CN108922790A - A kind of manganese dioxide/N doping porous carbon composite preparation method and application of sodium ion insertion - Google Patents

A kind of manganese dioxide/N doping porous carbon composite preparation method and application of sodium ion insertion Download PDF

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CN108922790A
CN108922790A CN201810761109.5A CN201810761109A CN108922790A CN 108922790 A CN108922790 A CN 108922790A CN 201810761109 A CN201810761109 A CN 201810761109A CN 108922790 A CN108922790 A CN 108922790A
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manganese dioxide
porous carbon
sodium ion
carbon composite
ion insertion
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CN108922790B (en
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武立立
张喜田
张慧杰
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Harbin Jiesen General Electromechanical Equipment Co ltd
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Heilongjiang University of Science and 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
    • 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 kind of manganese dioxide/N doping porous carbon composite preparation method and application of sodium ion insertion, it is related to a kind of preparation method and application of manganese dioxide composite material.Forthright difference is low with capacity retention again when the invention aims to solve the problems, such as that existing manganese dioxide is used as the electrode material of fake capacitance type supercapacitor.Method：One, the ZIF-67 of regular dodecahedron is prepared；Two, the derivative nanoporous carbon materials of preparation ZIF-67；Three, compound, obtain manganese dioxide/N doping porous carbon composite of sodium ion insertion.Manganese dioxide/N doping porous carbon composite of sodium ion insertion is used as the positive electrode material of supercapacitor.The present invention can get a kind of manganese dioxide/N doping porous carbon composite of sodium ion insertion.

Description

A kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion Methods and applications
Technical field
The present invention relates to a kind of preparation method and application of manganese dioxide composite material.
Background technique
Increase along with population in the world and the fast development of economy, non-renewable fossil energy gradually decrease, therefore, Energy crisis becomes the another big severe challenge that world's every country faces.Under such historical background, energy storage device (battery, capacitor, supercapacitor etc.) and conversion equipment (fuel cell, solar battery etc.) become major scientific research institution Research hotspot.Wherein the types such as battery such as lead-acid accumulator, nickel radical battery, sode cell, lithium ion battery, air cell have There is higher energy density, but its power density is lower, the charge and discharge time is long, limits its answering in some specific areas With.The invention of supercapacitor brings dawn to our life.Supercapacitor is between ordinary capacitor and chemical-electrical A kind of novel energy storage apparatus between pond has high power density, high charge-discharge rate, long service life and environmentally protective etc. excellent Point is expected to the green energy resource novel as this century.In supercapacitor, electrode material is crucial, its decision capacitor master Performance is wanted, and influences the key factor of capacitor capacitance performance and production cost.
The electrode material for the supercapacitor studied at present mainly has carbon-based material (including active carbon, carbon fiber, carbon nanometer Pipe and graphene etc.), carbon material (O adulterates carbon material, N adulterates carbon material), the conducting polymer (polypyrrole of exotic atom doping PPy, polyaniline PANI, polythiophene PTh etc.) and transition metal oxide/hydroxide (RuO2、MnO2、NiOx/Ni(OH)2Deng) Deng.In order to enhance the specific capacity and energy density of supercapacitor, transition metal hydroxide, oxide and polymer are as counterfeit The electrode material of capacitive supercapacitor is concerned.In these fake capacitance type electrode materials, manganese dioxide (MnO2) be A kind of black or dark brown crystallization or amorphous powder, its relative molecular mass are 86.94, relative density 5.03gm-3, Fusing point is 535 DEG C, and not soluble in water and nitric acid has the properties such as excellent electricity, optics, magnetics and calorifics.Manganese dioxide due to In nature rich content, it is cheap, with high theoretical specific capacitance (1370F g-1) and it is environmentally friendly the advantages that, It is considered as one of most promising fake capacitance type electrode material.But reaction mechanism of the manganese dioxide in supercapacitor It is that Faraday pseudo-capacitance occurs by the fast transition between manganese dioxide and water manganese stone to react to store and discharge charge, i.e., only On the surface of the material or one layer of very thin surface could occur fake capacitance reaction, and the active material inside electrode material is due to mass transfer This transformation relatively is cannoted be completed in a short period of time slowly, therefore in high current work, electrode capacity has significantly sacrificing, multiplying power Performance is low.In addition MnO2Poorly conductive, the short defect of cycle life is with seriously limiting it in the hair in supercapacitor field Exhibition.For example, Nanjing Univ. of Posts and Telecommunications's (Chinese Journal of Inorganic Chemistry 30 (11):2509-2515) the hollow sea urchin shape manganese dioxide prepared, Sweeping speed is 2mVs-1Under conditions of, specific capacitance value is 226Fg-1；However 100mVs is increased to when sweeping speed-1When, specific capacitance Value is but only 88.5Fg-1, multiplying power is about 40%.Since carbon material has good electric conductivity and stability, with manganese dioxide Compound, carbon material acts not only as the physical support of manganese dioxide, also provides the channel of charge transmission, electrode material can be improved The high rate performance and cyclical stability of material.Wenzhou University (44 (5) of Chemical Engineering Technology and exploitation:1-5) by MnO2It is multiple with carbon nanocoils It closes, sweeps speed from 2mVs-1To 100mVs-1Multiplying power promoted to 60% or so, 1000 circle loop test after capacity retention It is 89.3%.It can be seen that carbon material and the compound multiplying power for effectively improving electrode of manganese dioxide and cycle performance.
The common carbon material compound with manganese dioxide has carbon black, carbon plate official form for filing a lawsuit, graphene, carbon nanotube and mesoporous carbon Deng.Guangxi Normal University Wang Hong strong et al. (105788884 A of CN) is prepared for manganese dioxide/carbon paper combination electrode material, material Capacitance can reach 200~400F/g, however be applied to supercapacitor, the symmetry of constant current charge-discharge curve is but not to the utmost Such as people's will.It is compound that river Dalian Chemical Physics Research Institute Song Yu et al. (103972518 A of CN) is prepared for manganese dioxide/nanotube Electrode material, the conservation rate of capacitor is 80% after electrode cycle 1000 encloses.Existing carbon material and the compound experiment side of manganese dioxide The limitation of method and result in terms of high rate performance and cyclical stability is to facilitate cause of the invention.
Summary of the invention
The invention aims to solve existing manganese dioxide as the electrode material of fake capacitance type supercapacitor to use When the forthright difference problem low with capacity retention again, and the manganese dioxide/N doping porous carbon for providing a kind of sodium ion insertion is multiple The preparation method and application of condensation material.
A kind of manganese dioxide/N doping porous carbon composite preparation method of sodium ion insertion, is according to the following steps Preparation：
One, the ZIF-67 of regular dodecahedron is prepared：
1., cabaltous nitrate hexahydrate is dissolved into methanol, obtain cobalt nitrate solution；
Step 1 1. described in cabaltous nitrate hexahydrate quality and methanol volume ratio be (1g~2g):40mL；
2., 2-methylimidazole is dissolved into methanol, obtain 2-methylimidazole solution；
Step 1 2. described in 2-methylimidazole quality and methanol volume ratio be (1g~3g):40mL；
3., cobalt nitrate solution and 2-methylimidazole solution mixed, then room temperature and mixing speed be 500r/min~ It is stirred to react 15h~25h under 900r/min, then is filtered by vacuum, solid matter is collected；Collection is consolidated using dehydrated alcohol Body substance cleans 5 times~8 times, then the solid matter after washes of absolute alcohol is put into the baking oven that temperature is 55 DEG C~65 DEG C and is done Dry 10h~14h obtains the ZIF-67 of regular dodecahedron；
Step 1 3. described in cobalt nitrate solution and 2-methylimidazole solution volume ratio be (0.8~1.2):1；
Two, the derivative nanoporous carbon materials of preparation ZIF-67：
1., the ZIF-67 of 3. regular dodecahedron that step 1 obtains is dispersed in ceramic boat, then ceramic boat is put into pipe In formula furnace, the mixed gas of argon gas and hydrogen is passed through into tube furnace, then by tube furnace with 3 DEG C/min~8 DEG C/min heating Speed is warming up to 420 DEG C~450 DEG C, then argon gas and hydrogen mixed-gas atmosphere and temperature be 420 DEG C~450 DEG C condition Lower heat preservation 6h~10h obtains black powder finally by tube furnace cooled to room temperature；
2., by step 2 1. obtained in black powder be immersed in concentration be 0.8mol/L~1.2mol/L H2SO4Solution Middle 10h~14h, then be filtered by vacuum, solid matter is collected, cleans 5 times~8 using solid matter of the deionized water to collection It is secondary, then solid matter after deionized water is cleaned is put into dry 8h~10h in the baking oven that temperature is 55 DEG C~65 DEG C, obtains ZIF-67 derives nanoporous carbon materials；
Three, compound：
1., by the KMnO of 0.04mol/L~0.06mol/L4Solution and concentration are 0.04mol/L~0.06mol/L's Na2SO4Solution mixing, obtains KMnO4And Na2SO4Mixed solution；
Step 3 1. described in 0.04mol/L~0.06mol/L KMnO4Solution and concentration be 0.04mol/L~ The Na of 0.06mol/L2SO4The volume ratio of solution is (0.95~1):1；
2., the derivative nanoporous carbon materials of ZIF-67 are immersed in KMnO at room temperature4And Na2SO4Mixed solution in 3h~ 7h, then be filtered by vacuum, solid matter is collected, is cleaned 5 times~8 times using solid matter of the deionized water to collection, then will Solid matter after deionized water cleaning is put into dry 8h~10h in the baking oven that temperature is 55 DEG C~65 DEG C, and it is embedding to obtain sodium ion The manganese dioxide entered/N doping porous carbon composite.
Manganese dioxide/N doping porous carbon composite of sodium ion insertion makes as the electrode material of supercapacitor With.
The principle of the present invention：
The present invention uses solvent-thermal method, and using methanol as solvent, using cobalt as metal center ion, cobalt nitrate is as cobalt 2-methylimidazole crosslinking is assembled into transition metals cobalt at room temperature, obtains using 2-methylimidazole as nitrogenous organic ligand by source To the metal-organic framework materials ZIF67 of class zeolite imidazole ester skeleton structure with regular dodecahedron pattern.
The present invention sacrifices method using template, and using ZIF67 as template, derivatives composite material is made by simple pyrolysismethod Co/C-N, then erode metallic element Co with the concentrated sulfuric acid while lightening material mass density, increases porosity, obtains nitrogen and mix Miscellaneous porous carbon materials.
The present invention uses oxidation-reduction method, as follows using carbon in-situ reducing potassium permanganate reaction equation：
4MnO4 -+3C+H2O=4MnO2+CO3 2-+2HCO3 -；
While the reaction occurs, sodium ion is embedded into composite material by impregnating, and finally obtains sodium ion insertion Manganese dioxide/N doping porous carbon composite.
Advantages of the present invention：
One, it is heated labile feature the present invention is based on metal-organic framework material, using metal-organic backbone material Expect that ZIF67 as template is sacrificed, prepares porous carbon materials；Since the derivative porous carbon materials of ZIF67 have hollow regular dodecahedron Structure, uniform particle diameter distribution and higher specific surface area, being conducive to synthesis has hollow structure, morphological rules, uniform particle sizes Combination electrode material；
Two, the present invention lack ZIF67 that oxygen ligand is constituted, containing cobalt as sacrificing template using by rich nitrogen, 420 DEG C~ It is carbonized at 450 DEG C and obtains the derivative porous carbon materials of ZIF67 after removing metal Co；ZIF67 in an inert atmosphere low temperature pyrogenation when N atom can be retained to the greatest extent to be dispersed in carbon skeleton；In contrast, tradition prepares Heteroatom doping porous carbon materials Method not only condition is harsh, process is cumbersome, but also the pattern that material is made is irregular, and pore size is different, and specific surface Product is often very low, it is important to which hetero atom is difficult to be uniformly dispersed.The Uniform Doped of nitrogen-atoms can effectively adjust porous carbon materials Electronic structure and electric conductivity make it have richer performance.And the process of hetero atom cobalt is removed in experiment, both alleviate material The mass density of material also increases the porosity of material.Therefore using metal-organic framework material ZIF67 as sacrifice template The porous carbon materials nitrogen-doping of synthesis is uniform and porosity is high, help to obtain high performance combination electrode material；
Three, the present invention is porous as sodium ion insertion manganese dioxide/N doping of skeleton building block by the derivative porous carbon of ZIF67 Carbon composite, inherit metal-organic framework material high-specific surface area, high porosity, high thermal stability, easy functionalization and Lower-price characteristic has hollow nearly regular dodecahedron structure, and morphological rules, uniform particle sizes, porosity is high, aperture is consistent, It help to obtain good super capacitive energy；
Four, manganese dioxide/N doping porous carbon composite of sodium ion insertion prepared by the present invention, manganese dioxide is in carbon It is uniformly dispersed on skeleton, sufficiently, belongs to a kind of birnessite structure with layer structure, convenient for the absorption and deintercalation of ion, Thus it is suitable for super capacitor material；
Five, manganese dioxide/N doping porous carbon composite of sodium ion insertion prepared by the present invention is as super capacitor The positive electrode material of device is in use, under identical testing conditions, quality specific capacitance is better than individually with manganese dioxide or nitrogen Adulterating the derivative porous carbon of ZIF67 is positive material context；Manganese dioxide/N doping of sodium ion insertion prepared by the present invention is porous The quality specific capacitance of carbon composite is 5 times of pure manganese bioxide material；
Six, manganese dioxide/N doping porous carbon composite of sodium ion insertion prepared by the present invention is as super capacitor The positive electrode material of device shows good symmetry in use, constant current charge-discharge curve is the isosceles triangle of standard；
Seven, manganese dioxide/N doping porous carbon composite of sodium ion insertion prepared by the present invention is as super capacitor The positive electrode material of device is in use, sweep speed from 2mV s-1To 100mV s-1, the multiplying power of capacitor is 80%~90%；
Eight, manganese dioxide/N doping porous carbon composite of sodium ion insertion prepared by the present invention is as super capacitor The positive electrode material of device in use, cyclical stability is good, voltage window be 0V~0.8V, current density 1Ag-1Condition Under, capacity retention is 85%~95% after 5000 circle of circulation.
The present invention can get a kind of manganese dioxide/N doping porous carbon composite of sodium ion insertion.
Detailed description of the invention
The SEM figure that Fig. 1 is the ZIF-67 of the regular dodecahedron of one step 1 of embodiment preparation；
Fig. 2 is the SEM figure of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
Fig. 3 is the energy spectrum diagram of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
Fig. 4 is the specific surface area spectrogram of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
Fig. 5 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation SEM figure；
Fig. 6 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation TEM figure；
Fig. 7 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation XRD spectra；
Fig. 8 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Specific surface area spectrogram；
Fig. 9 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Pore-size distribution spectrogram；
Figure 10 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation VA characteristic curve；
Figure 11 is the VA characteristic curve of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
Figure 12 is the VA characteristic curve of the pure manganese dioxide of hydro-thermal method synthesis；
Figure 13 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation 1st~5 circle constant current charge-discharge curve；
Figure 14 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation 4995-5000 encloses constant current charge-discharge curve；
Figure 15 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Sweep the corresponding relationship of speed with capacitor；
Figure 16 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Cycle characteristics curve.
Specific embodiment
Specific embodiment one：Present embodiment is that a kind of manganese dioxide/N doping porous carbon of sodium ion insertion is compound The preparation method of material, prepares according to the following steps：
One, the ZIF-67 of regular dodecahedron is prepared：
1., cabaltous nitrate hexahydrate is dissolved into methanol, obtain cobalt nitrate solution；
Step 1 1. described in cabaltous nitrate hexahydrate quality and methanol volume ratio be (1g~2g):40mL；
2., 2-methylimidazole is dissolved into methanol, obtain 2-methylimidazole solution；
Step 1 2. described in 2-methylimidazole quality and methanol volume ratio be (1g~3g):40mL；
3., cobalt nitrate solution and 2-methylimidazole solution mixed, then room temperature and mixing speed be 500r/min~ It is stirred to react 15h~25h under 900r/min, then is filtered by vacuum, solid matter is collected；Collection is consolidated using dehydrated alcohol Body substance cleans 5 times~8 times, then the solid matter after washes of absolute alcohol is put into the baking oven that temperature is 55 DEG C~65 DEG C and is done Dry 10h~14h obtains the ZIF-67 of regular dodecahedron；
Step 1 3. described in cobalt nitrate solution and 2-methylimidazole solution volume ratio be (0.8~1.2):1；
Two, the derivative nanoporous carbon materials of preparation ZIF-67：
1., the ZIF-67 of 3. regular dodecahedron that step 1 obtains is dispersed in ceramic boat, then ceramic boat is put into pipe In formula furnace, the mixed gas of argon gas and hydrogen is passed through into tube furnace, then by tube furnace with 3 DEG C/min~8 DEG C/min heating Speed is warming up to 420 DEG C~450 DEG C, then argon gas and hydrogen mixed-gas atmosphere and temperature be 420 DEG C~450 DEG C condition Lower heat preservation 6h~10h obtains black powder finally by tube furnace cooled to room temperature；
2., by step 2 1. obtained in black powder be immersed in concentration be 0.8mol/L~1.2mol/L H2SO4Solution Middle 10h~14h, then be filtered by vacuum, solid matter is collected, cleans 5 times~8 using solid matter of the deionized water to collection It is secondary, then solid matter after deionized water is cleaned is put into dry 8h~10h in the baking oven that temperature is 55 DEG C~65 DEG C, obtains ZIF-67 derives nanoporous carbon materials；
Three, compound：
1., by the KMnO of 0.04mol/L~0.06mol/L4Solution and concentration are 0.04mol/L~0.06mol/L's Na2SO4Solution mixing, obtains KMnO4And Na2SO4Mixed solution；
Step 3 1. described in 0.04mol/L~0.06mol/L KMnO4Solution and concentration be 0.04mol/L~ The Na of 0.06mol/L2SO4The volume ratio of solution is (0.95~1):1；
2., the derivative nanoporous carbon materials of ZIF-67 are immersed in KMnO at room temperature4And Na2SO4Mixed solution in 3h~ 7h, then be filtered by vacuum, solid matter is collected, is cleaned 5 times~8 times using solid matter of the deionized water to collection, then will Solid matter after deionized water cleaning is put into dry 8h~10h in the baking oven that temperature is 55 DEG C~65 DEG C, and it is embedding to obtain sodium ion The manganese dioxide entered/N doping porous carbon composite.
The principle of present embodiment：
Present embodiment uses solvent-thermal method, using methanol as solvent, using cobalt as metal center ion, and cobalt nitrate conduct 2-methylimidazole crosslinking is assembled into transition metals cobalt by cobalt source at room temperature using 2-methylimidazole as nitrogenous organic ligand, Obtain the metal-organic framework materials ZIF67 of there is regular dodecahedron pattern class zeolite imidazole ester skeleton structure.
Present embodiment sacrifices method using template, and using ZIF67 as template, derivative composite wood is made by simple pyrolysismethod Expect Co/C-N, then erode metallic element Co with the concentrated sulfuric acid, while lightening material mass density, increases porosity, obtain nitrogen The porous carbon materials of doping.
Present embodiment uses oxidation-reduction method, as follows using carbon in-situ reducing potassium permanganate reaction equation：
4MnO4 -+3C+H2O=4MnO2+CO3 2-+2HCO3 -；
While the reaction occurs, sodium ion is embedded into composite material by impregnating, and finally obtains sodium ion insertion Manganese dioxide/N doping porous carbon composite.
The advantages of present embodiment：
One, present embodiment is based on metal-organic framework material and is heated labile feature, using the organic bone of metal- Frame material ZIF67 prepares porous carbon materials as template is sacrificed, since the derivative porous carbon materials of ZIF67 have hollow positive 12 Face body structure, uniform particle diameter distribution and higher specific surface area, being conducive to synthesis has hollow structure, morphological rules, partial size Uniform combination electrode material；
Two, present embodiment, which is used, lacks ZIF67 that oxygen ligand is constituted, containing cobalt as template is sacrificed, at 420 DEG C by rich nitrogen It is carbonized at~450 DEG C and obtains the derivative porous carbon materials of ZIF67 after removing metal Co；ZIF67 low temperature pyrogenation in an inert atmosphere When can retain N atom to the greatest extent and be dispersed in carbon skeleton；In contrast, tradition prepares Heteroatom doping porous carbon Not only condition is harsh, process is cumbersome for the method for material, but also the pattern that material is made is irregular, and pore size is different, and compares table Area is often very low, it is important to which hetero atom is difficult to be uniformly dispersed；The Uniform Doped of nitrogen-atoms can effectively adjust porous carbon materials Electronic structure and electric conductivity, so that it is had richer performance；And the process of hetero atom cobalt is removed in experiment, both alleviated The mass density of material also increases the porosity of material.Therefore using metal-organic framework material ZIF67 as sacrificial mold The porous carbon materials nitrogen-doping of plate synthesis is uniform and porosity is high, help to obtain high performance combination electrode material；
Three, present embodiment is embedded in manganese dioxide/N doping as the sodium ion of skeleton building block by the derivative porous carbon of ZIF67 Porous carbon composite inherits metal-organic framework material high-specific surface area, high porosity, high thermal stability, easy function Change and lower-price characteristic have hollow nearly regular dodecahedron structure, morphological rules, uniform particle sizes, porosity height, aperture one It causes, help to obtain good super capacitive energy；
Four, manganese dioxide/N doping porous carbon composite of the sodium ion insertion of present embodiment preparation, manganese dioxide It is uniformly dispersed on carbon skeleton, sufficiently, belongs to a kind of birnessite structure with layer structure, convenient for the absorption of ion and de- It is embedding, thus it is suitable for super capacitor material；
Five, manganese dioxide/N doping porous carbon composite of the sodium ion insertion of present embodiment preparation is as super The positive electrode material of capacitor in use, under identical testing conditions, quality specific capacitance be better than with individually with manganese dioxide or The derivative porous carbon of person's N doping ZIF67 is positive material context；Manganese dioxide/nitrogen of the sodium ion insertion of present embodiment preparation The quality specific capacitance of doping porous carbon composite is 5 times of pure manganese bioxide material；
Six, manganese dioxide/N doping porous carbon composite of the sodium ion insertion of present embodiment preparation is as super The positive electrode material of capacitor shows good symmetry in use, constant current charge-discharge curve is the isosceles triangle of standard；
Seven, manganese dioxide/N doping porous carbon composite of the sodium ion insertion of present embodiment preparation is as super The positive electrode material of capacitor is in use, sweep speed from 2mV s-1To 100mV s-1, the multiplying power of capacitor is 80%~90%；
Eight, manganese dioxide/N doping porous carbon composite of the sodium ion insertion of present embodiment preparation is as super The positive electrode material of capacitor in use, cyclical stability is good, voltage window be 0V~0.8V, current density 1Ag-1's Under the conditions of, capacity retention is 85%~95% after 5000 circle of circulation.
Present embodiment can get a kind of manganese dioxide/N doping porous carbon composite of sodium ion insertion.
Specific embodiment two：The differences between this implementation mode and the specific implementation mode are that：Step 1 1. described in six The quality of nitric hydrate cobalt and the volume ratio of methanol are (1.6g~2g):40mL.Other steps are same as the specific embodiment one.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference are：Step 1 2. in The quality of the 2-methylimidazole and the volume ratio of methanol are (1g~2g):40mL.Other steps and specific embodiment one Or two is identical.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference are：Step 1 3. in Cobalt nitrate solution and 2-methylimidazole solution are mixed, then stirred under being 600r/min~800r/min in room temperature and mixing speed 15h~20h is reacted, then is filtered by vacuum, solid matter is collected；It is cleaned 5 times using solid matter of the dehydrated alcohol to collection ~6 times, then the solid matter after washes of absolute alcohol is put into dry 10h~12h in the baking oven that temperature is 55 DEG C~60 DEG C, it obtains To the ZIF-67 of regular dodecahedron.Other steps are identical as specific embodiment one to three.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference are：Step 1 3. in The volume ratio of the cobalt nitrate solution and 2-methylimidazole solution is (0.9~1):1.Other steps and specific embodiment one It is identical to four.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference are：Step 2 1. in The ZIF-67 of 3. regular dodecahedron that step 1 obtains is dispersed in ceramic boat, then ceramic boat is put into tube furnace, Xiang Guan It is passed through the mixed gas of argon gas and hydrogen in formula furnace, then tube furnace is warming up to 3 DEG C/min~5 DEG C/min heating rate 425 DEG C~435 DEG C, then the mixed-gas atmosphere and temperature of argon gas and hydrogen be 425 DEG C~435 DEG C under conditions of heat preservation 6h~ 8h obtains black powder finally by tube furnace cooled to room temperature.Other steps are identical as specific embodiment one to five.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference are：Step 2 1. in The volume ratio of argon gas and hydrogen is 9 in the mixed gas of the argon gas and hydrogen:1.Other steps and specific embodiment one It is identical to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference are：Step 2 2. in By step 2 1. obtained in black powder be immersed in concentration be 0.9mol/L~1mol/L H2SO411h~12h in solution, then It is filtered by vacuum, collects solid matter, the solid matter of collection is cleaned 5 times~6 times using deionized water, then by deionization Solid matter after water cleaning is put into dry 8h~9h in the baking oven that temperature is 55 DEG C~60 DEG C, obtains the derivative nano-sized carbon of ZIF-67 Material.Other steps are identical as specific embodiment one to seven.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference are：Step 3 1. in By the KMnO of 0.04mol/L~0.05mol/L4The Na that solution and concentration are 0.04mol/L~0.05mol/L2SO4Solution mixing, Obtain KMnO4And Na2SO4Mixed solution.Other steps are identical as specific embodiment one to eight.
Specific embodiment ten：Present embodiment is manganese dioxide/N doping porous carbon composite of sodium ion insertion Positive electrode material as supercapacitor uses.
Embodiment one：A kind of manganese dioxide/N doping porous carbon composite preparation method of sodium ion insertion, be by Following steps preparation：
One, the ZIF-67 of regular dodecahedron is prepared：
1., 1.6g cabaltous nitrate hexahydrate is dissolved into 40mL methanol, obtain cobalt nitrate solution；
2., 2g 2-methylimidazole is dissolved into 40mL methanol, obtain 2-methylimidazole solution；
3., cobalt nitrate solution and 2-methylimidazole solution mixed, then stirred under being 800r/min in room temperature and mixing speed Reaction 20h is mixed, then is filtered by vacuum, solid matter is collected；It is cleaned 6 times using solid matter of the dehydrated alcohol to collection, then Solid matter after washes of absolute alcohol is put into dry 12h in the baking oven that temperature is 60 DEG C, obtains the ZIF- of regular dodecahedron 67；
Two, the derivative nanoporous carbon materials of preparation ZIF-67：
1., the ZIF-67 of 3. regular dodecahedron that step 1 obtains is dispersed in ceramic boat, then ceramic boat is put into pipe In formula furnace, the mixed gas of argon gas and hydrogen is passed through into tube furnace, then tube furnace is warming up to the heating rate of 5 DEG C/min 435 DEG C, then 8h is kept the temperature under conditions of the mixed-gas atmosphere and temperature of argon gas and hydrogen are 435 DEG C, certainly by tube furnace finally It is so cooled to room temperature, obtains black powder；
Step 2 1. described in argon gas and hydrogen mixed gas in the volume ratio of argon gas and hydrogen be 9:1；
2., by step 2 1. obtained in black powder be immersed in concentration be 1mol/L H2SO412h in solution, then carry out Vacuum filtration collects solid matter, is cleaned 6 times using deionized water to the solid matter of collection, then after deionized water is cleaned Solid matter to be put into temperature be dry 8h in 60 DEG C of baking oven, obtain the derivative nanoporous carbon materials of ZIF-67；
Three, compound：
1., by the KMnO of 0.05mol/L4The Na that solution and concentration are 0.05mol/L2SO4Solution mixing, obtains KMnO4With Na2SO4Mixed solution；
Step 3 1. described in 0.05mol/L KMnO4The Na that solution and concentration are 0.05mol/L2SO4The body of solution Product is than being 1:1；
2., the derivative nanoporous carbon materials of ZIF-67 are immersed in KMnO at room temperature4And Na2SO4Mixed solution in 5h, It is filtered by vacuum again, collects solid matter, the solid matter of collection is cleaned 6 times using deionized water, then by deionized water Solid matter after cleaning is put into dry 8h in the baking oven that temperature is 60 DEG C, obtains manganese dioxide/N doping of sodium ion insertion Porous carbon composite.
The pattern of the ZIF-67 of the regular dodecahedron of one step 1 of embodiment preparation is as shown in Figure 1；
The SEM figure that Fig. 1 is the ZIF-67 of the regular dodecahedron of one step 1 of embodiment preparation；
From fig. 1, it can be seen that the exterior appearance of the ZIF-67 of the regular dodecahedron of one step 1 of embodiment preparation, surface is smooth, Uniform particle diameter, with it to sacrifice template, the plurality of advantages of ZIF-67 is inherited, is help to obtain with regular dodecahedron knot The porous carbon materials of structure, uniform particle diameter.
Pattern, ingredient and the specific surface area difference of the derivative nanoporous carbon materials of the ZIF-67 of one step 2 of embodiment preparation As shown in Fig. 2,3 and 4.
Fig. 2 is the SEM figure of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
As can be seen from Figure 2, the derivative nanoporous carbon materials morphological rules of the ZIF-67 of one step 2 of embodiment preparation, partial size are equal It is even, there is hollow structure, and maintain the ZIF-67 skeleton structure of regular dodecahedron substantially, but surface is slightly recessed, surface is thick It is rough, it is no longer smooth.
Fig. 3 is the energy spectrum diagram of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
As can be seen from Figure 3, the derivative nanoporous carbon materials of the ZIF-67 of one step 2 of embodiment preparation largely retain N element, and be dispersed in carbon skeleton.The Uniform Doped of nitrogen-atoms can effectively adjust the electronic structure of porous carbon materials And electric conductivity, so that it is had richer performance, help to obtain high performance combination electrode material.
Fig. 4 is the specific surface area spectrogram of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
As can be seen from Figure 4, derivative nanoporous carbon materials are with higher compares table by the ZIF-67 of one step 2 of embodiment preparation Area, numerical value 152m2/g。
Fig. 5 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation SEM figure；
Fig. 6 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation TEM figure；
From Fig. 5,6 it is found that manganese dioxide/N doping porous carbon of sodium ion insertion prepared by one step 3 of embodiment is compound Material inherits the shape characteristic of the derivative nanoporous carbon materials of ZIF-67, the hollow structure with nearly regular dodecahedron, shape Looks rule, uniform particle sizes, about 1 micron of diameter, composite material outer layer is the manganese dioxide of sheet fine crushing, surface more overstriking It is rough.
Fig. 7 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation XRD spectra；
As can be seen from Figure 7, manganese dioxide/N doping porous carbon composite wood of the sodium ion insertion of one step 3 of embodiment preparation Expect that the manganese dioxide nano fragment of surface attachment has birnessite structure (JCPDS 18-0802,36 ° and 65 ° of diffraction maximum difference Corresponding (006) and (119) crystal face), convenient for the absorption and deintercalation of ion, thus it is suitable for super capacitor material.
Fig. 8 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Specific surface area spectrogram；
Fig. 9 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Pore-size distribution spectrogram；
From Fig. 8, Fig. 9 it is found that manganese dioxide/N doping porous carbon of the sodium ion insertion of one step 3 of embodiment preparation is multiple The porosity of condensation material is high, specific surface area 127m2/g；Aperture is consistent, and most apertures are help to obtain good having a size of 4nm Super capacitive energy.
Embodiment two：Manganese dioxide/N doping porous carbon of the sodium ion insertion of one step 3 of embodiment preparation is compound Material is used as the positive electrode material of three electrode super capacitor parts, and the preparation method of three electrode super capacitor parts is as follows：
One, the preparation of working electrode
1., by one step 3 of embodiment preparation sodium ion insertion manganese dioxide/N doping porous carbon composite and Acetylene black powder mixing, and with mortar grinder at sufficient powder is mixed, the manganese dioxide/N doping for obtaining sodium ion insertion is more The mixed-powder of hole carbon composite and acetylene black；By sodium ion insertion manganese dioxide/N doping porous carbon composite and The mixed-powder and Kynoar liquid of acetylene black mix, and are stirred for uniformly, obtaining uniform slurries；
Step 1 1. described in sodium ion insertion manganese dioxide/N doping porous carbon composite and acetylene black it is mixed Closing manganese dioxide/N doping porous carbon composite of sodium ion insertion and the mass ratio of acetylene black in powder is 8：1；
Step 1 1. described in Kynoar liquid be that Kynoar is dissolved into N-Methyl pyrrolidone solvent, The mass fraction of Kynoar is 4%~8% in Kynoar liquid；
Step 1 1. described in sodium ion insertion manganese dioxide/N doping porous carbon composite and acetylene black it is mixed The mass ratio for closing powder and Kynoar liquid is 9:1；
2., select carbon paper as collector, uniform slurries are dripped evenly dispersedly in sodium ion insertion on carbon paper, is made Manganese dioxide/N doping porous carbon composite/carbon paper；
Two, the building of supercapacitor：
Using sodium ion be embedded in manganese dioxide/N doping porous carbon composite/carbon paper be used as working electrode, platinum electrode with Saturated calomel electrode is respectively as to electrode and reference electrode, with the Na of 1.0mol/L2SO4Solution is as electrolyte, three electricity of building Pole super capacitor device；
Three, the test of chemical property
Using electrochemical workstation (VMP3, France) at room temperature, voltage window test three under conditions of being 0V to 0.8V The cyclic voltammetry curve and constant current charge-discharge curve of electrode super capacitor part.
The cyclic voltammetry curve of three electrode super capacitor parts prepared by embodiment two, constant current charge-discharge curve and forthright again It can see Figure 10, Figure 13~Figure 16.
Note：In order to carry out the comparison of three electrode super capacitor part properties, with method same as embodiment two and test The pure titanium dioxide of the ZIF-67 derivative nanoporous carbon materials and hydro-thermal method synthesis of condition test embodiment one step 2 preparation The C-V characteristic of three electrode super capacitor parts prepared by positive electrode material of the manganese respectively as three electrode super capacitor parts Curve, as is illustrated by figs. 11 and 12.
Figure 10 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation VA characteristic curve；
Figure 11 is the VA characteristic curve of the derivative nanoporous carbon materials of ZIF-67 of one step 2 of embodiment preparation；
Figure 12 is the VA characteristic curve of the pure manganese dioxide of hydro-thermal method synthesis；
From Figure 10~Figure 12 it is found that manganese dioxide/N doping of the sodium ion insertion of one step 3 of embodiment preparation is porous The quality specific capacitance of carbon composite is better than individually using manganese dioxide or the derivative porous carbon of N doping ZIF67 as positive electrode feelings Condition.Manganese dioxide/N doping porous carbon composite quality specific capacitance of the sodium ion insertion of one step 3 of embodiment preparation It is 5 times of pure manganese bioxide material for 217F/g.
Figure 13 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation 1st~5 circle constant current charge-discharge curve；
Figure 14 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation 4995-5000 encloses constant current charge-discharge curve；
From Figure 13 and Figure 14 it is found that manganese dioxide/N doping of the sodium ion insertion of one step 3 of embodiment preparation is porous The constant current charge-discharge curve of carbon composite is the isosceles triangle of standard, shows good symmetry.
Figure 15 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Sweep the corresponding relationship of speed with capacitor；
From figure 15, it can be known that manganese dioxide/N doping porous carbon of the sodium ion insertion of one step 3 of embodiment preparation is compound The positive electrode material as supercapacitor of material is in use, sweep speed from 2mV s-1To 100mV s-1, the multiplying power of capacitor is 85%.
Figure 16 is manganese dioxide/N doping porous carbon composite of the sodium ion insertion of one step 3 of embodiment preparation Cycle characteristics curve.
As can be seen from Figure 16, manganese dioxide/N doping porous carbon of the sodium ion insertion of one step 3 of embodiment preparation is compound Material as supercapacitor positive electrode material in use, cyclical stability is good, capacity retention is after 5000 circle of circulation 91%.

Claims (10)

1. a kind of manganese dioxide/N doping porous carbon composite preparation method of sodium ion insertion, it is characterised in that a kind of Manganese dioxide/N doping porous carbon composite preparation method of sodium ion insertion is prepared according to the following steps：
One, the ZIF-67 of regular dodecahedron is prepared：
1., cabaltous nitrate hexahydrate is dissolved into methanol, obtain cobalt nitrate solution；
Step 1 1. described in cabaltous nitrate hexahydrate quality and methanol volume ratio be (1g~2g):40mL；
2., 2-methylimidazole is dissolved into methanol, obtain 2-methylimidazole solution；
Step 1 2. described in 2-methylimidazole quality and methanol volume ratio be (1g~3g):40mL；
3., cobalt nitrate solution and 2-methylimidazole solution mixed, then in room temperature and mixing speed be 500r/min~900r/ It is stirred to react 15h~25h under min, then is filtered by vacuum, solid matter is collected；Using dehydrated alcohol to the solids of collection Matter is cleaned 5 times~8 times, then the solid matter after washes of absolute alcohol is put into drying in the baking oven that temperature is 55 DEG C~65 DEG C 10h~14h obtains the ZIF-67 of regular dodecahedron；
Step 1 3. described in cobalt nitrate solution and 2-methylimidazole solution volume ratio be (0.8~1.2):1；
Two, the derivative nanoporous carbon materials of preparation ZIF-67：
1., the ZIF-67 of 3. regular dodecahedron that step 1 obtains is dispersed in ceramic boat, then ceramic boat is put into tube furnace In, the mixed gas of argon gas and hydrogen is passed through into tube furnace, then by tube furnace with 3 DEG C/min~8 DEG C/min heating rate 420 DEG C~450 DEG C are warming up to, then is protected under conditions of the mixed-gas atmosphere and temperature of argon gas and hydrogen are 420 DEG C~450 DEG C Warm 6h~10h obtains black powder finally by tube furnace cooled to room temperature；
2., by step 2 1. obtained in black powder be immersed in concentration be 0.8mol/L~1.2mol/L H2SO4In solution 10h~14h, then be filtered by vacuum, solid matter is collected, cleans 5 times~8 using solid matter of the deionized water to collection It is secondary, then solid matter after deionized water is cleaned is put into dry 8h~10h in the baking oven that temperature is 55 DEG C~65 DEG C, obtains ZIF-67 derives nanoporous carbon materials；
Three, compound：
1., by the KMnO of 0.04mol/L~0.06mol/L4The Na that solution and concentration are 0.04mol/L~0.06mol/L2SO4It is molten Liquid mixing, obtains KMnO4And Na2SO4Mixed solution；
Step 3 1. described in 0.04mol/L~0.06mol/L KMnO4Solution and concentration are 0.04mol/L~0.06mol/ The Na of L2SO4The volume ratio of solution is (0.95~1):1；
2., the derivative nanoporous carbon materials of ZIF-67 are immersed in KMnO at room temperature4And Na2SO4Mixed solution in 3h~7h, Be filtered by vacuum again, collect solid matter, the solid matter of collection is cleaned 5 times~8 times using deionized water, then will go from Solid matter after sub- water cleaning is put into dry 8h~10h in the baking oven that temperature is 55 DEG C~65 DEG C, obtains sodium ion insertion Manganese dioxide/N doping porous carbon composite.
2. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 1 1. described in cabaltous nitrate hexahydrate quality and methanol volume ratio be (1.6g~2g): 40mL。
3. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 1 2. described in 2-methylimidazole quality and methanol volume ratio be (1g~2g):40mL.
4. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 1 3. in cobalt nitrate solution and 2-methylimidazole solution are mixed, then in room temperature and mixing speed It to be stirred to react 15h~20h under 600r/min~800r/min, then is filtered by vacuum, collects solid matter；Use anhydrous second Alcohol cleans the solid matter of collection 5 times~6 times, then it is 55 DEG C~60 that the solid matter after washes of absolute alcohol, which is put into temperature, DEG C baking oven in dry 10h~12h, obtain the ZIF-67 of regular dodecahedron.
5. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 1 3. described in cobalt nitrate solution and 2-methylimidazole solution volume ratio be (0.9~1): 1。
6. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 2 1. in the ZIF-67 of 3. regular dodecahedron that step 1 obtains is dispersed in ceramic boat, then Ceramic boat is put into tube furnace, is passed through the mixed gas of argon gas and hydrogen into tube furnace, then by tube furnace with 3 DEG C/min~ The heating rate of 5 DEG C/min is warming up to 425 DEG C~435 DEG C, then in the mixed-gas atmosphere and temperature of argon gas and hydrogen is 425 DEG C 6h~8h is kept the temperature under conditions of~435 DEG C obtains black powder finally by tube furnace cooled to room temperature.
7. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 2 1. described in argon gas and hydrogen mixed gas in the volume ratio of argon gas and hydrogen be 9:1.
8. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 2 2. in by step 2 1. obtained in black powder be immersed in concentration be 0.9mol/L~ The H of 1mol/L2SO411h~12h in solution, then be filtered by vacuum, solid matter is collected, collection is consolidated using deionized water Body substance cleans 5 times~6 times, then the solid matter after deionized water is cleaned is put into the baking oven that temperature is 55 DEG C~60 DEG C and does Dry 8h~9h obtains the derivative nano-carbon material of ZIF-67.
9. a kind of manganese dioxide/N doping porous carbon composite preparation of sodium ion insertion according to claim 1 Method, it is characterised in that step 3 1. in by the KMnO of 0.04mol/L~0.05mol/L4Solution and concentration be 0.04mol/L~ The Na of 0.05mol/L2SO4Solution mixing, obtains KMnO4And Na2SO4Mixed solution.
10. a kind of manganese dioxide/N doping porous carbon composite application of sodium ion insertion as described in claim 1, It is characterized in that manganese dioxide/positive electrode material of the N doping porous carbon composite as supercapacitor of sodium ion insertion It uses.
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CN109980179B (en) * 2019-04-11 2021-04-23 厦门大学 Nitrogen-carbon doped modified manganese dioxide composite material and preparation method thereof
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CN110243890A (en) * 2019-07-23 2019-09-17 合肥工业大学 A kind of preparation method of Mn-ZIF67 material and the detection method of mercury ion
CN110600690A (en) * 2019-08-09 2019-12-20 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
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CN110783115A (en) * 2019-11-06 2020-02-11 黑龙江科技大学 Preparation method and application of manganese dioxide/carbon/foam metal composite material
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
CN111403696A (en) * 2019-11-20 2020-07-10 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
CN115028167A (en) * 2022-05-12 2022-09-09 西南科技大学 Preparation method and energy storage application of hierarchical porous biomass carbon material
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

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