperature for 30 min.
1.2 to the solution described in 1.1, 0.7g of SnCl was added4·5H2And O, stirring to obtain a uniform solution, namely a precursor solution.
1.3, transferring the precursor solution 1.2 into a 50 mL reaction kettle, heating the reaction kettle to 160 ℃ in an oven, and carrying out closed reaction for 12 hours.
1.4 centrifugal washing is carried out on the cooled sample to obtain red SnS2The nano sheet is in a hexagonal structure, namely, a hexagon, SnS2The size of the hexagonal nano-sheet is 500 nm-1000nm, the thickness is about 50nm, the XRD pattern is shown in figure 1, and the scanning electron micrograph is shown in figure 2.
1.5 mixing SnS2The hexagonal nano-sheet is dispersed in 30ml of mixed aqueous solution containing 0.1g of ammonium heptamolybdate and 0.2g of EDTA-2Na, the pH of the solution is adjusted to 3 by using citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 2: 1.
1.6 transferring the solution in the 1.5 into a 50 mL reaction kettle, heating the solution to 200 ℃ in an oven, and sealing the reaction kettle for 12 hours to obtain MoO2/SnS2The XRD pattern of the nanocomposite material is shown in figure 3, and the scanning electron microscope is used for scanningFIG. 4 shows a transmission electron micrograph, and FIG. 5 shows a transmission electron micrograph. As can be seen from the figure, the nanocomposite material is composed of MoO2 nanoparticles and SnS2 hexagonal nanosheets, MoO2 nanoparticles are uniformly dispersed on the SnS2 hexagonal nanosheets without agglomeration, wherein the size of the MoO2 nanoparticles is 50-80nm, the size of the SnS2 hexagonal nanosheets is about 800 nm, the thickness of the SnS2 hexagonal nanosheets is 50nm, and through EDS analysis, the molar ratio of MoO2 to SnS2 in the nanocomposite material is about 0.27: 1.
example 2
2.1 dissolve 0.1824 g thiourea in 30mL deionized water and stir at room temperature for 30 min.
2.2 adding 1.4g SnCl 4.5H 2O into the solution 2.1, and stirring to obtain a uniform solution, namely a precursor solution.
2.3 transferring the precursor solution 2.2 into a 50 mL reaction kettle, heating the reaction kettle to 120 ℃ in an oven, and carrying out closed reaction for 24 hours.
And 2.4, centrifugally washing the cooled sample to obtain a red SnS2 nanosheet with a hexagonal structure.
2.5 mixing SnS2The hexagonal nano-sheet is dispersed in 30ml of solution containing 0.14g of ammonium heptamolybdate and 0.3g of EDTA-2Na, the pH of the solution is adjusted to 2.5 by using citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 3: 1.
2.6 transferring the solution in the 2.5 into a 50 mL reaction kettle, heating the reaction kettle to 200 ℃ in an oven, and sealing the reaction kettle for reaction for 12 hours to obtain MoO2/SnS2A scanning electron micrograph of the nanocomposite is shown in FIG. 6. As can be seen from the figure, the nano composite material consists of MoO2 nano particles and SnS2 hexagonal nano sheets, MoO2 nano particles are uniformly dispersed on the SnS2 hexagonal nano sheets without agglomeration, wherein the size of the MoO2 nano particles is about 50nm, the size of the SnS2 hexagonal nano sheets is 300-500 nm, and the thickness of the SnS2 hexagonal nano sheets is about 50 nm. The molar ratio of MnO2 to SnS2 in the nanocomposite was about 0.19 by EDS analysis: 1.
example 3
3.1 dissolve 0.912 g of thiourea in 30mL of deionized water and stir at room temperature for 30 min.
3.2 adding 0.7g of SnCl4 & 5H2O into the solution 3.1, and stirring to obtain a uniform solution, namely a precursor solution.
3.3, transferring the precursor solution 3.2 into a 50 mL reaction kettle, heating the reaction kettle to 140 ℃ in an oven, and carrying out closed reaction for 20 hours.
And 3.4, centrifugally washing the cooled sample to obtain a red SnS2 nanosheet with a hexagonal structure.
3.5 mixing SnS2The hexagonal nanosheets are dispersed in 30ml of a solution containing 0.03g of ammonium heptamolybdate and 0.06g of EDT-2Na, the pH of the solution is adjusted to 2 by citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 2: 1.
3.6 transferring the solution in the 3.5 into a 50 mL reaction kettle, heating the reaction kettle to 200 ℃ in an oven, and sealing the reaction kettle for 20 hours to obtain MoO2/SnS2A scanning electron micrograph of the nanocomposite is shown in FIG. 7. As can be seen from the figure, the nanocomposite material is composed of MoO2 nanoparticles and SnS2 hexagonal nanosheets, MoO2 nanoparticles are uniformly dispersed on the SnS2 hexagonal nanosheets without agglomeration, wherein the size of the MoO2 nanoparticles is 20-50nm, the size of the SnS2 hexagonal nanosheets is 500nm, and the thickness of the SnS2 hexagonal nanosheets is about 40 nm. The molar ratio of MnO2 to SnS2 in the nanocomposite was about 0.08 by EDS analysis: 1.
example 4
4.1 dissolve 0.9g thioacetamide in 30mL deionized water and stir at room temperature for 30 min.
4.2 adding 0.7g of SnCl 4.5H 2O into the solution of 4.1, and stirring to obtain a uniform solution, namely a precursor solution.
4.3 transferring the precursor solution 4.2 into a 50 mL reaction kettle, heating to 150 ℃ in an oven, and sealing for reaction for 16 h.
And 4.4, centrifugally washing the cooled sample to obtain a red SnS2 nanosheet with a hexagonal structure.
4.5 mixing SnS2The hexagonal nano-sheets are dispersed in 30ml of solution containing 0.07g of ammonium heptamolybdate and 0.15g of EDTA-2Na, the pH of the solution is adjusted to 2.7 by using citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 5: 1.
4.6 transfer the solution in 4.5 to a 50 mL reaction kettle, heat to 180 deg.C in an ovenPerforming closed reaction at the temperature of 24 hours to obtain MoO2/SnS2A scanning electron micrograph of the nanocomposite is shown in FIG. 8. As can be seen from the figure, the nanocomposite material is composed of MoO2 nanoparticles and SnS2 hexagonal nanosheets, MoO2 nanoparticles are uniformly dispersed on the SnS2 hexagonal nanosheets without agglomeration, wherein the size of the MoO2 nanoparticles is 50-80nm, the size of the SnS2 hexagonal nanosheets is 500-600 nm, and the thickness of the SnS2 hexagonal nanosheets is about 40 nm. The molar ratio of MnO2 to SnS2 in the nanocomposite was about 0.2 by EDS analysis: 1.
example 5
5.1 dissolve 0.9g thioacetamide in 30mL deionized water and stir at room temperature for 30 min.
5.2 adding 0.7g of SnCl4 & 5H2O into the solution 5.1, and stirring to obtain a uniform solution, namely a precursor solution.
And 5.3, transferring the precursor solution of 5.2 into a 50 mL reaction kettle, heating to 120 ℃ in an oven, and sealing for reaction for 24 hours.
And 5.4, centrifugally washing the cooled sample to obtain a red SnS2 nanosheet with a hexagonal structure.
5.5 mixing SnS2The hexagonal nano-sheet is dispersed in 30ml of solution containing 0.06g of ammonium heptamolybdate and 0.13g of EDTA-2Na, the pH of the solution is adjusted to 2.1 by citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 4: 1.
5.6 transferring the solution in the 5.5 into a 50 mL reaction kettle, heating the reaction kettle to 190 ℃ in an oven, and sealing the reaction kettle for 20 hours to obtain MoO2/SnS2Nanocomposite to obtain MoO2/SnS2The nano composite material consists of MoO2 nano particles and SnS2 hexagonal nano sheets, wherein the MoO2 nano particles are uniformly dispersed on the SnS2 hexagonal nano sheets without agglomeration, the size of the MoO2 nano particles is 60-80nm, the size of the SnS2 hexagonal nano sheets is 500nm, and the thickness of the nano composite material is about 40 nm. The molar ratio of MnO2 to SnS2 in the nanocomposite was about 0.17 by EDS analysis: 1.
example 6
6.1 dissolve 1.8g thioacetamide in 30mL deionized water and stir at room temperature for 30 min.
6.2 adding 1.4g of SnCl4 & 5H2O into the solution 6.1, and stirring to obtain a uniform solution, namely a precursor solution.
6.3 transferring the precursor solution 6.2 into a 50 mL reaction kettle, heating to 160 ℃ in an oven, and sealing for reaction for 10 h.
6.4, centrifugally washing the cooled sample to obtain a red SnS2 nanosheet, wherein the nanosheet is of a hexagonal structure.
6.5 mixing SnS2The hexagonal nano-sheets are dispersed in 30ml of solution containing 0.08g of ammonium heptamolybdate and 0.16g of EDTA-2Na, the pH of the solution is adjusted to 2.3 by using citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 2: 1.
6.6 transferring the solution in the 6.5 into a 50 mL reaction kettle, heating the reaction kettle to 200 ℃ in an oven, and sealing the reaction kettle for 20 hours to obtain MoO2/SnS2The nano composite material consists of MoO2 nano particles and SnS2 hexagonal nano sheets, wherein the MoO2 nano particles are uniformly dispersed on the SnS2 hexagonal nano sheets without agglomeration, the size of the MoO2 nano particles is about 60nm, the size of the SnS2 hexagonal nano sheets is 900 nm, and the thickness of the SnS2 hexagonal nano sheets is about 60 nm. The molar ratio of MnO2 to SnS2 in the nanocomposite was about 0.11 by EDS analysis: 1.
example 7
7.1 dissolve 0.9g thioacetamide in 30mL deionized water and stir at room temperature for 30 min.
7.2 adding 0.7g of SnCl4 & 5H2O into the solution of 7.1, and stirring to obtain a uniform solution, namely a precursor solution.
7.3 transferring the precursor solution of 7.2 into a 50 mL reaction kettle, heating to 120 ℃ in an oven, and sealing for reaction for 12 h.
7.4, centrifugally washing the cooled sample to obtain a red SnS2 nanosheet with a hexagonal structure.
7.5 SnS2The hexagonal nano-sheet is dispersed in 30ml of solution containing 0.05g of ammonium heptamolybdate and 0.11g of EDTA-2Na, the pH of the solution is adjusted to 2.8 by citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 2: 1.
7.6 transfer the solution in 7.5 to a 50 mL reaction kettle and heat in an oven toReacting at 200 ℃ in a closed manner for 20 hours to obtain MoO2/SnS2The nano composite material consists of MoO2 nano particles and SnS2 hexagonal nano sheets, wherein the MoO2 nano particles are uniformly dispersed on the SnS2 hexagonal nano sheets without agglomeration, the size of the MoO2 nano particles is about 60nm, the size of the SnS2 hexagonal nano sheets is 900 nm, and the thickness of the SnS2 hexagonal nano sheets is about 60 nm. The molar ratio of MnO2 to SnS2 in the nanocomposite was about 0.15 by EDS analysis: 1.
example 8
The product was prepared according to the method of example 1, except that: SnS2The hexagonal nanosheets were dispersed in 30ml of a mixed aqueous solution containing 0.1g of ammonium heptamolybdate and 0.2g of EDTA-2Na, and the pH of the solution was adjusted to 3 with hydrochloric acid. The obtained product consists of MoO2 nanoparticles and SnS2 hexagonal nanosheets, MoO2 nanoparticles are uniformly dispersed on the SnS2 hexagonal nanosheets without agglomeration, wherein the size of the MoO2 nanoparticles is 40-80nm, the size of the SnS2 hexagonal nanosheets is about 850nm, the thickness of the SnS2 hexagonal nanosheets is 40-50nm, and the molar ratio of MoO2 to SnS2 in the product is about 0.20 through EDS analysis: 1.
comparative example 1
The product was prepared according to the method of example 1, except that: SnS2The hexagonal nano-sheet is dispersed in 30ml of mixed aqueous solution containing 0.1g of ammonium heptamolybdate and 0.2g of EDTA-2Na, the pH of the solution is adjusted to 5 by using citric acid and tartaric acid, and the mass ratio of the citric acid to the tartaric acid is 2: 1.
The scanning electron micrograph of the obtained product is shown in FIG. 9, from which it can be seen that although SnS is formed2Hexagonal nanosheet, but SnS2The surface of the hexagonal nanosheet is almost free of MoO 2. It is shown that the adjustment of the pH is critical to the loading of MoO 2.
Comparative example 2
The product was prepared according to the method of example 1, except that: after the pH value is adjusted, the solution is transferred to a 50 mL reaction kettle, heated to 170 ℃ in an oven and sealed for reaction for 12 hours. The scanning electron micrograph of the resulting product is similar to that of FIG. 9, although SnS is formed2Hexagonal nanosheet, but SnS2The surface of the hexagonal nanosheet is almost free of MoO 2.
Comparative example 3
The product was prepared according to the method of example 1, except that: after the pH value is adjusted, the solution is transferred to a 50 mL reaction kettle, heated to 210 ℃ in an oven and sealed to react for 12 hours. The scanning electron microscope image of the obtained product is shown in fig. 10, and it can be seen from the image that the SnS2 hexagonal sheet structure is destroyed, and the obtained product is an irregular sheet structure with smooth surface, the size is more than 5 μm, and no MoO2 particle load exists.
Comparative example 4
The product was prepared according to the method of example 1, except that: no EDTA-2Na was added. The scanning electron micrograph of the resulting product is similar to that of FIG. 9, although SnS is formed2Hexagonal nanosheet, but SnS2The surface of the hexagonal nanosheet is almost free of MoO 2.

Claims (10)

1. MoO (MoO)2/SnS2A nanocomposite characterized by: from MoO2Nanoparticles and SnS2Hexagonal plates, the MoO2Nano particles loaded in SnS2The surface of the hexagonal piece; the MoO2The grain diameter of the nano-particles is 20-80nm, and the SnS2The thickness of the hexagonal piece is 40-60nm, and the size is 500 nm-1 μm; the molar ratio of Mo to Sn is 0.05-0.3: 1.
2. The MoO of claim 12/SnS2The preparation method of the nano composite material is characterized by comprising the following steps:
(1) mixing and stirring a sulfur source, a tin source and water uniformly to obtain a precursor solution;
(2) heating the precursor solution for hydrothermal reaction to obtain SnS2Hexagonal tablets;
(3) SnS2Dispersing the hexagonal tablets into an aqueous solution of ammonium heptamolybdate and EDTA-2Na, adjusting the pH value of the solution to 2-3, and then carrying out hydrothermal reaction to obtain MoO2/SnS2A nanocomposite material.
3. The method of claim 2, wherein: in the step (1), the molar ratio of the sulfur source to the tin source is 6:1, and the concentration of the tin source is 0.05-0.15 mol/L.
4. The method according to claim 2 or 3, wherein: in the step (3), the molar ratio of Mo to EDTA-2Na is 1:0.8-1.5, and the molar ratio of Mo to Sn is 0.05-0.3: 1.
5. The method of claim 2, wherein: in the step (3), the concentration of the ammonium heptamolybdate aqueous solution is 0.005-0.02 mol/L.
6. The method of claim 2, wherein: in the step (3), citric acid and tartaric acid are adopted to adjust the pH.
7. The method of claim 6, wherein: in the step (3), the mass ratio of the citric acid to the tartaric acid is 2-5: 1.
8. The method of claim 2, wherein: the sulfur source is thiourea or thioacetamide; the tin source is tin tetrachloride.
9. The method of claim 2, wherein: in the step (2), the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 6-24 h; in the step (3), the temperature of the hydrothermal reaction is 180-200 ℃, and the time of the hydrothermal reaction is 12-24 h.
10. The method of claim 2, wherein: in the steps (2) and (3), the hydrothermal reaction is carried out in a closed environment.
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