CN104909351A - Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof - Google Patents

Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof Download PDF

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CN104909351A
CN104909351A CN201510295239.0A CN201510295239A CN104909351A CN 104909351 A CN104909351 A CN 104909351A CN 201510295239 A CN201510295239 A CN 201510295239A CN 104909351 A CN104909351 A CN 104909351A
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organic
nano material
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cats product
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孙左松
沈绍典
周祖新
王根礼
毛东森
卢冠忠
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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

Abstract

The invention discloses a large-specific surface area nitrogen-doped mesoporous carbon sphere nanomaterial and a preparation method thereof. According to the preparation method, a cationic surfactant is taken as a template agent, a hydro-thermal reaction is performed on an organic silicon source, an organic carbon source and an organic nitrogen source to form an organic/inorganic composite, and then the organic/inorganic composite is roasted in a nitrogen atmosphere to obtain a silicon dioxide/nitrogenous carbon sphere nanomaterial, and removing silicon dioxide to obtain the nitrogen-doped mesoporous carbon sphere nanomaterial of a spherical mesoporous structure; the nitrogen-doped mesoporous carbon sphere nanomaterial has a large specific surface area, and preferably, the specific surface area is within the range of 1100-1200m<2>/g; and the pore size of the nanomaterial is within the range of 1.8-3.8, and the pore volume is within the range of 0.7-1.2cm<3>/g. Under the current density of 0.2A/g, the capacitance of the nanomaterial in a 6mol/L KOH electrolyte solution is 554.5F/g, and therefore, the nanomaterial has extremely high electrochemical capacitance and has a potential application prospect in the field of super capacitors. The preparation method is simple and easy to implement, low in cost, good in repeatability, and prone to large-scale production.

Description

A kind of N doping mesoporous carbon spheres nano material and preparation method thereof
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)

1. a preparation method for N doping mesoporous carbon spheres nano material, is characterized in that specifically comprising the steps:
(1), in a solvent, take cats product as template, organic carbon source, organic nitrogen source are as carbon source, nitrogenous source, in the presence of alkaline substances, control temperature is 30 ~ 100 DEG C and carries out reaction 48h, the reaction solution of gained is centrifugal, and the filter cake of gained 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), by the organic/inorganic composite of step (1) gained controlling temperature rise rate is in a nitrogen atmosphere that 1 DEG C/min is warming up to 600 ~ 1000 DEG C and carries out high-temperature roasting 6 ~ 20h, then naturally cools to room temperature, obtains 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: the ratio of concentration to be the aqueous sodium hydroxide solution of 2M be 1g:20-140ml calculates.
2. the preparation method of a kind of N doping mesoporous carbon spheres nano material as claimed in claim 1, is characterized in that in step (1):
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 organic nitrogen source 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.
3. the preparation method of a kind of N doping mesoporous carbon spheres nano material as claimed in claim 1, is characterized in that in step (1):
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.
4. the preparation method of a kind of N doping mesoporous carbon spheres nano material as claimed in claim 1, is characterized in that in step (1):
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.
5. the preparation method of a kind of N doping mesoporous carbon spheres nano material as claimed in claim 1, is characterized in that in step (1):
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.
6. a kind of N doping mesoporous carbon spheres nano material of obtaining of preparation method as claimed in claim 1, be spherical mesoporous structure, aperture is 1.8-3.8nm, and specific surface area is 1054-1200m 2/ g, pore volume is 0.7-1.2cm 3/ g, calculates by mass percentage, and the content of nitrogen is 2-5.5%.
7. a kind of N doping mesoporous carbon spheres nano material of obtaining of preparation method as claimed in claim 1, be spherical mesoporous structure, aperture is 1.8-3.8nm, and specific surface area is 1100-1200m 2/ g, pore volume is 0.7-1.2cm 3/ g, calculates by mass percentage, and the content of nitrogen is 3.16-5.15%.
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