CN111710529B - Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof - Google Patents

Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof Download PDF

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CN111710529B
CN111710529B CN202010431727.0A CN202010431727A CN111710529B CN 111710529 B CN111710529 B CN 111710529B CN 202010431727 A CN202010431727 A CN 202010431727A CN 111710529 B CN111710529 B CN 111710529B
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CN111710529A (en
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韩生
胡晓敏
刘顺昌
王露露
丛海山
蒋继波
孙瑶馨
陈宇凯
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Shanghai Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a Co/Mn-MOF/nitrogen-doped carbon-based composite material and a preparation method and application thereof, wherein the preparation method of the composite material comprises the following steps: 1) preparing a nitrogen-doped porous carbon and bimetal mixed solution; 2) adding nitrogen-doped porous carbon into the bimetal mixed solution, then carrying out hydrothermal reaction, and then cooling, washing and drying to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material. The composite material is prepared into a working electrode for being used in a super capacitor. Compared with the prior art, the supercapacitor electrode material with high specific capacitance, high conductivity and better cycling stability is formed by the synergistic effect of the three-dimensional porous structure of the nitrogen-doped porous carbon and the Co/Mn bimetallic organic framework, the preparation process is environment-friendly, the preparation method is simple, and an effective way is provided for preparing the high-performance supercapacitor electrode material.

Description

Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials, and relates to a Co/Mn-MOF/nitrogen-doped carbon-based composite material, and a preparation method and application thereof.
Background
With the gradual acceleration of social development and the increasing population density, the crisis of fossil energy shortage is becoming more serious, and the burning of fossil fuel causes a lot of irreversible pollution and destruction to the ecological environment, so that the green and environment-friendly alternative energy becomes the hot spot of people's attention. Super capacitors are one of the most potential energy storage devices due to their advantages of high power density, rapid charge and discharge, and long cycle life, but their low energy density limits their application in energy storage. The electrode material is the most important component of the super capacitor, and improving the energy storage of the super capacitor by changing the electrode material has great significance, but also faces great challenges.
The metal organic framework Materials (MOFs) are used as porous materials, have the characteristics of large specific surface area, high porosity, low density and adjustable pore size, contain a plurality of open active sites in the structure, can be widely applied to the application fields of gas storage and separation, sensors, catalysis and the like, and have great application prospects in the aspect of electrochemical energy storage. At present, researchers have conducted preliminary research on the preparation of morphology-controllable composite materials by using single-metal MOFs as templates and the application of the morphology-controllable composite materials as electrode materials. However, the MOFs material has poor conductivity and is not favorable for electron transport, which greatly limits the application of the MOFs material in electrochemical energy storage.
Disclosure of Invention
The invention aims to provide a Co/Mn-MOF/nitrogen-doped carbon-based composite material, and a preparation method and application thereof, so as to solve the problem of poor conductivity of MOFs materials. In the invention, the preparation process of the composite material is environment-friendly, the preparation method is simple, and the large-scale production is facilitated.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a Co/Mn-MOF/nitrogen-doped carbon-based composite material comprises the following steps:
1) preparing a nitrogen-doped porous carbon and bimetal mixed solution:
the preparation method of the nitrogen-doped porous carbon comprises the following steps: dissolving chitosan in acetic acid water solution, and then adding nano SiO2The suspension is evenly stirred and dried to obtain the chitosan/SiO2A composite material; mixing chitosan/SiO2The composite material is carbonized at high temperature, and then SiO is removed2Separating to obtain nitrogen-doped porous carbon;
the preparation process of the bimetal mixed solution comprises the following steps: dissolving Co salt and Mn salt in DMF, adding 2-methylimidazole, and uniformly mixing to obtain a bimetallic mixed solution;
2) and adding nitrogen-doped porous carbon into the bimetal mixed solution, then carrying out hydrothermal reaction, and then cooling, washing and drying to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
Further, in the step 1), the mass concentration of acetic acid in the acetic acid aqueous solution is 5-10%; the nano SiO2In suspension, nano SiO2The mass concentration of the active carbon is 20-30 percent; the chitosan, acetic acid water solution and nano SiO2The addition amount of the suspension is (3-5) g, (150) -200) mL and (5-10) mL.
Further, in the step 1), the stirring is magnetic stirring, the stirring temperature is normal temperature, and the stirring time is 12-16 h; in the drying process, the temperature is 120-150 ℃, and the time is 10-15 h.
Further, in the step 1), high-temperature carbonization is carried out on N2The process is carried out in the atmosphere, the temperature is 700-900 ℃ in the high-temperature carbonization process, and the time is 2-3 h; removal of SiO2The method comprises the following steps: and soaking the composite material carbonized at high temperature in an HF solution at room temperature, wherein the mass concentration of HF in the HF solution is 20-30%. The soaking time is preferably 1-3 h.
Further, in the step 1), the separation process is as follows: will remove SiO2The composite material is centrifuged and then repeatedly washed with water to a pH valueIs 6.8 to 7.2, and then drying is carried out. Preferably, the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
Further, in the step 1), the Co salt is CoCl2The Mn salt is Mn (NO)3)2(ii) a The addition amount ratio of the Co salt, the Mn salt, the 2-methylimidazole and the DMF is 1mmol (1-2) mmol (1-4) mmol (5-15) mL.
Further, in the step 2), the adding amount ratio of the nitrogen-doped porous carbon to the bimetal mixed solution is 0.3g (5-15) mL.
Further, in the step 2), the temperature is 120-160 ℃ and the time is 20-24h in the hydrothermal reaction process; after the hydrothermal reaction is finished, cooling to room temperature, washing with DMF and ethanol, and then drying in vacuum at 60-80 ℃ for 12-24h to obtain the Co/Mn-MOF/nitrogen doped carbon-based composite material.
In the invention, the drying process is vacuum drying.
The Co/Mn-MOF/nitrogen-doped carbon-based composite material is prepared by adopting the method.
The application of the Co/Mn-MOF/nitrogen-doped carbon-based composite material is to prepare the composite material into a working electrode for a super capacitor. The preparation process of the working electrode comprises the following steps: grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying to obtain the working electrode. The mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
In the process of preparing the Co/Mn-MOF/nitrogen-doped carbon-based composite material, the Co/Mn bimetallic MOFs electrode material is prepared by utilizing the synergistic effect of bimetal, and the Co/Mn bimetallic MOFs electrode material has multiple metal ions and multiple oxidation states (Co/Mn bimetallic MOFs)2+/Co3+，Mn2+/Mn3+) More pseudocapacitance can be provided for electrochemical energy storage.
In addition, in order to solve the problem of poor conductivity of the MOFs, the current carbon material generally adopts porous carbon with high specific surface area as a substrate, and the main reason is that the porous carbon material can enable more metal oxide electroactive substances to be embedded into the surface or inner wall space of the material, so as to improve the active sites of the material, and can also be used as an active material to provide a path for electron transfer, so that efficient electron transmission is realized, efficient energy storage of the active material is realized, the utilization of the electroactive substances is maximized, and the performance of the supercapacitor is improved. However, the pore diameter of the traditional carbon material is not controllable, and the metal oxide is easy to fall off in the charging and discharging process, so that the application of the carbon material is limited. In the invention, abundant nitrogen atoms in the carbon skeleton are beneficial to generating more active centers, improving the surface polarity and simultaneously being beneficial to improving the conductivity of the material and the wettability of the electrolyte.
Compared with the prior art, the invention has the following characteristics:
1) the Co/Mn-MOF/nitrogen-doped carbon-based composite material prepared by the invention is prepared by SiO2The method is characterized in that nanoparticles are hard templates, natural product chitosan is used as a precursor, a carbon material with a pore diameter controllable and a nitrogen-doped three-dimensional porous structure is prepared and used as a substrate, and abundant nitrogen atoms in a carbon skeleton contribute to generating more active centers, improve the surface polarity and improve the conductivity of the material and the wettability of electrolyte.
2) In the Co/Mn-MOF/nitrogen-doped carbon-based composite material prepared by the invention, the three-dimensional porous structure of the nitrogen-doped porous carbon and the Co/Mn bimetallic organic framework have a synergistic effect, so that the supercapacitor electrode material with high specific capacitance, high conductivity and better cycling stability is formed, and an effective way is provided for preparing the high-performance supercapacitor electrode material.
3) The raw materials adopted by the preparation method of the invention are pollution-free, and the solvent in the preparation process is non-toxic.
Drawings
FIG. 1 is a TEM image of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite prepared in example 1;
FIG. 2 is a long cycle plot of the Co/Mn-MOF/nitrogen-doped porous carbon-based composite prepared in example 1 at a current density of 20A/g;
FIG. 3 is a cyclic voltammogram of the Co/Mn-MOF/nitrogen-doped porous carbon-based composite prepared in example 1 at different sweep rates.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The raw materials used in the following examples are all commercially available unless otherwise specified.
Example 1:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. Fig. 1 is a TEM image of the prepared Co/Mn-MOF/nitrogen-doped porous carbon-based composite material, and it can be seen from fig. 1 that the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material is very thin and has wrinkles on the surface, and it can be clearly found that some dense pore structures are formed on the surface of the composite material, which is beneficial to increase the specific surface area of the nanomaterial to enhance the electrochemical performance thereof.
After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain the Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-1).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-1 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. FIG. 2 is a long cycle chart of the Co/Mn-MOF-nitrogen doped porous carbon working electrode under the current density of 20A/g, and it can be seen that after 10000 cycles, the capacity retention rate is still 90.74%, and good cycle stability is reflected. FIG. 3 is a cyclic voltammogram of a Co/Mn-MOF-nitrogen doped porous carbon working electrode at different sweep rates, and it can be seen that a pair of symmetric redox peaks exist, indicating that the material has excellent redox capability. The specific capacitance of the electrode material reaches 451F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 2:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 5.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolved in 10mL of DMF, 1mmol of 2-methylimidazole was added to the solution at room temperature, and the reaction mixture was transferred to an autoclave and simultaneously 0.3g of ANC was added to conduct hydrothermal reaction at the reaction temperatureThe temperature is 120 ℃, the reaction time is 24h, the mixture is cooled to room temperature, washed by DMF and ethanol, and dried in vacuum for 24h at the temperature of 80 ℃, and the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material is obtained. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-2).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-2 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reached 436F/g in a 2mol/L KOH solution and at a current density of 1A/g.
Example 3:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 15 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. Grinding the active materialAnd uniformly mixing the carbon black and the polytetrafluoroethylene in a mass ratio of 8:1:1 to obtain the Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-3).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-3 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reached 417F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 4:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 120 deg.C air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 700 deg.C for 3h at a heating rate of 5 deg.C/min under atmosphere, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-4).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-4 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reaches 394F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 5:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 800 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-5).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-5 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reaches 404F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 6:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 2h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-6).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-6 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reaches 428F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 7:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 2mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-7).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-7 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reaches 437F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 8:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 4mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-8).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-8 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reached 419F/g in a 2mol/L KOH solution and at a current density of 1A/g.
Example 9:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2The suspension (30% by weight) was added to the reactorMagnetically stirring the solution at normal temperature for 12h, and drying in a forced air drying oven at 150 ℃ for 10h to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, heating at 5 deg.C/min, and soaking the heat-treated composite material with 30% HF at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at 160 ℃ for 24h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-9).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-9 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reaches 367F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 10:
a preparation method of a Co/Mn-MOF/nitrogen-doped porous carbon-based composite material comprises the following steps:
firstly, 3.0g of chitosan is weighed and dissolved in 150.0mL of acetic acid water solution with mass fraction of 5%, and 6.0mL of nano SiO is dissolved2Adding the suspension (30 wt%) into the above solution, magnetically stirring at room temperature for 12 hr, and drying in 150 deg.C forced air drying oven for 10 hr to obtain chitosan/SiO2Composite material, subsequently placed in N2Carbonizing at 900 deg.C for 3h under atmosphere, and increasing the temperature rateAt 5 ℃/min, finally soaking the composite material after heat treatment by using HF with the mass fraction of 30% at room temperature to remove SiO2Centrifuging, repeatedly washing with deionized water until the pH value is 7, and drying at 60 ℃ to obtain nitrogen-doped porous carbon (ANC); 1mmol of CoCl2And 1mmol Mn (NO)3)2Dissolving the mixture in 10mL of DMF, adding 1mmol of 2-methylimidazole into the solution at room temperature, transferring the reaction mixture into a high-pressure kettle, adding 0.3g of ANC at the same time, carrying out hydrothermal reaction at 160 ℃ for 20h, cooling to room temperature, washing with DMF and ethanol, and drying in vacuum at 80 ℃ for 24h to obtain the Co/Mn-MOF/nitrogen-doped porous carbon-based composite material. After the active material is ground, the active material is uniformly mixed with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a Co/Mn-MOF-nitrogen doped porous carbon working electrode (CMNC-10).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CMNC-10 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material reaches 382F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 11:
a preparation method of a Co/Mn-MOF/nitrogen-doped carbon-based composite material comprises the following steps:
1) preparing a nitrogen-doped porous carbon and bimetal mixed solution:
the preparation method of the nitrogen-doped porous carbon comprises the following steps: dissolving chitosan in acetic acid water solution, and then adding nano SiO2The suspension is evenly stirred and dried to obtain the chitosan/SiO2A composite material; mixing chitosan/SiO2The composite material is carbonized at high temperature, and then SiO is removed2Separating to obtain nitrogen-doped porous carbon;
the preparation process of the bimetal mixed solution comprises the following steps: dissolving Co salt and Mn salt in DMF, adding 2-methylimidazole, and uniformly mixing to obtain a bimetallic mixed solution;
2) adding nitrogen-doped porous carbon into the bimetal mixed solution, then carrying out hydrothermal reaction, and then cooling, washing and drying to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
In the step 1), the mass concentration of acetic acid in the acetic acid aqueous solution is 5%; nano SiO2In suspension, nano SiO2The mass concentration of (2) is 30%; chitosan, acetic acid water solution and nano SiO2The ratio of the addition amount of the suspension was 3g:200mL:5 mL. Stirring is magnetic stirring, the stirring temperature is normal temperature, and the stirring time is 16 h; in the drying process, the temperature is 120 ℃ and the time is 15 h. Charring at high temperature in N2The carbonization is carried out in the atmosphere, the temperature is 700 ℃ in the high-temperature carbonization process, and the time is 3 h; removal of SiO2The method comprises the following steps: and (3) soaking the composite material carbonized at high temperature in an HF solution at room temperature, wherein the mass concentration of HF in the HF solution is 20%. The separation process is as follows: will remove SiO2The composite material was centrifuged, washed repeatedly with water to a pH of 7.2, and dried. The Co salt is CoCl2The Mn salt is Mn (NO)3)2(ii) a The addition amount ratio of the Co salt, the Mn salt, the 2-methylimidazole and the DMF is 1mmol:1mmol:4mmol:5 mL.
In the step 2), the adding amount ratio of the nitrogen-doped porous carbon to the bimetal mixed solution is 0.3g to 15 mL. In the hydrothermal reaction process, the temperature is 120 ℃, and the time is 24 hours; after the hydrothermal reaction is finished, cooling to room temperature, washing with DMF and ethanol, and then drying in vacuum at 60 ℃ for 24 hours to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
The composite material is prepared into a working electrode for being used in a super capacitor.
Example 12:
a preparation method of a Co/Mn-MOF/nitrogen-doped carbon-based composite material comprises the following steps:
1) preparing a nitrogen-doped porous carbon and bimetal mixed solution:
the preparation method of the nitrogen-doped porous carbon comprises the following steps: dissolving chitosan in acetic acid water solution, and then adding nano SiO2Suspending liquid, after stirring evenlyDrying to obtain chitosan/SiO2A composite material; mixing chitosan/SiO2The composite material is carbonized at high temperature, and then SiO is removed2Separating to obtain nitrogen-doped porous carbon;
the preparation process of the bimetal mixed solution comprises the following steps: dissolving Co salt and Mn salt in DMF, adding 2-methylimidazole, and uniformly mixing to obtain a bimetallic mixed solution;
2) adding nitrogen-doped porous carbon into the bimetal mixed solution, then carrying out hydrothermal reaction, and then cooling, washing and drying to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
In the step 1), the mass concentration of acetic acid in the acetic acid aqueous solution is 10%; nano SiO2In suspension, nano SiO2The mass concentration of (2) is 20%; chitosan, acetic acid water solution and nano SiO2The ratio of the addition amount of the suspension was 5g:150mL:10 mL. Stirring is magnetic stirring, the stirring temperature is normal temperature, and the stirring time is 12 hours; in the drying process, the temperature is 150 ℃ and the time is 10 h. Charring at high temperature in N2The carbonization is carried out in the atmosphere, the temperature is 900 ℃ in the high-temperature carbonization process, and the time is 2 hours; removal of SiO2The method comprises the following steps: and (3) soaking the composite material carbonized at high temperature in an HF solution at room temperature, wherein the mass concentration of HF in the HF solution is 30%. The separation process is as follows: will remove SiO2The composite material was centrifuged, washed repeatedly with water until the pH was 6.8, and dried. The Co salt is CoCl2The Mn salt is Mn (NO)3)2(ii) a The addition amount ratio of the Co salt, the Mn salt, the 2-methylimidazole and the DMF is 1mmol:2mmol:1mmol:15 mL.
In the step 2), the adding amount ratio of the nitrogen-doped porous carbon to the bimetal mixed solution is 0.3g to 5 mL. In the hydrothermal reaction process, the temperature is 160 ℃, and the time is 20 hours; after the hydrothermal reaction is finished, cooling to room temperature, washing with DMF and ethanol, and then drying in vacuum at 80 ℃ for 12h to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
The composite material is prepared into a working electrode for being used in a super capacitor.
Example 13:
a preparation method of a Co/Mn-MOF/nitrogen-doped carbon-based composite material comprises the following steps:
1) preparing a nitrogen-doped porous carbon and bimetal mixed solution:
the preparation method of the nitrogen-doped porous carbon comprises the following steps: dissolving chitosan in acetic acid water solution, and then adding nano SiO2The suspension is evenly stirred and dried to obtain the chitosan/SiO2A composite material; mixing chitosan/SiO2The composite material is carbonized at high temperature, and then SiO is removed2Separating to obtain nitrogen-doped porous carbon;
the preparation process of the bimetal mixed solution comprises the following steps: dissolving Co salt and Mn salt in DMF, adding 2-methylimidazole, and uniformly mixing to obtain a bimetallic mixed solution;
2) adding nitrogen-doped porous carbon into the bimetal mixed solution, then carrying out hydrothermal reaction, and then cooling, washing and drying to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
In the step 1), the mass concentration of acetic acid in the acetic acid aqueous solution is 7%; nano SiO2In suspension, nano SiO2The mass concentration of (2) is 25%; chitosan, acetic acid water solution and nano SiO2The amount of the suspension added was 4 g/175/7/mL. Stirring is magnetic stirring, the stirring temperature is normal temperature, and the stirring time is 14 hours; during the drying process, the temperature is 130 ℃ and the time is 12 h. Charring at high temperature in N2The carbonization is carried out under the atmosphere, the temperature is 800 ℃ in the high-temperature carbonization process, and the time is 2.5 h; removal of SiO2The method comprises the following steps: and (3) soaking the composite material carbonized at high temperature in an HF solution at room temperature, wherein the mass concentration of HF in the HF solution is 25%. The separation process is as follows: will remove SiO2The composite material was centrifuged, washed repeatedly with water until the pH was 7, and dried. The Co salt is CoCl2The Mn salt is Mn (NO)3)2(ii) a The addition amount ratio of the Co salt, the Mn salt, the 2-methylimidazole and the DMF is 1mmol:1.5mmol:2mmol:10 mL.
In the step 2), the adding amount ratio of the nitrogen-doped porous carbon to the bimetal mixed solution is 0.3g to 10 mL. In the hydrothermal reaction process, the temperature is 14 ℃, and the time is 22 h; after the hydrothermal reaction is finished, cooling to room temperature, washing with DMF and ethanol, and then drying in vacuum at 70 ℃ for 18h to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material.
The composite material is prepared into a working electrode for being used in a super capacitor.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. A preparation method of a Co/Mn-MOF/nitrogen-doped carbon-based composite material is characterized by comprising the following steps:
1) preparing a nitrogen-doped porous carbon and bimetal mixed solution:
the preparation method of the nitrogen-doped porous carbon comprises the following steps: dissolving chitosan in acetic acid water solution, and then adding nano SiO2The suspension is evenly stirred and dried to obtain the chitosan/SiO2A composite material; mixing chitosan/SiO2The composite material is carbonized at high temperature, and then SiO is removed2Separating to obtain nitrogen-doped porous carbon;
the preparation process of the bimetal mixed solution comprises the following steps: dissolving Co salt and Mn salt in DMF, adding 2-methylimidazole, and uniformly mixing to obtain a bimetallic mixed solution;
2) adding nitrogen-doped porous carbon into the bimetal mixed solution, then carrying out hydrothermal reaction, and then cooling, washing and drying to obtain the Co/Mn-MOF/nitrogen-doped carbon-based composite material;
in step 1), high-temperature carbonization is carried out on N2The process is carried out in the atmosphere, the temperature is 700-900 ℃ in the high-temperature carbonization process, and the time is 2-3 h; removal of SiO2The method comprises the following steps: the composite material after high-temperature carbonization is treated with HF at room temperatureSoaking in a solution, wherein in the HF solution, the mass concentration of HF is 20-30%;
in the step 2), the temperature is 120-; after the hydrothermal reaction is finished, cooling to room temperature, washing with DMF and ethanol, and then drying in vacuum at 60-80 ℃ for 12-24h to obtain the Co/Mn-MOF/nitrogen doped carbon-based composite material.
2. The preparation method of the Co/Mn-MOF/nitrogen-doped carbon-based composite material according to claim 1, characterized in that in the step 1), the mass concentration of acetic acid in the acetic acid aqueous solution is 5% -10%; the nano SiO2In suspension, nano SiO2The mass concentration of the active carbon is 20-30 percent; the chitosan, acetic acid water solution and nano SiO2The addition amount of the suspension is (3-5) g, (150) -200) mL and (5-10) mL.
3. The preparation method of the Co/Mn-MOF/nitrogen-doped carbon-based composite material according to claim 1, characterized in that in the step 1), the stirring is magnetic stirring, the stirring temperature is normal temperature, and the stirring time is 12-16 h; in the drying process, the temperature is 120-150 ℃, and the time is 10-15 h.
4. The preparation method of the Co/Mn-MOF/nitrogen-doped carbon-based composite material according to claim 1, wherein in the step 1), the separation process is as follows: will remove SiO2The composite material is centrifuged, washed repeatedly with water until the pH value is 6.8-7.2, and dried.
5. The method for preparing a Co/Mn-MOF/nitrogen-doped carbon-based composite material according to claim 1, wherein in the step 1), the Co salt is CoCl2The Mn salt is Mn (NO)3)2(ii) a The addition amount ratio of the Co salt, the Mn salt, the 2-methylimidazole and the DMF is 1mmol (1-2) mmol (1-4) mmol (5-15) mL.
6. The preparation method of the Co/Mn-MOF/nitrogen-doped carbon-based composite material according to claim 1, wherein in the step 2), the adding amount ratio of the nitrogen-doped porous carbon to the bimetal mixed solution is 0.3g (5-15) mL.
7. A Co/Mn-MOF/nitrogen doped carbon-based composite material prepared by the method of any one of claims 1 to 6.
8. Use of the Co/Mn-MOF/nitrogen doped carbon-based composite according to claim 7 to prepare a working electrode for use in a supercapacitor.
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