CN113772652B - Method for rapidly preparing cobalt selenide @ nitrogen-doped carbon composite electrode material - Google Patents
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- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 36
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 32
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
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- 230000035484 reaction time Effects 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 2
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 7
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- 229910052711 selenium Inorganic materials 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
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- 150000004763 sulfides Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material, which belongs to the technical field of material preparation, wherein the material is prepared by taking a metal organic framework Co-MOF as a precursor and selenium powder as a selenium source through microwave treatment, and comprises the following steps: firstly, respectively dissolving cobalt salt and an organic ligand in a methanol solution to form a solution A and a solution B, then quickly pouring the solution B into the solution A, stirring and mixing, reacting at room temperature for a period of time, and then centrifugally washing and drying to obtain a precursor Co-MOF; secondly, weighing Co-MOF with a certain mass, grinding and mixing the Co-MOF with selenium powder, and performing microwave treatment to obtain the cobalt selenide @ nitrogen-doped carbon composite electrode material. The preparation process is simple, short in time consumption and low in cost, and is beneficial to industrial production; the prepared composite electrode material has high specific capacity and excellent cycling stability, and has wide application prospects in the fields of energy storage, catalysis, sensing and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for quickly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material.
Background
With the rapid development of science and technology and the industrialization process of human society, the shortage of energy and environmental pollution are becoming more serious, and in order to solve the problem of the shortage of environment and fossil fuel and meet the requirement of rapid development of portable electronic products, wearable devices and electric automobiles, it is important to develop more competitive energy storage devices. The super capacitor is widely researched due to the advantages of high power density, ultra-long service life, rapid charge and discharge, high coulombic efficiency and the like, and the performance of the super capacitor depends on the electrochemical performance of an electrode material to a great extent.
In recent years, transition metal chalcogenides have been extensively studied for their excellent physicochemical properties, such as transition metal oxides and sulfides that exhibit good performance in supercapacitor applications due to their fast faradaic redox reactions, high theoretical specific capacities, low cost and wide sources, while their applications are limited by low conductivity and poor cycling stability. Se and O, S belong to the sixth main group, and they have similar electronic structures and thus similar electrochemical properties. Se has lower electronegativity and higher conductivity (1X 10) than O and S -3 S m -1 ) Therefore, the chemical bond between the transition metal atom and the Se atom is weaker, and the transition metal selenide has higher electrochemical activity and conductivity. However, the current preparation methods mainly include a hydrothermal method and an annealing selenization method, the two methods are long in time consumption and complex in steps, and the annealing selenization needs inert gas protection and has high requirements on equipment. In addition, the transition metal selenide is easy to generate volume expansion in the charge and discharge processes, so that the cycle stability of the transition metal selenide is poor.
Metal Organic Frameworks (MOFs) materials are a class of crystalline materials formed by the self-assembly of metal nodes and organic binders. The metal node and the organic connecting agent can be controlled to regulate and control the structural performance (such as morphology, pores and the like) according to the actual requirements of different storage devices, so that the metal node and the organic connecting agent are an electrode material with great prospect. In addition, the MOFs material can be used as a self-sacrifice template to prepare various hollow and porous nano materials through heat treatment or chemical treatment, so that the synthesized MOFs derivative material keeps the structure of parent MOFs, and the electrochemical performance of the electrode material is favorably improved.
Based on the problems, the invention discloses a method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material. The method has simple process and short time consumption, is beneficial to industrial production, and the Co-MOF can form nitrogen-doped carbon and a porous structure in the microwave selenization process, thereby being beneficial to improving the electrochemical performance of the electrode material and having great application prospect in the field of electrochemical energy storage.
Disclosure of Invention
The invention aims to: the invention provides a method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material, the method is simple in preparation process, short in time consumption and beneficial to industrial production, and the prepared electrode material has high specific capacity and excellent cycle stability and has wide application prospect in the field of electrochemical energy storage.
The technical scheme is as follows: in order to realize the purpose, the invention provides a method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material, which comprises the following steps:
(1) respectively dissolving a certain amount of cobalt nitrate hexahydrate and 2-methylimidazole in a methanol solution, and fully stirring to form a solution A and a solution B;
(2) quickly pouring the solution B into the solution A, continuously stirring, and reacting at room temperature for 20-24 h;
(3) washing and centrifuging the obtained product for multiple times, and placing the product in a vacuum drying oven for drying to obtain Co-MOF precursor powder;
(4) weighing a certain mass of Co-MOF precursor and selenium powder, continuously grinding the Co-MOF precursor and the selenium powder in a mortar, fully mixing the Co-MOF precursor and the selenium powder, transferring the mixed powder into a quartz crucible, and placing the quartz crucible into a microwave oven for microwave reaction to obtain the cobalt selenide @ nitrogen doped carbon composite electrode material.
Further, the molar ratio of the cobalt nitrate hexahydrate and the 2-methylimidazole added in the step (1) is 1/16-1/4, and the cobalt nitrate hexahydrate and the 2-methylimidazole are dissolved in 50ml-100ml of methanol solution respectively.
Further, in the step (3), the drying temperature of the vacuum drying oven is 60-80 ℃, and the drying time is 12-18 h.
Further, the mass ratio of the Co-MOF precursor to the selenium powder in the step (4) is 1/4-1/2, and the microwave reaction time is 2-5 min.
Further, the heating power of the microwave oven in the step (4) is 1000W-1200W, and the microwave absorbent is graphite powder.
Has the advantages that: compared with the prior art, the invention has the beneficial effects that:
1) the Co-MOF can generate aperture change in the microwave selenization process, the aperture is changed from micropore to mesopore, thereby being beneficial to the permeation and diffusion of electrolyte and improving the specific capacity of selenization products;
2) the Co-MOF can form a nitrogen-doped carbon-coated transition metal selenide material in the microwave selenizing process, and the introduction of the nitrogen-doped carbon increases the active sites and the conductivity on one hand, and relieves the volume expansion of the transition metal selenide in the charging and discharging processes on the other hand, thereby improving the cycle stability of the transition metal selenide material;
3) the preparation method disclosed by the invention is simple, short in time consumption, low in cost, beneficial to industrial production and wide in application prospect in the field of electrochemical energy storage.
Drawings
FIG. 1 is CoSe selenized over different microwave times 2 XRD patterns for @ NC electrode materials;
FIG. 2 is a scanning electron microscope image of the precursor Co-MOF;
FIG. 3 is CoSe selenized over different microwave times 2 Scanning electron microscopy of @ NC electrode material: 2min (a, e), 3min (b, f), 4min (c, g), 5min (d, h);
FIG. 4 is CoSe 2 Transmission electron micrograph of @ NC 2min electrode material;
FIG. 5 shows Co-MOF and CoSe 2 A nitrogen isothermal adsorption-desorption curve (a) and a pore size distribution diagram (b) of the electrode material @ NC 2 min;
FIG. 6 is CoSe 2 XPS spectra of @ NC 2min electrode material: full spectrum (a), C1 s (b), N1 s (C), Co 2p (d), Se 3d (e);
FIG. 7 is a plot of cyclic voltammograms (a), 1A g of Co-MOF versus samples prepared by microwave selenization over various times -1 A constant current charge-discharge curve (b) under current density and an electrochemical impedance comparison graph (c);
FIG. 8 is CoSe 2 @ NC 2min electrode material at 5A g -1 A specific capacity change curve (a) after 5000 cycles under the current density, and an electrochemical impedance comparison graph (b) before and after the cycles;
FIG. 9 is CoSe 2 The preparation flow diagram of the @ NC electrode material.
Detailed Description
The invention provides a method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material. Firstly, using cobalt nitrate hexahydrate as a cobalt source, using 2-methylimidazole as an organic ligand, using methanol as a solvent to react at room temperature, then performing centrifugal washing and drying for multiple times to obtain a Co-MOF precursor, weighing Co-MOF with a certain mass, grinding the Co-MOF and selenium powder to uniformly mix the Co-MOF precursor and the selenium powder, and preparing the cobalt selenide @ nitrogen-doped carbon composite electrode material by microwave treatment for 2-5 min. The morphology of a sample is observed by using a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), the phase structure of the composite material is detected by XRD, the surface elements and the valence state of the material are analyzed by X-ray photoelectron spectroscopy (XPS), and the specific surface area and the pore size distribution of the material are obtained by nitrogen isothermal adsorption and desorption test.
A method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material comprises the following steps:
1) respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in a methanol solution, and fully stirring to form a solution A and a solution B;
2) quickly pouring the solution B into the solution A, continuously stirring, and reacting at room temperature for 20-24 h;
3) washing and centrifuging the obtained product for multiple times, and placing the product in a vacuum drying oven for drying to obtain Co-MOF precursor powder;
4) weighing a certain mass of Co-MOF precursor and selenium powder, continuously grinding the Co-MOF precursor and the selenium powder in a mortar, fully mixing the Co-MOF precursor and the selenium powder, transferring the mixed powder into a quartz crucible, and placing the quartz crucible into a microwave oven for microwave reaction to obtain the cobalt selenide @ nitrogen doped carbon composite electrode material.
The molar ratio of the cobalt nitrate hexahydrate and the 2-methylimidazole in the step 1) is 1/16-1/4, and the cobalt nitrate hexahydrate and the 2-methylimidazole are respectively dissolved in 50ml-100ml of methanol solution.
In the step 3), the drying temperature of the vacuum drying oven is 60-80 ℃, and the drying time is 12-18 h.
And 4) the mass ratio of the Co-MOF precursor to the selenium powder is 1/4-1/2, and the microwave reaction time is 2-5 min.
And 4) heating power of the microwave oven is 1000W-1200W, and the microwave absorbent is graphite powder.
The invention is further described below with reference to the following figures and examples:
example 1
Respectively dissolving 10mmol of cobalt nitrate hexahydrate and 40mmol of 2-methylimidazole in 50ml of methanol solution, fully stirring to form a solution A, B, then quickly pouring the solution B into the solution A, continuously stirring to fully mix the solution A, reacting at room temperature for 24 hours, centrifugally separating a reaction product, alternately and repeatedly washing with ethanol and deionized water for multiple times, and then placing in a vacuum drying oven for drying at 60 ℃ for 18 hours to obtain a Co-MOF powder sample.
FIGS. 2(a) and (b) are SEM images of the product of this example at different magnifications, and it can be seen from FIG. 2(a) that the morphology of the obtained product is rhombohedral with a smooth surface and the size of the product is uniform, and further magnification (FIG. 2(b)) can see that the size of the product is about 1 μm-2 μm; FIG. 5 shows the isothermal adsorption and desorption curves and the distribution diagram of the pore size of the product nitrogen in this example, and it can be seen that the curve type is type I, which indicates that the product nitrogen has a microporous structure and the pore size is mainly concentrated in the range of 0-2 nm.
Example 2
Respectively dissolving 10mmol of cobalt nitrate hexahydrate and 40mmol of 2-methylimidazole in 50ml of methanol solution, fully stirring to form a solution A, B, then quickly pouring the solution B into the solution A, continuously stirring to fully mix the solutions, reacting at room temperature for 24 hours, centrifugally separating a reaction product, alternately and repeatedly washing with ethanol and deionized water for multiple times, and then placing in a vacuum drying oven for drying at 60 ℃ for 18 hours to obtain a Co-MOF precursor powder sample.
Weighing 0.08g of Co-MOF precursor powder and 0.08g of selenium powder, placing the Co-MOF precursor powder and the selenium powder in a mortar, fully grinding the Co-MOF precursor powder and the selenium powder to enable the Co-MOF precursor powder and the selenium powder to be uniformly mixed, transferring the mixture to a smaller quartz crucible, sleeving a larger crucible outside, filling graphite powder between the two crucibles to serve as a microwave absorbent, placing the mixture into a microwave oven to perform microwave treatment, wherein the heating power of the microwave oven is 1200W, the microwave time is 2min, and finally obtaining CoSe 2 @ NC 2min composite electrode material.
FIG. 1 shows the XRD pattern of the product of this example, and it can be seen that CoSe was successfully produced 2 The material consists of two phase structures of an orthorhombic phase and a cubic phase; FIG. 3(a) (e) is a scanning electron microscope image of the product of this example, showing that the morphology of the product after selenization in this example still maintains the rhombohedral structure, but the surface becomes rough, compared to the product of example 1; FIG. 4 is a transmission electron microscope photograph of the product of this example, and it can be seen that the sample has a porous structure and the rhombic dodecahedron edges appear similar to a rod-like structure, illustrating that CoSe was synthesized 2 Is in a rod-shaped structure; fig. 5 shows the nitrogen isothermal adsorption and desorption curve and the pore size distribution diagram of the product of this example, which can obtain a curve showing type IV, non-uniform pore size distribution and all being mesoporous compared with the product of example 1. FIG. 6 is an XPS spectrum of the product of this example, wherein the sample contains C, N, O, Co, and Se elements as shown in FIG. 6(a), a nitrogen-doped carbon material as shown in FIGS. 6(b) (C), and a CoSe as successfully synthesized as shown in FIGS. 6(d) (e) 2 A material.
Example 3
Respectively dissolving 10mmol of cobalt nitrate hexahydrate and 40mmol of 2-methylimidazole in 50ml of methanol solution, fully stirring to form a solution A, B, then quickly pouring the solution B into the solution A, continuously stirring to fully mix the solution A, reacting at room temperature for 24 hours, centrifugally separating a reaction product, alternately and repeatedly washing the reaction product with ethanol and deionized water for multiple times, and then placing the reaction product in a vacuum drying oven for drying at 60 ℃ for 18 hours to obtain a Co-MOF precursor powder sample.
Weighing 0.08g of Co-MOF precursor powder and 0.08g of selenium powder, placing the Co-MOF precursor powder and the selenium powder in a mortar, fully grinding the Co-MOF precursor powder and the selenium powder to enable the Co-MOF precursor powder and the selenium powder to be uniformly mixed, transferring the mixture to a smaller quartz crucible, sleeving a larger crucible outside, filling graphite powder between the two crucibles to serve as a microwave absorbent, placing the mixture into a microwave oven to perform microwave treatment, wherein the heating power of the microwave oven is 1200W, the microwave time is 3min, and finally obtaining CoSe 2 @ NC 3min composite electrode material.
FIG. 1 shows the XRD pattern of the product of this example, and it can be seen that CoSe was successfully produced 2 The material consists of two phase structures of an orthogonal phase and a cubic phase; FIG. 3(b)(f) Is a scanning electron microscope image of the product of the embodiment, and it can be seen that compared with the products of the embodiments 1 and 2, the morphology of the product after selenization in the embodiment still maintains the rhombic dodecahedron structure, but the surface becomes rough.
Example 4
Respectively dissolving 10mmol of cobalt nitrate hexahydrate and 40mmol of 2-methylimidazole in 50ml of methanol solution, fully stirring to form a solution A, B, then quickly pouring the solution B into the solution A, continuously stirring to fully mix the solution A, reacting at room temperature for 24 hours, centrifugally separating a reaction product, alternately and repeatedly washing with ethanol and deionized water for multiple times, and then placing in a vacuum drying oven for drying at 60 ℃ for 18 hours to obtain a Co-MOF precursor powder sample.
Weighing 0.08g of Co-MOF precursor powder and 0.08g of selenium powder, placing the Co-MOF precursor powder and the selenium powder in a mortar, fully grinding the Co-MOF precursor powder and the selenium powder to enable the Co-MOF precursor powder and the selenium powder to be uniformly mixed, transferring the mixture to a smaller quartz crucible, sleeving a larger crucible outside, filling graphite powder between the two crucibles to serve as a microwave absorbent, placing the mixture into a microwave oven to perform microwave treatment, wherein the heating power of the microwave oven is 1200W, the microwave time is 4min, and finally obtaining the CoSe 2 @ NC 4min composite electrode material.
FIG. 1 shows the XRD pattern of the product of this example, and it can be seen that CoSe was successfully produced 2 The material consists of two phase structures of an orthogonal phase and a cubic phase; fig. 3(c) (g) is a scanning electron microscope image of the product of this example, which shows that the morphology of the product after selenization in this example still maintains the rhombohedral structure, but the surface becomes rough and the morphology slightly collapses, comparing the products of examples 1, 2 and 3.
Example 5
Respectively dissolving 10mmol of cobalt nitrate hexahydrate and 40mmol of 2-methylimidazole in 50ml of methanol solution, fully stirring to form a solution A, B, then quickly pouring the solution B into the solution A, continuously stirring to fully mix the solutions, reacting at room temperature for 24 hours, centrifugally separating a reaction product, alternately and repeatedly washing with ethanol and deionized water for multiple times, and then placing in a vacuum drying oven for drying at 60 ℃ for 18 hours to obtain a Co-MOF precursor powder sample.
Weigh 0.08g Co-MOF precursorPowder, 0.08g selenium powder, placing the powder and the selenium powder in a mortar, fully grinding the powder and the selenium powder to enable the powder and the selenium powder to be mixed uniformly, transferring the mixture to a smaller quartz crucible, sleeving a larger crucible outside, filling graphite powder between the two crucibles to serve as a microwave absorbent, placing the crucible into a microwave oven to perform microwave treatment, wherein the heating power of the microwave oven is 1200W, and the microwave time is 5min, and finally obtaining the CoSe 2 @ NC 5min composite electrode material.
FIG. 1 shows the XRD pattern of the product of this example, and it can be seen that CoSe was successfully produced 2 The material consists of two phase structures of an orthorhombic phase and a cubic phase; fig. 3(d) (h) is a scanning electron microscope image of the product of this example, and it can be seen that compared with the products of examples 1, 2, 3 and 4, the morphology of the product after selenization in this example can roughly maintain the rhombic dodecahedron structure, the surface thereof becomes rough, and the morphology collapse is severe.
Example 6
The products of the examples 1, 2, 3, 4 and 5 are respectively mixed with acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1, 1-methyl-2 pyrrolidone is dripped into the mixture to be continuously ground into slurry, the slurry is coated on foamed nickel and then is placed in a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃ to obtain the working electrode.
The electrochemical performance of the working electrode is measured in a three-electrode system by using a platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode and 1M KOH solution as electrolyte.
FIG. 7(a) shows the results of examples 1, 2, 3, 4, and 5 at a scan rate of 10mV s -1 The cyclic voltammetry curves obtained under the voltage window of 0-0.7V can obtain that all the curves have redox peaks and show pseudocapacitance behaviors, and the graph in FIG. 7(b) shows that the redox peaks are in 1A g -1 The constant current charge-discharge curve under the current density can obtain a comparative precursor Co-MOF, the specific capacity of all selenization products is improved, and the CoSe prepared in the embodiment 2 2 The sample performance of @ NC 2min is optimal, and the specific capacity can reach 395F g -1 。
FIG. 8(a) shows the product of example 2 at 5A g -1 Current density ofAfter 5000 cycles, the capacity retention rate can still reach 96.8% after 5000 cycles, which shows that the compound has excellent cycle stability.
Claims (4)
1. A method for rapidly preparing a cobalt selenide @ nitrogen-doped carbon composite electrode material is characterized by comprising the following steps: the method comprises the following steps:
1) respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in a methanol solution, and fully stirring to form a solution A and a solution B;
2) pouring the solution B into the solution A, continuously stirring, and reacting at room temperature for 20-24 h;
3) washing and centrifuging the obtained product for multiple times, and placing the product in a vacuum drying oven for drying to obtain microporous Co-MOF precursor powder;
4) weighing a Co-MOF precursor and selenium powder, grinding the Co-MOF precursor and the selenium powder in a mortar, and then putting the mixed powder into a microwave oven for microwave reaction to obtain a mesoporous cobalt selenide @ nitrogen-doped carbon composite electrode material;
in the step 4), the microwave reaction time is 2-5min, the heating power of a microwave oven is 1000W-1200W, and the microwave absorbent is graphite powder;
the cobalt selenide in the cobalt selenide @ nitrogen-doped carbon composite electrode material consists of orthorhombic cobalt selenide and cubic cobalt selenide;
the cobalt selenide @ nitrogen-doped carbon composite electrode material is 5A g -1 After 5000 cycles of the current density, the capacity retention rate is 96.8%.
2. The method for rapidly preparing the cobalt selenide @ nitrogen-doped carbon composite electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the molar ratio of cobalt nitrate hexahydrate to 2-methylimidazole is 1/16-1/4, and the cobalt nitrate hexahydrate and the 2-methylimidazole are dissolved in 50ml-100ml of methanol solution respectively.
3. The method for rapidly preparing the cobalt selenide @ nitrogen-doped carbon composite electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the drying temperature of the vacuum drying oven is 60-80 ℃, and the drying time is 12-18 h.
4. The method for rapidly preparing the cobalt selenide @ nitrogen-doped carbon composite electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step 4), the mass ratio of the Co-MOF precursor to the selenium powder is 1/4-1/2.
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