CN114464465A - Carbon hollow sphere coated metal selenide composite material and preparation method and application thereof - Google Patents

Carbon hollow sphere coated metal selenide composite material and preparation method and application thereof Download PDF

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CN114464465A
CN114464465A CN202210247050.4A CN202210247050A CN114464465A CN 114464465 A CN114464465 A CN 114464465A CN 202210247050 A CN202210247050 A CN 202210247050A CN 114464465 A CN114464465 A CN 114464465A
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composite material
nise
hollow sphere
cbs
carbon hollow
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CN114464465B (en
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王晶
罗家还
牛永生
刘森
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Anyang Institute of 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/32—Carbon-based
    • H01G11/42—Powders or particles, e.g. composition thereof
    • 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 carbon hollow sphere coated metal selenide composite material, a preparation method and application thereof, and relates to the technical field of green energy materials. The composite material has a double-layer structure, and the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere. The invention also includes NiSexA preparation method and application of the @ CBs composite material. The invention successfully prepares the nickel selenide compound embedded by using an in-situ selenization method by taking Ni-soc-MOF as a templateComposite materials in hollow carbon spheres, NiSex@ CBs specific capacitance at Current Density 1A g‑1The time capacity is up to 1720F g‑1，NiSex@ CBs// AC asymmetric supercapacitor at 800kW kg‑1Has a power density of 45.2 Whhkg‑1High energy density, excellent energy storage performance, NiSexThe capacitance retention rate of the @ CBs// AC asymmetric supercapacitor is still up to 89% after 5000 cycles, and high cycle stability is shown.

Description

Carbon hollow sphere coated metal selenide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of green energy materials, and particularly relates to a carbon hollow sphere coated metal selenide composite material, and a preparation method and application thereof.
Background
With the development of human society, energy shortage and environmental problems are increasingly highlighted. Research and development of high performance energy storage devices is very important. The super capacitor is an important electrochemical energy storage device, and is concerned about the advantages of high charging and discharging speed, long cycle life, wide working temperature range, green safety and the like. However, the largest drawback of supercapacitors is the low energy density compared to lithium ion batteries, which also limits their large-scale commercial application. According to the super capacitor E-1/2 CV2The key to increasing the energy density (E) is to increase the specific capacitance (C) of the electrode active material and to broaden its operating voltage (V). The specific capacitance is an important index for measuring the energy storage capacity of the electrode material. The main approach to increasing the energy density of supercapacitors is to increase the specific capacitance of the electrode material. The controllable design of the electrode material has great significance for developing the electrode material with ultrahigh specific capacitance and high cycle stability.
Recently, hybrid nanomaterials have attracted a wide range of attention as advanced electrode materials compared to the corresponding single component materials. Transition metal selenides are a semiconductor material with excellent conductivity and electrochemical properties. It has attracted much attention in the fields of lithium ion batteries, sodium ion batteries, solar thin film batteries, electrochemical hydrogen production, supercapacitors and the like. So far, research on metal selenide materials in supercapacitors has also been reported in the literature. For example, selenide materials, such as NiSe and CoSe, exhibit excellent electrical properties for supercapacitors. These studies indicate that the transition metal selenide has a higher pseudocapacitance specific capacity and is suitable for assembling a high energy density supercapacitor. But is kinetically unfavorable and has poor cycle stability. However, the introduction of the carbon material into the electrode material can effectively improve the electron conductivity and thermal/chemical stability. Currently, electrode materials such as carbon-coated metals or metal selenides can be prepared under suitable conditions by direct pyrolysis or selenization of MOFs.
These current research projects are focused mainly on the preparation of metals or metal selenides as electrode materials in carbon matrices by adjusting the pyrolysis conditions of the MOFs prepared. The preparation of the metal selenide/carbon hollow sphere composite material by taking MOF as a precursor multiphase transition metal is seldom concerned. However, it is not easy to design a high performance hybrid structure based on MOFs. The materials are expected to design a new hybrid structure and exert a synergistic effect, so that the materials show good electrochemical performance. Therefore, the carbon hollow sphere coated metal selenide composite material, the preparation method and the application are provided for solving the technical problems.
Disclosure of Invention
The invention aims to provide a carbon hollow sphere coated metal selenide composite material and a preparation method and application thereof, wherein NiSe is prepared by mixing NiSexThe @ CBs nano particles are uniformly distributed in the carbon hollow sphere, and NiSe is preparedxThe @ CBs// AC asymmetric super capacitor is used for energy storage, and solves the problems in the prior art.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a carbon hollow sphere coated metal selenide composite material, which has a double-layer structure, wherein the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing nickel salt and H4Dissolving ABTC in an aqueous solution composed of N, N-dimethylacetamide, water and tetrafluoroboric acid, and uniformly stirring to prepare a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a drying oven at the temperature of 120-160 ℃ for drying for 3-6 days to obtain an intermediate product Ni-soc-MOF;
and step 3: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
Preferably, the volume ratio of the N, N-dimethylacetamide to the solvent water in the aqueous solution in the step 1 is 1.5-6, and the volume ratio of the tetrafluoroboric acid to the solvent water is 0.5-2.
Preferably, the structure of the Ni-soc-MOF in the step 2 consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and nickel trinuclear metal clusters together through ligands, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size of less than 1 nm.
Preferably, the nickel salt in step 1 is one or more of nickel sulfate, nickel nitrate and nickel chloride.
In the invention, Soc-MOFs is selected as a template to prepare the nitrogen-doped porous carbon-coated transition metal selenide composite electrode material, wherein the Soc-MOFs is prepared from 3,3 ', 5, 5' -azobenzene tetracarboxylic acid (H)4ABTC) is an organic ligand, and the MOFs material with the Soc topological structure is constructed by a trinuclear metal cluster. The Soc-MOFs organic ligand simultaneously contains carbon element and nitrogen element, a porous carbon layer is generated to interact with metal selenide in the process of preparing selenide at high temperature, the synergistic effect between metal ions and carbon hollow spheres in the structure is favorable for improving the conductivity and electrochemical comprehensive performance of the composite material, the metal atoms in the structure are connected with the organic ligand in a trinuclear cluster mode, and the metal selenide after high-temperature selenization is dispersed in the porous carbon to increase the contact area between the porous carbon and electrolyte and be favorable for the diffusion of the electrolyte.
The invention has the following beneficial effects:
1. according to the invention, Ni-soc-MOF is used as a template, the composite material with the nickel selenide compound embedded in the carbon hollow sphere is successfully prepared by adopting an in-situ selenization method, and a new opportunity is provided for manufacturing a high-performance super capacitor through a carbon network with higher mechanical flexibility.
2. The composite material NiSe of the inventionx@ CBs specific capacitance of electricityFluid density 1Ag-1The time capacity is up to 1720Fg-1，NiSex@ CBs// AC asymmetric supercapacitor at 800kWkg-1Has a power density of 45.2Whkg-1Exhibits excellent energy storage performance.
3. NiSe in the inventionxThe capacitance retention rate of the @ CBs// AC asymmetric supercapacitor is still up to 89% after 5000 cycles, and high cycle stability is shown.
4. NiSe prepared by the inventionxThe @ CBs nanoparticles are expected to be used in advanced hybrid supercapacitors as a novel electroactive material.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is NiSexScheme for synthesis of @ CBs composites.
FIG. 2 shows Ni-soc-MOF and simulated XRD patterns.
FIG. 3 is NiSex@ CBs and Ni3Se4XRD spectrum of (1).
FIG. 4 shows Ni-soc-MOF (a) and NiSexSEM picture of @ CBs (b).
FIG. 5 shows NiSexTEM image of @ CBs.
FIG. 6 is NiSex@ CBs composite XPS plots.
FIG. 7 shows NiSex@ CBs and NiSexAt 20mVs-1CV curves at different scan rates.
FIG. 8 shows NiSex@ CBs is in the range of 5-50 mVs-1CV curves at different scan rates.
FIG. 9 shows NiSex@ CBs and NiSexAt a current density of 1Ag-1Time charge and discharge curve diagram.
FIG. 10 shows NiSex@ CBs and NiSexSpecific capacitance at different current densities.
FIG. 11 is a diagram of: (a)20mVs-1Activated carbon and NiSe at scanning speedxCV curves of @ CBs; (b) NiSex@ CBs// AC asymmetric supercapacitor at scan rate of 50mVs-1CV curves for different potential windows; (c) different scan rates at 2MKOH (5, 10, 20 and 50 mVs)-1) A CV curve of (a); (d) GCD curves for different current densities in the 0-1.6V potential window.
FIG. 12 shows the current density at 1Ag-1Graph of capacity retention after 5000 cycles.
Fig. 13 is a Ragone plot of energy density and power density.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiment 1a carbon hollow sphere coated metal selenide composite material and a preparation method thereof
Referring to fig. 1 to 13, the present invention is a carbon hollow sphere coated metal selenide composite material, the composite material has a double-layer structure, and the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing Ni (SO)4)2·6H2O and H4ABTC dissolved in 3ml N, N-dimethylacetamide and 1ml H2Mixing O and 1ml of tetrafluoroboric acid, stirring uniformlyThen preparing a mixed solution A;
and 2, step: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a drying oven at 120 ℃ for drying for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and a nickel trinuclear metal cluster together through a ligand, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size smaller than 1 nm;
and step 3: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
Embodiment 2 carbon hollow sphere coated metal selenide composite material and preparation method thereof
The invention relates to a carbon hollow sphere coated metal selenide composite material, which has a double-layer structure, wherein the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing Ni (SO)4)2·6H2O and H4ABTC dissolved in 6ml N, N-dimethylacetamide and 1ml H2Mixing O and 1ml of tetrafluoroboric acid, and stirring uniformly to obtain a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a drying oven at 120 ℃ for drying for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and a nickel trinuclear metal cluster together through a ligand, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size smaller than 1 nm;
and step 3: mixing Ni-soc-MOF and Se powderMixing the materials in a mass ratio of 1:1, and placing the mixture in a high-temperature environment of 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
Embodiment 3 a carbon hollow sphere coated metal selenide composite material and preparation method thereof
The invention relates to a carbon hollow sphere coated metal selenide composite material which is of a double-layer structure, wherein the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing Ni (SO)4)2·6H2O and H4ABTC dissolved in 6ml N, N-dimethylacetamide and 2ml H2Mixing O and 1ml of tetrafluoroboric acid, and stirring uniformly to obtain a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle into a drying oven at 120 ℃ for drying for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and a nickel trinuclear metal cluster together through a ligand, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size smaller than 1 nm;
and step 3: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
Embodiment 4 a carbon hollow sphere coated metal selenide composite material and preparation method thereof
The invention relates to a carbon hollow sphere coated metal selenide composite material, which has a double-layer structure, wherein the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexUniformity of nano-particlesDispersed inside the hollow carbon sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing Ni (SO)4)2·6H2O and H4ABTC dissolved in 6ml N, N-dimethylacetamide and 2ml H2Mixing O and 2ml of tetrafluoroboric acid, and stirring uniformly to prepare a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle into a drying oven at 120 ℃ for drying for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and a nickel trinuclear metal cluster together through a ligand, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size smaller than 1 nm;
and step 3: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
Embodiment 5 a carbon hollow sphere coated metal selenide composite material and preparation method thereof
The invention relates to a carbon hollow sphere coated metal selenide composite material which is of a double-layer structure, wherein the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing Ni (SO)4)2·6H2O and H4ABTC dissolved in 3ml N, N-dimethylacetamide and 1ml H2Mixing O and 1ml of tetrafluoroboric acid, and stirring uniformly to obtain a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a drying oven at 160 ℃ for drying 3Obtaining an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and a nickel trinuclear metal cluster together through a ligand, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size smaller than 1 nm;
and step 3: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
Embodiment 6 a carbon hollow sphere coated metal selenide composite material and preparation method thereof
The invention relates to a carbon hollow sphere coated metal selenide composite material, which has a double-layer structure, wherein the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing Ni (SO)4)2·6H2O and H4ABTC dissolved in 3ml N, N-dimethylacetamide and 1ml H2Mixing O and 1ml of tetrafluoroboric acid, and stirring uniformly to obtain a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a drying oven at 120 ℃ for drying for 6 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF consists of H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and a nickel trinuclear metal cluster together through a ligand, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size smaller than 1 nm;
and step 3: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
FIGS. 2 and 3 study the crystal structure of Ni-soc-MOF and NiSe using x-ray diffraction pattern (XRD), respectivelyxThe crystal structure of @ CBs, the XRD spectrogram of the two materials and the simulation data of Ni-soc-MOF in the literature have similar diffraction peaks, which indicates that Ni-soc-MOF, NiSe are successfully synthesizedxXRD spectrogram and Ni of @ CBs composite material3Se4The spectra (JCPDS18-0890) were well matched.
FIG. 4 Studies of synthetic Ni-soc-MOF and NiSexThe surface morphology of @ CBs, Ni-soc-MOF particles exhibit a relatively smooth spherical structure which retains its original shape without collapse after selenization, while its surface becomes rougher in the structure. The TEM image in FIG. 5 further confirms the coating of NiSexMorphology and structural features of carbon bubbles of nanoparticles, and NiSe also displayed using High Resolution TEM (HRTEM) imagesxThe lattice of the surface and the degree of graphitization of the MOF derived carbon bubbles. By carefully investigating NiSex@ CBs, different fringe spacings 0.18nm and 0.53nm assigned to Ni3Se4020 and 002 planes of phase. There is a significant 0.34nm lattice spacing characteristic, corresponding to the (002) crystal plane of graphitic carbon. NiSe wrapped by carbon hollow ballxNanoparticles, as electrode materials, facilitate faster ion and electron transport. Corresponding TEM element mapping NiSex@ CBs is shown in FIG. 5e-g, indicating that the elements Ni, Se and C are uniformly distributed in NiSexInternal of @ CBs, element characterization further illustrates that Ni and Se elements are uniformly dispersed in the carbon hollow sphere, showing that high-purity NiSex@ CBs composites.
To further study NiSex@ CBs, surface elemental composition and oxidation state, XPS survey analysis indicates the presence of Ni, C and Se in the material. In the C1 spectrum, the characteristic peaks of 285.4eV and 284.2eV are derived from the C-C peak and sp2Hybridized carbon atom (C ═ C), and Se3d can be seen from Se spectrum3/2And 3d5/2The peaks of (a) are located at 54.6eV and 53.7eV, respectively. Further, the peak at 58.8eV represents the presence of Se — O bond, which is caused by the oxidation of the selenide surface. The spectrum of Ni2p is divided into four main peaks, and the characteristic peaks at 873.3 and 855.9eV belong to Ni2p1/2And Ni2p3/2And is combined withAccompanied by two characteristic peaks 878.9 and 861.1eV (abbreviated as "Sat"), as shown in fig. 6.
Embodiment 7 application of carbon hollow sphere coated metal selenide composite material
The application of the composite material prepared by the preparation method of the carbon hollow sphere coated metal selenide composite material in the super capacitor comprises the following specific processes: with NiSexThe @ CBs is a positive electrode, Pt is used as a counter electrode, and Ag/AgCl is used as a reference electrode to form a three-electrode system.
Respectively carrying out NiSe in a three-electrode system of 2MKOH aqueous solutionx@ CBs and NiSexCV and GCD measurements of the two nanomaterials. The scan rate was 20mVs-1And in the process, the potential window of the CV curves of the two electrodes ranges from 0V to 0.5V.
As can be seen from FIG. 7, under the same conditions, NiSe was presentxIntegration area ratio NiSe of @ CBs electrodexThe larger the nano material, the NiSe isx@ CBs has a high specific capacitance. NiSex@ CBs nano material is in the range of 5-50 mVs-1The CV curves at different scan rates over the range are shown in fig. 8, and the results show that as the scan rate increases, the CV curve area and peak current increase significantly. In addition, a pair of redox peaks was observed on each CV curve, indicating that both electrodes had typical cell behavior.
All these GCD curves show that the material has better charge-discharge curves, indicating that NiSexThe @ CBs electrode has excellent pseudocapacitance performance characteristics. The specific capacity was calculated from their respective discharge curves, and NiSe was foundx@ CBs electrode at 1Ag-1Specific capacity of hour is up to 1720Fg-1The above results show that, at the same current density, NiSexThe @ CBs electrode has the longest charge and discharge time, which is consistent with CV measurements. NiSex@ CBs electrodes at Current densities 1, 3, 5, 10 and 20Ag-1The specific capacity at time is 1720, 1549, 1438, 1320 and 1125Fg respectively-1(as shown in fig. 10).
NiSex@ CBs binding NiSexThe advantages of the structure and the carbon net, the carbon hollow spheres are uniformly distributed in the NiSexThe diffusion path of electrolyte ions and electrons can be effectively improved, and the carbon hollow sphere and the nano NiSe are formedxThe synergistic effect between the components ensures that the specific capacity of the composite material is higher.
According to NiSexThe @ CBs nano particle has excellent electrochemical performance, and NiSe is designed and prepared in a 2MKOH aqueous solutionx@ CBs is a positive electrode, and Activated Carbon (AC) is a negative electrode. NiSe in three-electrode systemxThe potential window ranges of the @ CBs nanoparticles and the AC are 0-0.6V and-1.0-0V respectively. Adjusting Activated Carbon (AC) and NiSe according to formulaxThe optimized mass ratio for the @ CBs electrode is about 3.5. To ensure the stability of the asymmetric supercapacitor device, NiSexThe CV characteristics of the @ CBs// AC asymmetric supercapacitor were measured over several potential ranges from 1.4 to 1.65V. The CV curve of the asymmetric supercapacitor device shows ideal reversibility and capacitance under different voltage windows. However, when the potential range is further expanded to 1.65V, polarization occurs. Thus, as NiSexThe optimal working voltage window of the @ CBs// AC asymmetric supercapacitor should be 0-1.6V. The CV curves of the asymmetric supercapacitor devices acquired at different scanning rates all present similar shapes, and the redox peaks are wide and weak, which indicates that the device has efficient pseudocapacitance behavior and double-layer capacitance behavior.
The almost symmetrical GCD plot shows that in NiSexIn the @ CBs// AC asymmetric supercapacitor, the electrochemical response at different current densities is highly reversible. Calculating NiSexSpecific capacity of @ CBs// AC asymmetric supercapacitor at current densities of 1, 3, 5, 8 and 10Ag-1When the specific capacity reaches 128, 119, 109, 95 and 79Fg respectively-1As shown in fig. 11.
To explore NiSexThe circulating life of the @ CBs// AC asymmetric supercapacitor device under the working voltage of 1.6V is found, and the capacitance retention rate is about 89% under 5000 charge-discharge cycles, so that the asymmetric supercapacitor device has good circulating stability. Due to the presence of carbon network and NiSexGood electrochemical activity and conductivity, so thatNiSexThe @ CBs// AC asymmetric supercapacitor has higher stability (as shown in FIG. 12).
Energy storage performance is one of the important characteristics of supercapacitor devices. NiSexThe energy density and power density plots for the @ CBs// AC asymmetric supercapacitor devices are shown in FIG. 13. NiSex@ CBs// AC asymmetric supercapacitor device at 800Wkg-1Has a high power density of 45.2Whkg-1At 8000Wkg-1Still maintain 27.8Whkg at the power density of-1Energy density of (2), which confirms NiSexThe @ CBs nanoparticles have great promise in potential energy storage applications. In addition NiSexThe Ragone plot for the @ CBs// AC asymmetric supercapacitor and some other reported supercapacitors, calculated from GCD data. It can be seen that the Ragon graph multiphase nanostructure has an important effect on improving the performance of the super capacitor, and the energy density of the super capacitor is superior to that of other asymmetric capacitors based on metal compounds and carbon materials.
In conclusion, Ni-soc-MOF is taken as a template, and an in-situ selenization strategy is adopted to successfully prepare spherical NiSex@ CBs composites, wherein nickel selenide nanoparticles are embedded in graphitic carbon hollow spheres. Ni-soc-MOF with interconnecting channels and nanocages contributes to high surface area and interconnected carbon hollow spheres. The selenization temperature can well control the chemical composition of the nickel selenide. This interconnection between metal selenides and carbon allows for more ions to be transported rapidly, so their synergistic effect contributes to increased capacitance and superior rate performance. Carbon networks with outstanding mechanical flexibility offer new opportunities for manufacturing high performance supercapacitors. NiSex@ CBs has remarkable electrochemical performance and the current density is 1Ag-1When it is used, its specific capacitance is 1720Fg-1. Further, NiSexThe asymmetric super capacitor of @ CBs// AC has a wide potential window of 1.6V and a power density of 800kWkg-1The high energy density was 45.2Whkg-1And excellent cycle stability (capacity retention of 87.6%) after 5000 cycles. Its excellent electrochemical performance shows that NiSex@ CBs nanoparticles as a novel electroactive material,possibly for advanced hybrid supercapacitors.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (7)

1. A carbon hollow sphere coated metal selenide composite material is characterized in that: the composite material is of a double-layer structure, and the inner layer of the composite material is NiSexNano particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSexThe nano particles are uniformly dispersed in the carbon hollow sphere;
the preparation method of the carbon hollow sphere coated metal selenide composite material mainly comprises the following steps:
step 1: mixing nickel salt and H4Dissolving ABTC in an aqueous solution composed of N, N-dimethylacetamide, water and tetrafluoroboric acid, and uniformly stirring to prepare a mixed solution A;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in an oven to be dried for 3-6 days to obtain an intermediate product Ni-soc-MOF;
and step 3: mixing Ni-soc-MOF and Se powder, and then carrying out high-temperature selenization reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
2. The carbon hollow sphere-coated metal selenide composite material according to claim 1, wherein the oven temperature in the step 2 is set to 120-160 ℃.
3. The carbon hollow sphere coated metal selenide composite material according to claim 1, wherein the specific method in the step 3 is as follows: mixing Ni-soc-MOF and Se powder according to the mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenylation reaction to prepare the NiSe composite material with the carbon hollow sphere coated with the metal selenidex@CBs。
4. The carbon hollow sphere-coated metal selenide composite material according to claim 1, wherein the volume ratio of N, N-dimethylacetamide to solvent water in the aqueous solution in the step 1 is 1.5-6, and the volume ratio of tetrafluoroboric acid to solvent water is 0.5-2.
5. The carbon hollow sphere-coated metal selenide composite material of claim 1, wherein the structure of Ni-soc-MOF in the step 2 is represented by H4ABTC and nickel ion; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid taking oxygen as a center and nickel trinuclear metal clusters together through ligands, and the three-dimensional framework comprises two interconnected channels and a nano-scale central cage with the particle size of less than 1 nm.
6. The carbon hollow sphere-coated metal selenide composite material according to claim 1, wherein the nickel salt in the step 1 is one or more of nickel sulfate, nickel nitrate and nickel chloride.
7. The composite prepared by the method of claim 1The application of the material in the super capacitor is characterized by comprising the following specific processes: with NiSexThe @ CBs is taken as a positive electrode, Pt is taken as a counter electrode, Ag/AgCl is taken as a reference electrode to form a three-electrode system, 2M KOH solution is taken as electrolyte, and NiSex@ CBs has remarkable electrochemical performance and the current density is 1Ag-1Its specific capacitance is 1720F g-1(ii) a Mixing NiSexPreparing a novel asymmetric supercapacitor device by taking @ CBs as a positive electrode and active carbon as a negative electrode, and preparing NiSe in a three-electrode systemxThe potential window ranges of the @ CBs nano particles and the activated carbon are respectively 0-0.6V and-1.0-0V, CV characteristic measurement of the novel asymmetric supercapacitor device is carried out in the potential range of 1.4-1.65V, and the novel asymmetric supercapacitor device is 800W kg-1Has a high power density of 45.2Wh kg-1The energy density of (1) is 8000W kg-1Still maintain 27.8Wh kg at the power density of-1The capacity retention rate of the capacitor is still up to 89% after 5000 charge-discharge cycles under the working voltage of 1.6V.
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