CN106960729A - A kind of preparation method of nitrogen sulphur codope carbon material - Google Patents
A kind of preparation method of nitrogen sulphur codope carbon material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
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Abstract
The invention discloses a kind of preparation method of nitrogen sulphur codope carbon material, following operating procedure is included：(1) copolymer of five-ring heterocycles containing ammonia nitrogen or hexa-member heterocycle copolymer are prepared：Ammonia nitrogen five member ring heterocyclic compound monomer will be contained and/or the monomer of 6-membered heterocyclic compound containing ammonia nitrogen is dissolved in solvent, initiator is added, reacted 2~12 hours under 0~10 DEG C of stirring condition, polymerization；(2) high-temperature process：Gained material filtering after step (1) is polymerize, dry, after resulting polymers solid abrasive under inert atmosphere protection, 600~1200 DEG C of high-temperature process 0.5~5 hour; it is cooled to room temperature; black powder is obtained, is then post-processed, that is, obtains nitrogen sulphur codope carbon material.The carbon material of nitrogen sulphur codope prepared by the present invention has technique simple, and nitrogen sulfur content is controllable, and specific surface area is big, the high advantage of specific capacitance, and its specific surface area reaches 1020m2/ g, pore-size distribution is mainly in 1 4nm.
Description
Technical field
The present invention relates to a kind of preparation method of codope carbon material, more particularly to a kind of system of nitrogen sulphur codope carbon material
Preparation Method.
Background technology
Ultracapacitor is a kind of novel energy storage apparatus, it have power density height, the short charging interval, long service life,
The features such as good temp characteristic, the saving energy and environmental protection.Develop a kind of energy density high, have good stability and technique is simple,
Electrode material for super capacitor with low cost is an urgent demand of new energy field development.Carbon material is led because of the excellent of its own
Electrically, the features such as high-specific surface area, rational pore-size distribution [Materials Horizons 2014,1,157-168], turn into
Most suitable electrode material for super capacitor.Graphene, CNT, porous carbon materials and its complex carbon material application it is equal
The technical problem of ultracapacitor is solved to a certain extent, is especially studied in the recent period in terms of Heteroatom doping carbon material
Constantly extension so that carbon material is more deep in the application of electrochemical field, and the research to carbon material foreign atom is mainly concentrated
In atoms such as nitrogen/sulphur/phosphorus/boron/oxygen, because the difference of electronegativity between foreign atom and carbon atom causes carbon material internal crystal framework
Defect, so as to produce electro-chemical activity site [Chem.Soc.Rev.2014,43,2841-2857], is introduced by foreign atom
The fake capacitance that brings of electro-chemical activity site increase the capacitance [J.Power Sources 2014,90-97] of material.It is miscellaneous
Atom doped carbon material has application widely in electrochemical fields such as hydrogen reduction, lithium-sulfur cell, ultracapacitors
[Adv.Mater.2012,24,5130-5135], wherein the research to nitrogen-doped carbon material is particularly deep.Nitrogen-atoms has than carbon
The more negative electronegativity of atom, and nitrogen carbon is located at the position closed in the periodic table of elements, the physicochemical properties ratio such as ionic radius
It is more close, so compared to other atoms during doping, nitrogen-atoms is easily accessible carbon skeleton, so, nitrating carbon material exists
The application of electrochemical field causes people's extensive concern, the especially application in terms of cathodic oxygen reduction catalyst, is to grind at present
The focus studied carefully.Meanwhile, there are some researches show, nitrating carbon material also have in ultracapacitor application well [Science,
2014,343,1210-1211], the doping of nitrogen-atoms can change the Cloud Distribution of carbon atom, increase carbon material and electrolyte
Wetability [Adv.Mater., 2012,24 of solution:5517-5641.], while the nitrogen-atoms that adulterates can increase as electron donor
Electric double layer area, increases the energy stores [CN102923088A, 2013-02-13] of capacitor, and compatibility is good
[Chem.Soc.Rev., 2012,41,797-828.], is a kind of very potential electrode material for super capacitor.It is wide at present
The nitrating carbon material of general application has nitrating activated carbon and nitrogen-doped graphene [Nano Lett., 2011,11 (6):2472-2477.].
In addition there are some researches show polyatom doping is compared with single atom doped carbon material, because of the cooperative effect between different hetero atoms, make
Obtaining it has more excellent chemical property [Carbon 2009,47,1576-1584], at present, polyatom codope carbon material
Using more widely there is nitrogen-sulphur, nitrogen-phosphorus, nitrogen-boron [ACS Nano, 2012,6,7084-7091] etc., nitrogen sulphur atom codope
Can be formed uniqueness electronic structure [CN105931855A, 2016-09-07], in the periodic table of elements, sulphur be located at nitrogen just under
Side, the doping that same sulphur atom enters carbon material also has certain advantage, and sulphur, which is successfully doped into after carbon material, can form length
N-S keys [Adv.Mater2008,120,373-376] this advantageously form new electro-chemical activity site.Surface nitrogen sulphur function
Faraday's reaction, which occurs, for group can increase the specific capacitance of material.Scientific worker is main for the research of Heteroatom doping carbon material
Focus on by different experimental methods or select different nitrogen, sulphur source introduces nitrogen, sulphur atom in the oxidation stone as substrate
In the carbon skeleton of black alkene, CNT, carbon nano-fiber, activated carbon etc., such doping way can utilize substrate carbon material
Excellent electric conductivity, big specific surface area, the advantages of, for example：Wu et al. [Adv.Mater 2012,24,5130-5135] will
The graphene of nitrogen-boron codope is applied on ultracapacitor, using PVA/H2SO4 gels as separator and electrolyte, than electricity
240F/g can be reached by holding, higher than the specific capacitance of pure Graphene electrodes.But the introducing of carbon material substrate can undoubtedly increase and be produced into
This, makes experimentation more cumbersome, the particularly disadvantageous industrialization in production.Huang et al. [Science 2015,350,1508] profits
The nitrogen-doped porous carbon material for designing synthesis with template has a superelevation specific capacitance 855F/g, but the preparation process of this method ratio
It is more complicated, it is necessary to CVD and template be introduced, while needing PFA as carbon source and nickel as catalyst.Although this method can be obtained
The specific capacitance of superelevation is obtained, but synthesis technique is excessively complicated, cost is of a relatively high, is not suitable for large-scale production.
The information for being disclosed in the background section is merely intended to understanding of the increase to the general background of the present invention, without answering
When the prior art for being considered as recognizing or implying the information structure in any form well known to persons skilled in the art.
The content of the invention
The present invention is in order to overcome the defect of prior art, and a kind of specific surface area of invention is high, specific capacitance is big and cyclical stability
Energy is good, the simple electrode material for super capacitor with low cost of skill, prepare in the prior art electrochemical capacitance material cost to overcome
The defects such as height, complex operation.
The present invention will contain five yuan of ammonia nitrogen first and 6-membered heterocyclic compound pyridines, miazines, triazines, pyroles are made
Applied for polymer monomer in terms of electrode material for super capacitor.From persulfate sulphur is also served as main initiator simultaneously
The carbon material that nitrogen sulphur codope is obtained after the sulphur source of doping, high-temperature calcination is applied to electrode material for super capacitor.The material is not
Only there is excellent chemical property, the specific capacitance value of superelevation, and do not have heavy metal pollution problem, it is cheap, it is easy to
Structure design freedom shape is high, is a kind of very excellent electrode material for super capacitor.
To achieve the above object, the technical scheme that the present invention is provided is as follows：
A kind of preparation method of nitrogen sulphur codope carbon material, includes following operating procedure：
(1) copolymer of five-ring heterocycles containing ammonia nitrogen or hexa-member heterocycle copolymer are prepared：Ammonia nitrogen five-ring heterocycles chemical combination will be contained
Thing monomer and/or the monomer of 6-membered heterocyclic compound containing ammonia nitrogen are dissolved in solvent, initiator are added, in 0~10 DEG C of stirring condition
Lower reaction 2~12 hours, polymerization；
(2) high-temperature process：Gained material is filtered, dried after step (1) is polymerize, lazy after resulting polymers solid abrasive
Property atmosphere protection under, 600~1200 DEG C of high-temperature process 0.5~5 hour are cooled to room temperature, obtain black powder, after then carrying out
Processing, that is, obtain nitrogen sulphur codope carbon material.
Wherein, the monomer of five member ring heterocyclic compound containing ammonia nitrogen described in step (1), 6-membered heterocyclic compound containing ammonia nitrogen
Monomer includes one kind in pyridines, miazines, triazines, purines, pyroles and its homologue containing five yuan of ammonia nitrogen and six
Membered heterocyclic compound.
Wherein, described pyridines are DAP, 3,4 diamino-pyridines, 2,3 diamino-pyridines, 4,4'- bis-
Amino -2,2'- bipyridyls, 4-aminopyridine；Described miazines is 2,4- di-amino-pyrimidines, 2,4,6- Triaminopyrimidines, 6-
Methyl -2,4- pyrimidinediamine, 2,4- di-amino-pyrimidine -5- nitriles, 4,5,6 Triaminopyrimidines, 4- aminopyrimidines, cytimidine, urine are phonetic
Pyridine, 2,3 diamino-pyridines；Described triazines are -6 phenyl of 2,4- diaminourea -1,3,5-triazines, 2,4- diaminourea -6- diformazans
Amino -1,3,5-triazines, the methyl isophthalic acid of 2,4- diaminourea -6,3,5- triazines, 4- diazanyls -6- (2- pyridines) -1,3,5-triazines -2-
Amine, 4,6-, tri- ammonia -1,3,5-triazines, 2,4- diamino-1,3,5-triazines, melamine, the triazine of 4- amino 1,3,5；Described
Purines are 2,6- diaminopurines, adenine, adenine, 6-benzyl aminopurine, guanine；Described pyroles are 1-
Amino-pyrroles, 2- amino-pyrroles, 3- amino-pyrroles, N- (2- amino-ethyls) pyrrolidines.
Wherein, the initiator described in step (1) is made up of or by main initiator mistake single main initiator persulfate
Sulfate and co initiator are according to mol ratio ratio 1~5:1 mixing composition；Described main initiator includes potassium peroxydisulfate, mistake
One kind in ammonium sulfate or sodium peroxydisulfate；Co initiator is the metal cation Fe with oxidisability3+、Co2+Or Cu2+In
One kind, or be one kind in potassium permanganate, nitric acid, hydrogen peroxide or potassium bichromate.
Wherein, the solvent described in step (1) is deionized water, alcohol, pyridine, dimethyl sulfoxide (DMSO), dimethylformamide, two
One or more kinds of mixtures in methylacetamide, monochloro methane, dichloromethane, chloroform or tetrachloromethane.
Wherein, the monomer of five member ring heterocyclic compound containing ammonia nitrogen or the chemical combination of hexa-member heterocycle containing ammonia nitrogen described in step (1)
The mol ratio of thing monomer and initiator is 1:1~1:10.
Wherein, reacted 4~6 hours under 5 DEG C of stirring conditions in step (1), polymerization.
Wherein, step (2) high temperature heat treatment temperature is 600~1000 DEG C, and described heat treatment heating rate is 1~10
DEG C/min, soaking time is 0.5-3 hours at high temperature.
Wherein, the post processing described in step (2) is mixed in the one or more of 0.5mol dilute sulfuric acid, nitric acid or hydrochloric acid
Close in acid and soak 4-8 hours, then rinsed well repeatedly with ethanol and deionized water.
The present invention, by the polymer formed containing five yuan of ammonia nitrogen and 6-membered heterocyclic compound monomer under initiator effect,
Pattern is uniform spherical, and many micropores are formed after high temperature cabonization, the specific surface area of carbon material are drastically increased, so
The electric capacity storage of material can be increased.Further, since the codope of nitrogen sulphur is acted in the carbon material, it is that carbon material brings counterfeit electricity
Hold, further increase the specific capacitance value of carbon material.
Compared with prior art, the present invention has the advantages that：
The carbon material of nitrogen sulphur codope prepared by the present invention has technique simple, and nitrogen sulfur content is controllable, and specific surface area is big, than
The high advantage of electric capacity, its specific surface area reaches 1020m2/ g, pore-size distribution is mainly in 1-4nm.The 1A/g in 6mol/L KOH solution
When specific capacitance value>The conservation rate of its capacitance is 93% after 250F/g, the circle of cycle charge-discharge 10000, shows as good circulation
Service life, and the preparation method technique shown in the present invention is simple, requires low to experimental facilities, is adapted to put into super electricity conscientiously
In the production of container electrode material industry metaplasia.
Brief description of the drawings
Fig. 1 embodiment of the present invention 1 prepares the XRD spectrum of gained nitrogen sulphur codope carbon material.
Fig. 2 embodiment of the present invention 1 prepares the HAADF-STEM photos of gained-nitrogen sulphur codope carbon material.
Fig. 3 embodiment of the present invention 1 prepares the stereoscan photograph of gained nitrogen sulphur codope carbon material.
Fig. 4 embodiment of the present invention 1 prepares the graph of pore diameter distribution of gained nitrogen sulphur codope carbon material
The preparation gained nitrogen sulphur codope carbon material of Fig. 5 embodiment of the present invention 1 is in 6.0MKOH solution under different scanning rates
Cyclic voltammetry curve.
The preparation gained nitrogen sulphur codope carbon material of Fig. 6 embodiment of the present invention 3 is in 6.0MKOH solution under different scanning rates
Constant current charge-discharge curve.
Fig. 7 embodiment of the present invention 1 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different scanning rates in solution
Under cyclic voltammetry curve.
Fig. 8 embodiment of the present invention 1 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different scanning rates in solution
Under constant current charge-discharge curve.
Fig. 9 embodiment of the present invention 2 prepares the scanning electron microscopic picture of gained nitrogen sulphur codope carbon material
Figure 10 embodiment of the present invention 1 prepares gained nitrogen sulphur codope carbon material different scanning rates in 6.0MKOH solution
Under cyclic voltammetry curve.
Figure 11 embodiment of the present invention 1 prepares gained nitrogen sulphur codope carbon material different current densities in 6.0MKOH solution
Under constant current charge-discharge curve.
Figure 12 embodiment of the present invention 2 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different scanning rates in solution
Under cyclic voltammetry curve.
Figure 13 embodiment of the present invention 2 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different current densities in solution
Under constant current charge-discharge curve.
Figure 14 embodiment of the present invention 3 prepares the scanning electron microscopic picture of gained nitrogen sulphur codope carbon material
Figure 15 embodiment of the present invention 3 prepares gained nitrogen sulphur codope carbon material different current densities in 6.0MKOH solution
Under cyclic voltammetry curve.
Figure 16 embodiment of the present invention 3 prepares gained nitrogen sulphur codope carbon material different scanning rates in 6.0MKOH solution
Under constant current charge-discharge curve.
The preparation gained nitrogen sulphur codope carbon material of Figure 17 embodiment of the present invention 3 is in 1.0M solution under different current densities
Cyclic voltammetry curve.
Figure 18 embodiment of the present invention 3 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different scanning rates in solution
Under constant current charge-discharge curve.
Figure 19 embodiment of the present invention 4 prepares the scanning electron microscopic picture of gained nitrogen sulphur codope carbon material.
Figure 20 embodiment of the present invention 4 prepares gained nitrogen sulphur codope carbon material different scanning rates in 6.0MKOH solution
Under cyclic voltammetry curve.
Figure 21 embodiment of the present invention 4 prepares gained nitrogen sulphur codope carbon material different current densities in 6.0MKOH solution
Under constant current charge-discharge curve.
Figure 22 embodiment of the present invention 4 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different scanning rates in solution
Under cyclic voltammetry curve.
Figure 23 embodiment of the present invention 4 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different current densities in solution
Under constant current charge-discharge curve.
Figure 24 embodiment of the present invention 5 prepares gained nitrogen sulphur codope carbon material different scanning rates in 6.0MKOH solution
Under cyclic voltammetry curve.
Figure 25 embodiment of the present invention 5 prepares gained nitrogen sulphur codope carbon material different current densities in 6.0MKOH solution
Under constant current charge-discharge curve.
Figure 26 embodiment of the present invention 5 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different scanning rates in solution
Under cyclic voltammetry curve.
Figure 27 embodiment of the present invention 5 prepares gained nitrogen sulphur codope carbon material in 1.0MH2SO4Different current densities in solution
Under constant current charge-discharge curve.
Embodiment
Embodiment is described in detail below in conjunction with the accompanying drawings, it is to be understood that protection scope of the present invention not by
The limitation of embodiment.
Embodiment 1
A kind of preparation method of nitrogen sulphur codope carbon material, operating procedure is as follows：
(1) copolymer of hexa-member heterocycle containing ammonia nitrogen is prepared：Weigh the diamino-pyridines of 2g 2,6 (i.e. 0.0183mol) in
In 200ml deionized waters, magnetic agitation adds 4.17g ammonium persulfates (i.e. 0.0183mol), in 0 DEG C of stirring condition to after dissolving
Lower reaction 2 hours, polymerization forms atropurpureus sediment；
(2) high-temperature process：By the sediment ethanol and deionization of acquisition after gained material suction filtration after step (1) is polymerize
Water is cleaned for several times repeatedly, is then dried 8 hours at 60 DEG C of vacuum drying chamber, resulting polymers solid is fully ground with mortar
Afterwards, in nitrogen atmosphere protection down enters tube furnace, heated with 2 DEG C/min heating rates, at 800 DEG C at high-temperature calcination
Reason 1 hour, naturally cools to room temperature, obtains black powder, is then soaked 4 hours in 0.5mol dilute sulfuric acid, then uses second
Alcohol and deionized water are rinsed well repeatedly, as the carbon material of nitrogen sulphur codope.
Embodiment 2
A kind of preparation method of nitrogen sulphur codope carbon material, operating procedure is as follows：
(1) copolymer of hexa-member heterocycle containing ammonia nitrogen is prepared：Weigh the diamino-pyridines of 1g 2,6 (i.e. 0.00915mol) in
In 200ml deionized waters, magnetic agitation adds 5.21g ammonium persulfates (i.e. 0.022875mol) and 3.71g is anhydrous to after dissolving
Ferric trichloride (i.e. 0.022875mol), reacts 4 hours under 2 DEG C of stirring conditions, and polymerization forms black precipitate；
(2) high-temperature process：By the sediment ethanol and deionization of acquisition after gained material suction filtration after step (1) is polymerize
Water is cleaned for several times repeatedly, is then dried 8 hours at 60 DEG C of vacuum drying chamber, resulting polymers solid is fully ground with mortar
Afterwards, in nitrogen atmosphere protection down enters tube furnace, heated with 10 DEG C/min heating rates, the high-temperature calcination at 1000 DEG C
Processing 3 hours, naturally cools to room temperature, obtains black powder, is then soaked 6 hours in 0.5mol nitric acid, then uses second
Alcohol and deionized water are rinsed well repeatedly, as the carbon material of nitrogen sulphur codope.
Embodiment 3
A kind of preparation method of nitrogen sulphur codope carbon material, operating procedure is as follows：
(1) copolymer of hexa-member heterocycle containing ammonia nitrogen is prepared：Weigh the diaminopurines of 1g 2,6 (i.e. 0.0067mol) in
100ml is gone in N-N NMF solution, and magnetic agitation adds 4.58g ammonium persulfates (i.e. 0.0201mol) to after dissolving,
Reacted 6 hours under 5 DEG C of stirring conditions, polymerization forms faint yellow floccule；
(2) high-temperature process：By the sediment ethanol and deionization of acquisition after gained material suction filtration after step (1) is polymerize
Water is cleaned for several times repeatedly, is then dried 8 hours at 60 DEG C of vacuum drying chamber, resulting polymers solid is fully ground with mortar
Afterwards, in nitrogen atmosphere protection down enters tube furnace, heated with 1 DEG C/min heating rates, at 600 DEG C at high-temperature calcination
Reason 2 hours, naturally cools to room temperature, obtains black powder, is then soaked 8 hours in the watery hydrochloric acid in 0.5mol, Ran Houyong
Ethanol and deionized water are rinsed well repeatedly, as the carbon material of nitrogen sulphur codope.
Embodiment 4
A kind of preparation method of nitrogen sulphur codope carbon material, operating procedure is as follows：
(1) copolymer of hexa-member heterocycle containing ammonia nitrogen is prepared：1g 2,4- diaminourea -6- methyl isophthalic acids are weighed, 3,5 triazines are (i.e.
0.00799mol) in 100ml deionized waters, magnetic agitation adds 12.76g ammonium persulfates (i.e. to after dissolving
0.05593mol) reacted 10 hours under 8 DEG C of stirring conditions with 1.78g anhydrous ferric trichlorides (i.e. 0.011186mol), polymerize shape
Into milky floccule；
(2) high-temperature process：By the sediment ethanol and deionization of acquisition after gained material suction filtration after step (1) is polymerize
Water is cleaned for several times repeatedly, is then dried 8 hours at 60 DEG C of vacuum drying chamber, resulting polymers solid is fully ground with mortar
Afterwards, in nitrogen atmosphere protection down enters tube furnace, heated with 6 DEG C/min heating rates, the high-temperature calcination at 1200 DEG C
Processing 0.5 hour, naturally cools to room temperature, obtains black powder, then in the dilute sulfuric acid and 0.25mol nitre in 0.25mol
Soak 4 hours, then rinsed well repeatedly with ethanol and deionized water, as the carbon material of nitrogen sulphur codope in sour mixed acid.
Embodiment 5
A kind of preparation method of nitrogen sulphur codope carbon material, operating procedure is as follows：
(1) copolymer of five-ring heterocycles containing ammonia nitrogen is prepared：Weigh 0.1g 2- amino-pyrroles (i.e. 0.00121mol) in
In 100mlN-N NMFs, magnetic agitation adds 2.4g ammonium persulfates (0.01121mol) to after dissolving, in 10 DEG C of stirrings
Under the conditions of react 12 hours, polymerization form White Flocculus；
(2) high-temperature process：By the sediment ethanol and deionization of acquisition after gained material suction filtration after step (1) is polymerize
Water is cleaned for several times repeatedly, is then dried 8 hours at 60 DEG C of vacuum drying chamber, resulting polymers solid is fully ground with mortar
Afterwards, in nitrogen atmosphere protection down enters tube furnace, heated with 8 DEG C/min heating rates, at 900 DEG C at high-temperature calcination
Reason 4 hours, naturally cools to room temperature, obtains black powder, is then soaked 4 hours in the dilute sulfuric acid in 0.5mol, Ran Houyong
Ethanol and deionized water are rinsed well repeatedly, as the carbon material of nitrogen sulphur codope.
Application of the carbon material of gained nitrogen sulphur codope in electrode material for super capacitor
Fig. 1 for the nitrogen sulphur codope of example 1 carbon material in high temperature, i.e., respectively 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C,
There is no sharp peak type in 950 DEG C, the lower XRD of 1000 DEG C of processing, figure, show the nitrogen sulphur codope carbon material for unformed knot
Structure.Fig. 2 is to be covered with cavernous structure inside HAADF-STEM pictures display bead, and this is by 2,6 diamino-pyridines formation polymer
Cause.Fig. 3 scanning electron microscopic picture display materials pattern is homogeneous chondritic.Fig. 4 show the BET apertures point of the material
Cloth test result, it can be seen that the material internal is mainly micropore and on a small quantity mesoporous, and the presence of micropore is very beneficial for carbon materials
Expect the storage of electric capacity.Be shown in Fig. 5 the nitrogen sulphur codope that embodiment 1 is obtained carbon material tested in 6.0M KOH solutions obtained by
Cyclic voltammetry curve under the conditions of different scanning rates, it can be seen that the curve approximation is not the rectangle of standard in rectangle,
This is due to have what Faraday effect was caused, but the area of cyclic voltammetry curve is very big, i.e., have very big as potential changes
Current-responsive, show fabulous capacitive property, specific capacitance value is up to 730F/g during 1A/g.Fig. 6 constant current charge-discharge is bent
Line is the good isosceles triangle of symmetry, shows that invertibity is good during the electrode material discharge and recharge, while can intuitively see
Go out under different current densities, the specific capacitance value with superelevation.Fig. 7 and Fig. 8 are the material respectively in 1.0M H2SO4Under solution
Cyclic voltammetry curve and constant current charge-discharge curve.There is small peak camel appearance in the middle of cyclic voltammetry curve, doping can be attributed to
Atom is internally formed what Faraday effect caused by functional group was caused into carbon material.
Specific capacitance method of testing is：The 5mg nitrogen sulphur codope carbon materials are weighed, mass fraction is 0.2% you is added
Finely dispersed slurries are made in Nafion solution 1ml, ultrasonic disperse 20min.20 μ l slurries are drawn with microsyringe, uniformly
On the working electrode (s, it is ZenniumIM6 electrochemical workstations to test the work station used to drop, using three electrode work systems, ginseng
It is reversible hydrogen electrode than electrode, to electrode from platinum to electrode.And with 6.0M KOH solutions and 1.0M H2SO4It is molten for electrolyte
Liquid, carries out constant current charge-discharge test, and be circulated volt-ampere under different sweep speeds under different current densities
The test of curve, to characterize its capacitive property, and carries out ac impedance measurement, potential window is 0-1V, in electricity to working electrode
The different capacitances that current density is measured when being 1A/g are as shown in table 1：
Table 1
| Embodiment | Specific capacitance (F/g)；(6.0MKOH) | Specific capacitance (F/g)；(1.0M H2SO4) |
| Embodiment 1 | 730F/g | 680F/g |
| Embodiment 2 | 210F/g | 180F/g |
| Embodiment 3 | 625F/g | 550F/g |
| Embodiment 4 | 574F/g | 456F/g |
| Embodiment 5 | 495F/g | 407F/g |
The preparation for the nitrogen sulphur codope carbon material that the present invention is introduced by one-step synthesis, this method do not need template and
Introduce carbon material and make substrate, nitrogen source and carbon source and master are served as with 6-membered heterocyclic compound from cheap five yuan of the ammonia nitrogen that contains
Initiator persulfate is sulphur source, polymerize to form homogeneous chondritic by simple chemical oxidation of gold.
It is foregoing to the present invention specific illustrative embodiment description be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that the certain principles and its reality of the present invention should
With so that those skilled in the art can realize and using the present invention a variety of exemplaries and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of preparation method of nitrogen sulphur codope carbon material, it is characterised in that include following operating procedure：
(1) copolymer of five-ring heterocycles containing ammonia nitrogen or hexa-member heterocycle copolymer are prepared：Ammonia nitrogen five member ring heterocyclic compound list will be contained
Body and/or the monomer of 6-membered heterocyclic compound containing ammonia nitrogen are dissolved in solvent, add initiator, anti-under 0~10 DEG C of stirring condition
Answer 2~12 hours, polymerize；
(2) high-temperature process：Gained material is filtered, dried after step (1) is polymerize, in indifferent gas after resulting polymers solid abrasive
Under atmosphere protection, then 600~1200 DEG C of high-temperature process 0.5~5 hour, cooling is post-processed, that is, obtains nitrogen sulphur codope carbon
Material.
2. preparation method according to claim 1, it is characterised in that：Five-ring heterocycles containing ammonia nitrogen described in step (1)
Compound monomer, the monomer of 6-membered heterocyclic compound containing ammonia nitrogen comprising pyridines, miazines, triazines, purines, pyroles and
One kind in its homologue contains five yuan of ammonia nitrogen and 6-membered heterocyclic compound.
3. preparation method according to claim 1, it is characterised in that：Described pyridines are DAP, 3,4
Diamino-pyridine, 2,3 diamino-pyridines, 4,4'- diaminourea -2,2'- bipyridyls, 4-aminopyridine；Described miazines is 2,
4- di-amino-pyrimidines, 2,4,6- Triaminopyrimidines, 6- methyl -2,4- pyrimidinediamine, 2,4- di-amino-pyrimidine -5- nitriles, 4,5,6 three
Aminopyrimidine, 4- aminopyrimidines, cytimidine, uracil, 2,3 diamino-pyridines；Described triazines are the benzene of 2,4- diaminourea -6
Base -1,3,5-triazines, 2,4- diaminourea -6- dimethylaminos -1,3,5-triazines, the methyl isophthalic acid of 2,4- diaminourea -6,3,5- triazines, 4-
Diazanyl -6- (2- pyridines) -1,3,5-triazines -2- amine, 4,6-, tri- ammonia -1,3,5-triazines, 2,4- diamino-1,3,5-triazines, three
Paracyanogen ammonia, the triazine of 4- amino 1,3,5；Described purines are 2,6- diaminopurines, adenine, adenine, 6- benzyl ammonia
Base purine, guanine；Described pyroles are 1- amino-pyrroles, 2- amino-pyrroles, 3- amino-pyrroles, N- (2- amino-ethyls) pyrrole
Cough up alkane.
4. preparation method according to claim 1, it is characterised in that：Initiator described in step (1) is by individually leading
Initiator persulfate is constituted or by main initiator persulfate and co initiator according to mol ratio ratio 1~5:1 mixing group
Into.
5. preparation method according to claim 4, it is characterised in that：Described main initiator is potassium peroxydisulfate, persulfuric acid
One kind in ammonium or sodium peroxydisulfate；Co initiator is Fe3+、Co2+Or Cu2+In one kind, or for potassium permanganate, nitric acid, mistake
One kind in hydrogen oxide or potassium bichromate.
6. preparation method according to claim 1, it is characterised in that：Solvent described in step (1) is deionized water,
Alcohol, pyridine, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, monochloro methane, dichloromethane, chloroform or tetrachloro
One or more kinds of mixtures in methane.
7. preparation method according to claim 1, it is characterised in that：Five-ring heterocycles containing ammonia nitrogen described in step (1)
The mol ratio of compound monomer or the monomer of 6-membered heterocyclic compound containing ammonia nitrogen and initiator is 1:1~1:10.
8. preparation method according to claim 1, it is characterised in that：4~6 are reacted in step (1) under 5 DEG C of stirring conditions
Hour, polymerization.
9. preparation method according to claim 1, it is characterised in that：Step (2) high temperature heat treatment temperature be 600~
1000 DEG C, described heat treatment heating rate is that soaking time is 0.5-3 hours at 1~10 DEG C/min, high temperature.
10. preparation method according to claim 1, it is characterised in that：Post processing described in step (2) is in 0.5mol
Dilute sulfuric acid, soak 4-8 hours in one or more of mixed acid of nitric acid or hydrochloric acid, then rushed repeatedly with ethanol and deionized water
Wash clean.
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