CN111924888B - Co9S8Nano-particle composite electrode material and preparation method and application thereof - Google Patents
Co9S8Nano-particle composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode materials, and particularly relates to Co9S8A nano-particle composite electrode material, a preparation method and application thereof. Placing ground vermiculite or pretreated ground vermiculite into a sucrose-containing impregnation liquid A for impregnation and calcination to obtain carbon-coated vermiculite; then, placing the carbon-coated vermiculite in an impregnation liquid B containing cobalt chloride hexahydrate, thiourea and urea for impregnation and calcination to obtain Co9S8A nanoparticle composite electrode material. The method adopts an immersion method to grow Co in situ on two-dimensional layered vermiculite9S8The preparation process of the nano-particles is simple, the energy consumption is low, the operation is easy, the two-dimensional layered structure of the vermiculite is maintained, the surface area of the material is increased, and the sucrose is used as a carbon source to coat the surface of the nano-particles, so that the conductivity of the electrode material is enhanced; in addition, thiourea and urea are used as a sulfur source and a nitrogen source to form double hetero atom N and S co-doping, so that the electrochemical performance of the material is further enhanced.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to Co9S8A nano-particle composite electrode material, a preparation method and application thereof.
Background
The energy shortage and environmental pollution caused by the use of fossil fuels have led people to focus their research on the storage and conversion of clean and renewable energy. At present, some renewable energy sources (solar energy, wind energy and biomass energy) gradually replace oil and natural gas, however, the intermittent energy sources and the non-uniform distribution of the renewable energy sources still exist, and the key point of the problem is how to convert the intermittent energy sources into storable modes (such as electric energy). In addition, rapid development of industries such as portable electronic devices and electric vehicles has led to higher standards for the ability to store and output energy. Driven by a plurality of factors, the super capacitor has the unique advantages of quick charge and discharge, high power density and long service life.
The super capacitor mainly comprises a diaphragm, a positive electrode, a negative electrode and an electrolyte, and the main parameter for evaluating the performance of the super capacitor is power density (W kg)-1) Energy density (Wh kg)-1) Cycle life and specific capacity (F g)-1Or mAh g-1) And the like. The electric double layer energy storage and the pseudo-capacitor energy storage are two classic energy storage mechanisms of a super capacitor, most of the currently developed electrode material energy storage mechanisms are pseudo-capacitor energy storage, and the mechanism is that energy storage is realized by reversible chemical adsorption-desorption or oxidation-reduction reaction on the surface of an electrode material. Therefore, the storage performance of the pseudocapacitive capacitor is determined by the electrode material, the specific surface area and the redox generating capacity.
The reasonable design of electrode materials is an important link for constructing a high-performance supercapacitor, and is mainly divided into three categories of carbon-based materials, metal oxides/sulfides and conductive polymers at present. The carbon-based material has the highest commercialization degree, but the energy density is also low due to the lower specific capacity; conductive polymers exhibit higher power densities, but much lower specific capacitances than the other two; the metal oxide/sulfide exhibits high energy and power densities. The reported metal oxides are RuO2And based on transition metal oxides/sulfides such as transition metals Fe, Co, Mn, Ni and Co, the initial structure of a simple metal oxide/sulfide material can be changed in a continuous reaction, the microstructure of the material is damaged, and the performance and the cycle stability of the material are finally influenced. Therefore, the material of the metal oxide/sulfide is required to depend on parameters such as porosity, crystallinity, active sites and specific surface area of the electrode material, and the energy storage performance of the metal oxide/sulfide is maximized by adjusting the parameters. Based on the above parameters, researchers not only make the metal oxide/sulfide into different shapes, such as nano-sheets, nano-rods, nano-particles, etc.; the metal oxide/sulfide can be encapsulated in a conductive network or loaded in graphene and carbon nanotubes, and the performance of the metal oxide/sulfide is improved by the shape and the regulation and control of the composite process. Noble metal based electricityThe pole material faces the problems of material scarcity and high price, and the composite structure also faces the problems of high construction process cost (such as graphene and MOF) and complex synthesis process. The preparation method of the metal oxide/sulfide electrode material is simple in preparation process and low in material cost, and has important significance for performance improvement and commercial application of the super capacitor.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a Co9S8The preparation method of the nano-particle composite electrode material comprises the steps of taking vermiculite as a carrier, taking cane sugar as a carbon source, taking thiourea as an S source and taking urea as an N source, and growing N, S-codoped carbon-coated Co in situ on the surface of the vermiculite9S8Nanoparticles to obtain Co9S8The nano-particle composite electrode material has the advantages of abundant and easily-obtained material sources, simple preparation process and the like.
The invention also aims to provide Co prepared by the preparation method9S8The nano-particle composite electrode material has good electrochemical performance.
It is still another object of the present invention to provide Co as described above9S8Application of the nano-particle composite electrode material.
The purpose of the invention is realized by the following technical scheme:
co9S8The preparation method of the nano-particle composite electrode material comprises the following steps:
(1) grinding and sieving expanded vermiculite to obtain ground vermiculite;
(2) further carrying out acid treatment, high-temperature treatment or acid treatment after high-temperature treatment on the ground vermiculite prepared in the step (1) to obtain pretreated ground vermiculite;
(3) preparing a 9-10% sucrose solution serving as an impregnation liquid A; then placing the ground vermiculite prepared in the step (1) or the pretreated ground vermiculite prepared in the step (2) into a dipping solution A for dipping for 20-28 h, and after dipping, carrying out solid-liquid separation and drying; drying in inert gas N2Heating to 500-700 ℃ at a heating rate of 1-3 ℃/min in the atmosphere, and keeping the temperature for 3-4 h to obtain carbon-coated vermiculite;
(4) dissolving cobalt chloride hexahydrate, thiourea and urea in a molar ratio of (0.5-1.5) to (1-3) to (90-110) in water to obtain a steeping liquor B, soaking the carbon-coated vermiculite prepared in the step (3) in the steeping liquor B for 20-28 h, and performing solid-liquid separation and drying after the soaking is finished; to obtain Co9S8A nanoparticle composite electrode material precursor;
(5) co prepared in the step (4)9S8The precursor of the nano-particle composite electrode material is subjected to staged heating calcination to obtain Co9S8A nanoparticle composite electrode material;
the sieving mesh number in the step (1) is preferably 200 meshes (100 mu m);
the specific operation of the acid treatment in the step (2) is preferably:
stirring ground vermiculite with 1-3 mol/L hydrochloric acid at a constant temperature of 70-90 ℃ for 20-28 h, filtering, washing with water to be neutral, and drying; during acid treatment, excessive hydrochloric acid is ensured to ensure that vermiculite is completely pickled, and if the vermiculite is not completely pickled, partial metal ions are remained; the drying temperature is preferably 60-70 ℃;
the specific operation of the high-temperature treatment in the step (2) is preferably:
heating the ground vermiculite in the air to 800-1000 ℃, keeping the temperature for 1-3 h, and naturally cooling; the heating rate is preferably 4-6 ℃/min;
the specific operation of the acid treatment after the high-temperature treatment in the step (2) is preferably:
firstly, heating the ground vermiculite in the air to 800-1000 ℃, keeping the temperature for 1-3 h, naturally cooling, then stirring with 1-3 mol/L hydrochloric acid at the constant temperature of 70-90 ℃ for 20-28 h, filtering, washing with water to be neutral and drying; the heating rate is preferably 4-6 ℃/min; the drying temperature is preferably 60-70 ℃;
the mass percentage of the sucrose solution in the step (3) is preferably 9.6%;
the drying condition in the step (3) is preferably 100-110 ℃ for 12 h;
the concentrations of the cobalt chloride hexahydrate, the thiourea and the urea in the impregnation liquid B in the step (4) are preferably 0.02mol/L, 0.04mol/L and 2mol/L in sequence;
the drying in the step (4) is preferably carried out for 48 hours by using a vacuum freeze dryer;
the conditions of the staged temperature-rising calcination in the step (5) are preferably as follows: inert gas N2Raising the temperature to 200 ℃ at the speed of 2 ℃/min in the atmosphere; then the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; then raising the temperature to 350 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h; finally, heating to 900 ℃ within 180 min, and cooling;
co9S8The nano-particle composite electrode material is prepared by the preparation method;
said Co9S8The application of the nano-particle composite electrode material in the field of preparation of super capacitors and batteries;
compared with the prior art, the invention has the following advantages and effects:
(1) co provided by the invention9S8The preparation method of the nano-particle composite electrode material adopts an immersion method to grow Co in situ on two-dimensional layered vermiculite9S8The preparation process of the nano-particles is simple, the energy consumption is low and the operation is easy.
(2) Co provided by the invention9S8The nano-particle composite electrode material is prepared by in-situ growth of double-heteroatom-doped (N, S-codoped) carbon-coated Co by taking vermiculite as a carrier9S8The nano-particle electrode material has clear morphological characteristics, maintains the two-dimensional layered structure of vermiculite and increases the surface area of the material; sucrose is used as a carbon source to coat the surface of the nano particles, so that the conductivity of the material is enhanced; in addition, thiourea and urea are used as a sulfur source and a nitrogen source to form a double-heteroatom N and S co-doped composite material, so that the electrochemical performance of the material is further enhanced.
(3) Co provided by the invention9S8The nano-particle composite electrode material has certain electrochemistryCan be used. Experimental results prove that the vermiculite has certain capacitor performance no matter the vermiculite is pure or treated at high temperature, treated by hydrochloric acid, and treated by hydrochloric acid after high temperature, and the material obtained by adopting the high temperature treatment in the pretreatment mode has the best performance, the specific capacity is 90.64F/g when the current density is 1A/g, and the specific capacities are 90.1F/g, 85.29F/g, 82.71F/g and 72.59F/g when the current densities are 2A/g, 4A/g, 5A/g and 8A/g.
(3) Co provided by the invention9S8The nano-particle composite electrode material takes vermiculite with rich Xinjiang reserves as a raw material, utilizes the unique two-dimensional layered structure of the vermiculite, and adopts an impregnation method to grow Co in situ in the vermiculite layered structure9S8The nano particles lay a foundation for the application of abundant vermiculite resources in Xinjiang in the field of energy.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of vermiculite.
Figure 2 is an X-ray diffraction (XRD) pattern for vermiculite.
FIG. 3 shows Co obtained in example 19S8SEM images of the nanoparticle composite electrode material; wherein, A: co9S8Nanoparticle composite electrode material SEM, B: a SEM after magnification.
FIG. 4 shows Co obtained in example 19S8XRD pattern of nanoparticle composite electrode material.
FIG. 5 shows Co obtained in example 19S8A graph of electrochemical performance of the nanoparticle composite electrode material; wherein (a): cyclic voltammogram at different scan speeds, (b): under the potential of 0.15V, the frequency range is 1-105HZ impedance profile, (c): charge-discharge curves of the materials at different current densities, (d): specific capacity at different current densities.
FIG. 6 shows Co obtained in example 29S8A graph of electrochemical performance of the nanoparticle composite electrode material; wherein (a): cyclic voltammogram at different scan speeds, (b): under the potential of 0.15V, the frequency range is 1-105HZ impedance profile, (c): charge-discharge curves of the materials at different current densities, (d): is differentSpecific capacity at current density.
FIG. 7 shows Co obtained in example 39S8A graph of electrochemical performance of the nanoparticle composite electrode material; wherein (a): cyclic voltammogram at different scan speeds, (b): under the potential of 0.15V, the frequency range is 1-105HZ impedance profile, (c): charge-discharge curves of the materials at different current densities, (d): specific capacity at different current densities.
FIG. 8 shows Co obtained in example 49S8A graph of electrochemical performance of the nanoparticle composite electrode material; wherein (a): cyclic voltammogram at different scan speeds, (b): under the potential of 0.15V, the frequency range is 1-105HZ impedance profile, (c): charge-discharge curves of the materials at different current densities, (d): specific capacity at different current densities.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
EXAMPLE 1 high temperature treatment of vermiculite + stepwise impregnation method
(1) Fully grinding commercial expanded vermiculite in a mortar, sieving the ground expanded vermiculite with a 200-mesh sieve, and collecting undersize products (less than 100 mu m) to obtain ground vermiculite;
(2) weighing 0.51g of ground vermiculite prepared in the step (1), heating to 900 ℃ at a heating rate of 5 ℃/min in air, keeping the temperature for 2 hours, and naturally cooling to obtain high-temperature treated vermiculite;
(3) weighing 10g of sucrose to prepare a 9.6 mass percent sucrose solution as an impregnation solution A; soaking the high-temperature treated vermiculite prepared in the step (2) in 50mL of soaking solution A for 24h, centrifuging after soaking is finished, reserving a lower-layer product, and drying at 105 ℃ for 12 h; drying in inert gas N2Keeping the temperature at 600 ℃ for 3h at the heating rate of 2 ℃/min in the atmosphere, and naturally cooling to obtain carbon-coated vermiculite;
(4) weighing 0.48g of cobalt chloride hexahydrate, 0.3g of thiourea and 12g of urea according to a molar ratio of 1:2:100 to prepare 100ml of impregnation liquid B, wherein the cobalt chloride hexahydrate and the thiourea in the impregnation liquid BAnd the concentration of the urea is 0.02mol/L, 0.04mol/L and 2mol/L in sequence; soaking the carbon-coated vermiculite prepared in the step (3) in 30mL of soaking liquid B for 24h, pouring out supernatant after soaking is finished, and drying the lower layer for 48h by using a vacuum freeze dryer to obtain Co9S8A nanoparticle composite electrode material precursor;
(5) co prepared in the step (4)9S8The precursor of the nano-particle composite electrode material is calcined by stage heating, and the conditions of the stage heating and calcining are as follows: in an inert gas N2Raising the temperature to 200 ℃ at the speed of 2 ℃/min in the atmosphere; then the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; then raising the temperature to 350 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h; finally heating to 900 ℃ within 180 min, and naturally cooling to room temperature to obtain Co9S8A nanoparticle composite electrode material.
The microscopic morphology and the structural composition of the material are characterized by a scanning electron microscope with the model number of FEI Quanta FEG 250 and an X-ray diffractometer with the model number of German Bruker D8 Advance. Fig. 1 is an SEM image of vermiculite after grinding, from which the two-dimensional layered structure of vermiculite itself can be clearly observed. FIG. 3 shows Co obtained by impregnating and calcining vermiculite step by step after high temperature treatment9S8Nano-particle composite electrode material (N, S-codoped carbon-coated Co in-situ growth by taking vermiculite as carrier9S8Nanoparticle electrode material), it can be seen that vermiculite still maintains a two-dimensional layered structure after a series of treatments, and Co of different sizes is uniformly distributed on the surface of the layer9S8And (3) nanoparticles. The unique two-dimensional layered structure of the vermiculite effectively reduces Co9S8Aggregation of the nanoparticles allows uniform dispersion thereof, thereby exposing more active sites. FIG. 2 and FIG. 4 show vermiculite and Co obtained by impregnating vermiculite step by step after high temperature treatment9S8XRD pattern of the nano-particle composite electrode material, after the same peaks as those in figure 2 are deducted from figure 4, characteristic peaks at 23.9 ℃, 27.1 ℃, 31.8 ℃, 35.1 ℃, 52.2 ℃, 59.3 ℃, 76.2 ℃ and the like and standard Co9S8(PDF #02-1459) on (422), (511), (440), (600), (640), (731), (662)) The crystal planes of (A) correspond to (B), indicating that Co9S8Nanoparticles were successfully grown on exfoliated vermiculite, which is consistent with SEM results.
Co prepared in this example was tested using a conventional three-electrode system9S8Capacitor performance of the nanoparticle composite electrode material. The foamed nickel, mercury/mercury oxide and platinum wires loaded with active substances are respectively used as a working electrode, a reference electrode and a counter electrode, and 6M KOH is used as electrolyte. Preparation of a working electrode: 0.0759 g of Co prepared in this example were weighed out9S8And (3) placing the nano-particle composite electrode material and 0.0208 g of conductive agent acetylene black in an agate mortar, fully grinding for 5-10 min, then placing the mixture into a sample tube, then adding 0.12 mL of binder Nafion solution and a few drops of ethanol, and carrying out ultrasonic treatment for 10-20 min to uniformly disperse the mixture. The nickel mesh was cut into small squares of 1cm by 1cm and weighed. And (3) smearing the slurry uniformly dispersed by ultrasonic on a nickel screen, naturally drying the slurry overnight, tabletting, and weighing. And calculating the loading capacity of the active substances according to the mass difference of the nickel net and the percentage of the active substances.
FIG. 5 (a) is a Cyclic Voltammogram (CV) at different scanning speeds of 30 mV/s, 40 mV/s and 50mV/s in a scanning range of 0 to 0.6V. As can be seen from the figure, all curves show a pair of redox peaks due to redox reactions occurring in the electrode material. Further, as the scanning speed increases, the oxidation peak of the CV curve moves toward a high potential and the reduction peak moves toward a low potential due to the polarization effect of the electrode. The AC impedance test proves the excellent conductivity of the material, generally a semicircle is observed under high frequency, and the material can be used as the charge transfer resistance (R) of the Faraday interface generated by ion transmission between the electrolyte and the electrodect) As shown in fig. 5 (b), the charge transfer resistance is about 0.7 Ω, and the low charge transfer resistance demonstrates that the material has high conductivity and rapid charge transfer capability, which is mainly attributed to the fact that the coating of carbon enhances the conductivity of the material. Fig. 5 (c) shows the charge-discharge curve (GCD) of the material at different current densities and the corresponding specific capacities as shown in fig. 5 (d). The specific capacity is calculated by adopting a formulaC=IΔt/mΔVWherein C is specific capacity, unit F/g; i is discharge powerStream, in units of A;Δtdischarge time in units of s; m is the mass of the active substance, and the unit is g;ΔVthe difference in discharge voltage is given in V. As can be seen from the figure, under the voltage window of 0-0.5V, the specific capacity is 90.64F/g when the current density is 1A/g, and when the current density is 2A/g, 4A/g, 5A/g and 8A/g, the specific capacity is 90.1F/g, 85.29F/g, 82.71F/g and 72.59F/g respectively. Along with the increase of current density, the specific capacity decay rate is slower, which indicates the good rate capability of the material. Excellent capacitor performance due to the large specific surface area of the two-dimensional layered structure of vermiculite, carbon coating strategy to enhance material conductivity, doping of heterogeneous heteroatoms and uniformly dispersed Co9S8And the nano particles expose more active sites, so that the electrochemical performance of the material is further enhanced.
Example 2 finely ground vermiculite + stepwise impregnation method
(1) Fully grinding commercial expanded vermiculite in a mortar, sieving the ground expanded vermiculite with a 200-mesh sieve, and collecting undersize products (less than 100 mu m) to obtain ground vermiculite;
(2) weighing 10g of sucrose to prepare a 9.6 mass percent sucrose solution as an impregnation solution A; soaking 0.51g of ground vermiculite prepared in the step (1) in 50mL of a soaking solution A for 24h, centrifuging after soaking is finished, reserving a lower-layer product, and drying at 105 ℃ for 12 h; drying in inert gas N2Keeping the temperature at 600 ℃ for 3h at the heating rate of 2 ℃/min in the atmosphere, and naturally cooling to obtain carbon-coated vermiculite;
(3) weighing 0.48g of cobalt chloride hexahydrate, 0.3g of thiourea and 12g of urea according to a molar ratio of 1:2:100 to prepare 100ml of impregnation liquid B, wherein the concentrations of the cobalt chloride hexahydrate, the thiourea and the urea in the impregnation liquid B are 0.02mol/L, 0.04mol/L and 2mol/L in sequence; soaking the carbon-coated vermiculite prepared in the step (2) in 30mL of soaking liquid B for 24h, pouring out supernatant after soaking is finished, and drying the lower layer for 48h by using a vacuum freeze dryer to obtain Co9S8A nanoparticle composite electrode material precursor;
(4) co prepared in the step (3)9S8The precursor of the nano-particle composite electrode material is calcined by stage heating, and the stage heating is calcinedThe conditions of (a) are as follows: in an inert gas N2Raising the temperature to 200 ℃ at the speed of 2 ℃/min in the atmosphere; then the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; heating to 350 deg.C at a rate of 1 deg.C/min, holding the temperature for 1 h, heating to 900 deg.C within 180 min, and naturally cooling to room temperature to obtain Co9S8A nanoparticle composite electrode material.
The performance of the synthetic material capacitor was further investigated using a three-electrode system (the specific method is the same as in example 1).
FIG. 6 (a) is a graph of CV curves over a voltage range of 0V to 0.56V at a scan rate of 35mV/s to 60mV/s, from which it can be seen that each curve has a typical pair of redox peaks and that there is a shift in redox potential as the scan rate increases. FIG. 6 (b) shows a frequency range of 1 to 10 at a potential of 0.15V5And HZ impedance spectrum, wherein the charge transfer impedance value is about 2.5 omega, and a smaller impedance value shows the rapid charge transfer and excellent conductivity in the charge and discharge process. As can be seen from FIGS. 6 (c) and 6 (d), the specific capacities at current densities of 1A/g to 6A/g were 78.66F/g, 75.06F/g, 74.12F/g, 73.52F/g, 72.28F/g and 71.99F/g, respectively. Along with the increase of the current density, the specific capacity shows a slow descending trend, which shows that the material obtained by the step-by-step impregnation method has excellent rate performance, and the step-by-step impregnation method has more advantages compared with the one-step impregnation synthesis method.
Example 3 acid treatment of vermiculite + stepwise impregnation
(1) Fully grinding commercial expanded vermiculite in a mortar, sieving the ground expanded vermiculite with a 200-mesh sieve, and collecting undersize products (less than 100 mu m) to obtain ground vermiculite;
(2) weighing 0.51g of ground vermiculite prepared in the step (1), stirring with 200mL of 2mol/L hydrochloric acid at a constant temperature of 80 ℃ for 24h, filtering, washing with water to neutrality, and drying at 70 ℃ to obtain acid-treated vermiculite;
(3) weighing 10g of sucrose to prepare a 9.6 mass percent sucrose solution as an impregnation solution A; immersing vermiculite prepared in the step (2) after hydrochloric acid treatment in 50mL of immersion liquid A for 24h, centrifuging after immersion is finished, reserving a lower-layer product, and drying at 105 ℃ for 12 h; dry matterDrying in inert gas N2Keeping the temperature at 600 ℃ for 3h at the heating rate of 2 ℃/min in the atmosphere, and naturally cooling to obtain carbon-coated vermiculite;
(4) weighing 0.48g of cobalt chloride hexahydrate, 0.3g of thiourea and 12g of urea according to a molar ratio of 1:2:100 to prepare 100ml of impregnation liquid B, wherein the concentrations of the cobalt chloride hexahydrate, the thiourea and the urea in the impregnation liquid B are 0.02mol/L, 0.04mol/L and 2mol/L in sequence; soaking the carbon-coated vermiculite prepared in the step (3) in 30mL of soaking liquid B for 24h, pouring out supernatant after soaking is finished, and drying the lower layer for 48h by using a vacuum freeze dryer to obtain Co9S8A nanoparticle composite electrode material precursor;
(5) co prepared in the step (4)9S8The precursor of the nano-particle composite electrode material is calcined by stage temperature rise, wherein the calcination conditions of the stage temperature rise are as follows: in an inert gas N2Raising the temperature to 200 ℃ at the speed of 2 ℃/min in the atmosphere; then the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; then raising the temperature to 350 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h; finally heating to 900 ℃ within 180 min, and naturally cooling to room temperature to obtain Co9S8A nanoparticle composite electrode material.
The performance of the synthetic material capacitor was further investigated using a three-electrode system (the specific method is the same as in example 1).
FIG. 7 (a) is a graph of CV curves over a voltage range of 0V to 0.56V at scan speeds of 50mV/s to 70mV/s, from which it can be seen that each curve has a typical pair of redox peaks and that there is a shift in redox potential as the scan speed increases. FIG. 7 (b) shows the frequency range of 1-10 at 0.15V potential5And the impedance spectrum in HZ and the smaller charge transfer impedance value indicate the rapid transfer of charges and good conductivity in the charge and discharge process. As can be seen from FIGS. 7 (c) and 7 (d), the specific capacities at current densities of 1A/g to 6A/g were 70.23F/g, 66.51F/g, 64.96F/g, 63.75F/g, 61.69F/g and 59.48F/g, respectively. Along with the increase of current density, the specific capacity shows a slow descending trend, which shows that the material obtained by the vermiculite step-by-step impregnation method after hydrochloric acid treatment has certain rate capability, but the performance is slightly lower than or not lower than that of the materialIs used as the material for processing vermiculite synthesis.
Example 4 high temperature treatment/acid treatment of vermiculite + stepwise impregnation
(1) Fully grinding commercial expanded vermiculite in a mortar, sieving the ground expanded vermiculite with a 200-mesh sieve, and collecting undersize products (less than 100 mu m) to obtain ground vermiculite;
(2) weighing 0.51g of ground vermiculite prepared in the step (1), firstly calcining at 900 ℃ (the heating rate is 5 ℃/min) for 2h, then stirring with 2mol/L hydrochloric acid at 80 ℃ for 24h, filtering, washing with water to be neutral, and drying at 70 ℃ to obtain high-temperature treated/acid treated vermiculite;
(3) weighing 10g of sucrose to prepare a 9.6 mass percent sucrose solution as an impregnation solution A; placing the high-temperature calcined/acid-treated vermiculite prepared in the step (2) into 50mL of impregnation liquid A for impregnation for 24h, centrifuging after the impregnation is finished, reserving a lower-layer product, and drying at 105 ℃ for 12 h; drying in inert gas N2Keeping the temperature at 600 ℃ for 3h at the heating rate of 2 ℃/min in the atmosphere, and naturally cooling to obtain carbon-coated vermiculite;
(4) weighing 0.48g of cobalt chloride hexahydrate, 0.3g of thiourea and 12g of urea according to a molar ratio of 1:2:100 to prepare 100ml of impregnation liquid B, wherein the concentrations of the cobalt chloride hexahydrate, the thiourea and the urea in the impregnation liquid B are 0.02mol/L, 0.04mol/L and 2mol/L in sequence; soaking the carbon-coated vermiculite prepared in the step (3) in 30mL of soaking liquid B for 24h, pouring out supernatant after soaking is finished, and drying the lower layer for 48h by using a vacuum freeze dryer to obtain Co9S8A nanoparticle composite electrode material precursor;
(5) co prepared in the step (4)9S8The precursor of the nano-particle composite electrode material is calcined by stage temperature rise, wherein the calcination conditions of the stage temperature rise are as follows: raising the temperature to 200 ℃ at the speed of 2 ℃/min under the inert gas nitrogen atmosphere; then the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; then raising the temperature to 350 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h; finally heating to 900 ℃ within 180 min, and naturally cooling to room temperature to obtain Co9S8A nanoparticle composite electrode material.
The three-electrode system is adopted to further research the electricity of the synthetic materialThe container properties. FIG. 8 (a) is a graph of CV curves over a voltage range of 0V to 0.6V at a scan rate of 20mV/s to 35mV/s, from which it can be seen that each curve has a typical pair of redox peaks and that there is a shift in redox potential as the scan rate increases. FIG. 8 (b) shows a frequency range of 1 to 10 at a potential of 0.15V5And in the HZ impedance spectrum, the charge transfer impedance value is about 2 omega, and the lower impedance value shows the rapid transfer of charges and good conductivity in the charge and discharge process. It can be seen from FIGS. 8 (c) and 8 (d) that the specific capacities at current densities of 1A/g to 6A/g were 88.46F/g, 82.98F/g, 79.86F/g, 76.64F/g, 73.36F/g, and 69.86F/g, respectively. Along with the increase of current density, the specific capacity shows a slow descending trend, and the specific capacity result shows that the performance of the material obtained by the step-by-step impregnation method of vermiculite after high-temperature treatment and then hydrochloric acid treatment is slightly lower than that of the material obtained by the step-by-step impregnation method of vermiculite after direct high-temperature treatment, but is superior to that of the untreated vermiculite by the step-by-step impregnation method, the step-by-step impregnation method and the hydrochloric acid treatment step-by-.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Co9S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
(1) grinding and sieving expanded vermiculite to obtain ground vermiculite;
(2) further carrying out acid treatment, high-temperature treatment or acid treatment after high-temperature treatment on the ground vermiculite prepared in the step (1) to obtain pretreated ground vermiculite;
(3) preparing a 9-10% sucrose solution serving as an impregnation liquid A; then placing the ground vermiculite prepared in the step (1) or the pretreated ground vermiculite prepared in the step (2) into a dipping solution A for dipping for 20-28 h, and after dipping, carrying out solid-liquid separation and drying; after drying, is inertGas N2Heating to 500-700 ℃ at a heating rate of 1-3 ℃/min in the atmosphere, and keeping the temperature for 3-4 h to obtain carbon-coated vermiculite;
(4) dissolving cobalt chloride hexahydrate, thiourea and urea in a molar ratio of (0.5-1.5) to (1-3) to (90-110) in water to obtain a steeping liquor B, soaking the carbon-coated vermiculite prepared in the step (3) in the steeping liquor B for 20-28 h, and performing solid-liquid separation and drying after the soaking is finished; to obtain Co9S8A nanoparticle composite electrode material precursor;
(5) co prepared in the step (4)9S8The precursor of the nano-particle composite electrode material is subjected to staged heating calcination to obtain Co9S8A nanoparticle composite electrode material.
2. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
the acid treatment in the step (2) comprises the following specific operations:
and (3) stirring the ground vermiculite with 1-3 mol/L hydrochloric acid at a constant temperature of 70-90 ℃ for 20-28 h, filtering, washing with water to be neutral, and drying.
3. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
the specific operation of the high-temperature treatment in the step (2) is as follows:
heating the ground vermiculite in the air to 800-1000 ℃, keeping the temperature for 1-3 h, and naturally cooling.
4. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
the specific operation of the acid treatment after the high-temperature treatment in the step (2) is as follows:
the fine vermiculite is firstly heated to 800-1000 ℃ in the air, is kept at the constant temperature for 1-3 h, is stirred with 1-3 mol/L hydrochloric acid at the constant temperature of 70-90 ℃ for 20-28 h, is filtered, is washed with water to be neutral and is dried.
5. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
the mass percentage of the sucrose solution in the step (3) is 9.6%.
6. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
the concentrations of the cobalt chloride hexahydrate, the thiourea and the urea in the impregnation liquid B in the step (4) are 0.02mol/L, 0.04mol/L and 2mol/L in sequence.
7. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
and (4) drying for 48 hours by using a vacuum freeze dryer.
8. Co according to claim 19S8The preparation method of the nano-particle composite electrode material is characterized by comprising the following steps:
the condition of the stage temperature-rising calcination in the step (5) is as follows: inert gas N2Raising the temperature to 200 ℃ at the speed of 2 ℃/min in the atmosphere; then the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; then raising the temperature to 350 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h; finally, the temperature is raised to 900 ℃ within 180 min, and the mixture is cooled.
9. Co9S8A nanoparticle composite electrode material, characterized by being produced by the production method according to any one of claims 1 to 8.
10. Co of claim 99S8The application of the nano-particle composite electrode material in the field of preparation of super capacitors and batteries.
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