CN113292099B - Preparation method of bismuth sulfide single crystal/carbon nanowire composite material - Google Patents
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Abstract
The invention belongs to the technical field of single crystal nano materials, and particularly discloses a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material, which comprises the steps of fully dissolving a polymer and excessive bismuth salt in a solvent A to obtain a supersaturated spinning precursor, and then carrying out electrostatic spinning to obtain the bismuth salt/polymer nanowire composite material; then calcining the bismuth salt/polymer nanowire composite material in multiple steps to obtain a bismuth/carbon nanowire composite material; oxidizing the bismuth/carbon nanowire composite material in an oxygen atmosphere to obtain a bismuth trioxide/carbon nanowire composite material; and vulcanizing the bismuth trioxide/carbon nanowire composite material in vacuum, and cleaning the vulcanized bismuth trioxide/carbon nanowire composite material by using a solvent B to finally obtain the bismuth sulfide single crystal/carbon nanowire composite material with a good crystal structure and uniform appearance. The composite material prepared by the method greatly improves the yield of the single-crystal bismuth sulfide and the conductivity of the bismuth sulfide material, and has extremely important significance for the application of the bismuth sulfide in the fields of energy storage and solar cells.
Description
Technical Field
The invention belongs to the technical field of single crystal nano materials, and particularly relates to a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material.
Background
Due to the unique properties of the single crystal material in structure and physical properties, such as symmetry, anisotropy, uniformity, regular shape and fixed melting point, the single crystal material has extremely important application value in the fields of chips, photoelectric detectors, solar cells and the like. Currently, the main methods for preparing single crystal materials include diffusion methods, temperature difference methods, contact methods, volatilization methods, autoclave methods, and the like. However, the preparation method has the defects of large environmental pollution, low yield, low efficiency, large energy consumption and the like, and the development of green ecological environment and energy-saving society is seriously influenced.
The bismuth sulfide single crystal material has the advantages of environmental friendliness, photoconduction, nonlinear optical response and the like, is widely applied to solar cells, photodiode arrays, infrared spectroscopy and the like, and can also be applied to preparation of other bismuth-based compounds, free-cutting steel additives and microelectronic industry. However, the main methods for preparing bismuth sulfide single crystal materials at present are hydrothermal and high-temperature sulfidation methods, and most of the obtained products are polycrystalline materials, which seriously affect the performance and application of bismuth sulfide materials. In addition, when bismuth sulfide is used as an energy storage material, the volume of bismuth sulfide increases by about 90% after alloying reaction, and the lower conductivity also limits the development of bismuth sulfide as an energy storage negative electrode material.
Therefore, the development of a preparation method of bismuth sulfide single crystal material with good conductivity, small volume expansion, high yield, low energy consumption and environmental friendliness is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material, which comprises the steps of firstly obtaining a bismuth salt/polymer nanowire by using a supersaturated bismuth salt spinning precursor under a spinning condition, and calcining the nanowire step by combining the different decomposition reduction temperature of bismuth salt and the different carbonization temperature of the polymer to fully reduce bismuth salt and completely carbonize the polymer to obtain the bismuth/carbon nanowire composite material with high metal bismuth particle content and uniformly distributed in the carbon nanowire, then oxidizing the bismuth/carbon nanowire composite material under an oxygen atmosphere to improve the reaction activity of bismuth, and further vulcanizing the bismuth sulfide single crystal/carbon nanowire composite material under vacuum. Aims to solve the problems that the existing pure bismuth sulfide single crystal material has poor conductivity, large volume expansion after alloying reaction and mostly has polycrystalline morphology in the prepared products.
In order to achieve the above object, the present invention provides a method for preparing a bismuth sulfide single crystal/carbon nanowire composite material, comprising the steps of:
s1, fully dissolving a polymer and excessive bismuth salt in a solvent A to obtain a supersaturated spinning precursor, and then performing electrostatic spinning to obtain a bismuth salt/polymer nanowire composite material;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps to obtain a bismuth/carbon nanowire composite material;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 in an oxygen atmosphere to obtain a bismuth trioxide/carbon nanowire composite material;
and S4, vulcanizing the bismuth trioxide/carbon nanowire composite material obtained in the step S3 under vacuum, and cleaning the vulcanized bismuth trioxide/carbon nanowire composite material by using a solvent B to obtain the bismuth sulfide single crystal/carbon nanowire composite material.
Preferably, in step S1, the polymer is one or more of polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol and polyacrylonitrile, the bismuth salt is one or more of bismuth nitrate, bismuth chloride and bismuth acetate, and the solvent a is N, N-dimethylformamide or water.
Preferably, in the step S1, the mass ratio of the polymer, the solvent A and the bismuth salt is (0.8-1.2): (5-12): (1.0-1.5).
Preferably, in step S2, the multi-step calcination specifically includes: firstly, calcining for 1h-3h at the temperature of 280-350 ℃; secondly, calcining for 6 to 8 hours at the temperature of 450 to 650 ℃; thirdly, calcining for 2 to 4 hours at the temperature of between 750 and 850 ℃.
Preferably, in step S3, the flow rate of the oxygen for oxidation is 5mL/min to 25mL/min.
Preferably, in the step S3, the temperature of the oxidation is 260-450 ℃, and the heating rate is 2-10 ℃/min.
Preferably, in step S4, the vulcanizing agent used for vulcanizing is one or more of sulfur powder, thiourea and dimethyl disulfide.
Preferably, in the step S4, the vulcanizing temperature is 400-550 ℃, and the heating rate is 0.5-5 ℃/min.
Preferably, in step S4, the solvent B is carbon disulfide, carbon tetrachloride, tetrahydrofuran or water.
According to another aspect of the invention, the bismuth sulfide single crystal/carbon nanowire composite material prepared by the method is also provided.
Generally, compared with the prior art, the technical scheme conceived by the invention has the following beneficial effects:
(1) The preparation method has the advantages of simple process, low cost, easy processing and design and the like, and the obtained bismuth sulfide single crystal/carbon nanowire composite material has the advantages of high yield, uniform appearance, good crystal form, high wire diameter ratio and the like.
(2) According to the invention, by setting excessive bismuth salt and reasonably controlling the addition proportion of the bismuth salt, the polymer and the solvent A, bismuth can completely cover the whole carbon nanowire, is uniformly and regularly arranged, and cannot be gathered on the surface of the carbon nanowire.
(3) According to the invention, the bismuth salt/polymer nanowire composite material is calcined step by analyzing the decomposition reduction temperature of bismuth salt and the carbonization temperature of polymer, the calcination temperature and time are accurately controlled, so that bismuth salt is fully reduced, the polymer is completely carbonized, and the bismuth/carbon nanowire composite material obtained has high content of metal bismuth particles and is uniformly distributed in the carbon nanowire.
(4) The bismuth sulfide in the bismuth sulfide single crystal/carbon nanowire composite material prepared by the method is in an excellent single crystal form, and compared with the bismuth sulfide which is used as an electrode material, the volume expansion after alloying reaction is reduced, and the bismuth sulfide single crystal/carbon nanowire composite material has good cycle performance and good electrical conductivity.
Drawings
FIG. 1 is a flow chart of a method for preparing a bismuth sulfide single crystal/carbon nanowire composite material provided by the invention;
FIG. 2 is an SEM image of a bismuth salt/polymer nanowire composite prepared in example 1 of the present invention;
fig. 3 is an SEM image of the bismuth/carbon nanowire composite prepared in example 1 of the present invention;
fig. 4 is a TEM image of the bismuth/carbon nanowire composite prepared in example 1 of the present invention;
FIG. 5 is a TEM image of a bismuth sulfide single crystal/carbon nanowire composite prepared in example 1 of the present invention;
fig. 6 is an energy spectrum of the bismuth sulfide single crystal/carbon nanowire composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
As shown in fig. 1, the preparation method of the bismuth sulfide single crystal/carbon nanowire composite material provided by the invention comprises the following steps:
s1, fully dissolving a polymer and excessive bismuth salt in a solvent A to obtain a supersaturated spinning precursor, and then performing electrostatic spinning to obtain a bismuth salt/polymer nanowire composite material;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps to obtain a bismuth/carbon nanowire composite material;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 in an oxygen atmosphere to obtain a bismuth trioxide/carbon nanowire composite material;
and S4, vulcanizing the bismuth trioxide/carbon nanowire composite material obtained in the step S3 under vacuum, and cleaning the composite material by using a solvent B to obtain the bismuth sulfide single crystal/carbon nanowire composite material.
In some embodiments, step S1 requires that the polymer and the excess bismuth salt are well dissolved in a solvent a to obtain the bismuth salt spinning precursor, the solvent a can dissolve both the polymer and the bismuth salt, without being limited by theory, the polymer can be one or more of polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB), polyvinyl alcohol (PVA), and Polyacrylonitrile (PAN), the bismuth salt can be one or more of bismuth nitrate, bismuth chloride, and bismuth acetate, and the solvent a can be N, N-Dimethylformamide (DMF) or water. The mass ratio of the polymer, the bismuth salt and the solvent A is (0.8-1.2): (1.0-1.5): 5-12). In order to enable bismuth nanoparticles in the bismuth/carbon nanowires to completely fill the whole carbon nanowires, the bismuth salt is set to be excessive; however, the concentration of bismuth should not be too high, otherwise, bismuth nanoparticles can agglomerate on the carbon nanowires in a large amount, thereby affecting the capacity and cycle performance of the bismuth sulfide single crystal/carbon nanowire composite material when the bismuth sulfide single crystal/carbon nanowire composite material is used as a battery cathode.
The electrostatic spinning is to overcome the surface tension of the bismuth salt spinning precursor solution under a high-voltage electrostatic field to generate a charged jet flow, jet and stretch jet fluid by means of electrostatic action, dry and solidify the solution in the jetting process, and finally fall on a receiving device to form a fiber felt or fibers in other shapes. It should be noted that the extrusion rate of the bismuth salt spinning precursor is reasonably controlled, and the positive and negative high pressures are slowly adjusted, so that the needle point of the injector uniformly and stably ejects the conical fiber. The diameter of the fiber obtained by electrospinning can be in the range of several tens to several hundreds nanometers, and has a continuous structure.
In some embodiments, the step S2 is performed by three calcination steps, so that the bismuth salt in the bismuth salt/polymer nanowire composite material is fully reduced, and the polymer is completely carbonized, thereby obtaining the bismuth/carbon nanowire composite material with high metal bismuth particle content and uniformly distributed in the carbon nanowire. Specifically, the three-step calcination comprises: the first step of calcination, wherein the temperature is 280-350 ℃, and the heat preservation time is 1-3 h; the second step of calcination, the temperature is 450 ℃ to 650 ℃, and the heat preservation time is 6h to 8h; and finally, calcining for 2-4 h at the temperature of 750-850 ℃. According to the invention, through a multi-step calcination process and reasonable control of the calcination temperature and the heat preservation time, bismuth particles and carbon nanofibers can be well fused together, and the bismuth/carbon nanowires with regular and uniform appearance can be obtained, so that the performance of the composite material is improved.
In some embodiments, in step S3, the bismuth/carbon nanowire composite material is sufficiently oxidized in a high-temperature oxygen atmosphere, so that the metal bismuth is oxidized into bismuth trioxide, thereby improving the reactivity of bismuth element in the carbon nanowire. Specifically, the flow rate of the introduced oxygen is 5mL/min-25mL/min, the temperature is slowly heated to 260-450 ℃, and the heating rate is 2 ℃/min-10 ℃/min. Slowly raising the temperature under the oxygen atmosphere to ensure that bismuth in the composite material is fully oxidized without damaging the structure of the composite material.
In some embodiments, in step S4, the bismuth trioxide/carbon nanowire composite material is vulcanized under vacuum, without being limited by theory, the vulcanizing agent used may be a conventional vulcanizing agent, such as sulfur powder, thiourea, and dimethyl disulfide, and after adding an excessive amount of vulcanizing agent, the temperature is slowly raised to 400 ℃ to 550 ℃, and the temperature raising rate is 0.5 ℃/min to 5 ℃/min; and after full vulcanization, cleaning residual vulcanizing agent by using a solvent B, wherein the solvent B is specifically carbon disulfide, carbon tetrachloride, tetrahydrofuran or water, and finally obtaining the bismuth sulfide single crystal/carbon nanowire composite material, wherein the bismuth sulfide is in a single crystal form which is regularly and periodically arranged. The bismuth sulfide single crystal/carbon nanowire composite material prepared by the invention has the advantages of uniform appearance, high crystallinity, high wire diameter ratio and the like.
The above technical solution is described in detail below with reference to specific examples.
Example 1
The embodiment provides a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material, which comprises the following steps:
s1, mixing PAN, DMF and bismuth chloride according to the mass ratio of 1.0;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps, wherein the calcining temperature in the first step is 300 ℃; the second step of calcining at 500 ℃; the calcining temperature in the last step is 800 ℃, so that the bismuth/carbon nanowire composite material is obtained;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 at a heating rate of 5 ℃/min to 400 ℃ under the condition that the oxygen flow is 10mL/min to obtain a bismuth trioxide/carbon nanowire composite material with high activity;
and S4, vulcanizing the bismuth trioxide/carbon nanowire composite material obtained in the step S3 in excessive thiourea at a heating rate of 1 ℃/min to 480 ℃, cooling, and then washing with water to finally obtain the bismuth sulfide single crystal/carbon nanowire composite material.
SEM, TEM and energy spectrum detection were performed on the intermediate product and the final product prepared in this example, as shown in fig. 2 to 6, there were many bismuth particles in the bismuth/carbon nanowire, and the distribution was uniform, the final product bismuth sulfide single crystal/carbon nanowire composite material had uniform morphology, good crystal form, and high wire diameter ratio, and the bismuth sulfide single crystal component therein was close to the theoretical ratio.
Example 2
The embodiment provides a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material, which comprises the following steps:
s1, mixing PVP, water and bismuth nitrate according to a mass ratio of 1.0;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps, wherein the calcining temperature in the first step is 300 ℃; the second step calcining temperature is 500 ℃; the calcining temperature in the last step is 750 ℃, so as to obtain the bismuth/carbon nanowire composite material;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 at a heating rate of 5 ℃/min to 400 ℃ under the condition that the oxygen flow is 15mL/min to obtain a bismuth trioxide/carbon nanowire composite material with high activity;
and S4, vulcanizing the bismuth trioxide/carbon nanowire composite material obtained in the step S3 in excessive dimethyl disulfide at a heating rate of 5 ℃/min to 500 ℃, cooling, and cleaning with carbon tetrachloride to finally obtain the bismuth sulfide single crystal/carbon nanowire composite material.
SEM, TEM and energy spectrum detection are carried out on the intermediate product and the final product prepared in the embodiment, the bismuth particles in the bismuth/carbon nano wire are more and are uniformly distributed, and the bismuth sulfide single crystal/carbon nano wire composite material as the final product has uniform appearance, good crystal form and high wire diameter ratio.
Example 3
The embodiment provides a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material, which comprises the following steps:
s1, mixing PVA, water and bismuth nitrate according to a mass ratio of 1.0;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps, wherein the calcining temperature in the first step is 280 ℃; the second step calcining temperature is 450 ℃; the calcining temperature in the last step is 800 ℃, so that the bismuth/carbon nanowire composite material is obtained;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 at a heating rate of 2 ℃/min to 260 ℃ under the condition that the oxygen flow is 5mL/min to obtain a bismuth trioxide/carbon nanowire composite material with high activity;
and S4, putting the bismuth trioxide/carbon nanowire composite material obtained in the step S3 into excessive sulfur powder, heating to 500 ℃ at a heating rate of 3 ℃/min for vulcanization, cooling, and cleaning with carbon disulfide to finally obtain the bismuth sulfide single crystal/carbon nanowire composite material.
SEM, TEM and energy spectrum detection are carried out on the intermediate product and the final product prepared in the embodiment, the bismuth particles in the bismuth/carbon nanowire are more and are uniformly distributed, and the bismuth sulfide single crystal/carbon nanowire composite material as the final product has uniform appearance, good crystal form and high wire diameter ratio.
Example 4
The embodiment provides a preparation method of a bismuth sulfide single crystal/carbon nanowire composite material, which comprises the following steps:
s1, mixing PAN, DMF and bismuth nitrate according to a mass ratio of 0.85 to 9, namely 1.2 to obtain a supersaturated spinning precursor, and carrying out electrostatic spinning to obtain a bismuth salt/polymer nanowire composite material;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps, wherein the calcining temperature in the first step is 350 ℃; the second step of calcining the mixture at the temperature of 650 ℃; the calcining temperature in the last step is 850 ℃, so as to obtain the bismuth/carbon nanowire composite material;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 at a heating rate of 10 ℃/min to 450 ℃ under the condition that the oxygen flow is 25mL/min to obtain a bismuth trioxide/carbon nanowire composite material with high activity;
and S4, vulcanizing the bismuth trioxide/carbon nanowire composite material obtained in the step S3 in excessive thiourea at a heating rate of 0.5 ℃/min to 550 ℃, cooling, and washing with water to finally obtain the bismuth sulfide single crystal/carbon nanowire composite material.
SEM, TEM and energy spectrum detection are carried out on the intermediate product and the final product prepared in the embodiment, the bismuth particles in the bismuth/carbon nanowire are more and are uniformly distributed, and the bismuth sulfide single crystal/carbon nanowire composite material as the final product has uniform appearance, good crystal form and high wire diameter ratio.
The preparation method has the advantages of simple process, good reproducibility, high yield and the like, and the prepared bismuth sulfide single crystal/carbon nanowire composite material has high wire diameter ratio, good crystallinity and uniform appearance.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of a bismuth sulfide single crystal/carbon nanowire composite material is characterized by comprising the following steps:
s1, fully dissolving a polymer and excessive bismuth salt in a solvent A to obtain a supersaturated spinning precursor, and then performing electrostatic spinning to obtain a bismuth salt/polymer nanowire composite material;
s2, calcining the bismuth salt/polymer nanowire composite material obtained in the step S1 in multiple steps to obtain a bismuth/carbon nanowire composite material;
s3, oxidizing the bismuth/carbon nanowire composite material obtained in the step S2 in an oxygen atmosphere to obtain a bismuth trioxide/carbon nanowire composite material;
and S4, vulcanizing the bismuth trioxide/carbon nanowire composite material obtained in the step S3 under vacuum, wherein vulcanizing agents adopted in the vulcanization are one or more of sulfur powder, thiourea and dimethyl disulfide, the vulcanization temperature is 400-550 ℃, the heating rate is 0.5-5 ℃/min, and the bismuth sulfide single crystal/carbon nanowire composite material is obtained after cleaning by a solvent B.
2. The method for preparing the bismuth sulfide single crystal/carbon nanowire composite material according to claim 1, characterized in that: in the step S1, the polymer is one or more of polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol and polyacrylonitrile, the bismuth salt is one or more of bismuth nitrate, bismuth chloride and bismuth acetate, and the solvent A is N, N-dimethylformamide or water.
3. The method for preparing the bismuth sulfide single crystal/carbon nanowire composite material according to claim 1, characterized in that: in the step S1, the mass ratio of the polymer, the solvent A and the bismuth salt is (0.8-1.2): (5-12): 1.0-1.5).
4. The method for preparing the bismuth sulfide single crystal/carbon nanowire composite material according to claim 1, wherein in the step S2, the multi-step calcination specifically comprises: firstly, calcining for 1h-3h at the temperature of 280-350 ℃; secondly, calcining for 6 to 8 hours at the temperature of 450 to 650 ℃; thirdly, calcining for 2 to 4 hours at the temperature of between 750 and 850 ℃.
5. The method for preparing the bismuth sulfide single crystal/carbon nanowire composite material according to claim 1, characterized in that: in step S3, the flow rate of the oxygen for oxidation is 5mL/min-25mL/min.
6. The method for preparing a bismuth sulfide single crystal/carbon nanowire composite material according to claim 1, characterized in that: in the step S3, the temperature of the oxidation is 260-450 ℃, and the heating rate is 2-10 ℃/min.
7. The method for preparing the bismuth sulfide single crystal/carbon nanowire composite material according to claim 1, characterized in that: in step S4, the solvent B is carbon disulfide, carbon tetrachloride, tetrahydrofuran, or water.
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