CN108922790B - Preparation method and application of composite material - Google Patents

Preparation method and application of composite material Download PDF

Info

Publication number
CN108922790B
CN108922790B CN201810761109.5A CN201810761109A CN108922790B CN 108922790 B CN108922790 B CN 108922790B CN 201810761109 A CN201810761109 A CN 201810761109A CN 108922790 B CN108922790 B CN 108922790B
Authority
CN
China
Prior art keywords
manganese dioxide
porous carbon
nitrogen
composite material
doped porous
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
Application number
CN201810761109.5A
Other languages
Chinese (zh)
Other versions
CN108922790A (en
Inventor
武立立
张喜田
张慧杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Jiesen General Electromechanical Equipment Co ltd
Original Assignee
Heilongjiang University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Heilongjiang University of Science and Technology filed Critical Heilongjiang University of Science and Technology
Priority to CN201810761109.5A priority Critical patent/CN108922790B/en
Publication of CN108922790A publication Critical patent/CN108922790A/en
Application granted granted Critical
Publication of CN108922790B publication Critical patent/CN108922790B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01G11/22—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
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • H01G11/46—Metal oxides
    • 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

A preparation method and application of a sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material relate to a preparation method and application of a manganese dioxide composite material. The invention aims to solve the problems of poor multiplying power and low capacitance retention rate when the existing manganese dioxide is used as an electrode material of a pseudo-capacitive super capacitor. The method comprises the following steps: firstly, preparing regular dodecahedral ZIF-67; secondly, preparing a ZIF-67 derived nanoporous carbon material; and thirdly, compounding to obtain the manganese dioxide/nitrogen doped porous carbon composite material with the sodium ions embedded. The manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions is used as a positive electrode material of a super capacitor. The invention can obtain the manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded.

Description

Preparation method and application of composite material
Technical Field
The invention relates to a preparation method and application of a manganese dioxide composite material.
Background
With the global population growth and rapid economic development, non-renewable fossil energy is gradually decreasing, and thus the energy crisis becomes another serious challenge facing countries in the world. Under such an era background, energy storage devices (batteries, capacitors, supercapacitors, etc.) and conversion devices (fuel cells, solar cells, etc.) have become the focus of research by various research institutes. The battery such as a lead-acid battery, a nickel-based battery, a sodium battery, a lithium ion battery, an air battery and the like has higher energy density, but the power density is lower, the charging and discharging time is long, and the application of the battery in some specific fields is limited. The invention of supercapacitors brings about an eosin to our lives. The super capacitor is a novel energy storage device between a common capacitor and a chemical battery, has the advantages of high power density, high charge and discharge rate, long service life, environmental protection and the like, and is expected to become a novel green energy source in the century. In a supercapacitor, electrode materials are critical, which determine the main properties of the capacitor and are also critical factors affecting the capacitive properties of the capacitor and the production cost.
The electrode materials of the currently researched super capacitor mainly include carbon-based materials (including activated carbon, carbon fibers, carbon nanotubes, graphene and the like), hetero-atom doped carbon materials (O-doped carbon materials, N-doped carbon materials), conductive polymers (polypyrrole PPy, polyaniline PANI, polythiophene PTh and the like) and transition metal oxides/hydroxides (RuO)2、MnO2、NiOx/Ni(OH)2Etc.) and the like. In order to enhance the specific capacity and energy density of the supercapacitor, transition metal hydroxides, oxides and polymers are attracting attention as electrode materials of the pseudocapacitive supercapacitor. Among these pseudocapacitive electrode materials, manganese dioxide (MnO)2) Is a black or dark brown crystalline or amorphous powder having a relative molecular mass of 86.94 and a relative density of 5.03 g.m-3The melting point is 535 ℃, the material is insoluble in water and nitric acid, and the material has excellent electrical, optical, magnetic and thermal properties. Manganese dioxide has high theoretical specific capacitance (1370F g) due to its abundant natural content, low cost-1) And is environmentally friendly, etc., and is considered to be one of the most promising pseudocapacitive electrode materials. However, the reaction mechanism of manganese dioxide in a supercapacitor is that a faradaic pseudocapacitance reaction occurs due to rapid transformation between manganese dioxide and hydromanganite to store and release charges, that is, the pseudocapacitance reaction can only occur on the surface of a material or a thin layer on the surface of the material, and an active substance in an electrode material cannot complete the transformation in a short time due to slow mass transfer, so that the electrode capacity is obviously lost and the rate capability is low during large-current operation. In addition, MnO2The poor conductivity and short cycle life of the composite lead to serious limitation on the development of the composite in the field of supercapacitors. For example, manganese dioxide in the form of hollow sea urchin prepared by Nanjing post and telecommunications university (inorganic chemistry journal 30(11):2509--1Under the condition (2), the specific capacitance value is 226F · g-1(ii) a However, when the sweep rate is increased to 100mV · s-1The specific capacitance value is only 88.5 Fg-1The magnification is about 40%. The carbon material has good conductivity and stability, and is compounded with manganese dioxide, so that the carbon material not only can be used as a physical support of the manganese dioxide, but also provides a charge transmission channel, and the rate capability and the cycling stability of the electrode material can be improved. MnO is introduced into Wenzhou university (chemical engineering and development 44(5):1-5)2Is compounded with carbon nano-wire with sweep rate of 2 mV.s-1To 100 mV. s-1The multiplying power of the capacitor is improved to about 60%, and the capacity retention rate is 89.3% after 1000-circle cycle test. Therefore, the composition of the carbon material and the manganese dioxide can effectively improve the multiplying power and the cycle performance of the electrode.
Common carbon materials compounded with manganese dioxide include carbon black, carbon flake paper, graphene, carbon nanotubes, mesoporous carbon, and the like. Manganese dioxide/carbon paper composite electrode materials are prepared by Wanghongqiang et al (CN 105788884A) in the university of Guangxi Master, the capacitance value of the materials can reach 200-400F/g, and the symmetry of a constant current charging and discharging curve of the material is unsatisfactory when the material is applied to a super capacitor. The manganese dioxide/nanotube composite electrode material prepared by Songyijiang et al (CN 103972518A) of the university of chemical and physical research institute has a capacity retention rate of 80% after 1000 cycles of electrode cycle. The limitations of the prior experimental methods and results of compounding carbon material and manganese dioxide in rate capability and cycling stability are the causes of the present invention.
Disclosure of Invention
The invention aims to solve the problems of poor multiplying power and low capacitance retention rate when the existing manganese dioxide is used as an electrode material of a pseudo-capacitive supercapacitor, and provides a preparation method and application of a manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded.
A preparation method of a sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material is prepared according to the following steps:
firstly, preparing regular dodecahedral ZIF-67:
①, dissolving cobalt nitrate hexahydrate in methanol to obtain a cobalt nitrate solution;
the volume ratio of the mass of the cobalt nitrate hexahydrate in the step one ① to the volume of the methanol is (1 g-2 g) 40 mL;
②, dissolving 2-methylimidazole in methanol to obtain 2-methylimidazole solution;
the volume ratio of the mass of the 2-methylimidazole to the methanol in the step I ② is (1 g-3 g) and is 40 mL;
③, mixing the cobalt nitrate solution and the 2-methylimidazole solution, stirring at room temperature and a stirring speed of 500-900 r/min for 15-25 h, carrying out vacuum filtration, collecting solid substances, washing the collected solid substances with absolute ethyl alcohol for 5-8 times, and drying the solid substances washed with the absolute ethyl alcohol in an oven at the temperature of 55-65 ℃ for 10-14 h to obtain the dodecahedron ZIF-67;
the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution in the first step ③ is (0.8-1.2): 1;
secondly, preparing a ZIF-67 derived nanoporous carbon material:
①, dispersing the regular dodecahedral ZIF-67 obtained in the step one ③ in a ceramic boat, then placing the ceramic boat in a tubular furnace, introducing mixed gas of argon and hydrogen into the tubular furnace, then heating the tubular furnace to 420-450 ℃ at the heating rate of 3-8 ℃/min, then keeping the temperature for 6-10 h under the condition of the mixed gas atmosphere of argon and hydrogen and the temperature of 420-450 ℃, and finally naturally cooling the tubular furnace to room temperature to obtain black powder;
②, immersing the black powder obtained in the step two ① into H with the concentration of 0.8 mol/L-1.2 mol/L2SO4Carrying out vacuum filtration on the solution for 10-14 h, collecting solid matters, washing the collected solid matters for 5-8 times by using deionized water, and then putting the solid matters washed by the deionized water into a drying oven with the temperature of 55-65 ℃ for drying for 8-10 h to obtain the ZIF-67 derived nanoporous carbon material;
thirdly, compounding:
①, 0.04 mol/L-0.06 mol/L KMnO4The solution and Na with the concentration of 0.04mol/L to 0.06mol/L2SO4Mixing the solutions to obtain KMnO4And Na2SO4The mixed solution of (1);
KMnO of 0.04 mol/L-0.06 mol/L described in step three ①4The solution and Na with the concentration of 0.04mol/L to 0.06mol/L2SO4The volume ratio of the solution is (0.95-1) to 1;
② immersing ZIF-67 derived nanoporous carbon material in KMnO at room temperature4And Na2SO4And carrying out vacuum filtration on the mixed solution for 3-7 h, collecting solid matters, washing the collected solid matters for 5-8 times by using deionized water, and drying the solid matters washed by the deionized water in a drying oven at the temperature of 55-65 ℃ for 8-10 h to obtain the manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions.
The manganese dioxide/nitrogen doped porous carbon composite material with the sodium ions embedded is used as an electrode material of a super capacitor.
The principle of the invention is as follows:
the invention adopts a solvothermal method, takes methanol as a solvent, takes cobalt as metal central ions, takes cobalt nitrate as a cobalt source and takes 2-methylimidazole as a nitrogen-containing organic ligand, and assembles the 2-methylimidazole on transition metal cobalt in a crosslinking way at room temperature to obtain the metal-organic framework material ZIF67 with a regular dodecahedron-shaped zeolite-like imidazolate framework structure.
According to the invention, a template sacrificial method is adopted, ZIF67 is taken as a template, a derivative composite material Co/C-N is prepared through a simple pyrolysis method, and concentrated sulfuric acid is used for corroding a metal element Co, so that the mass density of the material is reduced, and the porosity is increased, thus obtaining the nitrogen-doped porous carbon material.
The invention adopts an oxidation-reduction method, and utilizes carbon to reduce potassium permanganate in situ, wherein the reaction equation is as follows:
4MnO4 -+3C+H2O＝4MnO2+CO3 2-+2HCO3 -；
when the reaction occurs, sodium ions are embedded into the composite material through soaking, and finally the manganese dioxide/nitrogen doped porous carbon composite material with the embedded sodium ions is obtained.
The invention has the advantages that:
the preparation method is based on the characteristic that a metal-organic framework material is easily decomposed by heating, and the porous carbon material is prepared by adopting the metal-organic framework material ZIF67 as a sacrificial template; the ZIF 67-derived porous carbon material has a hollow regular dodecahedron structure, uniform particle size distribution and a higher specific surface area, so that the synthesis of a composite electrode material with a hollow structure, a regular appearance and uniform particle size is facilitated;
secondly, carbonizing and removing metal Co at 420-450 ℃ by taking cobalt-containing ZIF67 composed of nitrogen-rich and oxygen-poor ligands as a sacrificial template to obtain a ZIF 67-derived porous carbon material; the ZIF67 can furthest keep N atoms to be uniformly dispersed in a carbon framework during low-temperature pyrolysis in an inert atmosphere; in contrast, the traditional method for preparing the heteroatom-doped porous carbon material has the defects of harsh conditions and complex process, the prepared material has irregular appearance and different pore sizes, the specific surface area is often very low, and the key point is that the heteroatoms are difficult to disperse uniformly. The uniform doping of nitrogen atoms can effectively adjust the electronic structure and the conductivity of the porous carbon material, so that the porous carbon material has richer performance. And the process of removing the heteroatom cobalt in the experiment not only reduces the mass density of the material, but also increases the porosity of the material. Therefore, the porous carbon material synthesized by adopting the metal-organic framework material ZIF67 as a sacrificial template is uniformly doped with nitrogen elements and has high porosity, thereby being beneficial to obtaining a high-performance composite electrode material;
the sodium ion embedded manganese dioxide/nitrogen doped porous carbon composite material constructed by taking ZIF67 derived porous carbon as a framework inherits the characteristics of high specific surface area, high porosity, high thermal stability, easiness in functionalization, low price and the like of a metal-organic framework material, has a hollow nearly regular dodecahedron structure, is regular in appearance, uniform in particle size, high in porosity and consistent in pore size, and is beneficial to obtaining good super-capacity performance;
the manganese dioxide is uniformly and fully dispersed on a carbon skeleton, belongs to a birnessite structure with a layered structure, and is convenient for ion adsorption and desorption, so that the manganese dioxide/nitrogen-doped porous carbon composite material with the sodium ions embedded is suitable for a supercapacitor material;
when the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared by the invention is used as a positive electrode material of a supercapacitor, the mass specific capacitance is superior to that of the situation that the manganese dioxide or nitrogen-doped ZIF 67-derived porous carbon is used as a positive electrode material under the same test condition; the mass specific capacitance of the sodium ion embedded manganese dioxide/nitrogen doped porous carbon composite material prepared by the invention is 5 times that of a pure manganese dioxide material;
sixthly, when the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared by the invention is used as a positive electrode material of a super capacitor, a constant-current charge-discharge curve is a standard isosceles triangle and shows good symmetry;
seventhly, when the sodium ion embedded manganese dioxide/nitrogen doped porous carbon composite material prepared by the invention is used as a positive electrode material of a super capacitor, the sweeping speed is 2mV s-1To 100mV s-1The multiplying power of the capacitor is 80-90%;
eighthly, when the sodium ion embedded manganese dioxide/nitrogen doped porous carbon composite material prepared by the invention is used as a positive electrode material of a super capacitor, the circulation stability is good, the voltage window is 0V-0.8V, and the current density is 1A g-1Under the condition of (3), the capacity retention rate is 85-95% after 5000 cycles.
The invention can obtain the manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded.
Drawings
FIG. 1 is an SEM image of regular dodecahedral ZIF-67 prepared in one step one of the examples;
FIG. 2 is an SEM image of ZIF-67 derivatized nanoporous carbon material prepared in step two of the example;
FIG. 3 is a spectrum of a ZIF-67 derivatized nanoporous carbon material prepared in step two of the example;
FIG. 4 is a specific surface area spectrum of a ZIF-67 derived nanoporous carbon material prepared in step two of the example;
FIG. 5 is an SEM image of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in step three of the example;
FIG. 6 is a TEM image of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in one step three of the example;
FIG. 7 is an XRD spectrum of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in step three of the example;
FIG. 8 is a spectrum of the specific surface area of the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in step three of the example;
FIG. 9 is a pore size distribution spectrum of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in step three of the example;
FIG. 10 is a plot of the voltammetry characteristics of a sodium ion intercalated manganese dioxide/nitrogen doped porous carbon composite prepared in step three of the example;
FIG. 11 is a plot of the voltammetry characteristics of the ZIF-67 derivatized nanoporous carbon material prepared in example step two;
FIG. 12 is a plot of the voltammetric characteristics of pure manganese dioxide synthesized hydrothermally;
FIG. 13 is a constant current charging and discharging curve of circles 1 to 5 of the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in the third step of the example;
FIG. 14 is a 4995-;
FIG. 15 is a graph showing the relationship between the sweep rate and capacitance of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in step three of the example;
fig. 16 is a graph of the cycling characteristics of the sodium ion intercalated manganese dioxide/nitrogen doped porous carbon composite prepared in one step three of the example.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of a sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material, which comprises the following steps:
firstly, preparing regular dodecahedral ZIF-67:
①, dissolving cobalt nitrate hexahydrate in methanol to obtain a cobalt nitrate solution;
the volume ratio of the mass of the cobalt nitrate hexahydrate in the step one ① to the volume of the methanol is (1 g-2 g) 40 mL;
②, dissolving 2-methylimidazole in methanol to obtain 2-methylimidazole solution;
the volume ratio of the mass of the 2-methylimidazole to the methanol in the step I ② is (1 g-3 g) and is 40 mL;
③, mixing the cobalt nitrate solution and the 2-methylimidazole solution, stirring at room temperature and a stirring speed of 500-900 r/min for 15-25 h, carrying out vacuum filtration, collecting solid substances, washing the collected solid substances with absolute ethyl alcohol for 5-8 times, and drying the solid substances washed with the absolute ethyl alcohol in an oven at the temperature of 55-65 ℃ for 10-14 h to obtain the dodecahedron ZIF-67;
the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution in the first step ③ is (0.8-1.2): 1;
secondly, preparing a ZIF-67 derived nanoporous carbon material:
①, dispersing the regular dodecahedral ZIF-67 obtained in the step one ③ in a ceramic boat, then placing the ceramic boat in a tubular furnace, introducing mixed gas of argon and hydrogen into the tubular furnace, then heating the tubular furnace to 420-450 ℃ at the heating rate of 3-8 ℃/min, then keeping the temperature for 6-10 h under the condition of the mixed gas atmosphere of argon and hydrogen and the temperature of 420-450 ℃, and finally naturally cooling the tubular furnace to room temperature to obtain black powder;
②, immersing the black powder obtained in the step two ① into H with the concentration of 0.8 mol/L-1.2 mol/L2SO4Carrying out vacuum filtration on the solution for 10-14 h, collecting solid matters, washing the collected solid matters for 5-8 times by using deionized water, and then putting the solid matters washed by the deionized water into a drying oven with the temperature of 55-65 ℃ for drying for 8-10 h to obtain the ZIF-67 derived nanoporous carbon material;
thirdly, compounding:
①, 0.04 mol/L-0.06 mol/L KMnO4The solution and Na with the concentration of 0.04mol/L to 0.06mol/L2SO4Mixing the solutions to obtain KMnO4And Na2SO4The mixed solution of (1);
KMnO of 0.04 mol/L-0.06 mol/L described in step three ①4The solution and Na with the concentration of 0.04mol/L to 0.06mol/L2SO4The volume ratio of the solution is (0.95-1) to 1;
② immersing ZIF-67 derived nanoporous carbon material in KMnO at room temperature4And Na2SO4And carrying out vacuum filtration on the mixed solution for 3-7 h, collecting solid matters, washing the collected solid matters for 5-8 times by using deionized water, and drying the solid matters washed by the deionized water in a drying oven at the temperature of 55-65 ℃ for 8-10 h to obtain the manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions.
The principle of the present embodiment:
in the embodiment, a solvothermal method is adopted, methanol is used as a solvent, cobalt is used as a metal central ion, cobalt nitrate is used as a cobalt source, 2-methylimidazole is used as a nitrogen-containing organic ligand, and the 2-methylimidazole is assembled on the transition metal cobalt in a crosslinking manner at room temperature to obtain the metal-organic framework material ZIF67 with a regular dodecahedron-shaped zeolite-like imidazolate framework structure.
According to the embodiment, a template sacrificial method is adopted, ZIF67 is used as a template, a derivative composite material Co/C-N is prepared through a simple pyrolysis method, and concentrated sulfuric acid is used for corroding a metal element Co, so that the mass density of the material is reduced, the porosity is increased, and the nitrogen-doped porous carbon material is obtained.
The embodiment adopts an oxidation-reduction method, and the reaction equation of reducing potassium permanganate in situ by using carbon is as follows:
4MnO4 -+3C+H2O＝4MnO2+CO3 2-+2HCO3 -；
when the reaction occurs, sodium ions are embedded into the composite material through soaking, and finally the manganese dioxide/nitrogen doped porous carbon composite material with the embedded sodium ions is obtained.
The advantages of this embodiment:
the preparation method is based on the characteristic that a metal-organic framework material is easy to decompose when being heated, the metal-organic framework material ZIF67 is used as a sacrificial template to prepare the porous carbon material, and the ZIF67 derived porous carbon material has a hollow regular dodecahedron structure, uniform particle size distribution and a higher specific surface area, so that the synthesis of a composite electrode material with a hollow structure, regular appearance and uniform particle size is facilitated;
secondly, in the embodiment, cobalt-containing ZIF67 composed of nitrogen-rich and oxygen-poor ligands is used as a sacrificial template, and the cobalt-containing ZIF67 is carbonized at the temperature of 420-450 ℃ and the metal Co is removed to obtain a ZIF 67-derived porous carbon material; the ZIF67 can furthest keep N atoms to be uniformly dispersed in a carbon framework during low-temperature pyrolysis in an inert atmosphere; compared with the prior art, the traditional method for preparing the heteroatom-doped porous carbon material has the advantages of harsh conditions, complex process, irregular appearance of the prepared material, different pore sizes, very low specific surface area and difficulty in uniformly dispersing the heteroatoms; the uniform doping of nitrogen atoms can effectively adjust the electronic structure and the conductivity of the porous carbon material, so that the porous carbon material has richer performance; and the process of removing the heteroatom cobalt in the experiment not only reduces the mass density of the material, but also increases the porosity of the material. Therefore, the porous carbon material synthesized by adopting the metal-organic framework material ZIF67 as a sacrificial template is uniformly doped with nitrogen elements and has high porosity, thereby being beneficial to obtaining a high-performance composite electrode material;
in the embodiment, the ZIF 67-derived porous carbon is used as a skeleton to construct the sodium ion embedded manganese dioxide/nitrogen-doped porous carbon composite material, so that the characteristics of high specific surface area, high porosity, high thermal stability, easiness in functionalization, low price and the like of a metal-organic skeleton material are inherited, the hollow near-regular dodecahedron structure is realized, the appearance is regular, the particle size is uniform, the porosity is high, the pore diameter is consistent, and good super-capacity performance is obtained;
the manganese dioxide is uniformly and fully dispersed on a carbon skeleton, belongs to a birnessite structure with a layered structure, and is convenient for ion adsorption and desorption, so that the manganese dioxide/nitrogen-doped porous carbon composite material with the sodium ions embedded is suitable for a supercapacitor material;
when the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared by the embodiment is used as a positive electrode material of a supercapacitor, the mass specific capacitance is superior to that of the situation that the manganese dioxide or nitrogen-doped ZIF 67-derived porous carbon is used as the positive electrode material under the same test condition; the mass specific capacitance of the sodium ion embedded manganese dioxide/nitrogen doped porous carbon composite material prepared by the embodiment is 5 times that of a pure manganese dioxide material;
sixthly, when the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared by the embodiment is used as a positive electrode material of a super capacitor, a constant-current charge-discharge curve is a standard isosceles triangle and shows good symmetry;
seventhly, when the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared by the embodiment is used as a positive electrode material of a super capacitor, the sweeping speed is 2mV s-1To 100mV s-1The multiplying power of the capacitor is 80-90%;
eighthly, when the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared by the embodiment is used as a positive electrode material of a supercapacitor, the circulation stability is good, the voltage window is 0V-0.8V, and the current density is 1A g-1Under the condition of (3), the capacity retention rate is 85-95% after 5000 cycles.
According to the embodiment, the manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded can be obtained.
The second embodiment is different from the first embodiment in that the ratio of the mass of the cobalt nitrate hexahydrate to the volume of methanol in the first step ① is (1.6 g-2 g):40mL, and the other steps are the same as those in the first embodiment.
Third embodiment this embodiment is different from the first or second embodiment in that the mass-to-methanol volume ratio of 2-methylimidazole in the first step ② is (1g to 2g):40 ml.
Fourth specific embodiment, the difference between the first specific embodiment and the third specific embodiment is that in the first step ③, a cobalt nitrate solution and a 2-methylimidazole solution are mixed, the mixture is stirred and reacted for 15 to 20 hours at room temperature and a stirring speed of 600 to 800r/min, then vacuum filtration is carried out, solid matters are collected, the collected solid matters are washed for 5 to 6 times by using absolute ethyl alcohol, then the solid matters washed by the absolute ethyl alcohol are placed into an oven at a temperature of 55 to 60 ℃ to be dried for 10 to 12 hours, and the regular dodecahedron ZIF-67 is obtained.
Fifth embodiment five the present embodiment is different from the first to fourth embodiments in that the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution in the first step ③ is (0.9-1): 1, and the other steps are the same as the first to fourth embodiments.
A sixth specific embodiment is different from the first to fifth specific embodiments in that the difference between the first specific embodiment and the second specific embodiment is that in the second step ①, the regular dodecahedron ZIF-67 obtained in the first step ③ is dispersed in a ceramic boat, the ceramic boat is placed in a tube furnace, a mixed gas of argon and hydrogen is introduced into the tube furnace, the temperature of the tube furnace is raised to 425-435 ℃ at a heating rate of 3-5 ℃/min, the temperature is maintained for 6-8 h under the condition that the mixed gas atmosphere of argon and hydrogen and the temperature are 425-435 ℃, and finally the tube furnace is naturally cooled to room temperature to obtain black powder.
Seventh embodiment mode a seventh embodiment mode is different from the first to sixth embodiment modes in that the volume ratio of argon to hydrogen in the mixed gas of argon and hydrogen described in step two ① is 9:1, and other steps are the same as those in the first to sixth embodiment modes.
Eighth embodiment the present embodiment is different from the first to seventh embodiments in that the black powder obtained in the second step ① is immersed in H having a concentration of 0.9 to 1mol/L in the second step ②2SO4Carrying out vacuum filtration on the solution for 11 to 12 hours, collecting solid substances, and using deionized water to carry out vacuum filtration on the collected solid substancesAnd (3) washing the solid substance for 5-6 times, and then drying the solid substance washed by the deionized water in a drying oven at the temperature of 55-60 ℃ for 8-9 h to obtain the ZIF-67 derived nano carbon material. The other steps are the same as those in the first to seventh embodiments.
Ninth embodiment the present embodiment is different from the first to eighth embodiments in that KMnO is added in an amount of 0.04mol/L to 0.05mol/L in step III ①4The solution and Na with the concentration of 0.04mol/L to 0.05mol/L2SO4Mixing the solutions to obtain KMnO4And Na2SO4The mixed solution of (1). The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: in the embodiment, the manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded is used as a positive electrode material of a super capacitor.
The first embodiment is as follows: a preparation method of a sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material is prepared according to the following steps:
firstly, preparing regular dodecahedral ZIF-67:
①, dissolving 1.6g of cobalt nitrate hexahydrate in 40mL of methanol to obtain a cobalt nitrate solution;
②, dissolving 2g of 2-methylimidazole in 40mL of methanol to obtain a 2-methylimidazole solution;
③, mixing the cobalt nitrate solution and the 2-methylimidazole solution, stirring at room temperature and a stirring speed of 800r/min for 20 hours, carrying out vacuum filtration, collecting solid substances, washing the collected solid substances with absolute ethyl alcohol for 6 times, and drying the solid substances washed with the absolute ethyl alcohol in a drying oven at the temperature of 60 ℃ for 12 hours to obtain the regular dodecahedron ZIF-67;
secondly, preparing a ZIF-67 derived nanoporous carbon material:
①, dispersing the regular dodecahedral ZIF-67 obtained in the step one ③ in a ceramic boat, then placing the ceramic boat in a tube furnace, introducing mixed gas of argon and hydrogen into the tube furnace, then heating the tube furnace to 435 ℃ at the heating speed of 5 ℃/min, then keeping the temperature of the tube furnace for 8 hours under the condition that the mixed gas atmosphere of argon and hydrogen and the temperature are 435 ℃, and finally naturally cooling the tube furnace to room temperature to obtain black powder;
the volume ratio of the argon to the hydrogen in the mixed gas of the argon and the hydrogen in the step two ① is 9: 1;
②, immersing the black powder obtained in the step two ① in H with the concentration of 1mol/L2SO4Carrying out vacuum filtration on the solution for 12h, collecting solid substances, washing the collected solid substances for 6 times by using deionized water, and drying the solid substances washed by the deionized water in a drying oven at the temperature of 60 ℃ for 8h to obtain the ZIF-67 derived nanoporous carbon material;
thirdly, compounding:
①, 0.05mol/L KMnO4The solution and Na with the concentration of 0.05mol/L2SO4Mixing the solutions to obtain KMnO4And Na2SO4The mixed solution of (1);
KMnO of 0.05mol/L as described in step three ①4The solution is mixed with Na with the concentration of 0.05mol/L2SO4The volume ratio of the solution is 1: 1;
② immersing ZIF-67 derived nanoporous carbon material in KMnO at room temperature4And Na2SO4And (3) carrying out vacuum filtration on the mixed solution for 5 hours, collecting solid substances, washing the collected solid substances for 6 times by using deionized water, and drying the solid substances washed by the deionized water in a drying oven at the temperature of 60 ℃ for 8 hours to obtain the manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions.
Example one step one the morphology of the regular dodecahedral ZIF-67 prepared is shown in fig. 1;
FIG. 1 is an SEM image of regular dodecahedral ZIF-67 prepared in one step one of the examples;
as can be seen from fig. 1, the regular dodecahedral ZIF-67 prepared in the first step of the example has smooth surface and uniform particle size, and many advantages of the ZIF-67 are inherited by using the same as a sacrificial template, which is beneficial to obtaining a porous carbon material with a regular dodecahedral structure and uniform particle size.
Morphology, composition and specific surface area of the ZIF-67 derived nanoporous carbon materials prepared in example step two are shown in fig. 2, 3 and 4, respectively.
FIG. 2 is an SEM image of ZIF-67 derivatized nanoporous carbon material prepared in step two of the example;
as can be seen from fig. 2, the ZIF-67 derived nanoporous carbon material prepared in the second step of the example has a regular morphology, uniform particle size, and a hollow structure, and basically maintains a regular dodecahedral ZIF-67 framework structure, but has a slightly recessed surface, a rough surface, and no longer smooth.
FIG. 3 is a spectrum of a ZIF-67 derivatized nanoporous carbon material prepared in step two of the example;
as can be seen from fig. 3, the ZIF-67 derived nanoporous carbon material prepared in the second example step largely retains the N element and is uniformly dispersed in the carbon skeleton. The uniform doping of nitrogen atoms can effectively adjust the electronic structure and the conductivity of the porous carbon material, so that the porous carbon material has richer performance and is beneficial to obtaining a high-performance composite electrode material.
FIG. 4 is a specific surface area spectrum of a ZIF-67 derived nanoporous carbon material prepared in step two of the example;
as can be seen from FIG. 4, the ZIF-67 derived nanoporous carbon material prepared in the second step of the example has a high specific surface area of 152m2/g。
FIG. 5 is an SEM image of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in step three of the example;
FIG. 6 is a TEM image of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in one step three of the example;
as can be seen from fig. 5 and 6, the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material prepared in the third step of the example inherits the morphological characteristics of the ZIF-67-derived nanoporous carbon material, has a nearly regular dodecahedron hollow structure, is regular in morphology and uniform in particle size, has a diameter of about 1 micrometer, and has a rougher surface due to the fact that the outer layer of the composite material is finely-divided manganese dioxide in a sheet shape.
FIG. 7 is an XRD spectrum of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in step three of the example;
as can be seen from fig. 7, the manganese dioxide nano fragments attached to the surface of the manganese dioxide/nitrogen-doped porous carbon composite material with sodium ion intercalation prepared in the third step of the example have a birnessite structure (JCPDS 18-0802, diffraction peaks at 36 ° and 65 ° correspond to (006) and (119) crystal planes respectively), so that the adsorption and the deintercalation of ions are facilitated, and the manganese dioxide nano fragments are suitable for supercapacitor materials.
FIG. 8 is a spectrum of the specific surface area of the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in step three of the example;
FIG. 9 is a pore size distribution spectrum of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite prepared in step three of the example;
as can be seen from FIGS. 8 and 9, the manganese dioxide/nitrogen-doped porous carbon composite material with sodium ions embedded prepared in the third step of the example has high porosity and a specific surface area of 127m2(ii)/g; the apertures are consistent, and the sizes of most apertures are 4nm, which is beneficial to obtaining good super-capacity performance.
Example two: the manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded, prepared in the third step of the example, is used as a positive electrode material of a three-electrode supercapacitor device, and the preparation method of the three-electrode supercapacitor device is as follows:
preparation of working electrode
①, mixing the manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions and acetylene black powder prepared in the third step of the embodiment, grinding the mixture into fully mixed powder by using a mortar to obtain mixed powder of the manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions and acetylene black;
the mass ratio of the manganese dioxide/nitrogen-doped porous carbon composite material embedded with sodium ions to the acetylene black in the mixed powder of the manganese dioxide/nitrogen-doped porous carbon composite material embedded with sodium ions and the acetylene black in the first step ① is 8: 1;
the polyvinylidene fluoride liquid in the first step ① is prepared by dissolving polyvinylidene fluoride into an N-methyl pyrrolidone solvent, wherein the mass fraction of polyvinylidene fluoride in the polyvinylidene fluoride liquid is 4-8%;
the mass ratio of the mixed powder of the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material and acetylene black to the polyvinylidene fluoride liquid in the first step ① is 9: 1;
②, selecting carbon paper as a current collector, and uniformly and dispersedly dripping the uniform slurry on the carbon paper to prepare the manganese dioxide/nitrogen doped porous carbon composite material/carbon paper with sodium ions embedded;
secondly, constructing the super capacitor:
manganese dioxide/nitrogen-doped porous carbon composite material/carbon paper embedded with sodium ions is used as a working electrode, a platinum electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and 1.0mol/L of Na is used2SO4The solution is used as electrolyte to construct a three-electrode super capacitor device;
third, testing of electrochemical performance
The cyclic voltammetry curve and constant current charge and discharge curve of the three-electrode supercapacitor device were tested at room temperature using an electrochemical workstation (VMP3, france) with a voltage window of 0V to 0.8V.
The cyclic voltammetry curve, constant current charging and discharging curve and rate capability of the three-electrode supercapacitor device prepared in the second embodiment are shown in fig. 10, and fig. 13 to 16.
Note: for comparison of properties of the three-electrode supercapacitor devices, the voltammetry characteristic curves of the three-electrode supercapacitor devices prepared by using the ZIF-67-derived nanoporous carbon material prepared in the second step of the example and pure manganese dioxide synthesized by a hydrothermal method as positive electrode materials of the three-electrode supercapacitor devices, respectively, were tested by the same method and test conditions as those of the second step of the example, as shown in fig. 11 and 12.
FIG. 10 is a plot of the voltammetry characteristics of a sodium ion intercalated manganese dioxide/nitrogen doped porous carbon composite prepared in step three of the example;
FIG. 11 is a plot of the voltammetry characteristics of the ZIF-67 derivatized nanoporous carbon material prepared in example step two;
FIG. 12 is a plot of the voltammetric characteristics of pure manganese dioxide synthesized hydrothermally;
as can be seen from fig. 10 to 12, the mass specific capacitance of the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in the third step of the example is superior to that of the manganese dioxide or nitrogen-doped ZIF 67-derived porous carbon alone as the positive electrode material. The mass specific capacitance of the sodium ion intercalated manganese dioxide/nitrogen doped porous carbon composite material prepared in the third step of the example is 217F/g, which is 5 times that of a pure manganese dioxide material.
FIG. 13 is a constant current charging and discharging curve of circles 1 to 5 of the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in the third step of the example;
FIG. 14 is a 4995-;
as can be seen from fig. 13 and 14, the constant current charging and discharging curve of the manganese dioxide/nitrogen doped porous carbon composite material with sodium ions embedded in the third step of the example is a standard isosceles triangle, and shows good symmetry.
FIG. 15 is a graph showing the relationship between the sweep rate and capacitance of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in step three of the example;
from fig. 15, it can be seen that the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material prepared in the third step of the example is used as the positive electrode material of the supercapacitor, and the sweep rate is 2mV s-1To 100mV s-1The magnification of the capacitance is 85%.
Fig. 16 is a graph of the cycling characteristics of the sodium ion intercalated manganese dioxide/nitrogen doped porous carbon composite prepared in one step three of the example.
As can be seen from fig. 16, when the manganese dioxide/nitrogen-doped porous carbon composite material with sodium ions embedded therein prepared in the third step of the example is used as a positive electrode material of a supercapacitor, the cycle stability is good, and the capacity retention rate is 91% after 5000 cycles.

Claims (9)

1. A preparation method of a sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material is characterized in that the preparation method of the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material is prepared according to the following steps:
firstly, preparing regular dodecahedral ZIF-67:
①, dissolving cobalt nitrate hexahydrate in methanol to obtain a cobalt nitrate solution;
the volume ratio of the mass of the cobalt nitrate hexahydrate in the step one ① to the volume of the methanol is (1 g-2 g) 40 mL;
②, dissolving 2-methylimidazole in methanol to obtain 2-methylimidazole solution;
the volume ratio of the mass of the 2-methylimidazole to the methanol in the step I ② is (1 g-3 g) and is 40 mL;
③, mixing the cobalt nitrate solution and the 2-methylimidazole solution, stirring at room temperature and a stirring speed of 500-900 r/min for 15-25 h, carrying out vacuum filtration, collecting solid substances, washing the collected solid substances with absolute ethyl alcohol for 5-8 times, and drying the solid substances washed with the absolute ethyl alcohol in an oven at the temperature of 55-65 ℃ for 10-14 h to obtain the dodecahedron ZIF-67;
the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution in the first step ③ is (0.8-1.2): 1;
secondly, preparing a ZIF-67 derived nanoporous carbon material:
①, dispersing the regular dodecahedral ZIF-67 obtained in the step one ③ in a ceramic boat, then placing the ceramic boat in a tubular furnace, introducing mixed gas of argon and hydrogen into the tubular furnace, then heating the tubular furnace to 420-450 ℃ at the heating rate of 3-8 ℃/min, then keeping the temperature for 6-10 h under the condition of the mixed gas atmosphere of argon and hydrogen and the temperature of 420-450 ℃, and finally naturally cooling the tubular furnace to room temperature to obtain black powder;
the volume ratio of the argon to the hydrogen in the mixed gas of the argon and the hydrogen in the step two ① is 9: 1;
② immersing the black powder obtained in step two ① inTo a concentration of 0.8mol/L to 1.2mol/L of H2SO4Carrying out vacuum filtration on the solution for 10-14 h, collecting solid matters, washing the collected solid matters for 5-8 times by using deionized water, and then putting the solid matters washed by the deionized water into a drying oven with the temperature of 55-65 ℃ for drying for 8-10 h to obtain the ZIF-67 derived nanoporous carbon material;
thirdly, compounding:
①, 0.04 mol/L-0.06 mol/L KMnO4The solution and Na with the concentration of 0.04mol/L to 0.06mol/L2SO4Mixing the solutions to obtain KMnO4And Na2SO4The mixed solution of (1);
KMnO of 0.04 mol/L-0.06 mol/L described in step three ①4The solution and Na with the concentration of 0.04mol/L to 0.06mol/L2SO4The volume ratio of the solution is (0.95-1) to 1;
② immersing ZIF-67 derived nanoporous carbon material in KMnO at room temperature4And Na2SO4And carrying out vacuum filtration on the mixed solution for 3-7 h, collecting solid matters, washing the collected solid matters for 5-8 times by using deionized water, and drying the solid matters washed by the deionized water in a drying oven at the temperature of 55-65 ℃ for 8-10 h to obtain the manganese dioxide/nitrogen doped porous carbon composite material embedded with sodium ions.
2. The method for preparing the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, wherein the volume ratio of the mass of the cobalt nitrate hexahydrate to the volume of the methanol in the step one ① is (1.6 g-2 g):40 mL.
3. The method for preparing the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, wherein the volume ratio of the mass of the 2-methylimidazole to the methanol in the step one ② is (1 g-2 g):40 mL.
4. The preparation method of the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, characterized in that in the first step ③, a cobalt nitrate solution and a 2-methylimidazole solution are mixed, then the mixture is stirred at room temperature and a stirring speed of 600r/min to 800r/min for reaction for 15h to 20h, then vacuum filtration is carried out, solid matters are collected, the collected solid matters are washed by absolute ethyl alcohol for 5 times to 6 times, and then the solid matters washed by the absolute ethyl alcohol are placed into an oven at a temperature of 55 ℃ to 60 ℃ for drying for 10h to 12h, so that the regular dodecahedron ZIF-67 is obtained.
5. The preparation method of the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, characterized in that the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution in the step one ③ is (0.9-1): 1.
6. The preparation method of the sodium ion-embedded manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, characterized in that in step two ①, the regular dodecahedral ZIF-67 obtained in step one ③ is dispersed in a ceramic boat, the ceramic boat is placed in a tube furnace, a mixed gas of argon and hydrogen is introduced into the tube furnace, the tube furnace is heated to 425 ℃ to 435 ℃ at a heating rate of 3 ℃/min to 5 ℃/min, the temperature is kept for 6h to 8h under the condition that the mixed gas atmosphere of argon and hydrogen and the temperature are 425 ℃ to 435 ℃, and finally the tube furnace is naturally cooled to room temperature to obtain black powder.
7. The method for preparing sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, wherein the black powder obtained in the step two ① is immersed in H with the concentration of 0.9mol/L to 1mol/L in the step two ②2SO4And (3) carrying out vacuum filtration on the solution for 11-12 h, collecting solid matters, washing the collected solid matters for 5-6 times by using deionized water, and drying the solid matters washed by the deionized water in a drying oven at the temperature of 55-60 ℃ for 8-9 h to obtain the ZIF-67 derived nano carbon material.
8. The method for preparing sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material according to claim 1, wherein in the step three ①, KMnO is added in an amount of 0.04 mol/L-0.05 mol/L4The solution and Na with the concentration of 0.04mol/L to 0.05mol/L2SO4Mixing the solutions to obtain KMnO4And Na2SO4The mixed solution of (1).
9. The use of a sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material as claimed in claim 1, characterized in that the sodium ion-intercalated manganese dioxide/nitrogen-doped porous carbon composite material is used as positive electrode material for supercapacitors.
CN201810761109.5A 2018-07-11 2018-07-11 Preparation method and application of composite material Active CN108922790B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810761109.5A CN108922790B (en) 2018-07-11 2018-07-11 Preparation method and application of composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810761109.5A CN108922790B (en) 2018-07-11 2018-07-11 Preparation method and application of composite material

Publications (2)

Publication Number Publication Date
CN108922790A CN108922790A (en) 2018-11-30
CN108922790B true CN108922790B (en) 2020-04-21

Family

ID=64411827

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810761109.5A Active CN108922790B (en) 2018-07-11 2018-07-11 Preparation method and application of composite material

Country Status (1)

Country Link
CN (1) CN108922790B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109980179B (en) * 2019-04-11 2021-04-23 厦门大学 Nitrogen-carbon doped modified manganese dioxide composite material and preparation method thereof
CN110243890B (en) * 2019-07-23 2021-06-18 合肥工业大学 Preparation method of Mn-ZIF67 material and detection method of mercury ions
CN110600690B (en) * 2019-08-09 2022-05-13 广东工业大学 Zeolite-imidazole-framework-derived nitrogen-doped hierarchical porous carbon @ manganous manganic oxide @ carbon/sulfur and preparation method and application thereof
CN110783115B (en) * 2019-11-06 2021-06-01 黑龙江科技大学 Preparation method and application of manganese dioxide/carbon/foam metal composite material
CN111403696B (en) * 2019-11-20 2021-06-15 浙江工业大学 Flaky manganese dioxide hollow frame structure material and preparation method and application thereof
CN112723416A (en) * 2021-01-05 2021-04-30 贵州大学 Method for efficiently preparing potassium and sodium co-doped sheet layered manganese dioxide
CN115028167B (en) * 2022-05-12 2023-04-25 西南科技大学 Preparation method and energy storage application of hierarchical porous biomass carbon material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993111A (en) * 2015-06-12 2015-10-21 中南大学 Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof
CN105789628A (en) * 2014-12-15 2016-07-20 国家纳米科学中心 Aza-graphene and manganese dioxide hybrid aerogel, preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789628A (en) * 2014-12-15 2016-07-20 国家纳米科学中心 Aza-graphene and manganese dioxide hybrid aerogel, preparation method and application thereof
CN104993111A (en) * 2015-06-12 2015-10-21 中南大学 Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Enhancement effect of Na ions on capacitive behavior of amorphous MnO2;Qinglan Ye等;《Electrochimica Acta》;20140728;第141卷;第286-293页 *
Redox deposition of birnessite MnO2 on ZIF-8 derived porous carbon at room temperature for supercapacitor electrodes;Haibo Sun等;《Materials Letters》;20180103;第216卷;第123-126页 *

Also Published As

Publication number Publication date
CN108922790A (en) 2018-11-30

Similar Documents

Publication Publication Date Title
CN108922790B (en) Preparation method and application of composite material
Zhu et al. Construction of porous interface on CNTs@ NiCo-LDH core-shell nanotube arrays for supercapacitor applications
US11410819B2 (en) Method for preparing super capacitor electrode material Ni doped CoP3/foam nickel
US20150364265A1 (en) Method for preparing fluorine/nitrogen co-doped graphitized carbon microspheres with high volumetric specific capacitance
CN106935855B (en) A kind of porous carbon nanotubular materials and its preparation method and application
CN108054020B (en) Preparation method and application of nitrogen-doped carbon particle/graphitized carbon-nitrogen composite material
CN109860958B (en) Lithium-carbon dioxide battery and preparation method thereof
CN110783115B (en) Preparation method and application of manganese dioxide/carbon/foam metal composite material
AU2020101283A4 (en) Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage
CN113930866A (en) Supercapacitor electrode material with capsule structure and preparation method and application thereof
Zhao et al. Nickel cobalt oxide nanowires‐modified hollow carbon tubular bundles for high‐performance sodium‐ion hybrid capacitors
Guo et al. An excellent cycle performance of asymmetric supercapacitor based on ZIF-derived C/N-doped porous carbon nanostructures
Liu et al. Enhanced capacitive performance of nickel oxide on porous La0· 7Sr0· 3CoO3-δ ceramic substrate for electrochemical capacitors
CN113496823B (en) Symmetric hybrid supercapacitor and application thereof
CN110739159B (en) Preparation method of nanowire-shaped manganese dioxide/graphene aerogel composite material for supercapacitor
CN112927947A (en) Nickel-cobalt-sulfur electrode material based on yolk shell structure, preparation method and supercapacitor
CN109087820B (en) Graphene composite electrode material prepared in situ by ultrasonic chemical method
CN116544373A (en) Nitrogen doped carbon nano rod and NiCo 2 S 4 Method for preparing nanocrystalline composite and application thereof
Wang et al. Dodecahedral NC-doped CoSe2 nanoparticles with excellent stability for high-performance flexible solid-state supercapacitors
CN112885614B (en) Nitrogen-phosphorus-oxygen co-doped nickel/carbon composite material derived from nickel-based metal organic framework and preparation method and application thereof
CN112820866B (en) Capsule-shaped nickel ferrite composite carbon skeleton lithium ion battery cathode material and preparation method and application thereof
CN112960663B (en) LiFe X Co 1-X PO 4 Preparation method of/N-C/CC composite material
Liu et al. Tin-embedded carbon nanofibers as flexible and freestanding electrode materials for high-performance supercapacitors
CN111085691B (en) Mesoporous activated carbon material containing Co @ C structure and preparation method and application thereof
Jiang et al. ZIF-8 derived graphene-based nitrogen-doped porous carbonas highly efficient supercapacitor electrodes

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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20220610

Address after: 150000 Liming Village, Pingfang Township, Pingfang District, Harbin City, Heilongjiang Province

Patentee after: Harbin Jiesen general Electromechanical Equipment Co.,Ltd.

Address before: 150022 No. 2468 Puyuan Road, Songbei District, Harbin City, Heilongjiang Province

Patentee before: HEILONGJIANG University OF SCIENCE AND TECHNOLOGY