CN113072098A - Preparation method of antimony sulfide/graphene composite micro-nano material - Google Patents
Preparation method of antimony sulfide/graphene composite micro-nano material Download PDFInfo
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- CN113072098A CN113072098A CN202110368197.4A CN202110368197A CN113072098A CN 113072098 A CN113072098 A CN 113072098A CN 202110368197 A CN202110368197 A CN 202110368197A CN 113072098 A CN113072098 A CN 113072098A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 159
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 72
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- 229940026189 antimony potassium tartrate Drugs 0.000 claims abstract description 12
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims abstract description 12
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- 239000011734 sodium Substances 0.000 description 4
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/008—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a preparation method of an antimony sulfide/graphene composite micro-nano material, which comprises the following steps: weighing raw materials of graphene oxide dispersion liquid, antimony potassium tartrate, thioacetamide and absolute ethyl alcohol according to the proportion; mixing and dissolving graphene oxide dispersion liquid, antimony potassium tartrate and thioacetamide; dropwise adding absolute ethyl alcohol into the solution, and stirring to obtain a mixed solution; pouring the mixed solution into a reaction kettle, and continuously heating and reacting for 12 hours or 18 hours at the temperature of 120 ℃; cooling to normal temperature after the reaction is finished, taking out the material, and alternately cleaning the material for at least six times by using high-purity water and absolute ethyl alcohol; and (3) centrifugally separating the cleaned material, and drying at 60 ℃ for 12 hours to obtain the antimony sulfide/graphene composite micro-nano material. The graphene in the material of the invention presents a flexible veil-like appearance with good transparency and folds, shows that the graphene is well reduced, and Sb2S3The nanoparticles were encapsulated in a veil layer of graphene, revealing antimony sulfide and grapheneHas excellent recombination rate, so that the electrochemical performance of the material is stable.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage materials, in particular to an antimony sulfide/graphene composite micro-nano material prepared by a hydrothermal method and a preparation method thereof.
Background
The application of various clean energy sources is widely advocated. However, most clean energy sources have great storage difficulty, so the research on the energy storage mode is more urgent. The energy storage technologies that have been scaled up today are roughly classified into four types, namely direct electrical energy storage methods, mechanical energy storage, chemical energy storage, and electrochemical energy storage. Compared with other three energy storage technologies, the electrochemical energy storage technology has a series of advantages of fast response time, easy maintenance and the like, so that the electrochemical energy storage technology becomes one of the development directions of the existing large-scale energy storage technology and is generally regarded by all countries.
Graphene has excellent electrical properties. The characteristics of high chemical stability, large specific surface area and the like of the composite material cause wide attention of scientists. Particularly, the three-dimensional structure of the composite material has more attractive properties such as low apparent density, more complete continuous three-dimensional conductive network and porous structure with developed pores. Although the three-dimensional material has many advantages, the first cycle coulomb efficiency of the material is very low, so the industry can further improve the cycle efficiency of the three-dimensional graphene by means of doping, surface modification, compounding and the like, and fully exert the advantages of the three-dimensional graphene in the aspect of sodium storage performance. Antimony sulfide is used as a photoelectronic material and can be used in the fields of solar cells, photocatalysis, photochemistry and the like. In the existing research, the application of antimony sulfide materials in the field of photocatalysis is reported more, but the research on other properties of antimony sulfide, especially electrochemical properties, is still in the primary stage. The ionic bond between Sb and S is weaker than the bond between Na and S, so Sb2S3The reaction with sodium is of good reversibility. Meanwhile, Sb2S3 The antimony trisulfide has higher theoretical capacity and abundant resources. However, as an energy storage material, Sb2S3Still has the defects of poor conductivity, poor stability and the like. The graphene can be compounded for improving the conductivity and the cycling stability of the material, and the graphene with a three-dimensional structure with excellent conductivity becomes the first choice of the composite material.
Sb prepared by existing synthesis method2S3Most of the graphene particles are tubular, have large volume and cannot be completely attached to the surface of graphene. So that the recombination rate is not high and the electrochemical performance is not stable. Therefore, the problem to be solved in the industry is how to overcome the defects of poor recombination rate and unstable electrochemical performance of the existing antimony sulfide and graphene composite material.
Disclosure of Invention
The invention provides a preparation method of an antimony sulfide and graphene composite material, aiming at solving the problems of low recombination rate and unstable electrochemical performance of the existing antimony sulfide and graphene composite material.
The invention provides a preparation method of an antimony sulfide/graphene composite micro-nano material, which comprises the following steps:
step 1: weighing raw materials of graphene oxide dispersion liquid, antimony potassium tartrate, thioacetamide and absolute ethyl alcohol according to the formula proportion of the antimony sulfide/graphene composite micro-nano material;
step 2: mixing the graphene oxide dispersion liquid, antimony potassium tartrate and thioacetamide, and completely dissolving solids in the raw materials to obtain a dissolved solution;
and step 3: dropwise adding the absolute ethyl alcohol into the solution, and magnetically stirring for 5 hours to obtain a mixed solution;
and 4, step 4: pouring the mixed solution into a reaction kettle, adjusting the temperature to 120 ℃, and continuously heating for reaction for 12 hours or 18 hours;
and 5: after the reaction is finished, cooling to normal temperature, taking out the materials in the reaction kettle, and alternately cleaning the materials with pure water and absolute ethyl alcohol for at least six times;
step 6: and (3) centrifugally separating the cleaned material, and drying at 60 ℃ for 12 hours to obtain the antimony sulfide/graphene composite micro-nano material.
Preferably, the concentration of the graphene oxide dispersion is 0.5 mg/mL.
Preferably, the antimony sulfide/graphene composite micro-nano material is prepared from the following raw materials in parts by weight:
graphene oxide dispersion liquid: antimony potassium tartrate: thioacetamide: absolute ethanol = 2: 65: 15: 80.
preferably, the preparation steps of the graphene oxide dispersion liquid are as follows:
1. measuring concentrated sulfuric acid, sequentially adding graphite powder, potassium thiosulfate and phosphorus pentoxide, and heating in water bath at 80 ℃ for 6 hours to obtain a solution;
2. adding the solution into a container filled with pure water, centrifugally dewatering, and drying the obtained substance at 60 ℃;
3. adding the dried substance into a container containing another concentrated sulfuric acid, continuously stirring, then adding potassium permanganate, and stirring for 2 hours at 35 ℃; slowly adding pure water for two times when the solution turns into dark green, and continuously stirring for 2 hours; adding pure water and hydrogen peroxide for three times, and continuously stirring until the solution turns into earthy yellow;
4. the external solution turned to earthy yellow was centrifuged, washed with 1.5% hydrochloric acid and pure water, respectively, until the pH reached approximately 7. Drying the cleaned substance at 60 ℃ to obtain solid graphene oxide;
5. preparing the graphene oxide dispersion liquid with different concentrations according to requirements.
Preferably, 15ml of the concentrated sulfuric acid and 115ml of the other concentrated sulfuric acid in the step 3 of preparing the graphene oxide dispersion liquid are used.
Preferably, the pure water is deionized water, the pure water contained in the graphene oxide dispersion liquid in the step 2 is 2L, the pure water added in the step 3 for the second time is 250ml, and the pure water added in the third time is 700 ml; the hydrogen peroxide is 10 ml.
Compared with the prior art, the invention has the following beneficial effects:
in an XRD (X-ray diffraction) pattern of the antimony sulfide/graphene composite micro-nano material prepared by the invention, the peak value diffracted by the material is basically corresponding to the peak value on an XRD standard card, and is a clear diffraction peak which belongs to other impurities and is not detected, so that Sb is shown2S3The structure is well maintained in the composite. In addition, GO (graphene oxide) or graphite has no diffraction peak, indicating Sb2S3Decoration on graphene sheets disrupts the ordered stacking of graphite sheets, and non-uniformity in graphene layer spacing leads to disappearance of graphite or GO diffraction. From FIG. 1, it can be seen that graphene exhibits a flexible veil-like appearance with good transparency and wrinkles, indicating that graphene is well reduced, Sb being about 100 nm in size2S3Nano particleThe seed is coated in the yarn layer of the graphene, and the excellent recombination rate of antimony sulfide and the graphene is shown, so that the electrochemical performance of the antimony sulfide/graphene composite micro-nano material is stable.
Drawings
FIG. 1 is a scanning electron microscope image of an antimony sulfide/graphene composite micro-nano material of the invention;
FIG. 2 is an XRD (X-ray diffraction) pattern of an antimony sulfide/graphene composite micro-nano material in the embodiment of the invention;
FIG. 3 is a charge-discharge curve diagram of an antimony sulfide/graphene composite micro-nano material according to an embodiment of the invention;
FIGS. 4a to 4d are SEM images of antimony sulfide/graphene composite micro/nano materials prepared from graphene oxide with different concentrations;
5 a-5 d are SEM images of antimony sulfide/graphene composite micro/nano materials prepared under different reaction times respectively;
FIGS. 6a to 6d are SEM images and XRD images of antimony sulfide/graphene composite micro-nano materials obtained at different reaction temperatures.
Detailed Description
The invention is further illustrated by the following figures and examples:
the invention provides a preparation method of an antimony sulfide/graphene composite micro-nano material, which comprises the following steps:
step 1: and weighing raw materials of graphene oxide dispersion liquid, antimony potassium tartrate, thioacetamide and absolute ethyl alcohol according to the formula proportion of the antimony sulfide/graphene composite micro-nano material. The composite micro-nano material is prepared from the following raw materials in parts by weight: graphene oxide dispersion liquid: antimony potassium tartrate: thioacetamide: absolute ethanol = 2: 65: 15: 80.
Wherein the concentration of the graphene oxide dispersion liquid is 0.5 mg/mL.
The weight ratio of the selected raw materials in the embodiment is as follows: 0.4 kg of graphene oxide dispersion, 13 kg of antimony potassium tartrate, 3 kg of thioacetamide and 16 kg of absolute ethyl alcohol.
Step 2: and mixing the weighed graphene oxide dispersion liquid, antimony potassium tartrate and thioacetamide, and completely dissolving the solids in the raw materials by using ultrasonic waves to obtain a dissolved solution.
And step 3: and adding weighed absolute ethyl alcohol into the dissolved solution, and stirring for 5 hours in a magnetic stirrer to obtain a mixed solution.
And 4, step 4: pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, adjusting the temperature to 120 ℃, and continuously carrying out heat preservation reaction for 12 to 18 hours.
And 5: and after the reaction is finished, placing the reaction kettle in a ventilation place for cooling at room temperature, opening the reaction kettle after the reaction kettle is at normal temperature, pouring out supernatant in the reaction kettle, taking out materials in the reaction kettle, and alternately cleaning the materials by using high-purity water and absolute ethyl alcohol for at least six times.
Step 6: and centrifugally separating the cleaned material, putting the material into a container, then sending the container into a blast drying oven, and drying the material at the temperature of 60 ℃ for 12 hours to obtain the dark red powdery antimony sulfide/graphene composite micro-nano material.
The graphene oxide used in the present invention may be prepared by a modified Hummers method, for example, the following steps may be adopted:
1. 15ml of concentrated sulfuric acid is measured and added into a 50ml flask, graphite powder, potassium thiosulfate and phosphorus pentoxide are sequentially added in the stirring process, and the mixture is heated in a water bath at 80 ℃ for 6 hours.
2. 500ml of high purity water was measured out of a 2-liter beaker, and the above solution was slowly added to the beaker with continuous stirring. After centrifugation, the resulting material was placed in a petri dish, placed in an air-forced drying oven, and dried at 60 ℃.
3. Taking a 2L beaker, measuring 115ml of concentrated sulfuric acid (adding for the second time), adding the dried sample into the beaker, continuously stirring, immediately adding potassium permanganate, and stirring for 2 hours at 35 ℃. The solution turned into a dark green color. 250ml of high purity water was slowly added to the beaker and stirring was continued for 2 h. 700ml of high purity water and 10ml of hydrogen peroxide were further added thereto with continuous stirring. The solution turned to a yellow-earth color.
The liquid obtained above was centrifuged, washed with 1.5% hydrochloric acid and high purity water, respectively, and washed until pH was about 7. And (3) placing the sample in a forced air drying oven, and drying at 60 ℃ to obtain solid graphene oxide.
4. Preparing the graphene oxide dispersion liquid with different concentrations according to requirements.
The invention can also select and adjust the weight of the raw materials according to the requirement of industrial yield. According to the preparation method, a hydrothermal method is adopted to prepare the antimony sulfide/graphene composite micro-nano material, and a large number of different technical schemes are tried out through long-time continuous exploration and analysis, so that the use of absolute ethyl alcohol, the concentration of the graphene oxide dispersion liquid, the reaction time and the reaction temperature are comprehensively coordinated and controlled, and the composite rate of the composite material is fundamentally influenced.
Regarding the effect of the concentration of the graphene oxide dispersion on the composite material:
the weight ratio of potassium tartrate antimonate to thioacetamide is 13: and 3, heating the graphene oxide at 120 ℃ for 12 hours by a hydrothermal method. The concentration of graphene oxide was adjusted to 0mg/mL (pure antimony sulfide), 0.5mg/mL, 1mg/mL, 2 mg/mL. SEM images of the composite materials prepared by the graphene oxide with different concentrations are measured, and are shown in FIGS. 4a to 4 d: FIG. 4 a-is pure antimony sulfide; FIG. 4 b-is graphene oxide at 0.5 mg/mL; FIG. 4 c-is 1mg/mL graphene oxide; FIG. 4 d-is 2mg/mL graphene oxide.
In fig. 4a, it can be seen from the SEM image of the sample that in the system without graphene addition, i.e. antimony sulfide exists in a spherical shape with a diameter of about several hundred nanometers.
In fig. 4b, after 0.5mg/mL of graphene oxide is added to the system, it can be seen that the graphene presents a flexible thin veil-like appearance with good transparency and wrinkles, which indicates that the graphene is well reduced, and Sb2S3 nanoparticles with a size of about 100 nm are coated in the veil layer of the graphene, which indicates that the sample antimony sulfide and graphene are well compounded. In addition to the success of sample compounding, it can be seen from fig. 4b that the addition of graphene reduces the size of antimony sulfide in the system from hundreds of nanometers to about 100 nanometers, which is more beneficial to the electrochemical performance.
In fig. 4c, after 1mg/mL of graphene oxide is added to the system, it can be seen that the graphite still has good transparency and a wrinkled flexible veil-like appearance, which indicates that the graphene is well reduced, but the presence of antimony sulfide is not obvious and only has a partial shadow, which indicates that the composite effect of the material is general.
In fig. 4d, after 2mg/mL of graphene oxide is added into the system, it can be seen that although graphite has good transparency and a wrinkled flexible veil-like appearance, an agglomeration phenomenon occurs, graphene is well reduced, but the presence of antimony sulfide is not obvious, which indicates that the composite effect of the material is particularly poor.
Through the analysis of the figure, when the graphene in the system is 0.5mg/mL, the obtained antimony sulfide/graphene composite micro-nano material has a good appearance.
Regarding the effect of the reaction time on the composite:
the weight ratio of potassium tartrate antimonate to thioacetamide is 13: 3, adding 0.5mg/mL graphene oxide, and heating at 120 ℃ by a hydrothermal method. Adjusting the reaction time to 6h, 12h, 18h and 24h, and measuring SEM images of the composite materials prepared under different reaction times, as shown in FIGS. 5 a-5 d: FIG. 5 a-5 h of the composite; FIG. 5 b-12 h of composite material; FIG. 5 c-18 h composite; FIG. 5 d-is the composite for 24 h.
In fig. 5a only a small portion of the graphene has a flexible veil-like appearance with good transparency and wrinkles, mostly clustered together, first indicating that the graphene oxide is not well reduced, and second it can be observed that antimony sulfide is present on the surface of the graphene in the size of a few hundred nanometers in diameter, and the amount of antimony sulfide sample is very small, which sample has not been compounded successfully.
In fig. 5b, the graphene has good transparency and a wrinkled flexible veil-like appearance, and Sb2S3 nanoparticles with a size of about 100 nm are wrapped in a veil layer of graphene, indicating that this sample is well compounded with antimony sulfide and graphene.
In fig. 5c, the graphene has a good transparent appearance and is in a sheet shape, which still indicates that the graphene oxide is well reduced, and the Sb2S3 nanoparticles with the size of about 100 nm are wrapped in the yarn layer of the graphene and are uniformly compounded, which indicates that the sample is well compounded by antimony sulfide and graphene.
In FIG. 5d the graphene has a good transparent appearance, being thinThe flaky graphene is stacked together to form a layer, which shows that the graphene oxide is well reduced, and the size of Sb is about 100 nm2S3The nano particles are coated in the sheet layer of the graphene, most of the nano particles are uniformly compounded, and antimony sulfide at a few positions can be stacked together with the graphene. The sample is not ideal sample because the antimony sulfide and the graphene are compounded.
As shown by the picture and experimental analysis, the antimony sulfide/graphene composite micro-nano material is compounded within the range of 12h to 18h at the selected time, so that the effect is good.
Regarding the effect of the reaction temperature on the composite:
the weight ratio of potassium tartrate antimonate to thioacetamide is 13: 3, adding 0.5mg/mL graphene oxide, and heating for 12 hours under a hydrothermal method. The heating temperature was adjusted to 120 deg.C, 160 deg.C, 200 deg.C. And measuring SEM images and XRD images of the antimony sulfide/graphene composite micro-nano material obtained at different reaction temperatures. As shown in FIGS. 6 a-6 d: FIG. 6 a-composite at 120 ℃; FIG. 6 b-composite at 160 ℃ 1; FIG. 6 c-composite at 200 ℃ 1; figure 6 d-XRD pattern of composite material.
As can be seen from fig. 6d, in the XRD spectrum of the antimony sulfide/graphene composite micro-nano material, the peaks diffracted by the material itself substantially correspond to the peaks on the card, and are all clear diffraction peaks that are not detected to belong to other impurities, which indicates that the Sb2S3 structure is well maintained in the composite material. In addition, GO or graphite has no diffraction peaks, indicating Sb2S3Decoration on graphene sheets disrupts the ordered stacking of graphite sheets, and non-uniformity in graphene layer spacing leads to disappearance of graphite or GO diffraction.
From FIG. 6a it can be seen that graphene exhibits a flexible veil-like appearance with good transparency and wrinkles, indicating that graphene is well reduced, Sb being about 100 nm in size2S3The nanoparticles are coated in the graphene gauze layer, which shows that the sample antimony sulfide and graphene are well compounded.
From fig. 6b it can be seen that graphene exhibits a sheet-like appearance with good transparency and wrinkles, indicating that graphene is well reduced. However, antimony sulfide in this case is in the form of a tube having a large morphology, and the diameter of the tube is about one micron, but the length is about 10 microns, which is not in accordance with the small morphology desired for the problem. And most of antimony sulfide is exposed outside the graphene and is not well coated, so that the sample is not ideal in compounding.
From fig. 6c the following information can be obtained: graphene exhibits good transparency and a flaky appearance, and although a small number of sites are stacked, it can be said that graphene is well reduced. However, antimony sulfide in this case is in the form of a tube or a flower, and has a large morphology, the diameter of the tube is about one micron, but the length is about 10 microns, and the volume of the flower is somewhat larger, both of which are not in accordance with the small morphology desired for the subject. In addition, most of antimony sulfide is exposed outside the graphene and is not well coated, so that the sample is not ideal in compounding.
According to the above situation, the reference temperature of the antimony sulfide/graphene composite micro-nano material at 120 ℃ is preferably selected.
The traditional antimony sulfide preparation method comprises the following steps: hydrochloric acid, acetic acid, urea, PVP, EDTA, CTBA, DTBA and the like are used as surfactants to prepare the appearance which is smooth in surface and is similar to a nano tube and the like. For example, acetic acid as a surfactant at pH<7, the double spear shape Sb can be obtained2S3. Namely, most of the antimony sulfide prepared by the traditional method is in the shapes of nanotubes, nanobeams, double spears or nanobelts and the like. This nearly nanotube-shaped Sb2S3And the graphene has large volume and cannot be completely attached to the surface of graphene, so that the compounding rate of the graphene and the graphene is not high, and the electrochemical performance is unstable. In order to overcome the defects of the existing composite material, through consulting a large number of documents, continuous analysis and research and repeated tests, the fact that absolute ethyl alcohol exists as an organic solvent in a solvothermal method and an organic solvothermal reaction is carried out in an anhydrous system is found, hydrolysis and oxidation of a precursor and a product can be effectively eliminated, and a crystal material with perfect crystal form and regular orientation can be prepared more easily. Further research shows that Sb2S3Having a layered structure, in the c-axisThe growth is fastest and at its low concentration, the crystallization rate of the product is slow. When absolute ethanol is added, Sb2S3The Sb shrinks from the original tubular hollow structure and develops to a solid state, and after the reaction temperature and the reaction time are strictly and optimally controlled, the Sb2S3The large-sheet microspherical structure distribution appears, and the large-sheet microspherical structure distribution can be completely attached to the surface of graphene, so that the recombination rate of the large-sheet microspherical structure distribution and the graphene is greatly improved, as shown in figure 1. Through further research and observation, Sb is enabled to be2S3The graphene is effectively converted into a large-sheet microspherical structure distribution from an original tubular hollow structure, can be completely attached to the surface of graphene, and plays a main role because absolute ethyl alcohol is used as an organic solvent. Therefore, the invention successfully prepares the antimony sulfide/graphene composite micro-nano material with high recombination rate and regular appearance by using the anhydrous ethanol which is taken as the surfactant in the traditional method as the organic solvent of the hydrothermal method. Furthermore, anhydrous ethanol is preferred because it is inexpensive and non-toxic.
Therefore, the invention synthesizes the graphene oxide by using an improved Hummers method, takes the graphene oxide dispersion liquid, potassium tartrate antimonate, thioacetamide and absolute ethyl alcohol as raw materials, and adopts a simple hydrothermal method to prepare the antimony sulfide/graphene composite micro-nano material. The key technology of the invention is to take absolute ethyl alcohol as an organic solvent to participate in the reaction, strictly control the reaction temperature to be 120 ℃ and the reaction time to be 12 hours or 18 hours, and select the optimal concentration of the graphene oxide dispersion liquid to be 0.5mg/L, thereby preparing the antimony sulfide/graphene composite micro/nano material.
The composite nano material prepared by the invention is sampled and detected. XRD is used to characterize the composition and phase of the sample; the SEM is used for characterizing the appearance and the size of the prepared material; the properties were measured electrochemically.
1. XRD analytical test
The crystal structure of the sample was characterized by an automatic X-ray diffractometer (RigakuD/max 200PC, Shimadzu, Japan). Crystals in the sample can be used as an X-ray grating, and coherent scattering by these numerous particles (atoms, ions or molecules) can interfere with the light, thereby increasing or decreasing the intensity of the scattered X-rays. Due to superposition of a large number of scattered waves of the particles, the maximum intensity of the light beam generated by mutual interference becomes a diffraction line of the X-ray. Each crystal has its own diffraction peak. The composition of the crystals can be effectively analyzed by comparing the measured diffraction peaks with a standard powder demonstration card.
The detection setting parameters are as follows: the Cu-Kalpha radiation has the wavelength of 1.5406, the target current and the target voltage are 40mA and 40kV, the scanning range is set to be 10-80 degrees, and the scanning speed is 7 degrees/min.
The sample was examined to obtain an XRD pattern as shown in fig. 2. In the spectrum of XRD, the peak value diffracted by the material per se of the antimony sulfide/graphene composite micro-nano material is basically corresponding to the peak value on a standard powder demonstration card, and is a clear diffraction peak which belongs to other impurities and is not detected, which shows that Sb2S3The structure is well maintained in the composite.
2. SEM analysis test
The morphology of the samples was characterized using a field emission scanning electron microscope (SEM, JSM-7500F). Scanning electron microscopes use a focused, very fine, high-energy electron beam to scan a sample, where the electron beam interacts with the sample to produce various information (e.g., photoelectric signals). The signal randomly emitted from the surface of the sample corresponds to the corresponding bright spots on the fluorescent screen of the kinescope one by one, and the bright spots are combined one by one to form an image so as to convert the surface characteristics of the sample into image signals, so that the image of the sample can be clearly observed, and a series of microscopic information such as the appearance, the size and the like of the sample can be obtained. Testing parameters: the scanning voltage was 15kV, 30 kV.
The sample was examined to obtain an SEM image, as shown in FIG. 1. It can be seen that graphene exhibits a flexible veil-like appearance with good transparency and wrinkles, indicating that graphene is well reduced, with Sb about 100 nm in size2S3The nanoparticles are coated in the graphene gauze layer, which shows that the sample antimony sulfide and graphene are well compounded.
3. Electrochemical assay test
And respectively preparing the antimony sulfide micro-nano material to be detected and the antimony sulfide/graphene composite micro-nano material into a sodium ion battery cathode for research. Under the dry condition, mixing materials (an antimony sulfide micro-nano material to be detected and an antimony sulfide/graphene composite micro-nano material) in mass ratio: acetylene black: polyvinylidene fluoride = 8: 1: 1, placing the mixture in an agate mortar, grinding the mixture until the mixture is uniformly mixed, dropwise adding a certain amount of N-methyl pyrrolidone, and forming the powdery substance into black mud. The dried copper foil was made into a round shape and weighed, and the material was coated on the weighed copper foil. And drying the coated electrode slice at the shady position at normal temperature for 24 hours. Transferring the electrode plate into a glove operation box filled with argon atmosphere, taking a metal sodium sheet as a counter electrode, successfully assembling the battery, and standing for 12 hours after passing through a plate pressing sealing machine. And carrying out corresponding electrochemical tests on the prepared button cell. And (3) testing the constant current circulation stability of the assembled battery:
from the analysis of FIG. 3 it can be found that: the first charge-discharge specific capacity of the pure antimony sulfide micro-nano material is 525mAhg < -1 >, and the first charge-discharge specific capacity of the antimony sulfide/graphene composite micro-nano material is about 665mAhg < -1 >; the pure antimony sulfide material has a great change in specific capacity after being charged and discharged for 20 circles compared with 10 circles, the specific capacity of the composite material still has a little difference with that of the composite material after being charged and discharged for about 10 circles, and the electrochemical performance of the antimony sulfide/graphene composite micro-nano material is proved by the comparison.
In the spectrum of XRD, the peaks diffracted by the material itself are basically corresponding to the peaks on the XRD standard card, and are all clear diffraction peaks which are not detected and belong to other impurities, which indicates that Sb is Sb2S3The structure is well maintained in the composite. In addition, GO (graphene oxide) or graphite has no diffraction peak, indicating Sb2S3Decoration on graphene sheets disrupts the ordered stacking of graphite sheets, and non-uniformity in graphene layer spacing leads to disappearance of graphite or GO diffraction. It can be seen from FIG. 1 that
According to the antimony sulfide/graphene composite micro-nano material prepared by the invention, graphene presents a flexible thin veil-like appearance with good transparency and folds, and shows that the graphene is well reduced, and Sb with the size of about 100 nm is provided2S3Nano particle quiltThe coating is coated in the yarn layer of the graphene, and the excellent recombination rate of antimony sulfide and the graphene is shown, so that the electrochemical performance of the antimony sulfide/graphene composite micro-nano material is stable.
While the present invention has been described in detail with reference to the embodiments, those skilled in the art may make various changes or modifications to the embodiments, and such changes and modifications should fall within the scope of the present invention.
Claims (6)
1. A preparation method of an antimony sulfide/graphene composite micro-nano material comprises the following steps:
step 1: weighing raw materials of graphene oxide dispersion liquid, antimony potassium tartrate, thioacetamide and absolute ethyl alcohol according to the formula proportion of the antimony sulfide/graphene composite micro-nano material;
step 2: mixing the graphene oxide dispersion liquid, antimony potassium tartrate and thioacetamide, and completely dissolving solids in the raw materials to obtain a dissolved solution;
and step 3: dropwise adding the absolute ethyl alcohol into the solution, and magnetically stirring for 5 hours to obtain a mixed solution;
and 4, step 4: pouring the mixed solution into a reaction kettle, adjusting the temperature to 120 ℃, and continuously heating for reaction for 12 hours or 18 hours;
and 5: after the reaction is finished, cooling to normal temperature, taking out the materials in the reaction kettle, and alternately cleaning the materials with pure water and absolute ethyl alcohol for at least six times;
step 6: and (3) centrifugally separating the cleaned material, and drying at 60 ℃ for 12 hours to obtain the antimony sulfide/graphene composite micro-nano material.
2. The method of claim 1, wherein the graphene oxide dispersion is at a concentration of 0.5 mg/mL.
3. The preparation method of claim 1, wherein the antimony sulfide/graphene composite micro-nano material is prepared from the following raw materials in parts by weight:
graphene oxide dispersion liquid: antimony potassium tartrate: thioacetamide: absolute ethanol = 2: 65: 15: 80.
4. the production method according to any one of claims 1 to 3, wherein the graphene oxide dispersion liquid is produced by the following steps:
step 1, measuring concentrated sulfuric acid, sequentially adding graphite powder, potassium thiosulfate and phosphorus pentoxide into the concentrated sulfuric acid, and heating the mixture in water bath at 80 ℃ for 6 hours to obtain a solution;
step 2, adding the solution into a container filled with pure water, centrifugally dewatering, and drying the obtained substance at 60 ℃;
step 3, adding the dried substance into a container containing another concentrated sulfuric acid, continuously stirring, then adding potassium permanganate, and stirring for 2 hours at 35 ℃; slowly adding pure water for two times when the solution turns into dark green, and continuously stirring for 2 hours; adding pure water and hydrogen peroxide for three times, and continuously stirring until the solution turns into earthy yellow;
step 4, centrifuging the external solution which is changed into earthy yellow, respectively washing with 1.5% hydrochloric acid and pure water until the pH value is approximately equal to 7;
drying the cleaned substance at 60 ℃ to obtain solid graphene oxide;
and 5, preparing the graphene oxide dispersion liquid with different concentrations according to the requirement.
5. The method according to claim 4, wherein the concentrated sulfuric acid is 15ml, and the other concentrated sulfuric acid in the step 3 is 115 ml.
6. The method according to claim 4, wherein the pure water is deionized water, the amount of pure water contained in step 2 is 2L, the amount of pure water added in step 3 twice is 250ml, and the amount of pure water added in three times is 700 ml; the hydrogen peroxide is 10 ml.
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