CN111243871B - Novel NiSe2Coated mesoporous hollow carbon sphere composite material, preparation method thereof and application thereof in super capacitor - Google Patents
Novel NiSe2Coated mesoporous hollow carbon sphere composite material, preparation method thereof and application thereof in super capacitor Download PDFInfo
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- 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
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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
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Abstract
The invention discloses a novel NiSe2A coated mesoporous hollow carbon sphere composite material, a preparation method thereof and application thereof in a super capacitor. The invention adopts a one-step method without any surfactant, the mesoporous carbon nanospheres with adjustable pore diameter and particle size are synthesized in situ by stirring at normal temperature, and then a layer of Ni (OH) is uniformly deposited on the surface of the mesoporous carbon nanospheres in a water bath by a simple chemical precipitation method2Nanosheet, and finally selenizing to obtain the target product (HMCS/NiSe)2) Solve the problem of pure Ni (OH)2The problem of excessive aggregation of the nanoplatelets; at the same time, the introduction of carbon also increases the electrical conductivity of the whole material. The introduction of mesoporous carbon relieves the pure NiSe to a great extent2The volume of the nano sheet expands in the process of electrochemical test charging and discharging, and the composite material provided by the invention is used as the positive electrode active material of the super capacitor, so that the rate capability is good, and 80.5% of capacity can be still maintained after the circulation for 5000 times.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to novel NiSe2A coated mesoporous hollow carbon sphere composite material, a preparation method thereof and application thereof in a super capacitor.
Background
According to the energy formula of the super capacitor: 1/2CV2, the specific capacitance C and the working voltage V of the capacitor are increased, so that the energy density of the super capacitor can be effectively improved, and meanwhile, the decomposition voltage of the electrolyte is a key factor influencing the super capacitor. The positive electrode and the negative electrode of the traditional water system double electric layer super capacitor are both active carbon, but the active carbon has uneven pore size, and a plurality of pores are in a closed and closed state, so that the specific surface area is reduced, and the utilization rate of materials is not high. Meanwhile, the working voltage of the whole super capacitor is greatly limited due to the decomposition voltage of water, so in recent years, researchers focus on improving the specific capacitance of materials and the voltage window of electrolyte.
The mesoporous carbon has the advantages of high specific surface area, rich pore channel structures, good stability and the like, so that the mesoporous carbon is widely used for research of electrode materials of super capacitors. Transition metal oxides (hydroxides) allow higher specific capacitance to be achieved due to their unique energy storage principle. In recent years, the electrolyte is also increasingly applied to the aspect of super capacitors due to the fact that the ionic liquid is not easy to volatilize, is not flammable, has low toxicity and has a higher voltage window.
The patent application with the application number of CN201610258568.2 discloses NiSe with selenium-rich surface2A preparation method and application of the nano-sheet. Which is first synthesized by Ni (OH)2Nano-sheet is selenized at high temperature to obtain NiSe with selenium-rich surface2The nanosheet is stable in chemical property, simple in process and convenient to operate, and is applied to the field of new energy. But the hydrothermal process has higher requirements on equipment, higher technical difficulty and poor safety performance, and the high-temperature selenization process needs sectional temperature setting and is complex in working procedures. In addition, patent application No. CN201711449574.7 discloses a method for preparing monodisperse mesoporous carbon microspheres. Firstly, SiO is prepared2Then the mesoporous carbon microsphere is used as an inorganic template agent and is subjected to organic-inorganic hybrid reaction with an organic precursor to prepare the mesoporous carbon microsphere. The prepared mesoporous carbon microspheres have uniform particle size and controllable pore diameter, but the process is complicated, the preparation conditions are harsh, and the requirements on equipment are high.
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or disadvantages of the prior art, it is an object of the present invention to provide a novel NiSe2A coated mesoporous hollow carbon sphere composite material, a preparation method and application thereof.
In order to achieve the first object of the present invention, the present invention adopts the following technical solutions:
novel NiSe2Coating a mesoporous hollow carbon sphere composite material, wherein the composite material is integrally of a spherical structure and has a diameter of 400-500 nm; the NiSe2Is a nanosheet; the mesoporous hollow carbon spheres have the particle size of 300-400nm, the pore size distribution is concentrated in 8-12 nm, and the thickness of a carbon layer is 20-40 nm.
The second purpose of the invention is to provide the novel NiSe2The preparation method of the coated mesoporous hollow carbon sphere composite material specifically comprises the following steps:
(1) adding a silicon source into an aqueous solution dissolved with ethanol and ammonia water according to a ratio, and uniformly dispersing by ultrasonic; sequentially adding resorcinol and formaldehyde into the obtained mixed solution, magnetically stirring at room temperature for reaction for 20-30 h, and after the reaction is finished, performing suction filtration, washing and drying to obtain SiO2/SiO2@ RF composite structures;
(2) SiO obtained in the step (1)2/SiO2The @ RF composite structure is placed in a tube furnace, then the temperature is raised to 600-800 ℃ in the inert gas atmosphere, and the heat is preserved for 2-5 h to obtain SiO2/SiO2The material @ C;
(3) SiO obtained in the step (2)2/SiO2The material of @ C is put into concentrated nitric acid for acidification, and then is filtered, washed and dried to obtain pretreated SiO2/SiO2@C；
(4) The pretreated SiO obtained in the step (3) is used2/SiO2Ultrasonically dispersing the @ C in deionized water, then sequentially adding nickel nitrate hexahydrate and urea, mixing, heating in a water bath to 70-90 ℃, reacting at a constant temperature for 4-6 h, after the reaction is finished, performing suction filtration, washing and drying to obtain SiO2/SiO2@C/Ni(OH)2A material;
(5) SiO obtained in the step (4)2/SiO2@C/Ni(OH)2Placing the material in the middle of a porcelain boat, placing selenium powder on two sides of the porcelain boat, and placing the porcelain boat in a tube furnaceHeating to 300-500 ℃ in an inert gas atmosphere, and keeping the temperature for 1-3 h to obtain SiO2/SiO2@C/NiSe2A material;
(6) SiO obtained in the step (5)2/SiO2@C/NiSe2The material is placed in NaOH aqueous solution for etching for 20-30 h to obtain the NiSe2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2)。
Further, in the above technical solution, the silicon source in step (1) is Tetraethoxysilane (TEOS), propyl orthosilicate (TPOS), methyl orthosilicate (TMOS), or sodium silicate (Na)2SiO3) And the like.
Further, according to the technical scheme, the dosage ratio of the silicon source in the step (1) to the ethanol, the ammonia water and the deionized water is 2 mmol: 60 ml: 3 ml: 20 ml.
Further, in the above technical scheme, in the step (1), the silicon source and resorcinol are 2 mmol: (0.3-0.5) g.
Further, according to the technical scheme, the molar ratio of the formaldehyde to the resorcinol in the step (1) is 1-2: 1.
further, in the above technical scheme, the time for the ultrasonic dispersion in the step (1) is not limited, as long as the uniform dispersion of the silicon source in the aqueous solution is achieved, and the ultrasonic dispersion time is preferably 10 to 20min generally.
Specifically, according to the technical scheme, ethanol in the step (1) is used as a solvent, ammonia water is used for providing alkaline conditions for condensation reaction, resorcinol is used for providing phenolic hydroxyl groups, and formaldehyde is used for providing aldehyde hydroxyl groups.
The reaction mechanism of the above step (1) of the present invention is as follows: in the process of stirring at room temperature, the silicon source is hydrolyzed and condensed to generate SiO2Which nucleate internally first (from an infinite number of SiO)2Monomers are assembled) followed by continued formation of SiO2At the same time of the monomer, two hydrogen atoms on ortho-position of resorcinol hydroxyl group are more active, and are combined with oxygen atom on formaldehyde group to form water molecule, the rest part is connected to form high molecular compound-phenolic Resin (RF), SiO produced after nucleation2The template used as a subsequent mesoporous is embedded in the phenolic aldehydeIn the resin, the final self-assembly forms spherical SiO2/SiO2@ RF composite structures.
Further, in the technical scheme, the high-temperature calcination in the step (2) aims to calcine SiO2/SiO2The phenolic Resin (RF) in the @ RF composite structure is completely carbonized to obtain SiO2/SiO2@C。
Further, according to the technical scheme, the acidification in the step (3) is preferably performed at 70-90 ℃, the acidification time is preferably 10-20 min, and the purpose of acidification in the step is to increase hydrophilic functional groups on the surface of mesoporous carbon.
Further, in the technical scheme, the nickel nitrate hexahydrate in the step (4) is used as a nickel source, and the urea is used for generating Ni (OH)2Supply of sufficient OH-。
Further, in the above technical scheme, the molar ratio of nickel nitrate hexahydrate to urea in step (4) is 1:1 to 3, preferably 1: 2.
further, in the technical scheme, the high-temperature calcination in the step (5) is to ensure that the selenium powder is reduced, so that the target product HMCS/NiSe is obtained2。
Further, in the above technical solution, the SiO in the step (5)2/SiO2@C/Ni(OH)2The mass ratio of the material to the selenium powder is 1: 2-5, preferably 1: 3.
further, according to the technical scheme, the concentration of the NaOH aqueous solution in the step (6) is 1-5 mol/L.
Further, in the above technical scheme, SiO is used in the step (6)2/SiO2@C/NiSe2The material is etched in NaOH aqueous solution, and the aim is to use the NaOH aqueous solution to etch SiO2/SiO2@C/NiSe2SiO in material2All are etched away.
Further, in the above technical scheme, the etching temperature in the step (6) is preferably 60-90 ℃.
Further, in the above technical solution, the inert gas in step (2) and step (5) is preferably argon gas with a volume percentage of 99.95% or more.
It is a third object of the present invention to provide the novel NiSe described above2The coated mesoporous hollow carbon sphere composite material is applied to a super capacitor as a positive electrode material.
The super capacitor comprises the novel NiSe2Coating the mesoporous hollow carbon sphere composite material.
An asymmetric super capacitor comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, electrolyte and a shell, wherein the positive electrode is formed by uniformly mixing a positive active substance, a conductive agent and an adhesive and then coating and/or filling the mixture on the surface of a current collector; the negative electrode is formed by uniformly mixing a negative electrode active substance, a conductive agent and a binder and then coating and/or filling the mixture on the surface of a current collector; wherein: the positive active material is the novel NiSe2Coating the mesoporous hollow carbon sphere composite material; the negative active material is the mesoporous hollow carbon sphere HCMS; the electrolyte is EMIMBF4An ionic liquid.
Further, according to the technical scheme, the mesoporous hollow carbon sphere HCMS is prepared by the following method, comprising the following steps:
(i) adding a silicon source into an aqueous solution dissolved with ethanol and ammonia water according to a ratio, and uniformly dispersing by ultrasonic; sequentially adding resorcinol and formaldehyde into the obtained mixed solution, magnetically stirring at room temperature for reaction for 20-30 h, and after the reaction is finished, performing suction filtration, washing and drying to obtain SiO2/SiO2@ RF composite structures;
(ii) (ii) subjecting the SiO obtained in step (i)2/SiO2The @ RF composite structure is placed in a tube furnace, then the temperature is raised to 600-800 ℃ in the inert gas atmosphere, and the heat is preserved for 2-5 h to obtain SiO2/SiO2The material @ C;
(iii) (iii) subjecting the SiO obtained in step (ii) to a reaction at room temperature2/SiO2And (3) putting the @ C material into a NaOH aqueous solution to react for 20-30 h, and then carrying out suction filtration, washing and drying to obtain the mesoporous hollow carbon sphere HMCS.
Further, in the technical scheme, the concentration of the NaOH aqueous solution in the step (iii) is 1-5 mol/L.
Further, the air conditioner is provided with a fan,in the above technical scheme, SiO in step (iii)2/SiO2The material @ C is placed in an aqueous NaOH solution for reaction, the purpose being to use the aqueous NaOH solution to react SiO2/SiO2SiO in @ C material2All are etched away.
Compared with the prior art, the invention has the following beneficial effects:
(1) the mesoporous carbon material prepared by the invention has open pores, and the novel NiSe of the invention2The mesoporous carbon sphere-coated composite material is also coated with nano-flaky NiSe on the surface of mesoporous carbon2The surface area of the material can be greatly improved, and the utilization rate of the material is improved.
(2) The invention adopts a simple water bath method to synthesize Ni (OH)2The nano-sheet and the selenization process are simple and easy to implement.
(3) The invention adopts a one-step method without any surfactant, the mesoporous carbon nanospheres with adjustable pore diameter and particle size are synthesized in situ by stirring at normal temperature, and then a layer of Ni (OH) is uniformly deposited on the surface of the mesoporous carbon nanospheres in a water bath by a simple chemical precipitation method2The method is simple and easy to implement, and the safety performance is good. Solves the problem of pure Ni (OH)2The problem of excessive aggregation of the nanosheets, and at the same time, the introduction of carbon also increases the conductivity of the overall material. The introduction of mesoporous carbon relieves the pure NiSe to a great extent2The nano sheet expands in volume in the process of electrochemical test charging and discharging. Therefore, the super capacitor positive electrode active material has good rate capability, and still maintains 80.5 percent of capacity after 5000 cycles.
(4) The invention adopts NaOH to etch SiO2Greatly reducing the risk of the experiment. The whole preparation process is simple, easy to operate and high in safety performance. In addition, the super capacitor prepared by the invention is green and environment-friendly, the specific capacitance and the stability are both beneficial to being greatly improved, the energy density is higher, and the defect of lower energy density of the super capacitor is overcome to a certain extent.
Drawings
FIG. 1 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) Schematic structural diagram of (a);
FIG. 2 shows mesoporous hollow carbon spheres (HMCS) prepared in step (1) and NiSe prepared in step (2) in example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) XRD diffractogram of (a);
fig. 3 is an SEM photograph of mesoporous hollow carbon spheres (HMCS) prepared in step (1) of example 1 of the present invention;
FIG. 4 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) SEM photograph of (a);
FIG. 5 is a TEM photograph of mesoporous hollow carbon spheres (HMCS) prepared in step (1) of example 1 of the present invention;
FIG. 6 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) A TEM photograph of;
FIG. 7 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) Nitrogen adsorption and desorption and aperture distribution diagram; wherein: the interpolation map is the aperture distribution map;
FIG. 8 shows mesoporous hollow carbon spheres (HMCS) prepared in step (1) and NiSe prepared in step (2) in example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) A Raman map of (a);
fig. 9 is a graph showing the results of rate performance tests of the battery prepared in application example 1;
fig. 10 is a graph showing the results of cycle performance tests of the battery prepared in application example 1.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The novel NiSe of the embodiment2The preparation method of the coated mesoporous hollow carbon sphere composite material specifically comprises the following steps:
(1) preparation of mesoporous hollow carbon spheres
(i) Ultrasonically dispersing n-propyl orthosilicate (TPOS) and ethyl orthosilicate (TEOS) serving as silicon sources in an aqueous solution in which ethanol (solvent) and ammonia water (alkaline condition) are dissolved for 10min, then adding resorcinol (for providing phenolic hydroxyl) and formaldehyde (for providing aldehyde hydroxyl), magnetically stirring the obtained mixed solution at room temperature for 20h, and finally performing suction filtration, washing and drying to obtain SiO2/SiO2@ RF composite structures. Wherein the dosage of TPOS and TEOS is 0.5mmol and 1.5mmol respectively; the dosage of ethanol, ammonia water and deionized water is 60ml, 3ml and 20ml in sequence, the dosage of resorcinol is 0.4g, and the dosage of formaldehyde is 0.56ml (the density of formaldehyde is 300 mg/ml);
(ii) subjecting the mixture of step (i) toSiO prepared by the method2/SiO2The @ RF composite structure is placed in a high-temperature tube furnace, heat preservation is carried out for 2 hours in argon atmosphere, phenolic resin is completely carbonized, the carbonization temperature is kept at 700 ℃, and SiO is obtained2/SiO2@ C material.
(iii) At room temperature, the SiO prepared by the method in the step (ii) is used2/SiO2The material of @ C is put into NaOH aqueous solution to react for 30 hours, ensuring that all SiO in the material2Etching by NaOH, and finally performing suction filtration, washing and drying; wherein the concentration of the NaOH aqueous solution is 1mol/L, and the hollow mesoporous carbon nanosphere (HMCS) is finally obtained.
(2) Preparation of NiSe2Coated mesoporous hollow carbon sphere composite material
(a) Taking 0.1g of SiO prepared in the step (ii)2/SiO2And the material @ C is ultrasonically dispersed in 50ml of concentrated nitric acid, then heated to 80 ℃ and stirred for 15min, and hydrophilic functional groups on the surface of the mesoporous carbon are increased. And sequentially carrying out suction filtration and washing by using deionized water and absolute ethyl alcohol, and finally drying to obtain the pretreated hollow mesoporous carbon nanospheres.
(b) Ultrasonically dispersing the pretreated hollow mesoporous carbon nanospheres obtained in the step (a) in 100ml of deionized water, ultrasonically treating for 30min, adding 0.29g of nickel nitrate hexahydrate (nickel source), heating to 80 ℃, magnetically stirring for 15min, and adding 1.2g of urea (enough OH is provided)-) Continuously heating in water bath at 80 ℃ for 5h, finally performing suction filtration, washing, collecting solid products, and drying to obtain SiO2/SiO2@C/Ni(OH)2A material.
(c) Taking 0.1g of SiO prepared by the method in the step (b)2/SiO2@C/Ni(OH)2Putting the materials in the middle of a porcelain boat, respectively putting 0.15g (total 0.3g) of selenium powder at two sides of the porcelain boat, putting the porcelain boat in a tube furnace, heating to 400 ℃ under argon atmosphere, and keeping the temperature for 2h under 400 ℃ and argon atmosphere to ensure that the selenium powder is reduced to obtain SiO2/SiO2@C/NiSe2A material.
(d) Subjecting the SiO obtained in step (c)2/SiO2@C/NiSe2The material was placed in a 100ml aqueous solution of 4mol/L NaOHHeating to 80 ℃ in the liquid, and etching for 20 hours at constant temperature to obtain the novel NiSe2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2)。
FIG. 1 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) Schematic structural diagram of (a); as can be seen from the figure, the whole composite structure has abundant porous carbon layers, and a thin NiSe layer is grown outside the composite structure2Nanosheet, porous Structure to NiSe2The volume expansion in the charging and discharging process has good inhibition effect. In addition, the introduction of carbon shell enables NiSe2More active sites are exposed, so that the performance of the composite material is further improved.
FIG. 2 shows mesoporous hollow carbon spheres (HMCS) prepared in step (1) and NiSe prepared in step (2) in example 12Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) XRD diffractogram of (a). As can be seen from comparison with the standard card JCPDS number 41-1445, the diffraction peak positions (2 θ ═ 29.95 °,33.58 °,36.89 °,42.86 °,50.74 °,53.17 °,55.52 °,57.81 °, 62.23 °) correspond to crystal planes ((200), (210), (211), (220), (311), (222), (023), (321), (400), and the diffraction peak positions are determined to be cubic NiSe according to the lattice constants a ═ b ═ c ═ 5.96042Meanwhile, the product has a wide carbon peak at 2 theta-24.9 degrees, and is determined to be pure HMCS/NiSe2And no other impurities.
Fig. 3 is an SEM photograph of the mesoporous hollow carbon spheres (HMCS) prepared in step (1) of example 1, which shows that the overall shape is spherical, the sizes thereof are similar, and the dispersibility thereof is good.
FIG. 4 shows NiSe prepared in step (2) of example 12Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) From the SEM photograph, it can be seen that NiSe prepared as described in this example2The mesoporous hollow carbon sphere-coated composite material is of a spherical structure, and NiSe grows on the surface of the mesoporous hollow carbon sphere-coated composite material2The diameter of the whole spherical structure of the nano-sheet is 400-400 nm, the particle diameter of the mesoporous carbon sphere is 300-400nm, the most part of the pore diameter is about 10nm, and the thickness of the carbon layer is about 30 nm. NiSe can also be seen2The nano-sheets are uniformly coated on the surface of the hollow sphere and exposed outMore active sites, which make it possess higher specific capacitance. In addition, the existence of hollow mesopores in the composite material also lays a foundation for subsequent excellent electrochemical performance.
Fig. 5 is a TEM photograph of the mesoporous hollow carbon spheres (HMCS) prepared in step (1) of example 1, which can be clearly seen to have a pore structure, and a thin carbon shell is clearly seen at the outer edge. The pore structure can relieve the problem of volume expansion of the material caused by rapid adsorption and desorption of ions in high-current charging and discharging.
FIG. 6 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) TEM photograph of (a). From fig. 5, it can be confirmed that the composite material shape remains spherical, and the nanosheet is on the surface, which completely conforms to the above characteristic description.
FIG. 7 shows NiSe prepared in step (2) of example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) Nitrogen adsorption and desorption and pore size distribution diagram. The composite material was tested to have a surface area of 381.4 m2 g-1Far exceeds pure NiSe2The nano-sheet further proves that the introduction of mesoporous carbon can expose more active sites. It can be also clearly seen from fig. 6 that the mesoporous lithium iron phosphate has a typical type iv curve, which indicates the existence of mesopores, and also can be visually seen from the pore size distribution, the mesopores with the size of about 10nm exist in a large amount, which is very beneficial to the storage of ions.
FIG. 8 shows mesoporous hollow carbon spheres (HMCS) prepared in step (1) and NiSe prepared in step (2) in example 1 of the present invention2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) Raman map of (a). As can be seen from FIG. 7, two distinct peaks of HMCS are at 1300cm-1And 1580cm-1Matching with D band (disordered carbon) and G band (graphitic carbon), the strength of D band: g band (ID/IG) ═ 0.98, further illustrated as amorphous carbon with fewer defects, compare HMCS/NiSe2The ratio of the Raman curve to the Raman curve is increased to 1.2, which further shows that after the two materials are compounded, the defects are further increased, the graphitization degree is higher, the conductivity is higher, and the electron transfer of the subsequent electrochemical performance test is quicker.
Example 2
The novel NiSe of the embodiment2The preparation method of the coated mesoporous hollow carbon sphere composite material specifically comprises the following steps:
(1) preparation of mesoporous hollow carbon spheres
(i) Ultrasonically dispersing methyl orthosilicate (TMOS) serving as a silicon source in an aqueous solution in which ethanol (solvent) and ammonia water (alkaline condition) are dissolved for 15min, then adding resorcinol (for providing phenolic hydroxyl) and formaldehyde (for providing aldehyde hydroxyl), magnetically stirring the obtained mixed solution at room temperature for 25h, and finally performing suction filtration, washing and drying to obtain SiO2/SiO2@ RF composite structures. Wherein the amount of TMOS is 2 mmol; the dosage of ethanol, ammonia water and deionized water is 60ml, 3ml and 20ml in sequence, the dosage of resorcinol is 0.3g, and the dosage of formaldehyde is 0.56ml (the density of formaldehyde is 300 mg/ml);
(ii) (ii) SiO prepared by the method described in step (i)2/SiO2The @ RF composite structure is insulated for 3 hours in a high-temperature tube furnace under the argon atmosphere, the phenolic resin is completely carbonized, the carbonization temperature is kept at 800 ℃ to obtain SiO2/SiO2@ C material.
(iii) At room temperature, the SiO prepared by the method in the step (ii) is used2/SiO2The material of @ C is put into NaOH aqueous solution to react for 25 hours, ensuring that all SiO in the material2Etching by NaOH, and finally performing suction filtration, washing and drying; wherein the concentration of the NaOH aqueous solution is 2mol/L, and the hollow mesoporous carbon nanosphere (HMCS) is finally obtained.
(2) Preparation of NiSe2Coated mesoporous hollow carbon sphere composite material
(a) Taking 0.1g of SiO prepared in the step (ii)2/SiO2And the material @ C is ultrasonically dispersed in 50ml of concentrated nitric acid, then heated to 70 ℃ and stirred for 20min, and hydrophilic functional groups on the surface of the mesoporous carbon are increased. Then sequentially using deionized water and absolute ethyl alcohol to carry out suction filtration, washing and drying to obtain the pretreated SiO2/SiO2@C。
(b) Subjecting the pretreated SiO obtained in step (a)2/SiO2@ C allUltrasonic dispersing in 100ml deionized water, ultrasonic treating for 30min, adding 0.29g nickel nitrate hexahydrate (nickel source), heating to 80 deg.C, magnetically stirring for 15min, and adding 1.8g urea (providing enough OH)-) Continuously heating in water bath for 6h at 70 ℃, finally performing suction filtration and washing, collecting a solid product, and drying to obtain SiO2/SiO2@C/Ni(OH)2A material.
(c) Taking 0.1g of SiO prepared by the method in the step (b)2/SiO2@C/Ni(OH)2Placing the materials in the middle of a porcelain boat, respectively placing 0.1g (total 0.2g) selenium powder at two sides of the porcelain boat, placing the porcelain boat in a tube furnace, heating to 500 deg.C under argon atmosphere, and keeping the temperature at 500 deg.C for 1h under argon atmosphere to ensure that the selenium powder is reduced to obtain SiO2/SiO2@C/NiSe2A material.
(d) Subjecting the SiO obtained in step (c)2/SiO2@C/NiSe2The material is put into 100ml NaOH aqueous solution with the concentration of 2mol/L, heated to 90 ℃ and etched for 30 hours at constant temperature to obtain the novel NiSe2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2)。
Example 3
The novel NiSe of the embodiment2The preparation method of the coated mesoporous hollow carbon sphere composite material specifically comprises the following steps:
(1) preparation of mesoporous hollow carbon spheres
(i) With sodium silicate (Na)2SiO3) Ultrasonically dispersing as silicon source in water solution containing ethanol (solvent) and ammonia water (alkaline condition) for 20min, adding resorcinol (for providing phenolic hydroxyl group) and formaldehyde (for providing aldehyde hydroxyl group), magnetically stirring the obtained mixed solution at room temperature for 30h, suction filtering, washing, and drying to obtain SiO2/SiO2@ RF composite structures. Wherein the using amount of the sodium silicate is 2 mmol; the dosage of the ethanol, the ammonia water and the deionized water is 60ml, 3ml and 20ml in sequence, the dosage of the resorcinol is 0.5g, and the dosage of the formaldehyde is 0.56ml (the density of the formaldehyde is 300 mg/ml);
(ii) (ii) SiO prepared by the method described in step (i)2/SiO2@ RF complexKeeping the temperature of the composite structure in a high-temperature tube furnace under argon atmosphere for 5 hours, completely carbonizing the phenolic resin, and keeping the carbonization temperature at 600 ℃ to obtain SiO2/SiO2@ C material.
(iii) At room temperature, the SiO prepared by the method in the step (ii) is used2/SiO2The material of @ C is put into NaOH aqueous solution to react for 20 hours, ensuring that all SiO in the material2Etching by NaOH, and finally performing suction filtration, washing and drying; wherein the concentration of the NaOH aqueous solution is 3mol/L, and the hollow mesoporous carbon nanosphere (HMCS) is finally obtained.
(2) Preparation of NiSe2Coated mesoporous hollow carbon sphere composite material
(a) Taking 0.1g of SiO prepared in the step (ii)2/SiO2And the material @ C is ultrasonically dispersed in 50ml of concentrated nitric acid, then heated to 90 ℃ and stirred for 10min, and hydrophilic functional groups on the surface of the mesoporous carbon are increased. And sequentially carrying out suction filtration and washing by using deionized water and absolute ethyl alcohol, and finally drying to obtain the pretreated hollow mesoporous carbon nanospheres.
(b) Subjecting the pretreated (0.1g) SiO obtained in step (a)2/SiO2Ultrasonic dispersing @ C in 100ml deionized water, ultrasonic treating for 30min, adding 0.29g nickel nitrate hexahydrate (nickel source), heating to 80 deg.C, magnetically stirring for 15min, and adding 0.9g urea (providing enough OH)-) Continuously heating in water bath for 6h at 70 ℃, finally performing suction filtration and washing, collecting a solid product, and drying to obtain SiO2/SiO2@C/Ni(OH)2A material.
(c) Taking 0.1g of SiO prepared by the method in the step (b)2/SiO2@C/Ni(OH)2Placing the material in the middle of a porcelain boat, respectively placing 0.25g (total 0.5g) selenium powder at two sides of the porcelain boat, placing the porcelain boat in a tube furnace, heating to 300 deg.C under argon atmosphere, and keeping the temperature at 300 deg.C under argon atmosphere for 3h to ensure that the selenium powder is reduced to obtain SiO2/SiO2@C/NiSe2A material.
(d) Subjecting the SiO obtained in step (c)2/SiO2@C/NiSe2The material is put into 100ml of NaOH aqueous solution with the concentration of 5mol/L, heated to 60 ℃ and etched for 25 hours at constant temperature to obtain the novel materialNiSe2Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2)。
Application example 1
The embodiment provides an asymmetric supercapacitor, which comprises an anode, a cathode, a diaphragm arranged between the anode and the cathode, electrolyte and a shell, wherein the anode is formed by uniformly mixing an anode active substance, acetylene black and PTFE according to a mass ratio of 8:1:1 and then coating the mixture on the surface of foamed nickel; the negative electrode is formed by uniformly mixing a negative electrode active material, acetylene black and PTFE according to the mass ratio of 8:1:1 and then coating the mixture on the surface of foamed nickel; wherein: the positive electrode active material was the novel NiSe prepared in step (2) of example 12Coated mesoporous hollow carbon sphere composite material (HMCS/NiSe)2) (ii) a The negative active material is the hollow mesoporous carbon nanospheres (HMCS) prepared in step (1) of example 1; the diaphragm is a PTFE film; the electrolyte is ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF)4). And assembling the asymmetric super capacitor by using a CR 2032 button cell to perform electrochemical performance test.
Fig. 9 is a graph showing the rate performance test result of the asymmetric supercapacitor prepared in the application example. As is clear from fig. 9, as the current density increases, the capacity decreases more slowly, which is substantially consistent with the analytical prediction of the performance of the material as described above in the description of its structure. Further illustrates that the introduction of the mesoporous carbon not only can play a role of buffering, so that the deformation of the material is smaller under the condition of large current density. Meanwhile, the conductivity of the ion-exchange membrane is integrally improved, more ions are transmitted in the same time, and more energy is stored.
Fig. 10 is a graph showing the cycle performance test results of the asymmetric supercapacitor prepared in the example of the present application. As can be seen from fig. 10, after 5000 cycles, the capacity fade was less, and 80.5% of the capacity was still maintained, indicating that the stability was superior, further confirming the foregoing.
Claims (7)
1. Novel NiSe2The coated mesoporous hollow carbon sphere composite material is characterized in that: the composite material is integrally of a spherical structure, and the diameter of the composite material is 400-500 nm; the NiSe2Is a nanosheet; the particle size of the mesoporous hollow carbon spheres is 300-400nm, the pore size distribution is concentrated in 8-12 nm, and the thickness of the carbon layer is 20-40 nm; wherein: the NiSe2The coated mesoporous hollow carbon sphere composite material is prepared by the following method, comprising the following steps:
(1) adding a silicon source into an aqueous solution dissolved with ethanol and ammonia water according to a ratio, and uniformly dispersing by ultrasonic; sequentially adding resorcinol and formaldehyde into the obtained mixed solution, magnetically stirring at room temperature for reaction for 20-30 h, and after the reaction is finished, performing suction filtration, washing and drying to obtain SiO2/SiO2@ RF composite structures; the molar ratio of the formaldehyde to the resorcinol is 1-2: 1;
(2) SiO obtained in the step (1)2/SiO2The @ RF composite structure is placed in a tube furnace, then the temperature is raised to 600-800 ℃ in the inert gas atmosphere, and the heat is preserved for 2-5 h to obtain SiO2/SiO2The material @ C;
(3) SiO obtained in the step (2)2/SiO2The material of @ C is put into concentrated nitric acid for acidification, and then is filtered, washed and dried to obtain pretreated SiO2/SiO2@C；
(4) The pretreated SiO obtained in the step (3) is used2/SiO2Ultrasonically dispersing the @ C in deionized water, then sequentially adding nickel nitrate hexahydrate and urea, mixing, heating in a water bath to 70-90 ℃, reacting at a constant temperature for 4-6 h, after the reaction is finished, performing suction filtration, washing and drying to obtain SiO2/SiO2@C/Ni(OH)2A material; the molar ratio of the nickel nitrate hexahydrate to the urea is 1: 1-3;
(5) SiO obtained in the step (4)2/SiO2@C/Ni(OH)2Placing the material in the middle of a porcelain boat, placing selenium powder on two sides of the porcelain boat, then placing the porcelain boat in a tube furnace, heating to 300-500 ℃ in an inert gas atmosphere, and preserving heat for 1-3 hours to obtain SiO2/SiO2@C/NiSe2A material;
(6) SiO obtained in the step (5)2/SiO2@C/NiSe2The material is placed in NaOH aqueous solution for etching for 20-30 h to obtain the NiSe2HMCS/NiSe composite material coated with mesoporous hollow carbon spheres2。
2. The NiSe of claim 12The coated mesoporous hollow carbon sphere composite material is characterized in that: the silicon source in the step (1) is any one or more of ethyl orthosilicate, propyl orthosilicate, methyl orthosilicate or sodium silicate.
3. The NiSe of claim 12The coated mesoporous hollow carbon sphere composite material is characterized in that: SiO in step (5)2/SiO2@C/Ni(OH)2The mass ratio of the material to the selenium powder is 1: 2 to 5.
4. NiSe of any one of claims 1 to 32The application of the coated mesoporous hollow carbon sphere composite material in a super capacitor.
5. A supercapacitor positive electrode, characterized in that: comprising the NiSe of any one of claims 1 to 32Coating the mesoporous hollow carbon sphere composite material.
6. An asymmetric supercapacitor, comprising: the positive electrode is formed by uniformly mixing a positive active substance, a conductive agent and an adhesive and then coating and/or filling the mixture on the surface of a current collector; the negative electrode is formed by uniformly mixing a negative electrode active substance, a conductive agent and a binder and then coating and/or filling the mixture on the surface of a current collector; wherein: the positive electrode active material is NiSe according to any one of claims 1 to 32Coating the mesoporous hollow carbon sphere composite material; the negative active material is mesoporous hollow carbon spheres HMCS; the electrolyte is EMIMBF4An ionic liquid.
7. The asymmetric ultracapacitor of claim 6, wherein: the mesoporous hollow carbon sphere HMCS is prepared by the following method, and comprises the following steps:
(i) adding a silicon source into an aqueous solution dissolved with ethanol and ammonia water according to a ratioIn the middle, the ultrasonic dispersion is uniform; sequentially adding resorcinol and formaldehyde into the obtained mixed solution, magnetically stirring at room temperature for reaction for 20-30 h, and after the reaction is finished, performing suction filtration, washing and drying to obtain SiO2/SiO2@ RF composite structures;
(ii) (ii) subjecting the SiO obtained in step (i)2/SiO2The @ RF composite structure is placed in a tube furnace, then the temperature is raised to 600-800 ℃ in the inert gas atmosphere, and the heat is preserved for 2-5 h to obtain SiO2/SiO2The material @ C;
(iii) (iii) subjecting the SiO obtained in step (ii) to a reaction at room temperature2/SiO2And (3) putting the @ C material into a NaOH aqueous solution to react for 20-30 h, and then carrying out suction filtration, washing and drying to obtain the mesoporous hollow carbon sphere HMCS.
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