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 PDFInfo
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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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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 221
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 102
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 80
- 238000003780 insertion Methods 0.000 title claims abstract description 78
- 230000037431 insertion Effects 0.000 title claims abstract description 78
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 56
- 239000007787 solid Substances 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 33
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007832 Na2SO4 Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims 1
- 229910021392 nanocarbon Inorganic materials 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 17
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 39
- 239000003990 capacitor Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000000877 morphologic effect Effects 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- KRQKZTCYIWEUIV-UHFFFAOYSA-N cobalt(2+) 2-methylimidazol-3-ide Chemical compound [Co++].Cc1ncc[n-]1.Cc1ncc[n-]1 KRQKZTCYIWEUIV-UHFFFAOYSA-N 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012966 insertion method Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- -1 manganese dioxide Compound Chemical class 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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
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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| 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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| 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 |
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