CN104909351A - Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof - Google Patents
Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 98
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 36
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 239000003093 cationic surfactant Substances 0.000 claims abstract 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract 11
- 239000010703 silicon Substances 0.000 claims abstract 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- MWOZJZDNRDLJMG-UHFFFAOYSA-N [Si].O=C=O Chemical compound [Si].O=C=O MWOZJZDNRDLJMG-UHFFFAOYSA-N 0.000 claims 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 claims 1
- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 229960001866 silicon dioxide Drugs 0.000 description 22
- 241000282326 Felis catus Species 0.000 description 21
- 239000003575 carbonaceous material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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Classifications
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- 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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- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明公开一种大比表面积的氮掺杂介孔碳球纳米材料及制备方法。即以阳离子表面活性剂为模板剂，用有机硅源、有机碳源、有机氮源通过水热反应形成有机/无机复合物，然后在氮气氛下焙烧，得到的二氧化硅/含氮碳球纳米材料除去二氧化硅后即得球形介孔结构的氮掺杂介孔碳球纳米材料，其具有很大的比表面积，比表面积优选为1100-1200m2/g，其孔径为1.8-3.8nm，孔体积为0.7-1.2cm3/g。在0.2A/g的电流密度下，6mol/LKOH电解质溶液中电容量为554.5F/g，因此其具有很高的电化学电容量，在超级电容器领域有潜在的应用前景。且其制备方法简单易行、成本低、重复性好，易于规模化生产。
The invention discloses a nitrogen-doped mesoporous carbon sphere nano material with a large specific surface area and a preparation method thereof. That is, cationic surfactants are used as templates, organic silicon sources, organic carbon sources, and organic nitrogen sources are used to form organic/inorganic composites through hydrothermal reaction, and then roasted under nitrogen atmosphere to obtain silica/nitrogen-containing carbon spheres After removing silicon dioxide from nanomaterials, nitrogen-doped mesoporous carbon nanomaterials with spherical mesoporous structure can be obtained, which has a large specific surface area, preferably 1100-1200m 2 /g, and a pore diameter of 1.8-3.8nm , the pore volume is 0.7-1.2 cm 3 /g. At a current density of 0.2A/g, the capacitance in 6mol/L KOH electrolyte solution is 554.5F/g, so it has a high electrochemical capacitance and has potential application prospects in the field of supercapacitors. Moreover, the preparation method is simple and easy, low in cost, good in repeatability, and easy in large-scale production.
Description
Technical field
The present invention designs a kind of N doping mesoporous carbon spheres nano material and preparation method, belongs to field of inorganic nano material.
Background technology
The exploitation of new forms of energy becomes an important topic of the world today.In many Application Areass, more and more higher to the requirement of energy storage device, ultracapacitor is rapidly developed.The performance of ultracapacitor determines primarily of the electrode materials forming electrical condenser, and the electrode materials preparing high-specific capacitance super is the emphasis of ultracapacitor research.
The performance of carbon ball material display excellence in some applications, comprises ultracapacitor, fuel cell, solar cell, lithium ion battery, CO
2collect, heavy metal adsorption, photochemical catalysis and bio-pharmaceuticals.Study Heteroatom doping carbon material such as N, S and B simultaneously and play important role, because they can change the surface chemical property of electronics and crystalline structure and carbon main body at decision carbon aspect of performance.Such as, doping nitrogen enhances the catalytic activity of electroconductibility, alkalescence, oxidative stability and carbon in the skeleton of carbon, makes nitrogen-doped carbon at support of the catalyst, CO
2absorption, particularly there is potential application prospect ultracapacitor aspect.
Li etc. prepare N doping meso-porous carbon material, they by use trimeric cyanamide as nitrogenous source, two dimension graphene carbon structure as conductive substrates, in order to improve the performance of nitrogen-doped carbon material.Compare with simple mesoporous carbon, the nitrogen-doped carbon/Graphene electrodes material of preparation represents suitable pore size distribution, ordered mesopore structure, the doping of adjustable nitrogen.The character of these uniquenesses makes its electrode materials as ultracapacitor have excellent performance.Especially, N doping and graphene modified electrode achieve 238 and 289F/g, are in the three-electrode system of 0.2A/g in current density, and under equal conditions, electrical capacity is 2 times that do not have doped meso-porous carbon ball to the mesoporous carbon of N doping.Symmetrical twin electrodes shows that high content nitrogen doping carbon electrode provides outstanding high rate during charging-discharging and superior cyclical stability.（Li M, Xue J. Integrated synthesis of nitrogen-doped mesoporous carbon from melamine resins with superior performance in supercapacitors[J]. The Journal of Physical Chemistry C, 2014, 118(5): 2507-2517.）
Xu etc. propose a simple method and prepare porous carbon nanometer ball, gather difluoroethylene by using business-like spherical PVDF() as presoma.By the defluorinate of organic bases low temperature, then pass through high temperature cabonization.PVDF nanometer ball is converted into porous carbon nanometer ball simply.The carbon ball prepared shows good monodispersity, and specific surface area is 523m
2/ g.This N doping material has 190F/g to have good heavy-current discharge .(Xu B in the ionogen of 6mol/L KOH, Yue S, Qiao N, et al. Easy preparation of nitrogen-doped porous carbon nanospheres and their application in supercapacitors [J]. Materials Letters, 2014,131:49-52.)
Wei etc. prepare the N doping ordered mesopore carbon (NMC) of high nitrogen content by the method for evaporation-induced self-assembly, wherein use Dyhard RU 100 as nitrogenous source.In this synthesis, resol resin can connect F127 template and Dyhard RU 100 by hydrogen bond and electrostatic interaction.Form resol carbonization decomposition at 600 DEG C subsequently at 100 DEG C, Dyhard RU 100 provides nitrogenous source and resol provides stable carbon skeleton, and therefore, assure success synthesizing ordered N doping mesoporous carbon.This N doping ordered mesopore carbon has adjustable meso-hole structure and aperture size, high specific surface area and high nitrogen content.Be 262F/g under sulfuric acid medium, be 227F/g under NaOH medium.Show as the good performance of electrode of super capacitor.（Wei J, Zhou D, Sun Z, et al. A Controllable Synthesis of Rich Nitrogen‐Doped Ordered Mesoporous Carbon for CO
2Capture and Supercapacitors[J]. Advanced Functional Materials, 2013, 23(18): 2322-2328.）
Li Zhiguos etc. adopt one-step synthesis method to have unique morphology structure, nitrogen-doped carbon material that nitrogen content is higher, but due to its specific surface area too little, be not too applicable to the electrode materials of ultracapacitor.(Li Zhiguo, Chen Xiujuan, Li Xiaoli. nitrogen-doped carbon material and preparation method thereof: China, CN103130206A [P] .2013-06-05)
In sum, in the carbon material prepared, the content of nitrogen and specific surface area size are the principal elements determining its chemical property, can not obtain having bigger serface at present, the nitrogen-doped carbon material of high nitrogen content simultaneously.Specific surface area can be made to increase by the method for activated carbon material, but nitrogen content contained in carbon material will reduce, the specific surface area of current nitrogen-doped carbon material is 400-1000m
2/ g, nitrogen content is 0.5-3%, thus have impact on the chemical property of electrode materials.The report that the carbon ball simultaneously with more high nitrogen doped amount and high-specific surface area does not also have document and patent to carry out being correlated with and open.
Summary of the invention
The object of the invention is to that specific surface area in order to solve above-mentioned nitrogen-doped carbon material is too small, nitrogen content is lower is not too applicable to the technical problems such as the electrode materials of ultracapacitor and provides a kind of preparation method of N doping mesoporous carbon spheres nano material, the nitrogen-doped carbon material of the final gained of this preparation method has high nitrogen content and the advantage such as specific surface area is large.
Know-why of the present invention
In the process preparing nitrogen-doped carbon ball, add inorganic precursor in advance, when removing inorganics again after formation carbon ball, thus increasing the specific surface area of carbon ball, increasing the electrical capacity of nitrogen-doped carbon ball further.Introduce particularly: be namely template with cats product, at temperature 30 ~ 100 DEG C, between solvent and organic carbon source, form emulsion droplets by hydrogen bonded; Outside in emulsion droplets, by the katalysis of alkaline matter, organosilicon source and organic nitrogen source and organic carbon source polymerization form colloidal spheres.Subsequently, product hydro-thermal reaction obtained in a nitrogen atmosphere control temperature carries out high-temperature roasting between 600 ~ 1000 DEG C, obtains silicon-dioxide/nitrogenous carbon ball nano material; Then silicon-dioxide/nitrogenous carbon ball nano material mixes with 2M aqueous sodium hydroxide solution, stirring reaction 2 ~ 12h, dry after centrifugation, obtains N doping mesoporous carbon spheres nano material.
Technical scheme of the present invention
A preparation method for N doping mesoporous carbon spheres nano material, specifically comprises the steps:
(1), in a solvent, take cats product as template, utilize organosilicon source and organic nitrogen source and organic carbon source as organic precursor, in the presence of alkaline substances, control temperature is 30 ~ 100 DEG C and carries out reaction 48h, the reacting liquid filtering of gained, gained filter cake is dried at 80 DEG C, obtains organic/inorganic composite;
Described solvent is deionized water, dehydrated alcohol or methyl alcohol;
Described cats product is the mixture of one or both compositions in myristyl benzyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, stearyl dimethyl benzyl ammonium chloride;
Described organic carbon source is the mixture of Resorcinol and formaldehyde or the mixture of furfuryl alcohol and formaldehyde;
Described organosilicon source is the mixture of one or more compositions in positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four butyl ester;
Described organic nitrogen source is the mixture of one or more compositions in trimeric cyanamide, Dyhard RU 100, pyrroles, acetonitrile;
Described alkaline matter is the mixture of one or more compositions in sodium hydroxide, potassium hydroxide, sodium carbonate, ammoniacal liquor;
The consumption of above-mentioned cats product, alkaline matter, organic carbon source, organosilicon source, organic nitrogen source and solvent; calculate in mass ratio, i.e. cats product: alkaline matter: organic carbon source: organosilicon source: organic nitrogen source: solvent is that the ratio of 1:0.2-10:0.2-10:0.2-10:0.1-30:20-120 calculates;
(2), the organic/inorganic composite of step (1) gained being controlled in a nitrogen atmosphere temperature rise rate is that 1 DEG C/min is warming up to 600 ~ 1000 DEG C and carries out high-temperature roasting 6 ~ 20h with decationize tensio-active agent, then naturally cool to room temperature, obtain silicon-dioxide/nitrogenous carbon ball nano material;
(3), by step (2) obtain the aqueous sodium hydroxide solution that silicon-dioxide/nitrogenous carbon ball nano material is 2M with concentration and mix; stirring reaction 2 ~ 12h; the reaction solution centrifugation of gained; the precipitation control temperature of gained is 80 DEG C and carries out drying, obtains N doping mesoporous carbon spheres nano material;
Above-mentioned silicon-dioxide/nitrogenous carbon ball nano material and concentration are the consumption of the aqueous sodium hydroxide solution of 2M, in silicon-dioxide/nitrogenous carbon ball nano material: concentration be 2M aqueous sodium hydroxide solution be 1g:20-140ml ratio calculate.
The N doping mesoporous carbon spheres of above-mentioned gained belongs to meso-hole structure, and its aperture is about 1.8-3.8nm, and specific surface area is comparatively large, about 1054-1200m
2/ g, is preferably 1100-1200 m
2/ g, pore volume is 0.7-1.2cm
3/ g.This N doping meso-porous carbon material is under the current density of 0.2A/g, and in 6mol/L KOH ionogen, electrical capacity is 328.6-554.5F/g.Results of elemental analyses shows, in N doping mesoporous carbon spheres nano material of the present invention, calculates by mass percentage, and the content of nitrogen is 2-5.5%, is preferably 3.16-5.15%.
Beneficial effect of the present invention
The preparation method of a kind of N doping mesoporous carbon spheres nano material of the present invention, due to by original position soft/hard template method combine method, utilize nitrogenous source and carbon source to react, pass through N
2calcining under atmosphere obtains nitrogenous carbon ball, then removes SiO
2template, namely obtains the nitrogenous mesoporous carbon spheres of relatively large specific surface area.The feature in this larger specific surface area of N doping mesoporous carbon spheres, pore volume and aperture, is conducive to the migration improving electrochemical process intermediate ion/electronics, thus has potential application prospect in ultracapacitor field.
Further, the preparation method of a kind of N doping mesoporous carbon spheres nano material of the present invention, owing to using hydrothermal method preparation, therefore have low production cost, preparation process is simple to operate, controlled, is applicable to the features such as scale operation.
Accompanying drawing explanation
The scanning electron microscope collection of illustrative plates of Fig. 1, embodiment 1 gained N doping mesoporous carbon spheres nano material;
The little angle XRD figure of Fig. 2, embodiment 1 gained N doping mesoporous carbon spheres nano material;
Nitrogen adsorption-desorption curve the figure of Fig. 3, embodiment 1 gained N doping mesoporous carbon spheres nano material;
The graph of pore diameter distribution of Fig. 4, embodiment 1 gained N doping mesoporous carbon spheres nano material;
The cyclic voltammogram of Fig. 5, embodiment 1 gained N doping mesoporous carbon spheres nano material;
The constant current charge-discharge figure of Fig. 6, embodiment 1 gained N doping mesoporous carbon spheres nano material.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth below by way of specific embodiment, but the present invention is not limited to following examples.
In various embodiments of the present invention, raw materials used equal can purchase from open commercial sources obtains.
The model of the instrument that various embodiments of the present invention are used or equipment and the information of manufacturer as follows:
Air dry oven, model DHG-9920A, manufacturer: Shanghai one is permanent;
Tube furnace, model SL1700 II type, manufacturer: Shanghai Sheng Li testing tool company limited;
X-ray diffractometer (XRD), PANalytical company of X PERT PRO Holland;
Scanning electronic microscope (SEM), S-3400N HIT;
Full-automatic physical Sorption Analyzer, Merck & Co., Inc of the ASAP2020 U.S.;
Elemental analyser, Thermo Flash 2000 Thermo Electron Corp.;
Electrochemical workstation, CHI660E Shanghai Chen Hua Instrument Ltd.;
embodiment 1
A preparation method for N doping mesoporous carbon spheres nano material, specifically comprises the steps:
(1), 0.3g cats product is scattered in 6g solvent, at room temperature stir 5min, add 0.06g alkaline matter to stir, add 0.06g organosilicon source, 0.06g organic carbon source and 0.06g organic nitrogen source successively, control temperature is 30 DEG C, carries out reaction 48h under agitation condition, the reacting liquid filtering of gained, the filter cake of gained dries 12h at 80 DEG C, obtains organic/inorganic composite;
Described solvent is deionized water;
Described alkaline matter is sodium hydroxide;
Described cats product is cetyl trimethylammonium bromide;
Described organic carbon source be Resorcinol with formaldehyde in mass ratio for 1:4 carries out mixing the mixture of gained;
Described organosilicon source is positive quanmethyl silicate;
Described organonitrogen is trimeric cyanamide;
The amount of cats product used, alkaline matter, organic carbon source, organosilicon source, organic nitrogen source and solvent, calculate in mass ratio, i.e. cats product: alkaline matter: organic carbon source: organosilicon source: organic nitrogen source: solvent is 1:0.2:0.2:0.2:0.2:20;
(2), the organic/inorganic composite of step (1) gained is put into tube furnace, controlling temperature rise rate is in a nitrogen atmosphere that 1 DEG C/min is warming up to 600 DEG C and carries out high-temperature roasting 20h with decationize tensio-active agent, then naturally cool to room temperature, obtain silicon-dioxide/nitrogenous carbon ball nano material;
(3), by 1g step (2) obtain the aqueous sodium hydroxide solution that silicon-dioxide/nitrogenous carbon ball nano material is 2M with 20ml concentration and mix, stirring reaction 2h, it is that 6000r/min carries out centrifugation that the reaction solution of gained controls rotating speed, the precipitation control temperature of gained is 80 DEG C and carries out dry 12h, obtains N doping mesoporous carbon spheres nano material;
Above-mentioned silicon-dioxide/nitrogenous carbon ball nano material and concentration are the consumption of the aqueous sodium hydroxide solution of 2M, in silicon-dioxide/nitrogenous carbon ball nano material: the ratio of concentration to be the aqueous sodium hydroxide solution of 2M be 1g:20ml calculates.
The N doping mesoporous carbon spheres nano material of scanning electronic microscope to above-mentioned gained is adopted to observe, the scanning electron microscope (SEM) photograph of the N doping mesoporous carbon spheres nano material of gained as shown in Figure 1, as can be drawn from Figure 1, the grain size of the N doping mesoporous carbon spheres nano material of above-mentioned gained is at about 180nm, regular appearance, spherical in shape;
The N doping mesoporous carbon spheres nano material of x-ray diffractometer to above-mentioned gained is adopted to measure, the little angle XRD figure of the N doping mesoporous carbon spheres nano material of gained as shown in Figure 2, as can be seen from Figure 2, there is certain diffraction peak, illustrate that the N doping mesoporous carbon spheres nano material of gained has ordered mesopore structure.
Full-automatic physical Sorption Analyzer is adopted to measure the specific surface area of the N doping mesoporous carbon spheres nano material of above-mentioned gained, pore volume and aperture situation, in mensuration process, by N doping mesoporous carbon spheres nano material degassed 10h at 200 DEG C, test under liquid nitrogen (-196 DEG C) constant temperature, nitrogen adsorption-desorption curve the figure of gained as shown in Figure 3, as can be seen from the nitrogen adsorption-desorption curve figure of Fig. 3, the N doping mesoporous carbon spheres nano material of gained of the present invention has larger specific surface area, is about 1065.13m
2/ g, pore volume are about 0.84cm
3/ g.
Adopt the pore size distribution situation of Full-automatic physical Sorption Analyzer to the N doping mesoporous carbon spheres nano material of above-mentioned gained to test, as shown in Figure 4, as can be seen from Figure 4, aperture is about 2.0nm to result.
Adopt the N doping mesoporous carbon spheres nano material of elemental analyser to above-mentioned gained to analyze, result shows, in N doping mesoporous carbon spheres nano material, to calculate by mass percentage, and the content of nitrogen is 2.32%.
Adopt electrochemical workstation, it is 25 DEG C in room temperature, do electrode with platinum electrode, mercurous chloride electrode is reference electrode, and ionogen is the KOH solution of 6mol/L, measures the cyclical stability of the N doping mesoporous carbon spheres nano material of above-mentioned gained and constant current charge-discharge performance, the cyclic voltammogram of gained as shown in Figure 5, as can be seen from Figure 5, the N doping mesoporous carbon spheres nano material of gained of the present invention has the cyclic curve of similar rectangular shape, and the electric capacity response of double layer capacitor is described.
As shown in Figure 6, as can be seen from Figure 6, obtain electrical capacity under the current density of 0.2A/g in the N doping mesoporous carbon spheres nano material charge and discharge process of gained of the present invention, in 6mol/L KOH ionogen, electrical capacity is 328.6F/g to the constant current charge-discharge figure of gained.
embodiment 2
A preparation method for N doping mesoporous carbon spheres nano material, specifically comprises the steps:
(1), the cats product of 0.3g is scattered in 21g solvent, at room temperature stir 5min, add 1.5g alkaline matter to stir, add 1.5g organosilicon source, 1.5g organic carbon source and 1.5g organic nitrogen source successively to stir, control temperature is 50 DEG C and carries out reaction 48h, the reacting liquid filtering of gained, the filter cake of gained dries 12h at 80 DEG C, obtains organic/inorganic composite;
Described solvent is deionized water;
Described alkaline matter is potassium hydroxide;
Described cats product is myristyl benzyl dimethyl ammonium chloride;
Described organic carbon source is that furfuryl alcohol and formaldehyde calculate in mass ratio, i.e. furfuryl alcohol: formaldehyde is the mixture of 1:4 composition;
Described organosilicon source is tetraethyl orthosilicate;
Described organic nitrogen source is Dyhard RU 100;
The amount of cats product used, alkaline matter, organic carbon source, organosilicon source, organic nitrogen source and solvent; calculate in mass ratio, i.e. cats product: alkaline matter: organic carbon source: organosilicon source: organic nitrogen source: solvent is 1:5:5:5:5:70;
(2), the organic/inorganic composite of step (1) gained is put into tube furnace, controlling temperature rise rate is in a nitrogen atmosphere that 1 DEG C/min is warming up to 700 DEG C and carries out high-temperature roasting 10h with decationize tensio-active agent, then naturally cool to room temperature, obtain silicon-dioxide/nitrogenous carbon ball nano material;
(3), by 1g step (2) obtain the aqueous sodium hydroxide solution that silicon-dioxide/nitrogenous carbon ball nano material is 2M with 40ml concentration and mix; 8h is stirred in reaction; it is that 6000r/min carries out centrifugation that the reaction solution of gained controls rotating speed; the precipitation control temperature of gained is 80 DEG C and carries out dry 12h, obtains N doping mesoporous carbon spheres nano material;
Above-mentioned silicon-dioxide/nitrogenous carbon ball nano material and concentration are the consumption of the aqueous sodium hydroxide solution of 2M, in silicon-dioxide/nitrogenous carbon ball nano material: the ratio of concentration to be the aqueous sodium hydroxide solution of 2M be 1g:40ml calculates.
Adopt Full-automatic physical Sorption Analyzer to measure the specific surface area of the N doping mesoporous carbon spheres nano material of above-mentioned gained, pore volume and aperture situation, after measured, its aperture is at about 1.8nm, and specific surface area is about 1100m
2/ g, pore volume is 0.7cm
3/ g.
Adopt the N doping mesoporous carbon spheres nano material of elemental analyser to above-mentioned gained to analyze, result shows, in N doping mesoporous carbon spheres nano material, to calculate by mass percentage, and the content of nitrogen is 3.16%.
Electrochemical workstation is adopted to measure the cyclical stability of the N doping mesoporous carbon spheres nano material of above-mentioned gained and constant current charge-discharge performance, the N doping mesoporous carbon spheres nano material of gained of the present invention has the cyclic curve of similar rectangular shape, and the electric capacity response of double layer capacitor is described.Obtain electrical capacity under the current density of 0.2A/g in the N doping mesoporous carbon spheres nano material charge and discharge process of gained of the present invention, in 6mol/L KOH ionogen, electrical capacity is 428.6 F/g.
embodiment 3
A preparation method for N doping mesoporous carbon spheres nano material, specifically comprises the steps:
(1), 0.3g cats product is scattered in 24g solvent, at room temperature stir 5min, add 2.4g alkaline matter to stir, add 2.4g organosilicon source, 2.4g organic carbon source successively and 2.4g is organic stirs, control temperature is 80 DEG C and carries out reaction 48h, the reacting liquid filtering of gained, the filter cake of gained dries 12h at 80 DEG C, obtains organic/inorganic composite;
Described solvent is deionized water;
Described alkaline matter to be mass percent concentration be 25% ammoniacal liquor;
Described cats product is stearyl dimethyl benzyl ammonium chloride;
Described organic carbon source is that furfuryl alcohol and formaldehyde calculate in mass ratio, i.e. furfuryl alcohol: formaldehyde is the mixture of 1:4 composition;
Described organosilicon source is positive silicic acid orthocarbonate;
Described organic nitrogen source is pyrroles;
The amount of cats product used, alkaline matter, organic carbon source, organosilicon source, organic nitrogen source and solvent; calculate in mass ratio, i.e. cats product: alkaline matter: organic carbon source: organosilicon source: organic nitrogen source: solvent is 1:8:8:8:8:80;
(2), the organic/inorganic composite of step (1) gained is put into tube furnace, controlling temperature rise rate is in a nitrogen atmosphere that 1 DEG C/min is warming up to 800 DEG C and carries out high-temperature roasting 16h with decationize tensio-active agent, then naturally cool to room temperature, obtain silicon-dioxide/nitrogenous carbon ball nano material;
(3), by 1g step (2) obtain the aqueous sodium hydroxide solution that silicon-dioxide/nitrogenous carbon ball nano material is 2M with 80ml concentration and mix; stirring reaction 6h; it is that 6000r/min carries out centrifugation that the reaction solution of gained controls rotating speed; the precipitation control temperature of gained is 80 DEG C and carries out dry 12h, obtains N doping mesoporous carbon spheres nano material;
Above-mentioned silicon-dioxide/nitrogenous carbon ball nano material and concentration are the consumption of the aqueous sodium hydroxide solution of 2M, in silicon-dioxide/nitrogenous carbon ball nano material: the ratio of concentration to be the aqueous sodium hydroxide solution of 2M be 1g:80ml calculates.
Adopt Full-automatic physical Sorption Analyzer to measure the specific surface area of the N doping mesoporous carbon spheres nano material of above-mentioned gained, pore volume and aperture situation, after measured, its aperture is at about 3.8nm, and specific surface area is about 1200m
2/ g, pore volume is 1.2cm
3/ g.
Adopt the N doping mesoporous carbon spheres nano material of elemental analyser to above-mentioned gained to analyze, result shows, in N doping mesoporous carbon spheres nano material, to calculate by mass percentage, and the content of nitrogen is 5.15%.
Electrochemical workstation is adopted to measure the cyclical stability of the N doping mesoporous carbon spheres nano material of above-mentioned gained and constant current charge-discharge performance, result shows, the N doping mesoporous carbon spheres nano material of gained of the present invention has the cyclic curve of similar rectangular shape, and the electric capacity response of double layer capacitor is described; Obtain electrical capacity under the current density of 0.2A/g in the N doping mesoporous carbon spheres nano material charge and discharge process of gained of the present invention, in 6mol/L KOH ionogen, electrical capacity is 554.5F/g.
embodiment 4
A preparation method for N doping mesoporous carbon spheres nano material, specifically comprises the steps:
(1), 0.3g cats product is scattered in 36g solvent, at room temperature stir 5min, add 3g alkaline matter to stir, add 3g organosilicon source, 3g organic carbon source and 3g organic nitrogen source successively to stir, control temperature is 100 DEG C and carries out reaction 48h, the reaction solution of gained is centrifugal, filtration, and the filter cake of gained dries 12h at 80 DEG C, obtains organic/inorganic composite;
Described solvent is deionized water;
Described alkaline matter is sodium carbonate;
Described cats product is palmityl trimethyl ammonium chloride;
Described organic carbon source is that furfuryl alcohol and formaldehyde calculate in mass ratio, i.e. furfuryl alcohol: formaldehyde is the mixture of 1:4 composition;
Described organosilicon source is positive silicic acid four butyl ester;
Described organic nitrogen source is acetonitrile;
The amount of cats product used, alkaline matter, organic carbon source, organosilicon source, organic nitrogen source and solvent; calculate in mass ratio, i.e. cats product: alkaline matter: organic carbon source: organosilicon source: organic nitrogen source: solvent is 1:10:10:10:10:120;
(2), the organic/inorganic composite of step (1) gained is put into tube furnace, controlling temperature rise rate is in a nitrogen atmosphere that 1 DEG C/min is warming up to 1000 DEG C and carries out high-temperature roasting 6h with decationize tensio-active agent, then naturally cool to room temperature, obtain silicon-dioxide/nitrogenous carbon ball nano material;
(3), by 1g step (2) obtain the aqueous sodium hydroxide solution that silicon-dioxide/nitrogenous carbon ball nano material is 2M with 140ml concentration and mix; stirring reaction 24h; it is that 6000r/min carries out centrifugation that the reaction solution of gained controls rotating speed; the precipitation control temperature of gained is 80 DEG C and carries out dry 12h, obtains N doping mesoporous carbon spheres nano material;
Above-mentioned silicon-dioxide/nitrogenous carbon ball nano material and concentration are the consumption of the aqueous sodium hydroxide solution of 2M, in silicon-dioxide/nitrogenous carbon ball nano material: concentration is that the ratio of the aqueous sodium hydroxide solution 1g:140ml of 2M calculates.
After measured, its pore size distribution is at about 2.8nm, and specific surface area is about 1054m for the mesoporous carbon spheres/Manganse Dioxide composite nano materials of above-mentioned gained
2/ g, pore volume is 0.98cm
3/ g.
Adopt the N doping mesoporous carbon spheres nano material of elemental analyser to above-mentioned gained to analyze, result shows, in N doping mesoporous carbon spheres nano material, to calculate by mass percentage, and the content of nitrogen is 2.85%.
Electrochemical workstation is adopted to measure the cyclical stability of the N doping mesoporous carbon spheres nano material of above-mentioned gained and constant current charge-discharge performance, result shows, the above-mentioned N doping mesoporous carbon spheres nano material obtained of the present invention has the cyclic curve of similar rectangular shape, and the electric capacity response of double layer capacitor is described; Obtain under the current density of 0.2A/g in the N doping mesoporous carbon spheres nano material charge and discharge process of above-mentioned gained, in 6mol/L KOH ionogen, electrical capacity is 404.5F/g.
In sum, N doping mesoporous carbon spheres nano material of the present invention is spherical morphology, has meso-hole structure, and its aperture is about 1.8-3.8nm, and specific surface area is comparatively large, about 1054-1200m
2/ g, pore volume is 0.7-1.2cm
3/ g.It in the electrolytic solution, be conducive to the migration of electronics, the doping of nitrogen-atoms simultaneously adds the electrical capacity of N doping mesoporous carbon spheres nano material, and obtain it in charge and discharge process under the current density of 0.2A/g, in 6mol/L KOH ionogen, electrical capacity is 328.6-554.5F/g.Therefore, N doping mesoporous carbon spheres nano material of the present invention can as electrode materials, and it will have potential application prospect in ultracapacitor field.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification all should be considered as protection scope of the present invention.
Claims (7)
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