CN114464465B - 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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CN114464465B
CN114464465B CN202210247050.4A CN202210247050A CN114464465B CN 114464465 B CN114464465 B CN 114464465B CN 202210247050 A CN202210247050 A CN 202210247050A CN 114464465 B CN114464465 B CN 114464465B
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composite material
nise
hollow sphere
cbs
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CN114464465A (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 of the invention has a double-layer structure, and the inner layer of the composite material is NiSe x The nanometer particles, the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The nano particles are uniformly dispersed in the carbon hollow sphere. The invention also includes NiSe x Preparation method and application of @ CBs composite material. The invention takes Ni-soc-MOF as a template, and adopts an in-situ selenizing method to successfully prepare the composite material of the nickel selenium compound embedded in the carbon hollow sphere, and NiSe x The @ CBs specific capacitance is at a current density of 1A g ‑1 Up to 1720 and F g hours capacity ‑1 ，NiSe x At 800kW kg @ CBs// AC asymmetric supercapacitor ‑1 Has a power density of 45.2Wh kg ‑1 Exhibits excellent energy storage properties, niSe x The capacitance retention of the @ CBs// AC asymmetric supercapacitor is still up to 89% after 5000 cycles, showing high cycling stability.

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, a preparation method and application thereof.
Background
With the development of human society, energy shortage and environmental problems are increasingly prominent. Research and development of high performance energy storage devices is very important. Super capacitor is an important electrochemical energy storage device, and is paid attention to because of the advantages of fast charge and discharge speed, long cycle life, wide working temperature range, green and safe performance and the like. However, compared to lithium ion batteries, superThe biggest disadvantage of capacitors is the low energy density, which also limits their large-scale commercial application. According to supercapacitor e=1/2 CV 2 The key to increasing the energy density (E) is to increase the specific capacitance (C) of the electrode active material and widen the operating voltage (V) thereof. The specific capacitance is an important index for measuring the energy storage capacity of the electrode material. The main way to increase the energy density of super capacitors is to increase the specific capacitance of the electrode material. The controllable design of the electrode material has important significance for developing the electrode material with ultrahigh specific capacitance and high cycle stability.
Recently, hybrid nanomaterials have attracted a great deal of attention as advanced electrode materials, as compared to the corresponding single component materials. The transition metal selenide is a semiconductor material having excellent conductivity and electrochemical properties. It has attracted a great deal of attention in the fields of lithium ion batteries, sodium ion batteries, solar thin film batteries, electrochemical hydrogen production, super capacitors 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 high pseudocapacitance specific capacity and is suitable for assembling a high-energy-density supercapacitor. But are kinetically disadvantageous and have poor cycling stability. However, the incorporation of a carbon material in the electrode material can effectively improve 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 have focused mainly on the preparation of metals or metal selenides as electrode materials in carbon matrices by adjusting the pyrolysis conditions of the MOFs produced. The preparation of metal selenide/carbon hollow sphere composites with MOF as the precursor multiphase transition metal is of little interest. However, it is not easy to design a high performance hybrid structure based on MOF. These materials are expected to design a new hybrid structure and exert synergistic effects, thus exhibiting good electrochemical properties. Therefore, we provide a carbon hollow sphere coated metal selenide composite material, a preparation method and application thereof, which are used for solving the technical problems.
Disclosure of Invention
The invention aims to provide a carbon hollow sphere coated metal selenide composite material, a preparation method and application thereof, wherein NiSe is used for preparing a composite material x Uniformly distributing the @ CBs nano particles into the carbon hollow sphere, and preparing the NiSe x The @ CBs// AC asymmetric supercapacitor is used for storing energy, 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 NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: combining nickel salt with H 4 Dissolving ABTC in an aqueous solution consisting of N, N-dimethylacetamide, water and tetrafluoroboric acid, and uniformly stirring 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 baking oven at 120-160 ℃ to be dried for 3-6 days to obtain an intermediate product Ni-soc-MOF;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @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 is represented by H 4 ABTC and nickel ions; the specific structure of the Ni-soc-MOF is that carboxylic acid taking oxygen as a center and nickel trinuclear metal cluster are connected with one another through ligandThe three-dimensional framework comprises two interconnected channels and a nanoscale center cage with the particle size smaller than 1 nm.
Preferably, the nickel salt in the step 1 is one or more of nickel sulfate, nickel nitrate and nickel chloride.
In the invention, soc-MOFs are selected as templates to prepare the nitrogen-doped porous carbon-coated transition metal selenide composite electrode material, and Soc-MOFs are prepared from 3,3', 5' -azobenzene tetracarboxylic acid (H) 4 ABTC) is an organic ligand, and MOFs material with a Soc topological structure constructed by trinuclear metal clusters. The Soc-MOFs organic ligand contains carbon element and nitrogen element at the same time, in the process of preparing selenide at high temperature, a porous carbon layer is generated to interact with metal selenide, and the synergistic effect between metal ions and carbon hollow spheres in the structure is beneficial to improving the conductivity and electrochemical comprehensive performance of the composite material, and metal atoms in the structure are connected with the organic ligand in a trinuclear cluster form, so that the metal selenide is dispersed in the porous carbon after high temperature selenide, the contact area between the metal selenide and electrolyte is increased, and the diffusion of the electrolyte is facilitated.
The invention has the following beneficial effects:
1. the invention takes Ni-soc-MOF as a template, adopts an in-situ selenizing method to successfully prepare the composite material of the nickel-selenium compound embedded in the carbon hollow sphere, and simultaneously provides a new opportunity for manufacturing the high-performance super capacitor through a carbon network with higher mechanical flexibility.
2. The composite material NiSe of the invention x The @ CBs specific capacitance is equal to the current density of 1Ag -1 The time capacity is up to 1720Fg -1 ，NiSe x At 800kWkg @ CBs// AC asymmetric supercapacitor -1 Has a power density of 45.2Whkg -1 Exhibits excellent energy storage properties.
3. In the invention, niSe x The capacitance retention of the @ CBs// AC asymmetric supercapacitor is still up to 89% after 5000 cycles, showing high cycling stability.
4. The NiSe prepared by the invention x The @ CBs nanoparticle is expected to be used for advanced hybrid supercapacitors as a novel electroactive material.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is NiSe x Synthesis flow diagram of @ CBs composite.
FIG. 2 is a chart of Ni-soc-MOF and simulated XRD patterns.
FIG. 3 is NiSe x @ CBs and Ni 3 Se 4 Is a XRD spectrum of (C).
FIG. 4 is a diagram of Ni-soc-MOF (a) and NiSe x SEM image of @ CBs (b).
FIG. 5 is NiSe x TEM image of @ CBs.
FIG. 6 is NiSe x XPS plot of @ CBs composite.
FIG. 7 is NiSe x @cbs and NiSe x At 20mVs -1 CV graphs at different scan rates.
FIG. 8 is NiSe x The @ CBs is between 5 and 50mVs -1 CV graphs at different scan rates.
FIG. 9 is NiSe x @cbs and NiSe x At a current density of 1Ag -1 Charge-discharge curve graph at the time.
FIG. 10 is NiSe x @cbs and NiSe x Specific capacitance at different current densities.
Fig. 11 is: (a) 20mVs -1 Activated carbon and NiSe at scanning speed x CV curve of @ CBs; (b) NiSe x The @ CBs// AC asymmetric supercapacitor was at a scan rate of 50mVs -1 CV curves for different potential windows; (c) Different scan rates at 2mKOH (5, 10, 20 and 50mVs -1 ) Is a CV curve of (2); (d) GCD curves of different current densities in the 0-1.6V potential window.
FIG. 12 is a graph showing the current flowDensity of 1Ag -1 Capacitance retention plot after 5000 cycles.
Fig. 13 is a Ragone plot of energy density and power density.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1 carbon hollow sphere coated metal selenide composite material and preparation method thereof
Referring to FIGS. 1-13, the present invention is a composite material of a carbon hollow sphere coated with metal selenide, wherein the composite material has a double-layer structure, and an inner layer of the composite material is NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: ni (SO) 4 ) 2 ·6H 2 O and H 4 ABTC was dissolved in 3ml N, N-dimethylacetamide, 1ml H 2 Mixing O and 1ml of tetrafluoroboric acid, and uniformly stirring 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 baking oven at 120 ℃ for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF is represented by H 4 ABTC and nickel ions; 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, wherein the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing in a high-temperature environment at 600 DEG CSelenizing to obtain the composite material NiSe of metal selenide coated with hollow carbon spheres x @CBs。
Example 2 carbon hollow sphere coated Metal selenide composite Material and preparation method
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 NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: ni (SO) 4 ) 2 ·6H 2 O and H 4 ABTC was dissolved in 6ml of N, N-dimethylacetamide, 1ml of H 2 Mixing O and 1ml of tetrafluoroboric acid, and uniformly stirring 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 baking oven at 120 ℃ for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF is represented by H 4 ABTC and nickel ions; 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, wherein the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs。
Example 3 carbon hollow sphere coated Metal selenide composite Material and method for preparing the same
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 NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: ni (SO) 4 ) 2 ·6H 2 O and H 4 ABTC was dissolved in 6ml of N, N-dimethylacetamide, 2ml of H 2 Mixing O and 1ml of tetrafluoroboric acid, and uniformly stirring 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 baking oven at 120 ℃ for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF is represented by H 4 ABTC and nickel ions; 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, wherein the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs。
Example 4 carbon hollow sphere coated Metal selenide composite Material and method for preparing the same
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 NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: ni (SO) 4 ) 2 ·6H 2 O and H 4 ABTC was dissolved in 6ml of N, N-dimethylacetamide, 2ml of H 2 Mixing O and 2ml of tetrafluoroboric acid, and uniformly stirring 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 baking oven at 120 ℃ for 3 days to obtain an intermediate product Ni-soc-MOF; wherein Ni-soc-MOF is of the structure of H 4 ABTC and nickel ions; 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, wherein the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs。
Example 5 carbon hollow sphere coated Metal selenide composite Material and method for preparing the same
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 NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: ni (SO) 4 ) 2 ·6H 2 O and H 4 ABTC was dissolved in 3ml N, N-dimethylacetamide, 1ml H 2 Mixing O and 1ml of tetrafluoroboric acid, and uniformly stirring 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 160 ℃ oven for drying for 3 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF is represented by H 4 ABTC and nickel ions; 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, wherein the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs。
Example 6 carbon hollow sphere coated Metal selenide composite Material and method for preparing the same
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 NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: ni (SO) 4 ) 2 ·6H 2 O and H 4 ABTC was dissolved in 3ml N, N-dimethylacetamide, 1ml H 2 Mixing O and 1ml of tetrafluoroboric acid, and uniformly stirring 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 baking oven at 120 ℃ for 6 days to obtain an intermediate product Ni-soc-MOF; wherein the structure of the Ni-soc-MOF is represented by H 4 ABTC and nickel ions; 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, wherein the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm;
step 3: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs。
FIGS. 2 and 3 study the crystal structure of Ni-soc-MOF and NiSe, respectively, using x-ray diffraction patterns (XRD) x The XRD spectra of the two materials have similar diffraction peaks with the simulation data of Ni-soc-MOF in the literature, which shows that Ni-soc-MOF and NiSe are successfully synthesized x XRD spectrum of @ CBs composite material and Ni 3 Se 4 The spectrogram (JCPCDS 18-0890) is matched well.
FIG. 4 study of synthetic Ni-soc-MOF and NiSe x The surface morphology of @ CBs, the Ni-soc-MOF particles showed a relatively smooth spherical structure that remained in its original shape after selenization without collapse, while the surface was at the junctionThe texture becomes coarser. The TEM image in FIG. 5 further demonstrates the coating of NiSe x Morphology and structural features of the carbon bubbles of the nanoparticles, in addition to displaying NiSe using High Resolution TEM (HRTEM) images x The lattice of the surface and the degree of graphitization of the MOF-derived carbon bubbles. By careful investigation of NiSe x @ CBs, different stripe spacings of 0.18nm and 0.53nm are assigned to Ni 3 Se 4 020 and 002 plane of phase. There is a pronounced 0.34nm lattice spacing characteristic corresponding to the (002) crystal plane of graphitic carbon. Carbon hollow sphere wrapped NiSe x Nanoparticles, as electrode materials, promote faster ion and electron transport. Corresponding TEM element map NiSe x The @ CBs are shown in FIGS. 5e-g, indicating that nickel, selenium and carbon elements are uniformly distributed in NiSe x Inside @ CBs, the elemental characterization further illustrates that the Ni and Se elements are uniformly dispersed in the carbon hollow sphere, showing high purity NiSe x @ CBs composite.
To further study NiSe x The surface element composition and oxidation state of @ CBs, XPS investigation analysis showed 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 sp 2 A hybridized carbon atom (c=c), se3d as can be seen from the Se spectrum 3/2 And 3d 5/2 The peaks of (2) lie in 54.6eV and 53.7eV respectively. Furthermore, the peak at 58.8eV represents the presence of Se-O bonds, which is caused by selenide surface oxidation. Dividing the Ni2p spectrum into four main peaks, the characteristic peaks at 873.3 and 855.9eV belong to Ni2p 1/2 And Ni2p 3/2 Accompanied by two characteristic peaks 878.9 and 861.1eV (abbreviated as "Sat"), as shown in fig. 6.
Example 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: by NiSe x The @ 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.
Separate NiSe runs in a three electrode system with 2M KOH aqueous solution x @cbs and NiSe x CV and two nanomaterialsMeasurement of GCD. The scanning rate is 20mVs -1 In the case of the CV curves of the two electrodes, the potential window ranges from 0 to 0.5V.
As can be seen from FIG. 7, under the same conditions, niSe x Integral area ratio NiSe of @ CBs electrode x The nano material is large and illustrates NiSe x The @ CBs has a higher specific capacitance. NiSe x the@CBs nano material is 5-50 mVs -1 The CV curves at different scan rates over the range are shown in fig. 8, and the results indicate that the CV curve area and peak current increase significantly with increasing scan rate. Furthermore, a pair of redox peaks can be observed on each CV curve, indicating that both electrodes have typical cell behavior.
All these GCD curves show that the material has better charge-discharge curve, indicating NiSe x The @ CBs electrode has excellent pseudocapacitance performance characteristics. Calculating specific capacities from their respective discharge curves, finding NiSe x At 1Ag for CBs electrode -1 The specific capacity is up to 1720Fg -1 The above results indicate that, at the same current density, niSe x The @ CBs electrode had the longest charge-discharge time, which is consistent with CV measurements. NiSe x At current densities 1, 3, 5, 10 and 20Ag @ CBs electrodes -1 Specific capacities at 1720, 1549, 1438, 1320, and 1125Fg, respectively -1 (as shown in fig. 10).
NiSe x @CBs incorporate NiSe x The advantages of the structure and the carbon net are that the carbon hollow spheres are uniformly distributed in the NiSe x Around the periphery, the diffusion path of electrolyte ions and electrons can be effectively improved, and the carbon hollow sphere and the nano NiSe x The synergy between the two components ensures that the two components have higher specific capacity.
According to NiSe x Excellent electrochemical performance of @ CBs nano-particles, in 2MKOH aqueous solution, a method for preparing the nano-particles by using NiSe is designed and prepared x The @ CBs is a novel asymmetric supercapacitor device with a positive electrode and Activated Carbon (AC) as the negative electrode. NiSe in a three electrode system x The potential window ranges of the @ CBs nano-particles and the AC are respectively 0-0.6V and-1.0-0V. Adjusting Activated Carbon (AC) and NiSe according to formulas x Optimized quality of @ CBs electrodeThe ratio is about 3.5. To ensure the stability of the asymmetric supercapacitor device, niSe x CV characteristics of @ CBs// AC asymmetric supercapacitors were measured over several potential ranges from 1.4 to 1.65V. The CV curves of asymmetric supercapacitor devices exhibit desirable reversibility and capacitance at different voltage windows. However, when the potential range is further enlarged to 1.65V, polarization occurs. Thus, as NiSe x The optimal operating voltage window for the @ CBs// AC asymmetric supercapacitor should be 0-1.6V. CV curves of the asymmetric supercapacitor device collected at different scanning rates all show similar shapes, and oxidation-reduction peaks are wide and weak, so that the device has efficient pseudo-capacitance behavior and double-layer capacitance behavior.
The almost symmetrical GCD diagram shows that in NiSe x In an @ CBs// AC asymmetric supercapacitor, the electrochemical response at different current densities is highly reversible. Calculation of NiSe x Specific capacity of @ CBs// AC asymmetric supercapacitor at current densities of 1, 3, 5, 8 and 10Ag -1 Its specific capacities reach 128, 119, 109, 95 and 79Fg, respectively -1 As shown in fig. 11.
To investigate NiSe x The cycle life of the @ CBs// AC asymmetric supercapacitor device at the working voltage of 1.6V is found that the capacitor retention rate is about 89% under 5000 charge and discharge cycles, which indicates that the asymmetric supercapacitor device has good cycle stability. Due to the presence of the carbon network and NiSe x Good electrochemical activity and conductivity, so that NiSe x The @ CBs// AC asymmetric supercapacitor has higher stability (as shown in FIG. 12).
Energy storage performance is one of the important characteristics of supercapacitor devices. NiSe x The energy density and power density plot for the @ CBs// AC asymmetric supercapacitor device is shown in fig. 13. NiSe x The @ CBs// AC asymmetric supercapacitor device was at 800Wkg -1 Has a power density of 45.2Whkg at high power density -1 And at 8000Wkg -1 Is still kept at 27.8Whkg at a power density of (C) -1 Is proved by NiSe x The @ CBs nanoparticle has great promise in potential energy storage applications.Furthermore NiSe x Ragone plots of @ CBs// AC asymmetric supercapacitors and some other reported supercapacitors were calculated from GCD data. It can be seen that the Ragone graph multiphase nanostructure has an important role in improving supercapacitor performance, with energy density superior to other asymmetric capacitors based on metal compounds and carbon materials.
In combination, the spherical NiSe is successfully prepared by taking Ni-soc-MOF as a template and adopting an in-situ selenizing strategy x A @ CBs composite wherein nickel selenide nanoparticles are embedded in graphitic carbon hollow spheres. The Ni-soc-MOF with interconnecting channels and nanocages contributes to a high surface area and interconnecting carbon hollow spheres. The chemical composition of nickel selenide can be well controlled by the selenization temperature. This interconnection between the metal selenide and carbon allows for more ions to be transported rapidly, so their synergistic effect helps to improve capacitance and excellent rate capability. Carbon webs with outstanding mechanical flexibility offer new opportunities for manufacturing high performance supercapacitors. NiSe x The @ CBs have remarkable electrochemical properties at a current density of 1Ag -1 At the time of its specific capacitance is 1720Fg -1 . In addition, niSe x Asymmetric supercapacitor @ CBs// AC with wide potential window of 1.6V and power density of 800kWkg -1 The high energy density at this time was 45.2Whkg -1 And has excellent cycle stability (87.6% capacitance retention) after 5000 cycles. The excellent electrochemical properties of the NiSe indicate that x The @ CBs nanoparticle is possible to use as a novel electroactive material for advanced hybrid supercapacitors.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form 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 understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.

Claims (6)

1. The composite material of the metal selenide coated by the carbon hollow sphere is characterized in that: the composite material has a double-layer structure, and the inner layer of the composite material is NiSe x Nano particles, wherein the outer layer of the composite material is a carbon hollow sphere, and the inner layer of the composite material is NiSe x The 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: nickel salt and 3,3',5,5' -azobenzene tetracarboxylic acid (H) 4 ABTC) is dissolved in an aqueous solution consisting of N, N-dimethylacetamide, water and tetrafluoroboric acid, and mixed solution a is prepared after uniform stirring;
step 2: placing the mixed solution A into a stainless steel reaction kettle, and placing the stainless steel reaction kettle into an oven for drying for 3-6 days to obtain an intermediate product Ni-soc-MOF;
step 3: mixing Ni-soc-MOF and Se powder, and then carrying out high-temperature selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs；
The structure of the Ni-soc-MOF in the step 2 is represented by H 4 ABTC and nickel ions; the specific structure of the Ni-soc-MOF is a three-dimensional framework formed by connecting carboxylic acid and nickel trinuclear metal clusters which take oxygen as the center together through ligands, and the three-dimensional framework comprises two interconnection channels and a nanoscale center cage with the particle size smaller than 1 nm.
2. The carbon hollow sphere coated metal selenide composite of claim 1, wherein the oven temperature in step 2 is set to 120 ℃ to 160 ℃.
3. The composite material of metal selenide coated with carbon hollow spheres according to claim 1, wherein the specific method of the step 3 is as follows: mixing Ni-soc-MOF and Se powder according to a mass ratio of 1:1, and placing the mixture in a high-temperature environment at 600 ℃ for selenizing reaction to obtain the carbon hollow sphere coated metal selenide composite material NiSe x @CBs。
4. The carbon hollow sphere coated metal selenide composite according to claim 1, wherein the volume ratio of N, N-dimethylacetamide to solvent water in the aqueous solution of step 1 is 1.5 to 6, and the volume ratio of tetrafluoroboric acid to solvent water is 0.5 to 2.
5. The composite material of claim 1, wherein the nickel salt in step 1 is one or more of nickel sulfate, nickel nitrate and nickel chloride.
6. The application of the carbon hollow sphere coated metal selenide composite material in the super capacitor according to claim 1, wherein the specific process is as follows: by NiSe x The @ 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 the current density is 1A g -1 When the specific capacitance is 1720Fg -1 The method comprises the steps of carrying out a first treatment on the surface of the NiSe is mixed with x Preparing an asymmetric supercapacitor device by taking @ CBs as a positive electrode and active carbon as a negative electrode, and preparing NiSe in a three-electrode system x Potential window ranges of @ CBs nanoparticle and activated carbon are 0-0.6V and-1.0-0V, respectively, CV characteristic measurement is performed on an asymmetric supercapacitor device in a potential range of 1.4-1.65V, and the asymmetric supercapacitor device is under 800W kg -1 Has a power density of 45.2Wh kg at high power density -1 Is at 8000W kg -1 At a power density of (2)Still keep 27.8Wh kg -1 The retention of capacitance after 5000 charge and discharge cycles at an operating voltage of 1.6V is still up to 89%.
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