CN113611547B - Metal organic framework derived cobaltosic oxide composite carbon material and preparation method and application thereof - Google Patents
Metal organic framework derived cobaltosic oxide composite carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113611547B CN113611547B CN202110892387.6A CN202110892387A CN113611547B CN 113611547 B CN113611547 B CN 113611547B CN 202110892387 A CN202110892387 A CN 202110892387A CN 113611547 B CN113611547 B CN 113611547B
- Authority
- CN
- China
- Prior art keywords
- metal
- carbon material
- organic framework
- composite carbon
- derived
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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 relates to the technical field of preparation of supercapacitor electrode materials, in particular to cobaltosic oxide derived from a metal-organic frameworkComposite carbon material and its preparation method and application. The invention firstly uses 1, 4-bis (imidazole-1-yl) benzene and Co (NO) 3 ) 2 ·6H 2 The CP-3-ZX material is prepared by adopting a solvent diffusion method or a mixed precipitation method; and then preparing the cobalt oxide composite carbon material derived from the metal organic framework by adopting a calcining pyrolysis method for the CP-3-ZX material, and applying the cobalt oxide composite carbon material derived from the metal organic framework to a positive electrode material of the supercapacitor. The present application utilizes a multivalent coordination framework assembled from organic ligands and metal-containing nodes, and utilizes a convenient solvent diffusion method to develop coordination polymer materials; in addition, the carbon content of the material is controlled by properly controlling the calcination conditions, and the capacitance of the active electrode material is further controlled.
Description
Technical Field
The invention relates to the technical field of preparation of supercapacitor electrode materials, in particular to a cobaltosic oxide composite carbon material derived from a metal-organic framework, and a preparation method and application thereof.
Background
To address energy and environmental crisis, it is becoming increasingly important to develop efficient energy storage devices. Supercapacitors are considered as the largest green devices for their high power density, long term stability and fast charge and discharge capabilities as one of the most promising alternatives in energy storage systems. The energy storage of supercapacitors is based on two principles: an electric double layer capacitor (Electrical Double Layer Capacitance) and a pseudocapacitor (pseudocapacitor), while a carbon-based double layer capacitor can achieve high power density and good cycling stability, the energy density is low due to the limited specific capacitance of the carbon material. In contrast, pseudocapacitive materials, such as transition metal oxides and hydroxides, e.g. RuO 2 、MnO 2 、Ni(OH) 2 、NiO、Co(OH) 2 、Co 3 O 4 And carbides, etc. can provide a higher specific capacitance. However, most pseudocapacitive materials suffer from poor rate performance and low electrical conductivity, and a common approach to improving supercapacitor performance is to use pseudocapacitive materials and carbon composites as electrodes.
The multi-oxidation state transition metal oxide has high theoretical capacitance and high chemical activity, and is widely used as pseudocapacitive material. Among the numerous transition metal oxide candidates, co 3 O 4 Due to its ultrahigh theoretical capacitance (3560F g) -1 ) And excellent electrochemical properties, and is called pseudocapacitor, butAnd Co 3 O 4 In the charge and discharge process, the poor conductivity and corrosion in electrolyte lead to poor capacitor retention rate and reversibility, which limit the application of the electrolyte in super capacitors, and one method for solving the problem is to find effective carriers, such as various carbon materials, to uniformly disperse Co 3 O 4 And (3) nanoparticles.
Therefore, it has become urgent to synthesize carbon and metal composite materials by using suitable precursors and synthesis methods; as a precursor, metal Organic Frameworks (MOFs), also known as Coordination Polymers (CPs), are ordered crystalline solids composed of coordination bonds between metal ions and organic ligands, of interest. In the heat treatment process, the metal center is converted into the high-activity metal oxide electrode material, the organic ligand content is high, rich carbon sources are provided, the structural integrity of the electrode material is improved, and the conductivity of the electrode material is improved. However, how to obtain a unique spatial structure and excellent performance of metal oxides remains a great challenge.
Disclosure of Invention
Aiming at the technical defects, the invention provides a cobaltosic oxide composite carbon material derived from a metal-organic framework, a preparation method and application thereof, wherein the application utilizes a multivalent coordination framework assembled by an organic ligand and metal-containing nodes, and utilizes a convenient solvent diffusion method to develop a coordination polymer material; in addition, the carbon content of the material is controlled by controlling the calcination condition, and the capacitance of the active electrode material is further controlled.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the cobaltosic oxide composite carbon material derived from the metal-organic framework comprises the following steps:
(1) 1, 4-bis (imidazol-1-yl) benzene and Co (NO) 3 ) 2 ·6H 2 O adopts a solvent diffusion method or a mixed precipitation method to prepare a CP-3-ZX material;
(2) Preparation of a cobaltosic oxide composite carbon material:
and (3) heating the CP-3-ZX material prepared in the step (1) to 320-450 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving heat for 60-90min, and cooling to room temperature to obtain the cobaltosic oxide composite carbon material derived from the metal-organic framework.
Preferably, the solvent diffusion method for preparing the CP-3-ZX material comprises the following steps:
s1, preparation of a solution:
preparing a bottom layer: dissolving 1, 4-bis (imidazol-1-yl) benzene in chloroform to obtain a bottom solution;
preparing a buffer layer: mixing methanol and chloroform according to the volume ratio of 0.5-2:1 to prepare buffer layer solution;
preparing a top layer: co (NO) 3 ) 2 ·6H 2 O is dissolved in methanol to prepare a top layer solution;
s2, preparing CP-3-ZX crystals: laying a bottom layer solution, a buffer layer solution and a top layer solution in sequence from bottom to top, then placing at room temperature until crystals are formed, and cleaning to obtain CP-3-ZX crystals;
wherein Co (NO) 3 ) 2 ·6H 2 The ratio of O to the amount of material of 1, 4-bis (imidazol-1-yl) benzene is 3-5:2.
Preferably, the steps for preparing the CP-3-ZX material by the mixed precipitation method are as follows:
dissolving 1, 4-bis (imidazol-1-yl) benzene in chloroform to obtain a 1, 4-bis (imidazol-1-yl) benzene solution;
co (NO) 3 ) 2 ·6H 2 O is dissolved in methanol to obtain Co (NO) 3 ) 2 ·6H 2 An O solution;
1, 4-bis (imidazol-1-yl) benzene solution was added dropwise to Co (NO) 3 ) 2 ·6H 2 Stirring and reacting in O solution at room temperature for 2-6h, centrifuging, washing and drying to obtain CP-3-ZX powder;
wherein Co (NO) 3 ) 2 ·6H 2 The ratio of O to the amount of material of 1, 4-bis (imidazol-1-yl) benzene is 3-5:2.
The invention also protects the metal-organic framework-derived cobaltosic oxide composite carbon material prepared by the preparation method of the metal-organic framework-derived cobaltosic oxide composite carbon material.
The invention also protects a working electrode prepared from the cobaltosic oxide composite carbon material derived from the metal-organic framework.
Preferably, the preparation method of the working electrode comprises the following steps:
mixing a cobaltosic oxide composite carbon material derived from a metal-organic framework, acetylene black and polyvinylidene fluoride, adding ethanol, grinding to obtain homogeneous black slurry, uniformly paving the black slurry on foam nickel, drying and pressing to obtain a working electrode;
wherein the mass ratio of the cobaltosic oxide composite carbon material derived from the metal-organic framework, the acetylene black and the polyvinylidene fluoride is 8-9:1:1.
The invention also protects the application of the working electrode in preparing the working electrode of the super capacitor.
Preferably, the supercapacitor is prepared according to the following steps:
the Hg/HgO electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, a three-electrode system is formed by the platinum wire electrode and a working electrode, the three-electrode system is connected to an electrochemical workstation, and an alkaline solution with the concentration of 2-6mol/L is used as an electrolyte for electrochemical test.
Preferably, the alkali solution is a KOH solution or a NaOH solution.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes CP-3-ZX as a precursor and prepares the cobaltosic oxide composite carbon material derived from the metal organic framework by a calcination pyrolysis method.
2. Co with larger metal oxide ratio and improved conductivity obtained by the invention in 2-6M KOH or NaOH electrolyte 3 O 4 The @ C electrode exhibited a substantial specific capacity: the sweeping speed is 5mV s -1 The specific capacitance at the time was 316F g -1 A current density of 0.5. 0.5A g -1 Specific volume value at the time of being 317F g -1 . In addition, co 3 O 4 At a current density of 2A g @ C electrode -1 The following presents an excellent long-term cycle life and high reversibility throughout the cycle; at 2000 charge-discharge cyclesAfter that, the specific volume value still keeps 85% of the initial value; co calcined by CP-3-ZX 3 O 4 The @ C material can be applied as an electrode material in a supercapacitor.
Drawings
FIG. 1 is a crystal structure diagram of CP-3-ZX prepared in example 1; in fig. 1, (a) is a metal ion coordination diagram; (b) is a one-dimensional ladder chain; (c) a one-dimensional quadrilateral pore path diagram;
FIG. 2 is a simulated and experimental XRD spectrum of CP-3-ZX prepared in example 1;
FIG. 3 is an XRD spectrum of a metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1;
FIG. 4 is a Raman spectrum of the metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1;
FIG. 5 is a spectrum of XPS spectra of (a) full-scale, (b) high resolution Co 2p, (C) O1s and (d) C1s of the metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1;
FIG. 6 shows (a) N of the metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1 2 Adsorption-desorption isotherms and (b) a porosity size distribution curve;
FIG. 7 is a FESEM image of (a) CP-3-ZX prepared in example 1; (b) FESEM image of the metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1; (c) EDX spectra and element distribution images;
FIGS. 8 (a-c) are Co of the metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1, respectively 3 O 4 (d) is an electron diffraction (SAED) pattern of the selected region of (b);
FIG. 9 is a graph showing the results of electrochemical performance test of the metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared in example 1, wherein (a) in FIG. 9 is a cyclic voltammetry graph at different sweep rates; (b) is a graph of GCD at different current densities; (c) an ac impedance performance test chart; (d) is an electrochemical impedance test chart.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific 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. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
Example 1
The preparation method of the cobaltosic oxide composite carbon material derived from the metal-organic framework comprises the following steps:
(1) Synthesizing CP-3-ZX crystal by solvent diffusion method:
preparing a bottom layer: 1, 4-bis (imidazol-1-yl) benzene ligand (bib) (32.5 mg,0.15 mmol) was dissolved in CHCl 3 (6 mL) of the solution was placed at the bottom of the tube;
preparing a buffer layer: will CH 3 OH and CHCl 3 Is added dropwise as a buffer layer to a trichloro solution for Fang Xiaoxin stratification (8 mL,1:1 v/v);
preparing a top layer: 0.1mmol Co (NO) 3 ) 2 ·6H 2 O (26.1 mg) was dissolved in 6mL CH 3 Forming a clear solution in OH, slowly dripping an ethanol solution on the buffer layer, sealing the test tube with a preservative film, and standing for 20 days at normal temperature, wherein pink blocky samples appear on the wall of the test tube; after separating out the crystal sample, washing with water and ethanol for 2-3 times, and finally drying at room temperature to obtain CP-3-ZX crystal, wherein the yield is about 45% based on bib;
(2) Composite material (Co) 3 O 4 Preparation of @ C):
transferring the collected CP-3-ZX powder precursor sample into a corundum dry pot, transferring the corundum dry pot to a high-temperature tube furnace with a programmed temperature for calcining, completely opening one side of the high-temperature tube furnace, completely closing the other side of the high-temperature tube furnace by using a flange, heating the tube furnace at a heating rate of 10 ℃/min, heating at 400 ℃ for 80min, and opening a flange knob to enable N in the furnace to be N when the heating time is reached 2 Circulating, cooling the furnace to room temperature to obtain a black sample, and verifying that Co is 3 O 4 The @ C composite, i.e., a metal organic framework-derived tricobalt tetraoxide composite carbon material, was collected and tested accordingly.
Example 2
The preparation method of the cobaltosic oxide composite carbon material derived from the metal-organic framework comprises the following steps:
(1) The CP-3-ZX powder is synthesized by adopting a mixed precipitation method:
1, 4-bis (imidazol-1-yl) benzene (bib) (32.5 mg,0.15 mmol) was dissolved in chloroform (6 mL) to give a 1, 4-bis (imidazol-1-yl) benzene solution;
0.1mmol of Co (NO 3 ) 2 ·6H 2 O (26.1 mg) was dissolved in methanol (6 mL) to obtain Co (NO) 3 ) 2 ·6H 2 An O solution;
1, 4-bis (imidazol-1-yl) benzene solution was added dropwise to Co (NO) via a constant pressure dropping funnel 3 ) 2 ·6H 2 Stirring and mixing the solution in O solution for 6 hours at room temperature, centrifugally collecting pink precipitate, washing the precipitate with deionized water and ethanol for 3 times, and finally drying the powder at 80 ℃ overnight for further use to obtain CP-3-ZX powder;
(2) Composite material (Co) 3 O 4 Preparation of @ C):
transferring the collected CP-3-ZX powder precursor sample into a corundum dry pot, transferring the corundum dry pot to a high-temperature tube furnace with a programmed temperature for calcining, completely opening one side of the high-temperature tube furnace, completely closing the other side of the high-temperature tube furnace by using a flange, heating the tube furnace at a heating rate of 10 ℃/min, heating at 400 ℃ for 80min, and opening a flange knob to enable N in the furnace to be N when the heating time is reached 2 Circulating, cooling the furnace to room temperature to obtain a black sample, and verifying that Co is 3 O 4 The @ C composite, i.e., a metal organic framework-derived tricobalt tetraoxide composite carbon material, was collected and tested accordingly.
Example 3
The preparation method of the cobaltosic oxide composite carbon material derived from the metal-organic framework comprises the following steps:
(1) Synthesizing CP-3-ZX crystal by solvent diffusion method:
preparing a bottom layer: 1, 4-bis (imidazol-1-yl) benzene ligand (bib) (43 mg,0.2 mmol) was dissolved in CHCl 3 (8 mL) of the solution was placed at the bottom of the tube;
preparing a buffer layer: will CH 3 OH and CHCl 3 (8 mL, 0.5:1v/v) as a buffer layer was added dropwise to a trichloro solution for Fang Xiaoxin delamination;
preparing a top layer: 0.1mmol Co (NO) 3 ) 2 ·6H 2 O (26.1 mg) was dissolved in 6mL CH 3 Forming a clear solution in OH, slowly dripping an ethanol solution on the buffer layer, sealing the test tube with a preservative film, and standing at normal temperature for 25 days, wherein pink blocky samples appear on the wall of the test tube; after separating out the crystal sample, washing with water and ethanol for 2-3 times, and finally drying at room temperature to obtain CP-3-ZX crystals;
(2) Composite material (Co) 3 O 4 Preparation of @ C):
transferring the collected CP-3-ZX powder precursor sample into a corundum dry pot, transferring the corundum dry pot to a high-temperature tube furnace with a programmed temperature for calcining, completely opening one side of the high-temperature tube furnace, completely closing the other side of the high-temperature tube furnace by using a flange, heating the tube furnace at a heating rate of 10 ℃/min, heating at 320 ℃ for 90min, and opening a flange knob to enable N in the furnace to be N when the heating time is reached 2 Circulating, cooling the furnace to room temperature to obtain a black sample, and verifying that Co is 3 O 4 The @ C composite, i.e., a metal organic framework-derived tricobalt tetraoxide composite carbon material, was collected and tested accordingly.
Example 4
The preparation method of the cobaltosic oxide composite carbon material derived from the metal-organic framework comprises the following steps:
(1) Synthesizing CP-3-ZX crystal by solvent diffusion method:
preparing a bottom layer: 1, 4-bis (imidazol-1-yl) benzene ligand (bib) (54 mg,0.25 mmol) was dissolved in CHCl 3 (10 mL) of the solution was placed at the bottom of the tube;
preparing a buffer layer: will CH 3 OH and CHCl 3 (8 mL,2:1 v/v) as a buffer layer was added dropwise to a trichloro solution for Fang Xiaoxin layering；
Preparing a top layer: 0.1mmol Co (NO) 3 ) 2 ·6H 2 O (26.1 mg) was dissolved in 6mL CH 3 Forming a clear solution in OH, slowly dripping an ethanol solution on the buffer layer, sealing the test tube with a preservative film, and standing at normal temperature for 28 days, wherein pink blocky samples appear on the wall of the test tube; after separating out the crystal sample, washing with water and ethanol for 2-3 times, and finally drying at room temperature to obtain CP-3-ZX crystals;
(2) Composite material (Co) 3 O 4 Preparation of @ C):
transferring the collected CP-3-ZX powder precursor sample into a corundum dry pot, transferring the corundum dry pot to a high-temperature tube furnace with a programmed temperature for calcining, completely opening one side of the high-temperature tube furnace, completely closing the other side of the high-temperature tube furnace by using a flange, heating the tube furnace at a heating rate of 10 ℃/min, heating for 60min at 450 ℃, and opening a flange knob to enable N in the furnace to be N when the heating time is up 2 Circulating, cooling the furnace to room temperature to obtain a black sample, and verifying that Co is 3 O 4 The @ C composite, i.e., a metal organic framework-derived tricobalt tetraoxide composite carbon material, was collected and tested accordingly.
The metal-organic framework-derived tricobalt tetraoxide composite carbon materials (Co) prepared in examples 1-4 of the present invention 3 O 4 @ C composite) properties were similar, and a performance study was performed using example 1, with the following specific study methods and results:
results and discussion
1. Crystal structure analysis of CP-3-ZX
Two-thirds of the 1, 4-bis (imidazol-1-yl) benzene (bib) ligands adopt a trans-coordinated bidentate conformation to Co II The ions are linked into one-dimensional chains [ Co (bib)] ∞ While the other third of 1, 4-bis (imidazol-1-yl) benzene (bib) ligands also adopt a trans-coordination bidentate mode to connect two metal nodes on different chains together to form a one-dimensional double track ladder [ Co (bib) 1.5 ] ∞ The structure of which is shown in figure 1.
2. Morphology and characterization of CP-3-ZX material
In the invention, an X-ray powder diffraction test is carried out on CP-3-ZX, and FIG. 2 reveals the comparison relation between powder diffraction data and crystal simulation data, and the comparison relation shows that the experimental diffraction peak and the theoretical diffraction peak are well matched, so that the purity of a test sample is higher.
FIG. 3 is Co 3 O 4 X-ray powder diffraction patterns of the @ C composite showed six peaks at positions 19.00, 31.27, 36.85, 44.81, 55.66 and 59.36, respectively, with Co 3 O 4 The (111), (220), (311), (400), (422) and (511) crystal planes of (JCPDS No. 42-1467) are identical; in addition, a weak broad peak was observed around 25 °, which is related to the (002) plane diffraction of carbon.
As shown in the Raman diagram of FIG. 4, the sample has four peaks 469cm -1 、511cm -1 、609cm -1 、673cm -1 These four peaks are respectively associated with crystalline Co 3 O 4 E of (2) g 、F 2g 、F 2g And A g The vibration modes are related to Co 3 O 4 And (3) effectively synthesizing the @ C composite material.
The surface elemental composition and chemical phases of the samples were studied by XPS analysis, co in the XPS full spectrum (FIG. 5 a) 3 O 4 The composite material at the temperature of C can obviously observe peaks corresponding to Co, O and C.
Furthermore, high resolution spectra were also studied (FIG. 5 b), co 2p for Co 2p spectra 1/2 Is composed of two peaks with binding energy of 796.8eV and 795.2eV, co 2p 3/2 The deconvolution high-resolution wave distribution of (c) is in 781.5eV and 780.0eV, which are assigned to Co (II) and Co (III) states, respectively, which confirm Co 3 O 4 With mixed valence Co.
Similarly, in FIG. 5c, O1s shows two well resolved peaks with binding energies of 529.98eV and 531.35eV, respectively, corresponding to spinel Co 3 O 4 And the obtained microstructure surface-adsorbed OH - The components are as follows.
In the enlargement of the C1s region (FIG. 5 d), we observe 3 peaks at 284.82eV, 285.6eV and 288.4eV, separatedCorresponds to C-C, C-O-C and carbonyl/quinone groups (C=O), and the XPS analysis further confirms Co in the product 3 O 4 And C.
Co is adsorbed by nitrogen at low temperature 3 O 4 Porous characteristic specific surface area of the @ C composite was evaluated. FIG. 6 is Co 3 O 4 N of the @ C composite sample 2 Adsorption and desorption isotherm graphs and pore diameter distribution graphs; as shown in FIG. 6a Co 3 O 4 N of the @ C composite 2 The adsorption and desorption isotherms are IV type adsorption in IUPAC classification, and one obvious characteristic is P/P 0 Between 0.7 and 1.0H 3 A hysteresis loop, which indicates that there are mesopores and macropores coexisting in the carbon material. Co (Co) 3 O 4 Specific surface area @ C of 30.211m 2 g -1 Total volume of 0.0982cm 3 g -1 Reflecting that the composite material shows better electrochemical performance.
The corresponding pore size distribution pattern (fig. 6 b) has a broad peak between 20nm and 100nm, which further illustrates that a large number of mesoporous structures exist in the material, and the mesopores can provide electron transport channels, so that the electron transport distance is shortened, the electron transport speed is increased, and the electron transport resistance is reduced.
As can be seen from the representative field emission electron scan (FESEM) plot, CP-3-ZX powder is uniform in particle size and suitable as a precursor (fig. 7 a);
after calcination, co is formed 3 O 4 The particles are packed in a block-like structure in which carbon is randomly dispersed (fig. 7 b);
EDS analysis (FIG. 7C) showed that only Co, O, C elements were contained and mapping analysis (FIG. 7C) found that Co, O, C and other substances were uniformly dispersed in Co 3 O 4 In the @ C composite.
Further characterization by High Resolution Transmission Electron Microscopy (HRTEM) (FIGS. 8 a-c), co 3 O 4 Co in the @ C composite 3 O 4 The (400), (311) and (220) cubic crystal planes of (a) coincide well with the lattice fringes of ca.0.20nm, 0.24nm and 0.29nm, respectively, and show that the amorphous carbon is randomly distributed;
selected region electron diffractionDiffraction ring and Co in the emission (SAED) pattern (FIG. 8 d) 3 O 4 Is consistent with all diffraction rings, indicating that the resulting material has good crystallinity.
3、Co 3 O 4 Electrochemical Properties of @ C composite
Mixing a cobaltosic oxide composite carbon material derived from a metal-organic framework, acetylene black and polyvinylidene fluoride, adding ethanol, grinding to obtain homogeneous black slurry, uniformly paving the black slurry on foam nickel, drying and pressing to obtain a working electrode;
the mass ratio of the cobaltosic oxide composite carbon material derived from the metal organic framework, the acetylene black and the polyvinylidene fluoride is 8:1:1;
Co 3 O 4 the @ C electrochemical performance test was performed under a three electrode system: the prepared electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, KOH aqueous solution with concentration of 2mol/L is used as electrolyte, and the performance of the electrode is evaluated through Cyclic Voltammetry (CV), constant current charge-discharge (GCD), alternating current impedance performance test and cyclic life test;
the specific capacitance is calculated according to the following equation (1):
C＝∫IdV/2vΔVm eqn(1)
C(F g -1 ): a specific capacitance; i (A): a current; deltaV (V): a voltage range; v (mV s) -1 ): a scan rate; m (g): the mass of active material in the electrode;
by calculation, the electrode has a scanning speed of 5mV s -1 The specific capacitance at the time was 316F g -1 When the sweep speed is increased to 100mV s -1 When the specific volume is reduced to 153F g -1 。
As shown in FIG. 9a, cyclic Voltammetry (CV) was performed at different sweep rates of 5mV s over a corresponding potential range (0-0.5V) -1 、10mV s -1 、20mV s -1 、50mV s -1 And 100mV s -1 When tested, a distinct redox peak was observed from the curve, the shape of the CV curve indicated that the capacitance characteristics were different from the conventional double layer capacitance, and that the CV area was larger with increasing sweep rate. In additionThe scanning rate is 100mV s -1 The CV curve of (c) is deformed to some extent due to the presence of internal active sites, and a certain deformation and a decrease in specific capacitance occur, which cannot completely maintain the redox transition.
FIG. 9b is Co 3 O 4 The GCD curve graph of the electrode prepared from the @ C composite material under different current densities can be seen that all curves show nonlinear charge and discharge curves, and pseudocapacitance behaviors are further determined; these approximate symmetry curves indicate Co 3 O 4 The electrode prepared from the @ C composite material has good electrochemical capacitance characteristics.
The specific capacitance of the discharge curve is calculated according to the following equation (2)
C＝IΔt/ΔVm eqn(2)
C(F g -1 ): a specific capacitance; i (A): a current; deltaV (V): a voltage difference of the discharge; Δt(s): a discharge time; m (g): the mass of active material in the electrode;
by calculation, co 3 O 4 The electrode material prepared from the @ C composite material has 0.5Ag at different current densities -1 、1.0A g -1 、2.0A g -1 、5.0A g -1 And 10A g -1 The specific capacitance values at the time were 317F g respectively -1 、302F g -1 、280F g -1 、262F g -1 And 210F g -1 The method comprises the steps of carrying out a first treatment on the surface of the Notably, as the current density increases, the specific capacity gradually decreases, which is mainly related to the reduction of ions and surface area at high charge-discharge current densities.
In addition, co 3 O 4 The electrode made of the @ C composite material has a current density of 2A g -1 The supercapacitors still have strong capacitive performance after 2000 charge and discharge cycles (fig. 9 c), exhibiting excellent long cycle life and high reversibility throughout the cycle.
To further illustrate the capacitive properties of the electrode materials, electrochemical Impedance (EIS) tests were performed at open circuit potential conditions and at frequencies ranging from 100kHz to 10mHz; as shown in fig. 9d, the impedance profile consists essentially of two parts: one is in the high frequency regionThe other is a straight line at a low frequency region, and the intersection of the axis of the impedance and the curve exhibits a combined resistance, i.e., the intrinsic resistance of the electrode material, the ionic resistance of the electrolyte, and the contact resistance of the active material with the current collector surface (R s ). The enlarged graph of the impedance spectrum (fig. 9d is an embedded graph) shows a lower equivalent series resistance, a more vertical straight line and a smaller diameter semicircle shape, which proves that the electrode has the characteristics of better conductivity, faster ion diffusion rate, lower charge transfer resistance and the like, and is more beneficial to improving the capacitance performance.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The preparation method of the cobaltosic oxide composite carbon material derived from the metal-organic framework is characterized by comprising the following steps of:
(1) 1, 4-bis (imidazol-1-yl) benzene and Co (NO) 3 ) 2 ･6H 2 O adopts a solvent diffusion method to prepare a CP-3-ZX material;
(2) Preparation of a cobaltosic oxide composite carbon material:
heating the CP-3-ZX material prepared in the step (1) to 320-450 ℃ at a heating rate of 10 ℃/min in nitrogen atmosphere, preserving heat for 60-90min, and cooling to room temperature to prepare the cobaltosic oxide composite carbon material derived from the metal-organic framework;
the method for preparing the CP-3-ZX material by the solvent diffusion method comprises the following steps:
s1, preparation of a solution:
preparing a bottom layer: dissolving 1, 4-bis (imidazol-1-yl) benzene in chloroform to obtain a bottom solution;
preparing a buffer layer: mixing methanol and chloroform according to the volume ratio of 0.5-2:1 to prepare buffer layer solution;
top layer preparation: co (NO) 3 ) 2 ･6H 2 O is dissolved in methanol to prepare a top layer solution;
s2, preparing CP-3-ZX crystals: laying a bottom layer solution, a buffer layer solution and a top layer solution in sequence from bottom to top, then placing at room temperature until crystals are formed, and cleaning to obtain CP-3-ZX crystals;
wherein Co (NO) 3 ) 2 ･6H 2 The ratio of O to the amount of material of 1, 4-bis (imidazol-1-yl) benzene is 3-5:2.
2. A metal-organic framework-derived tricobalt tetraoxide composite carbon material prepared by the method for preparing the metal-organic framework-derived tricobalt tetraoxide composite carbon material of claim 1.
3. A working electrode prepared using the metal-organic framework-derived tricobalt tetraoxide composite carbon material of claim 2.
4. A method of preparing a working electrode according to claim 3, comprising the steps of:
mixing a cobaltosic oxide composite carbon material derived from a metal-organic framework, acetylene black and polyvinylidene fluoride, adding ethanol, grinding to obtain homogeneous black slurry, uniformly paving the black slurry on foam nickel, drying and pressing to obtain a working electrode;
wherein the mass ratio of the cobaltosic oxide composite carbon material derived from the metal-organic framework, the acetylene black and the polyvinylidene fluoride is 8-9:1:1.
5. Use of the working electrode of claim 3 for the preparation of a supercapacitor working electrode.
6. The use according to claim 5, wherein the supercapacitor is prepared according to the following steps:
the Hg/HgO electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, a three-electrode system is formed by the platinum wire electrode and a working electrode, the three-electrode system is connected to an electrochemical workstation, and an alkaline solution with the concentration of 2-6mol/L is used as an electrolyte for electrochemical test.
7. The use according to claim 6, wherein the alkaline solution is a KOH solution or a NaOH solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110892387.6A CN113611547B (en) | 2021-08-04 | 2021-08-04 | Metal organic framework derived cobaltosic oxide composite carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110892387.6A CN113611547B (en) | 2021-08-04 | 2021-08-04 | Metal organic framework derived cobaltosic oxide composite carbon material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113611547A CN113611547A (en) | 2021-11-05 |
| CN113611547B true CN113611547B (en) | 2023-05-16 |
Family
ID=78306824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110892387.6A Active CN113611547B (en) | 2021-08-04 | 2021-08-04 | Metal organic framework derived cobaltosic oxide composite carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113611547B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114635151B (en) * | 2022-05-20 | 2022-09-27 | 潍坊学院 | Metal oxide-organic ligand composite electrode material and preparation method thereof |
| CN115947950B (en) * | 2022-12-07 | 2024-02-27 | 电子科技大学长三角研究院(湖州) | Micron-sized monocrystalline ZIFs and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866747A (en) * | 2017-04-11 | 2017-06-20 | 江西理工大学 | A kind of cobalt-based metal organic frame and preparation method thereof |
| CN109390163B (en) * | 2018-10-29 | 2020-10-16 | 西北大学 | Preparation method of two-dimensional Cu-MOF-derived porous carbon nanosheet |
| CN111303445B (en) * | 2020-03-20 | 2022-03-08 | 三峡大学 | Cobalt-based metal organic framework material and application |
| CN113013427A (en) * | 2021-02-26 | 2021-06-22 | 华南理工大学 | High-performance electrocatalyst carrier derived based on Metal Organic Framework (MOF) material and preparation method thereof |
-
2021
- 2021-08-04 CN CN202110892387.6A patent/CN113611547B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113611547A (en) | 2021-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Facile synthesis route of porous MnCo 2 O 4 and CoMn 2 O 4 nanowires and their excellent electrochemical properties in supercapacitors | |
| Gai et al. | A self-template synthesis of porous ZnCo 2 O 4 microspheres for high-performance quasi-solid-state asymmetric supercapacitors | |
| Niu et al. | Towards three-dimensional hierarchical ZnO nanofiber@ Ni (OH) 2 nanoflake core–shell heterostructures for high-performance asymmetric supercapacitors | |
| Tan et al. | Facile synthesis and supercapacitive properties of Zr-metal organic frameworks (UiO-66) | |
| Meng et al. | Porous Co 3 O 4 materials prepared by solid-state thermolysis of a novel Co-MOF crystal and their superior energy storage performances for supercapacitors | |
| Bigdeli et al. | Cobalt terephthalate MOF-templated synthesis of porous nano-crystalline Co3O4 by the new indirect solid state thermolysis as cathode material of asymmetric supercapacitor | |
| Chen et al. | Rational design and synthesis of Ni x Co 3− x O 4 nanoparticles derived from multivariate MOF-74 for supercapacitors | |
| Liu et al. | Ultrafine nickel–cobalt alloy nanoparticles incorporated into three-dimensional porous graphitic carbon as an electrode material for supercapacitors | |
| Hu et al. | Ultrahigh energy density asymmetric electrochemical capacitors based on flower-like ZnO/Co 3 O 4 nanobundle arrays and stereotaxically constricted graphene | |
| Chen et al. | In situ construction of porous Ni/Co-MOF@ Carbon cloth electrode with honeycomb-like structure for high-performance energy storage | |
| Ye et al. | A high-performance asymmetric supercapacitor based on Ni 3 S 2-coated NiSe arrays as positive electrode | |
| CN113611547B (en) | Metal organic framework derived cobaltosic oxide composite carbon material and preparation method and application thereof | |
| Fan et al. | Facile growth of hollow porous NiO microspheres assembled from nanosheet building blocks and their high performance as a supercapacitor electrode | |
| Khan et al. | Novel MoS2-sputtered NiCoMg MOFs for high-performance hybrid supercapacitor applications | |
| Xu et al. | Three-dimensional hollow microtubular carbonized kapok fiber/cobalt-nickel binary oxide composites for high-performance electrode materials of supercapacitors | |
| Naveen et al. | Novel synthesis of highly porous three-dimensional nickel cobaltite for supercapacitor application | |
| Fu et al. | Rose-like ZnNiCo layered double hydroxide grown on Co3O4 nanowire arrays for high energy density flexible supercapacitors | |
| CN108735523B (en) | Preparation method and application of Zn-MOF (Zinc-organic framework) with window beam structure and carbon material derived from Zn-MOF | |
| Wang et al. | Electro-synthesized Ni coordination supermolecular-networks-coated exfoliated graphene composite materials for high-performance asymmetric supercapacitors | |
| Zhang et al. | Porous ZnO/NiO microspherical structures prepared by thermolysis of heterobimetallic metal-organic framework as supercapacitor electrodes | |
| An et al. | Porous nickel cobaltite nanorods: desired morphology inherited from coordination precursors and improved supercapacitive properties | |
| Wang et al. | Mesoporous Co 3 O 4@ carbon composites derived from microporous cobalt-based porous coordination polymers for enhanced electrochemical properties in supercapacitors | |
| Han et al. | Addition of dissimilar metal nodes to improve the electrochemical performance of MOF as a supercapacitor | |
| Li et al. | Preparation and electrochemical properties of nanostructured porous spherical NiCo 2 O 4 materials | |
| Han et al. | Fabrication of strontium bismuth oxides as novel battery-type electrode materials for high-performance supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |