CN112490018B - Composite material based on silicon dioxide metal sulfide and preparation method and application thereof - Google Patents

Composite material based on silicon dioxide metal sulfide and preparation method and application thereof Download PDF

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CN112490018B
CN112490018B CN202011425106.8A CN202011425106A CN112490018B CN 112490018 B CN112490018 B CN 112490018B CN 202011425106 A CN202011425106 A CN 202011425106A CN 112490018 B CN112490018 B CN 112490018B
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silicon dioxide
composite material
metal sulfide
silica
reaction
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CN112490018A (en
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向翠丽
徐洁
邹勇进
杨学英
方淞文
黄涛
王顺香
陈同祥
李天硕
徐芬
孙立贤
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Guilin University of Electronic Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a silicon dioxide-based metal sulfide composite material, which adopts a two-step hydrothermal method to grow a nanometer flower-shaped structure of manganese disulfide and cobalt disulfide on the outer surface of template silicon dioxide, and simultaneously, through a vulcanization reaction, silicon dioxide is etched by hydroxyl, so that a part of silicon dioxide is released from the hydrolysis of sulfide ions, a certain hole is etched on an inner silicon dioxide template, and the silicon dioxide-based layered nanometer metal sulfide composite material can be prepared by facilitating ion migration. The preparation method comprises the following steps: 1, preparing a composite metal oxide precursor; 2 preparation of silica-based metal sulfide composites. The electrode material of the super capacitor is applied to charge/discharge in the range of 0-0.55V, and the specific capacitance is 1150-1160F/g when the discharge current density is 1A/g. Has excellent material stability and excellent ion transmission capacity.

Description

Composite material based on silicon dioxide metal sulfide and preparation method and application thereof
Technical Field
The invention relates to the technical field of supercapacitors, in particular to a preparation method of a composite material based on silicon dioxide metal sulfide and application of the composite material in the field of supercapacitors.
Background
With the increase of economy, the demand of people for energy is also rapidly increasing. Although humans can obtain demand from traditional fossil energy sources, they inevitably contribute to greenhouse effect and pollution. In the past decades, renewable energy sources such as wind energy, solar energy, tidal energy and the like have been developed vigorously and are considered as effective ways to solve energy crisis. However, these energy sources need to be stored in efficient devices, such as lithium ion batteries or supercapacitors. Currently, supercapacitors are at the forefront of this research in various energy storage devices. As one of the representative modern energy storage devices, supercapacitors are a research hotspot in the field of energy storage due to their required power density, high safety, long life, etc.
The performance of supercapacitors depends to a large extent on the electrode material. Therefore, there is an urgent need to develop new electrode materials and structures with advanced pseudocapacitive properties. In general, transition metal oxides (e.g., MnO) due to rapid reversible redox reactions, high flexibility, low cost and low toxicity2，NiO，MoO3And NiCo2O4) Is the most widely used electrode material for preparing pseudo-capacitance with excellent pseudo-capacitance performance. Recently, studies have also found transition metal sulfides (e.g., NiS) as compared to transition metal oxides2，CoS，NiCo2S4And MoS2) Has smaller band gap and higher conductivity. Therefore, pseudocapacitive electrodes prepared using these transition metal sulfides exhibit higher pseudocapacitive performance and have been successfully assembled in supercapacitors. Although pseudocapacitance performance of pseudocapacitors has been improved by using transition metal sulfides as electrode materials, further applications of these materials are limited by their volume change during charge/discharge, resulting in low power capacity and poor cycle stability.
Aiming at the problem of low power capacity, the electrochemical performance of the pseudo capacitor is improved by using the higher pseudo capacitance performance of the transition metal sulfide from the electrode material. In the prior art, Pujari et al used hydrothermal method to sulfurize manganese carbonate microparticles and successfully transform them into manganese disulfide nanoparticles (Controlled sulfonation of MnCO)3microcubes architectured MnS2 nanoparticles with 1.7 fold capacitance increment for high energy density supercapacitor》[J]Electrochimica Acta 301 (2019) 366-. However, the specific capacitance of the obtained material only reaches 713F/g. According to the experimental data analysis recorded in the literature, the inventor discovers that the reason that the specific capacitance of the material obtained by the technical scheme is low, from the surface phenomenon, the manganese carbonate growing on the stainless steel can be simply vulcanized into manganese disulfide, and the performance advantage of the material cannot be fully exerted by the vulcanization of the single metal oxide; from deep analysis, the aggregation phenomenon of manganese disulfide growing on the flexible stainless steel is obvious, the structure and the pore size distribution are not uniform, and the existence of the phenomenon influences the transmission of electrons and ions, so that the conductivity of the material is reduced.
Next, starting from the material structure, efforts are made to adjust the structure of the electrode material to improve the performance of the supercapacitor. The porous nanomaterial has special structural characteristics such as large specific surface area, low density, short ion/electron transfer path, controllable size, internal structure, element composition and the like, and has excellent application in a plurality of fields such as catalysts, chemical sensors, biomedicine, new energy sources and the like.
The combination of the silica template and the metal oxide avoids the aggregation of the metal oxide, which not only improves the conductivity of the electrode, but also enhances the electrochemical performance, and can improve the problems to a certain extent. For example, in the prior art, Wang et al synthesized porous hollow spherical nano-structured metal silicate (manganese silicate, cobalt silicate, nickel silicate) by hydrothermal method using silica spheres as templates, a porous electronic material for a flexible inorganic-state electrochemical metal super-capacitor [ J ] Chemical Engineering Journal, 2019, 362: 818 829 ], excellent electrochemical properties were mainly based on the large surface area of metal silicate, and the porous hollow spherical structure facilitated rapid electrolyte ion and electron transport. Cobalt silicate showed a capacitance of 452.8F/g at a current density of 0.5A/g, and 89% of the initial capacitance was maintained after 10000 electrochemical cycles. Manganese silicate exhibits a capacitance of 517F/g at a current density of 0.5A/g, but after 3600 electrochemical cycles it can only retain 34% of the initial capacitance, and the decrease in specific capacitance may be due to expansion and contraction of the crystal structure, which leads to destruction of the hollow sphere structure and the minute lamellar/bubble-like structure, resulting in a decrease in charge storage capacity of manganese silicate during charging. Therefore, this document expects to assemble a high capacity performance, flexible asymmetric solid state supercapacitor by using manganese silicate as the positive electrode and activated carbon as the negative electrode material in a polyvinyl alcohol-potassium hydroxide gel electrolyte to improve the stability of the material, but the result obtained is that the combined device shows a capacity retention of 32% after 900 electrochemical cycles. This unsatisfactory cycle stability is due to the decrease in the conductivity of the manganese silicate during long charge/discharge, resulting in the decomposition of the manganese silicate.
The technique still has the following two problems: after the silicon dioxide template agent is introduced, the structure of the formed porous hollow sphere is easy to break; in an attempt to solve the problem of the cycling stability of the electrode material, the specific capacitance performance and the electrochemical stability are still not well considered, and the application value of the electrode material is seriously influenced.
In order to solve the problems of electrochemical stability and electrochemical performance of the metal sulfide, the comprehensive performance of the material can be obviously improved by utilizing the synergistic effect of the binary composite material. Binary metal sulfides have received much attention as having higher electrochemical capacitance than single metal sulfides due to their high electrochemical redox potential and excellent electronic conductivity, tendency to form various nanostructures, and higher electrically active surface area. For this purpose, Wu et al (High energy dense asymmetry supercapacitors from mesoporous NiCo)2S4 nanosheets》[J]Electrochimica Acta 2015 174: 238-2S4The specific capacitance of 744F/g is obtained under the current density of 1A/g, and after 1500 cycles, the capacitance retention rate is still 93.4%. The inventor analyzes and finds that the metal is seen from the microscopic morphology in the documentThe agglomeration phenomenon of sulfide is serious, which seriously influences the transmission of electrons and limits the improvement of electrochemical performance.
Therefore, when the transition metal sulfide is used as the electrode material of the supercapacitor, the technical problem to be solved is to select a suitable template material, and the structure of the transition metal sulfide is not easy to collapse as the electrode material of the supercapacitor, and when the transition metal sulfide is used for solving the problem, the following three aspects can be considered:
1. selecting silicon dioxide sol with a stable structure as a template agent;
2. the characteristics of the surface of the silica sol with negative electricity are utilized, and metal ions are adsorbed by static electricity and are uniformly distributed;
3. and the metal manganese salt with higher theoretical specific capacitance and the metal cobalt salt with better stability are selected and matched with the strategy of the inner-layer template silicon dioxide, and the synergistic effect between the metal manganese salt and the metal cobalt salt is explored.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon dioxide-based metal sulfide composite material and application of the silicon dioxide-based metal sulfide composite material in the field of supercapacitors.
According to the work of the applicant and the research and analysis of the above technical solutions, the following conclusions can be drawn: at present, the composition of metal sulfide and silicon dioxide materials still cannot realize the synchronous improvement of material performance and cycle stability, and the factor directly influences the comprehensive performance of the materials.
Among them, the applicant has noticed that the use of relatively stable silica sol and the control of the amount of silica used have a significant impact on the morphology and performance of the metal sulfides:
the method comprises the steps that a hydrothermal method is adopted to generate metal sulfide with silicon dioxide as a template, manganese disulfide and cobalt disulfide which are formed after vulcanization are of nanoscale irregular sheet structures, other methods are used for coating the template agent thickly, the stacking phenomenon is heavier, and a thicker coating layer can be formed on the surface of the template agent;
in the preparation process, the use of the template-free agent can cause the agglomeration phenomenon of the metal material, thereby influencing the electron transmission.
The applicant adopts a scheme of combining the relative dosage of different silicon dioxide templates to realize the shape control of the metal sulfide, and firstly, the ratio of the quantity of substances is 2:1:2, hydrothermally treating the silica sol, manganese sulfate and cobalt nitrate at 120 ℃ to form a spherical compound precursor, and then vulcanizing the formed spherical compound precursor at the hydrothermal temperature of 160 ℃ by taking sodium sulfide as a sulfur source to form the uneven lamellar manganese disulfide and cobalt disulfide nanosphere composite material. The binary metal sulfide grows on the template agent silicon dioxide, so that more active sites can be created for the electrolyte to contact the electrode material, and the electrochemical performance of the electrode material is improved by utilizing the synergistic effect of different components. Due to the existence of the template agent silicon dioxide, the stacking of metal sulfides can be effectively avoided, so that the electrolyte can be favorably transmitted to the interior of the electrode material, and ideal electrochemical performance can be obtained.
By adopting the preparation method, the metal sulfides with different shapes can be obtained, the hierarchical structure is established, and more active sites are created.
In addition to the influence of the relative dosage of the template agent silicon dioxide on the material morphology, in an unsulfurized composite metal oxide precursor, the metal oxide is directly exposed in an electrolyte to carry out the rapid charge/discharge process, and the problems of structural degradation and low conductivity are solved.
Such as Yang et al (Template method to controllable synthesis 3D porous NiCo)2O4 with enhanced capacitance and stability for supercapacitors》[J]. Journal of Colloid &Interface, 2016, 468: 1-9.) successful in depositing nickel and cobalt metal ions on a negatively charged silica surface via electrostatic interaction, successfully synthesizing a controllable 3D porous NiCo with enhanced capacitance and stability2O4A composite material. The applicant finds through experiments that the technical scheme of guiding the growth of the metal sulfide by adopting the template agent silicon dioxide can firstly carry out self-polymerization reaction under mild conditions, adsorb free positively charged metal ions on the surface of the negatively charged silicon dioxide sol through electrostatic attraction of the sol and electrostatic interaction, and then carry out hydrothermal reaction in the first stepThen the oxide is vulcanized through a second step of hydrothermal reaction to generate the metal sulfide nano particles. The electrical conductivity, the pore structure and the electrochemical active sites of the material can be adjusted in the vulcanization process, and the introduced pseudocapacitance can play a role in improving the specific capacity.
In addition, the introduction of the silicon dioxide template can maintain the stable appearance of the metal sulfide in the charging/discharging process, maintain the appearance of the metal sulfide in the charging/discharging process for many times and realize the excellent electrochemical cycle performance of the electrode material.
Therefore, aiming at the technical problems in the prior art, the invention adopts the silica sol as the template agent, changes the preparation method and the reasonable structure design method, and realizes the following purposes:
1. in order to realize the shape regulation of the metal sulfide, the active substance is grown on the surface of the silicon dioxide by introducing a template agent, and the shape of the active substance can be regulated by controlling the relative dosage of the silicon dioxide template agent.
2. In order to realize the synergistic effect among different metal sulfides, the manganese disulfide particles with high quality and low price and the cobalt disulfide particles are combined together to generate a flaky nano structure, so that the permeation channel of an electrolyte in an electrode structure is increased to improve the electrochemical utilization rate.
3. In order to inhibit the structural degradation of the metal sulfide in the charging/discharging process and improve the conductivity of the composite material, the metal sulfide is supported by the silicon dioxide so as to maintain the shape of the metal sulfide in the charging/discharging process without being damaged. After vulcanization, the silicon dioxide template forms a certain hole structure, the appearance, the hole structure and the electrochemical active sites of the material can be adjusted by the existence of the silicon dioxide, and the introduced pseudocapacitance can play a role in improving the specific capacity.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a nano flower-shaped structure of manganese disulfide and cobalt disulfide grows on the outer surface of template silicon dioxide by adopting a two-step hydrothermal method, and meanwhile, through a vulcanization reaction, silicon dioxide is etched by hydroxyl, so that a part of silicon dioxide is released from the hydrolysis of sulfide ions, a certain hole is etched on an inner silicon dioxide template, and the silicon dioxide-based layered nano metal sulfide composite material can be prepared by ion migration conveniently.
The template agent silicon dioxide is used as a carrier of the composite material and plays a role in providing a supporting framework, a pore structure and an active site.
The manganese and cobalt metal sulfide coated on the outer surface of the silicon dioxide is used as a conductive layer, so that the conductivity of the composite material is improved, and the pseudo-capacitance effect is provided.
Growing a manganese disulfide and cobalt disulfide composite material by the two-step hydrothermal method, namely growing an oxide precursor of manganese and cobalt on the surface of silicon dioxide by the first-step hydrothermal method, and carrying out vulcanization treatment by using sodium sulfide to generate manganese disulfide and cobalt disulfide by the second-step hydrothermal method;
the template agent silica sol used in the first step of hydrothermal reaction is in a spherical structure, and the effect of providing pseudo-capacitance is achieved by performing rapid Faraday reaction on the surface and the interior of the silica; the manganese disulfide and cobalt disulfide compound generated by the hydrothermal reaction in the second step is in an irregular nano flaky structure, and is coated on the surface of silicon dioxide to perform a rapid Faraday reaction, so that a pseudo capacitor is provided.
A preparation method of a silicon dioxide-based metal sulfide composite material comprises the following steps:
step 1) preparation of a composite metal oxide precursor, firstly, dispersing silica sol in pure water under certain conditions to obtain a solution A, then, dissolving soluble manganese salt and soluble cobalt salt in ethanol and water together according to a certain mass ratio to obtain a solution B, then, dropwise adding the solution B into the solution A, after metal cations are fully adsorbed by silica colloid through electrostatic action, slowly adding urea under a certain mass ratio under stirring conditions, stirring for a certain time to obtain a mixed reaction solution, finally, carrying out a first hydrothermal reaction on the mixed reaction solution under certain conditions, washing and drying after the reaction is finished to obtain the composite metal oxide precursor, wherein the obtained material is marked as MCO;
and 2) preparing the composite material based on the silicon dioxide metal sulfide, dissolving the composite metal oxide precursor and the soluble sulfide obtained in the step 1 in water according to a certain mass ratio to prepare a solution C, then carrying out a second hydrothermal reaction under a certain condition, washing and drying after the reaction is finished to obtain the composite material based on the silicon dioxide metal sulfide, wherein the obtained material is marked as MCS 12.
The mass ratio of the raw materials of the silica sol, the manganese sulfate, the cobalt nitrate, the urea and the sodium sulfide is 2:1:2:6: 5.
The conditions of the hydrothermal methods in the steps 1 and 2 are different, specifically, the reaction temperature of the first hydrothermal reaction in the step 1 is 110-; the reaction temperature of the second hydrothermal reaction in the step 2 is 150-170 ℃, and the reaction time is 7-9 h.
The stirring time of the silicon dioxide sol dispersion liquid in the step 1 is 6-12 h; the stirring time of the composite metal oxide precursor in the step 1 is 0.5-1 h; the stirring time of the step 2 is 0.25-0.5 h.
An application of a composite material based on silicon dioxide metal sulfide as an electrode material of a super capacitor is characterized in that the composite material is charged/discharged within the range of 0-0.55V, and when the discharge current density is 1A/g, the specific capacitance is 1150-channel 1160F/g.
The beneficial technical effects of the silicon dioxide-based metal sulfide composite material obtained by the invention are detected as follows:
according to the silicon dioxide metal sulfide composite material, through scanning electron microscope tests, it can be seen that a sample after vulcanization still maintains a spherical structure of silicon dioxide, and an irregular nano flaky structure grows on the surface of the sample, and the nano sheets are considered as structures formed by growth of manganese disulfide and cobalt disulfide composites on the surface of the silicon dioxide.
Based on the electrochemical performance test of the silicon dioxide metal sulfide composite material, the detection shows that the charging/discharging is carried out within the range of 0-0.55V, and when the discharging current density is 1A/g, the specific capacitance of the super capacitor anode material based on the silicon dioxide metal sulfide composite material is 1158F/g, so that the super capacitor performance is good.
Therefore, compared with the prior art, the silicon dioxide-based metal sulfide composite material has the following advantages:
1) the silicon dioxide as a template agent can slow down the corrosion of electrolyte to electrode materials in the reaction process, provide excellent conductivity and allow electrolyte ions to rapidly pass through in the charging and discharging processes;
2) by utilizing the electrostatic action, metal ions with positive charges are attracted to the surface of silica sol with negative charges to form a nano flower-shaped structure with irregular nano sheets growing on the surface of a sphere, the stacking and agglomeration of electrode materials are effectively inhibited by adopting the method, more contactable sites are provided for electrolyte, the ion transmission distance is effectively shortened, and a guarantee is provided for good electrochemical performance.
3) The three components are tightly combined together under the synergistic effect among the silicon dioxide template, the manganese disulfide and the cobalt disulfide which are different components, so that the synergistic effect of improving the conductivity, the specific capacitance and the electrochemical stability is achieved.
4) By adjusting the relative amount of silica sol, the morphology of the nanostructure can be adjusted, can be generated using a simple hydrothermal method and has simple experimental conditions.
5) By adding urea in the step 1, hydrolysis is controlled to slowly release hydroxyl in the hydrothermal process, so that the hydrothermal reaction is prevented from being too violent, the collapse of the structure is avoided, and the formation of the shape of the nano flower-shaped structure is facilitated.
Therefore, compared with the prior art, the invention has the advantages of faster and more green preparation method, better material stability, improved ion transmission capability and wide application prospect in the field of super capacitors.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of a silica-based metal sulfide composite prepared in example 1;
FIG. 2 is a scanning electron microscope photograph of a silica-based metal sulfide composite prepared in example 1;
FIG. 3 is a transmission electron micrograph of a silica-based metal sulfide composite prepared according to example 1;
FIG. 4 is an energy dispersive X-ray energy spectrum of a silica-based metal sulfide composite prepared in example 1;
FIG. 5 is a cyclic voltammogram of the silica-based metal sulfide composite prepared in example 1;
FIG. 6 is a graph of the charge/discharge curve of the silica-based metal sulfide composite prepared in example 1;
FIG. 7 is a graph showing cycle life curves for the silica-based metal sulfide composite prepared in example 1 and the silica-based composite metal oxide precursor prepared in comparative example 6.
FIG. 8 is a scanning electron microscope photograph of silica-based metal sulfide composites prepared in comparative example 1 with different amounts of silica sol added;
FIG. 9 is a scanning electron microscope photograph of silica-based metal sulfide composites prepared in comparative example 2 with different amounts of silica sol added;
FIG. 10 is a cyclic voltammogram of silica-based metal sulfide composites prepared in example 1, and silica-based metal sulfide composites prepared in comparative example 1 and comparative example 2 with different amounts of silica sol added;
FIG. 11 is a graph of the charge/discharge curves of silica-based metal sulfide composites prepared in example 1, and silica-based metal sulfide composites prepared in comparative example 1 and comparative example 2 with different added silica sol masses;
figure 12 is an X-ray diffraction pattern of a silica-based metal sulfide material of manganese disulfide prepared in comparative example 3;
figure 13 is an X-ray diffraction pattern of a silica metal sulfide-based material of cobalt disulfide prepared in comparative example 4;
FIG. 14 is a silica-based metal sulfide composite, pair, prepared in example 1MnS prepared in proportion 32Materials and comparative example 4 preparation of CoS2A charge/discharge profile of the material;
FIG. 15 is a graph of the charge/discharge curves of a silica-based metal sulfide composite prepared in example 1 and a silica templating agent-free metal sulfide composite prepared in comparative example 5;
fig. 16 is a charge/discharge graph of the silica-based metal sulfide composite prepared in example 1 and the silica-based composite metal oxide precursor prepared in comparative example 6.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Example 1
A preparation method of a silicon dioxide-based metal sulfide composite material comprises the following steps:
step 1) preparation of a composite metal oxide precursor, firstly, under magnetic stirring, dispersing 1 mL of silicon dioxide sol in 50 mL of ultrapure water for 6 h to obtain a solution A, and then, mixing 0.5071 g of MnSO4·2H2O and 1.7462 g Co (NO)3)2·6H2Dissolving O in 20 mL of ethanol and 20 mL of ultrapure water together to obtain a solution B, dropwise adding the solution B into the solution A, after the metal cations are fully adsorbed by the silica colloid through electrostatic interaction, slowly adding 1.0811 g of urea under the stirring condition, stirring for 30 min to obtain a mixed reaction solution, finally transferring the mixed reaction solution into a stainless steel autoclave lined with a polytetrafluoroethylene inner container, carrying out a first hydrothermal reaction under the conditions that the hydrothermal reaction temperature is 120 ℃ and the hydrothermal time is 12 h, and after the reaction is finished, washing and drying to obtain a composite metal oxide precursor;
step 2) based on the preparation of a silica metal sulfide composite, 0.1 g of the composite metal oxide precursor obtained in step 1 and 0.3603 g of Na were added2S·9H2Dissolving O in 40 mL of ultrapure water, stirring for 15 min to prepare a solution C, and transferring the solution C to a lining with polytetrafluoroethyleneAnd (3) carrying out a second hydrothermal reaction in a stainless steel autoclave with an ethylene inner container under the conditions that the hydrothermal reaction temperature is 160 ℃ and the hydrothermal time is 8 h, washing and drying after the reaction is finished to obtain the silicon dioxide-based metal sulfide composite material, wherein the obtained material is marked as MCS 12.
In order to confirm the composition of the material obtained in the present invention, an X-ray diffraction (XRD) test was performed. The test result is shown in figure 1, and the peaks at 25.28 degrees, 29.25 degrees and 41.78 degrees respectively correspond to the (111), (200) and (220) crystal faces of the manganese disulfide; the peaks at 32.3 °, 46.33 ° and 54.94 ° correspond to the (200), (220) and (311) crystal planes of cobalt disulfide, respectively. The test results prove that the components of the material obtained by the invention are manganese disulfide and cobalt disulfide.
In order to prove the microstructure characteristics of the composite material based on the silicon dioxide metal sulfide, a Scanning Electron Microscope (SEM) test is performed, and the test result is shown in fig. 2, the vulcanized composite material of the manganese disulfide and the cobalt disulfide has an irregular lamellar structure, a rough surface and a certain pore structure on the surface of a sphere of the silicon dioxide, and some accumulated particles can be observed, so that the lamellar structure is finally formed.
In order to further prove the microstructure characteristics of the silicon dioxide metal sulfide composite material, a Transmission Electron Microscope (TEM) test is carried out, and the test result is shown in fig. 3, the material has a certain pore structure, and silicon dioxide is etched by hydroxide radicals released by sulfide ion hydrolysis under hydrothermal conditions through a vulcanization reaction, so that a certain pore structure is finally formed.
In order to prove that the surface of the silicon dioxide is successfully loaded with the metal manganese and the metal cobalt, an energy dispersive X-ray energy spectrum (EDS) test is carried out, the test result is shown in figure 4, and the test result shows that Mn, Co and S elements are successfully and uniformly distributed on the surface of the silicon dioxide sphere.
The electrochemical performance test based on the silicon dioxide metal sulfide composite material comprises the following specific steps: weighing 0.008 g of silicon dioxide-based metal sulfide composite material, 0.001 g of acetylene black and 0.001 g of polytetrafluoroethylene micro powder, placing the materials in a small agate grinding bowl, and adding 0.5 mL of ethanol for grinding; and pressing the ground sample with a foamed nickel current collector with the thickness of 1 mm under the pressure of 10 kPa, drying in the air at room temperature, cutting into 2 cm multiplied by 2 cm to obtain the supercapacitor electrode, and testing the electrochemical performance of the supercapacitor electrode.
The detection results are as follows:
to demonstrate the rate capability of silica-based metal sulfide composites, CV tests were performed. Cyclic voltammetry curves at different scanning speeds are shown in fig. 5, the shapes of the curves are similar, and redox peaks exist, which indicates that redox reaction occurs in the process, and the silicon dioxide-based metal sulfide composite material is proved to have better rate performance.
To demonstrate the capacitive properties of the silica-based metal sulfide composites, GCD testing was performed. When the composite material is charged and discharged in the range of 0-0.55V, the charging/discharging curve based on the silicon dioxide metal sulfide composite material is shown in figure 6 when the discharging current density is 1A/g, and the specific capacitance reaches 1158F/g.
In order to investigate the effect of adding different amounts of silica sol on the morphology and electrochemical performance of metal sulfide materials, comparative examples 1 and 2 were provided, i.e., the ratio of the amounts of manganese sulfate and silica was 1: 1 and 1: 3.
in order to prove the cycle performance of the composite material based on the silica metal sulfide, the performance after 2000 cycles at the current density of 10A/g is shown in FIG. 7, and the specific capacitance retention rates are respectively 90.53%, which shows that the composite material based on the silica metal sulfide has good cycle stability.
Comparative example 1
A preparation method of a composite material based on silicon dioxide metal sulfide, which is added with different amounts of silicon dioxide sol, is characterized in that the ratio of the amounts of manganese sulfate and silicon dioxide substances is 1: 1, denoted as MCS 11. The steps not specifically described in the specific steps are the same as the preparation method of the composite material in the embodiment 1, except that: the amount of 1 mL of the silica sol was changed to 0.5 mL in the above step 1.
In order to demonstrate the microstructure characteristics of the MCS11 composite material prepared in comparative example 1, a Scanning Electron Microscope (SEM) test was performed, and the test results are shown in fig. 8, in which MCS11 composite material was observed that irregular flakes were grown on the surface of the spheres, but clump-like masses were grown, indicating that the material had poor electron transport ability and poor conductivity.
Comparative example 2
A preparation method of a composite material based on silicon dioxide metal sulfide, which is added with different amounts of silicon dioxide sol, is characterized in that the ratio of the amounts of manganese sulfate and silicon dioxide substances is 1: 3, as MCS 13. The steps not specifically described in the specific steps are the same as the preparation method of the composite material in the embodiment 1, except that: the amount of 1 mL of the silica sol was changed to 1.5 mL in the above step 1.
In order to demonstrate the microstructure characteristics of the MCS13 composite material prepared in comparative example 2, a Scanning Electron Microscope (SEM) test was performed, and the test results are shown in fig. 9, in which MCS13 composite material was observed that irregular flakes were grown on the surface of the spheres, but clump-like masses were grown, indicating that the material had poor electron transport ability and poor conductivity. However, the morphology of the MCS13 composite was less severe than that of the MCS11 composite prepared in comparative example 1 in terms of clustering and the electrons were more easily transported than in comparative example 1.
To demonstrate the rate capability of the MCS11 composite material prepared in comparative example 1 and the MCS13 composite material prepared in comparative example 2, CV tests were performed in the same manner as in example 1, cyclic voltammograms at a scanning rate of 5 mV/s are shown in FIG. 10, and the shapes of the respective curves are similar, and a redox peak is present, indicating that a redox reaction occurs during the process, i.e., a Faraday pseudocapacitance is generated.
To demonstrate the capacitive performance of the MCS11 composite prepared in comparative example 1 and the MCS13 composite prepared in comparative example 2, GCD testing was performed. The test method was the same as in example 1, and the charging/discharging curves of the MCS11 and MCS13 composite materials were as shown in FIG. 11 with the charging/discharging current density of 1A/g in the range of 0-0.55V, and the specific capacitances were 390F/g and 636F/g, respectively.
According to the results obtained from the foregoing experimental tests,
under the same current density, the discharge time of the composite material based on the silicon dioxide metal sulfide prepared in the example 1 is obviously longer than that of the MCS11 composite material prepared in the comparative example 1 and that of the MCS13 composite material prepared in the comparative example 2, the discharge time is improved by more than 2.9 times, the specific capacitance is obviously improved compared with that of the MCS11 and MCS13 materials, and the composite material in the example 1 has good super-capacitance performance.
To demonstrate the synergy between the monometallic sulphides in silica-based metal sulphide composites, comparative examples 3 and 4 were provided, with monometallic sulphides containing only manganese metal and cobalt metal, respectively, being prepared.
Comparative example 3
A preparation method of a manganese disulfide based silicon dioxide single metal sulfide material prepares a single metal sulfide containing only manganese metal, and is marked as MnS2. The steps not specifically described in the specific steps are the same as the preparation method of the composite material in the embodiment 1, except that: for the preparation of the monometallic sulphide of manganese disulphide, 1.7462 g of Co (NO) were not added in step 13)2·6H2O。
In order to confirm the composition of the material obtained in comparative example 3, XRD test was performed. The test result is shown in fig. 12, wherein peaks at 29.25 °, 36.04 °, 49.46 ° and 51.75 respectively correspond to the (200), (211), (311) and (222) crystal faces of manganese disulfide, and the successful synthesis of manganese disulfide is proved.
Comparative example 4
A preparation method of cobalt disulfide based on silicon dioxide single metal sulfide material prepares single metal sulfide only containing metal cobalt, which is marked as CoS2. The steps not specifically described in the specific steps are the same as the preparation method of the composite material in the embodiment 1, except that: in the preparation of the monometallic sulfide of cobalt disulfide, 0.5071 g of MnSO from said step 1 was not added4·2H2O。
In order to confirm the composition of the material obtained in comparative example 4, XRD test was performed. The test result is shown in fig. 13, wherein the peaks at 32.3 °, 36.23 ° and 54.94 ° correspond to the (200), (210) and (311) crystal faces of cobalt disulfide, respectively, and the successful synthesis of cobalt disulfide is proved.
To demonstrate MnS prepared in comparative example 32Materials and CoS prepared in comparative example 42The capacitance performance of the material is tested by GCD. The test method was the same as in example 1, charging and discharging were carried out in the range of 0-0.55V, and MnS was observed at a discharge current density of 1A/g2And CoS2The charge/discharge curves of the material are shown in FIG. 14, and the specific capacitances are 145F/g and 335F/g, respectively.
According to the results obtained from the foregoing experimental tests,
MnS prepared from comparative example 32Materials and CoS prepared in comparative example 42The specific capacitance of the material and the silica-based metal sulfide composite prepared in example 1 is known: mixing MnS2And CoS2After the single metal sulfide is compounded, the specific capacitance is improved to 1158F/g from 145F/g at the lowest; it can be further demonstrated that MnS2And CoS2The synergistic effect exists between the two components, and finally higher specific capacitance performance is obtained.
To investigate the effect of the silica templating agent on the electrochemical performance of the metal sulfide composite, comparative example 5 was provided, and a metal sulfide composite without the silica templating agent was prepared.
Comparative example 5
A preparation method of a metal sulfide composite material without a silica template agent prepares the metal sulfide composite material without the silica template agent, and is marked as MCS-pure. The steps not specifically described in the specific steps are the same as the preparation method of the composite material in the embodiment 1, except that: and (3) preparing the metal sulfide composite material without the silica template agent, wherein 1 mL of silica sol in the step (1) is not added.
To demonstrate the capacitive properties of the silica templat agent-free metal sulfide composite prepared in comparative example 5, a GCD test was performed. The test method was the same as in example 1, and the charging/discharging curve of the MCS-pure composite material at a discharging current density of 1A/g was as shown in FIG. 15 with a specific capacitance of 184F/g when charging/discharging was carried out in the range of 0 to 0.55V.
According to the results obtained from the foregoing experimental tests,
the specific capacitance of the MCS-pure composite prepared in comparative example 5 and the silica-based metal sulfide composite prepared in example 1 can be seen: after the silicon dioxide template agent is added into the metal sulfide composite material, the specific capacitance is improved from 204F/g to 1158F/g; it can be further proved that the silica template can provide certain conductivity and increase the effect of active sites, and finally higher specific capacitance performance is obtained.
To investigate the effect of sulfidation reaction on the electrochemical performance of the silica-based metal sulfide composite, comparative example 6 was provided, and a silica-based composite metal oxide precursor was prepared.
Comparative example 6
A method for preparing a composite metal oxide precursor without a sulfidation reaction, a silica-based composite metal oxide precursor is prepared, denoted as MCO. The steps not specifically described in the specific steps are the same as the preparation method of the composite material in the embodiment 1, except that: the preparation of the silica-based composite metal oxide precursor according to the step 2 is not performed.
To demonstrate the capacitive properties of the silica-based composite metal oxide precursor prepared in comparative example 6, a GCD test was performed. The test method is the same as that of example 1, the MCO composite material is charged/discharged within the range of 0-0.55V, the charging/discharging curve of the MCO composite material is shown in figure 16 when the discharging current density is 1A/g, and the specific capacitance is 184F/g.
According to the results obtained from the foregoing experimental tests,
the specific capacitance of the MCO composite prepared in comparative example 6 and the silica-based metal sulfide composite prepared in example 1 is known as follows: after the MCO composite material is vulcanized, the specific capacitance is increased from 184F/g to 1158F/g; it can be further proved that in the process of converting the composite metal oxide precursor MCO composite material into the silicon dioxide-based metal sulfide composite material under the hydrothermal condition through the vulcanization reaction, the silicon dioxide is etched by hydroxyl, so that a part of the silicon dioxide is released from the hydrolysis of sulfide ions, and a certain hole is etched on the internal silicon dioxide template, which is more favorable for ion migration, further enhances the electrochemical activity of the silicon dioxide-based metal sulfide composite material, and finally obtains the ultrahigh specific capacitance performance.
In order to demonstrate the cycle performance of the MCO composite material prepared in comparative example 6, the performance after 2000 cycles at a current density of 10A/g is shown in fig. 7, and the specific capacity retention rates are 82.48%, respectively. The specific capacitance retention rate of the silica-based metal sulfide composite material prepared in example 1 is 90.53%, which shows that the silica-based metal sulfide composite material has good cycling stability, and the electrochemical performance of the electrode material can be improved while the cycling stability is maintained.
Therefore, the electrochemical performance of the obtained composite material can be fully exerted only by the process technology provided by the invention.

Claims (8)

1. A composite material based on silica metal sulfide is characterized in that: a two-step hydrothermal method is adopted, a nanoflower-shaped structure of manganese disulfide and cobalt disulfide grows on the outer surface of template agent silicon dioxide, and meanwhile, through a vulcanization reaction, silicon dioxide is etched by hydroxyl, so that a part of silicon dioxide is released from the hydrolysis of sulfide ions, a certain hole is etched on an inner silicon dioxide template, and the layered nano metal sulfide composite material based on silicon dioxide can be prepared through ion migration;
the template agent silicon dioxide is used as a template of the composite material and plays a role in providing a supporting framework, a pore structure and an active site;
the manganese and cobalt metal sulfide coated on the outer surface of the silicon dioxide is used as a conductive layer, so that the conductivity of the composite material is improved, and the pseudo-capacitance effect is provided.
2. The silica-based metal sulfide composite according to claim 1, wherein: the method comprises the following steps of growing a manganese disulfide and cobalt disulfide composite material by a two-step hydrothermal method, wherein the first step of hydrothermal method is to grow manganese and cobalt oxide precursors on the surface of silicon dioxide, and the second step of hydrothermal method adopts sodium sulfide to carry out vulcanization treatment to generate manganese disulfide and cobalt disulfide.
3. The silica-based metal sulfide composite material according to claim 2, wherein: the silica in the first step is used as a template agent, specifically is silica sol with a spherical structure, and has the function of providing pseudo capacitance by performing rapid Faraday reaction on the surface and the interior of the silica; the manganese disulfide and cobalt disulfide compound generated by the hydrothermal reaction in the second step is in an irregular nano flaky structure, and is coated on the surface of silicon dioxide to perform a rapid Faraday reaction, so that a pseudo capacitor is provided.
4. The method for preparing a silica-based metal sulfide composite material according to claim 1, comprising the steps of:
step 1) preparation of a composite metal oxide precursor, firstly, dispersing silica sol in pure water under certain conditions to obtain a solution A, then, dissolving soluble manganese salt and soluble cobalt salt in ethanol and water according to a certain mass ratio to obtain a solution B, then, dropwise adding the solution B into the solution A, after metal cations are fully adsorbed by silica colloid through electrostatic action, slowly adding urea under a certain mass ratio under stirring conditions, stirring for a certain time to obtain a mixed reaction solution, finally, carrying out a first hydrothermal reaction on the mixed reaction solution under certain conditions, and after the reaction is finished, washing and drying to obtain the composite metal oxide precursor;
and 2) preparing the composite material based on the silicon dioxide metal sulfide, dissolving the composite metal oxide precursor and the soluble sulfide obtained in the step 1 in water according to a certain mass ratio to prepare a solution C, then carrying out a second hydrothermal reaction under a certain condition, and after the reaction is finished, washing and drying to obtain the composite material based on the silicon dioxide metal sulfide.
5. The method of claim 4, wherein: the mass ratio of the silicon dioxide, the soluble manganese salt, the soluble cobalt salt, the urea and the soluble sulfide is 2:1:2:6: 5.
6. The method of claim 4, wherein: the conditions of the hydrothermal methods in the steps 1 and 2 are different, specifically, the reaction temperature of the first hydrothermal reaction in the step 1 is 110-; the reaction temperature of the second hydrothermal reaction in the step 2 is 150-170 ℃, and the reaction time is 7-9 h.
7. The method of claim 4, wherein: the stirring time of the silicon dioxide sol dispersion liquid in the step 1 is 6-12 h; the stirring time of the composite metal oxide precursor in the step 1 is 0.5-1 h; the stirring time of the step 2 is 0.25-0.5 h.
8. The use of the silica-based metal sulfide composite material as an electrode material for a supercapacitor according to claim 1, wherein: charging/discharging in the range of 0-0.55V, and at a discharge current density of 1A/g, the specific capacitance is 1150-1160F/g.
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