CN110127652A - A kind of nitrogen-doped carbon material and preparation method thereof and the application in supercapacitor - Google Patents
A kind of nitrogen-doped carbon material and preparation method thereof and the application in supercapacitor Download PDFInfo
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- CN110127652A CN110127652A CN201910408208.XA CN201910408208A CN110127652A CN 110127652 A CN110127652 A CN 110127652A CN 201910408208 A CN201910408208 A CN 201910408208A CN 110127652 A CN110127652 A CN 110127652A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 28
- 150000003751 zinc Chemical class 0.000 claims abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000004246 zinc acetate Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229960002050 hydrofluoric acid Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 description 14
- 239000011701 zinc Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- -1 poly(ethylene glycol) Polymers 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006776 Si—Zn Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Semiconductor Integrated Circuits (AREA)
- Weting (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Application the present invention relates to a kind of nitrogen-doped carbon material and preparation method thereof and in supercapacitor, the preparation method of the nitrogen-doped carbon material includes: (1) using dehydrated alcohol as solvent, zinc salt, surfactant, pyrroles, ethyl orthosilicate and dilute hydrochloric acid is added and mixes, colloidal sol is obtained, the zinc salt is at least one of zinc nitrate and zinc acetate；(2) it after gained colloidal sol being stood the stipulated time, then is dried, obtains gel；(3) after gained gel being heat-treated at 700 DEG C~1100 DEG C, then etched and cleaning, obtain the nitrogen-doped carbon material.
Description
Technical field
Application the present invention relates to a kind of nitrogen-doped carbon material and preparation method thereof and in supercapacitor, and in particular to
A kind of method using silica sol-gel bind metal ion auxiliary improves the nitrogen doped concentration of carbon material, belongs to material
Science and technology field.
Background technique
Energy shortage, environmental pollution are the huge challenges of face of mankind nowadays, we need cleaning, it is safe and efficient, cheap
New energy alleviate environment and energy problem.Supercapacitor is since high with power density, the response time is rapid, the circulation longevity
The advantages that life is long and safe is used for the fields such as new-energy automobile and smart grid, is the research of performance source domain in recent years
Hot spot.In supercapacitor, carbon material due to it is conductive it is high, have extended cycle life the advantages that be more common electrode material
Material.Graphene is a kind of novel two-dimensional material, it has high conductivity, at room temperature electron mobility be up to 2.5 ×
105cm2/ (VS), theoretical specific surface area is up to 2630m2/ g, this two o'clock make it possible to become the electric double layer capacitance haveing excellent performance
Equipment material.Studies have shown that the capacitive property in water based electrolyte reaches 135F/g when graphene is as electrode material, having
99F/g can be reached in machine electrolyte, 75F/g can be reached in ionic liquid.It can be seen that its capacitive property and bad.The reason is that,
Two-dimensional graphene sheet layer is very easy to polymerization in actual application, reduces its specific surface area significantly, electric conductivity also drops
It is low, therefore we need to design a kind of three-dimensional grapheme with the porous, electrically conductive network structure interconnected, to solve reality
Application problem.Having result of study to show can be by the capacity boost of graphene to 222F/g by building three-dimensional network.
The doping of nitrogen-atoms is to improve the effective way of carbon material capacitive property, and reason is that N doping can change carbon materials
Expect the Local Electronic Structure of itself, the binding ability of reinforcing material and electrolyte improves the specific capacity of material.The nitrogen in carbon material
There are mainly three types of form, pyridine type nitrogen (N-6), pyrroles's type nitrogen (N-5) and graphite mould nitrogen (N-Q) for doping.Wherein pyrroles's type nitrogen
The charge density of π plane can be effectively improved with pyridine type nitrogen, generate fake capacitance, and then effectively improve the specific capacity of carbon material.
But in carbon material, high nitrogen doped there is contradictions between high conductivity, the reason is that, typically resulting in the carbon of high conductivity
Material needs to carry out high-temperature heat treatment (1000 DEG C), and the nitrogen-atoms of defective locations can be at 800 DEG C or so with N2Form be detached from
Carbon material.Therefore how to be realized while prepare three-dimensional conductive network the doping of high nitrogen-containing to the design of material with prepared
Journey proposes higher requirement.
Summary of the invention
In view of the problems of the existing technology, in order to prepare the high carbon material of nitrogen doped concentration, the present invention provides one
The method of kind silica sol-gel method bind metal ion auxiliary prepares high nitrogen doped porous carbon materials, and makes obtained
Carbon material has excellent performance of the supercapacitor, to meet the needs of energy storage field.
On the one hand, the present invention provides a kind of preparation methods of nitrogen-doped carbon material, comprising:
(1) using dehydrated alcohol as solvent, zinc salt, surfactant, pyrroles, ethyl orthosilicate and dilute hydrochloric acid is added and mixes,
Colloidal sol is obtained, the zinc salt is at least one of zinc nitrate, zinc acetate；
(2) it after gained colloidal sol being stood the stipulated time, then is dried, obtains gel；
(3) after gained gel being heat-treated at 700 DEG C~1100 DEG C, then etched and cleaning, obtain the N doping
Carbon material.
In the silica sol gel method that the present invention utilizes, zinc salt can dissolve Zn ion and can be with pyrrole in colloidal sol
Complexing is coughed up, rock-steady structure is formed.It is primarily due to the ion that zinc ion is two positive charges of band, contains unoccupied orbital.And in pyrroles
Oxygen have stronger electronegativity, containing lone pair electrons, thus can with zinc ion occur bonding complexing.To make pyrroles compared with
Low temperature carbonation stage is difficult to volatilize, therefore particularly significant to the reservation of carbon and nitrogen.Zinc nitrate turns during heat treatment simultaneously
Metallic zinc is turned to, there is pore-creating effect；P-123 (poly- (the propylene glycol)-block- poly(ethylene glycol) of poly(ethylene glycol)-block-) etc.
Make material that there is pore structure abundant as surfactant；Pyrroles is carbon source and nitrogen source, and ethyl orthosilicate is colloidal sol main body, water
Three-dimensional net structure is formed after solution, and as the substrate during growth graphene, a small amount of hydrochloric acid, which is added, reduces ethyl orthosilicate
Hydrolysis rate, complete network structure can be formed.Big (the > of the nitrogen-doped carbon material specific surface area that the present invention is prepared
1500m2/ g), nitrogen content (> 5.5at.%) with higher, is the suitable material of supercapacitor.
Preferably, zinc salt in the colloidal sol, surfactant, pyrroles, ethyl orthosilicate and dilute hydrochloric acid content be respectively
0.001~0.005mol/ml, 0.1~0.5g/ml, 0.05~0.5ml/ml, 0.05~1ml/ml and 0.01~0.1ml/ml,
Preferably 0.002mol/ml, 0.2g/ml, 0.2ml/ml, 0.4ml/ml and 0.04ml/ml；The concentration of the hydrochloric acid is 1mol/
L。
Preferably, the surfactant is P123.
Preferably, the ethyl orthosilicate and the mass ratio of pyrroles are 1:(0.2~1).
Preferably, the temperature of the standing is room temperature, the time is 1~5 day, preferably 2 days；The temperature of the drying process
It is 30~50 DEG C, the time is 1~5 day；Preferably, the temperature of the drying process is 50 DEG C, and the time is 2 days.
Preferably, the temperature of the heat treatment is 800 DEG C~1000 DEG C；It is preferred that before the heat treatment, by gained gel into
Row pulverization process.
Preferably, the time of the heat treatment is preferably 2 hours no more than 4 hours.
Preferably, the gas being passed through in the heat treatment process is argon gas, hydrogen, ammonia and methane mixed gas；Institute
The flow for stating argon gas, hydrogen, ammonia and methane mixed gas is respectively 10~1000sccm, 0~100sccm, 0~500sccm
With 0~50sccm, preferably 300sccm, 50sccm, 100sccm and 5sccm.
Preferably, etching liquid used in the etching is the mixed acid solution of hydrofluoric acid and hydrochloric acid.
On the other hand, the present invention provides a kind of nitrogen-doped carbon material prepared according to above-mentioned preparation method, the nitrogen
Doping carbon material contains microcellular structure and meso-hole structure, nitrogen atom content > 5.5at%, and specific surface area is more than 1500m2/g；Institute
Stating N doping form in nitrogen-doped carbon material is at least one of graphite mould nitrogen, pyridine type nitrogen and pyrroles's type nitrogen.
In another aspect, the present invention provides a kind of as above-mentioned nitrogen-doped carbon material is preparing answering in supercapacitor
With.
The present invention is that its nitrogen doped concentration is improved on the basis of silica template prepares carbon material.Specifically, exist
Creative in the preparation of colloidal sol to joined Zn salt, the complexing of Zn ion and pyrroles can be fixed on colloidal sol and gel
In the middle, in the cold stage of subsequent heat treatment, pyrroles can be effectively retained and be occurred the carbon materials that cracking forms N doping
Material.This technique can be such that the nitrogen doped concentration of carbon material significantly improves.The carbon material being prepared is applied to super by the present invention
Grade capacitor area, and there is extraordinary application prospect.
Detailed description of the invention
Fig. 1 shows the scanning electron microscope (a) and transmission electron microscope photo (b) of the porous carbon materials of the preparation of the embodiment of the present invention 1；
Fig. 2 shows the pore size distribution curves of porous carbon materials prepared by the embodiment of the present invention 1 and comparative example 1；
Fig. 3 shows the infrared spectroscopy of sample of the gel in the embodiment of the present invention 1 and comparative example 1 after 300 DEG C of heat treatment；
The N1s that Fig. 4 is shown in the XPS spectrum of porous carbon materials prepared by the embodiment of the present invention 1 and comparative example 1 is finely composed；
Fig. 5 shows the cyclic voltammetry curve of nitrogen-doped carbon material prepared by the embodiment of the present invention 1 and comparative example 1.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the disclosure, nitrogen-doped carbon material is prepared using silica sol gel method for the first time, it is main to utilize
Zn ion can be complexed in colloidal sol with pyrroles, form rock-steady structure, pyrroles is made to be difficult to volatilize in lower temperature carbonation stage, because
This is particularly significant to the reservation of carbon and nitrogen.Illustrate to following exemplary the method provided by the invention for preparing nitrogen-doped carbon material.
Prepare colloidal sol.Using dehydrated alcohol as solvent, sequentially add zinc salt, surfactant, pyrroles, ethyl orthosilicate and
A small amount of hydrochloric acid, preparation obtain a kind of colloidal sol.Wherein, zinc salt is zinc nitrate, zinc acetate etc..Pyrroles is as nitrogen source and carbon source.Surface
Activating agent can be P123.Zinc salt in gained colloidal sol, surfactant, pyrroles, ethyl orthosilicate and dilute hydrochloric acid content be respectively
0.001~0.005mol/ml, 0.1~0.5g/ml, 0.05~0.5ml/ml, 0.05~1ml/ml and 0.01~0.1ml/ml,
Preferably 0.002mol/ml, 0.2g/ml, 0.2ml/ml, 0.4ml/ml and 0.04ml/ml.The concentration of the hydrochloric acid is 1mol/
L.Zinc salt and the mass ratio of pyrroles can be 1:(0.2~1).If zinc salt is excessive, it will affect the formation of collosol and gel, make silicon and zinc
It is easy to reunite, material specific surface area is caused to reduce.The too high levels for leading to carbon if pyrroles is excessive, the pore-creating for influencing silica are made
With the same specific surface area for reducing material.The detailed example that colloidal sol is prepared as one, takes 10mL dehydrated alcohol, sequentially adds 0
~0.005mol Zn (NO3)2·6H2O, 1~5g P-123,0~5ml pyrroles, 1~10ml ethyl orthosilicate and 0.1~1ml
Dilute hydrochloric acid (1mol/L).Raw material to be added is completely dissolved to form clear solution after, continue stirring a period of time, obtain colloidal sol.
Gelation processing.Prepared colloidal sol is poured into and stands the stipulated time in surface plate, hydrolyzes it slowly.Then again
Being put into baking oven makes its gelation.After gel be completely dried and (harden and crack) afterwards take out.It is preferred that crushing (for example, grinding, ball milling
Deng) it is uniform powder.The time stood in the surface plate is 1~5 day, preferably 2 days, hydrolyzes it slowly.It is then placed in
Make its gel in baking oven, gelling temp cannot be excessively high.The temperature that (gelling temp) is dried in baking oven can be 30~50 DEG C, preferably
50 DEG C, the time can be 1~5 day, preferably 2 days.
Heat treatment.The heat treatment of gained gel or gel powder is heat-treated in tube furnace.Heat preservation a period of time
Start to be cooled to room temperature later.Heat treatment temperature can be 700 DEG C~1100 DEG C, preferably 800 DEG C~1000 DEG C.It is heated from room temperature
To set temperature, heating rate is preferably 5 DEG C/min.The heat treatment soaking time can be for no more than 4h, preferably 2h.At heat
The gas being passed through during reason is argon gas, hydrogen, ammonia and methane mixed gas.The flow of four kinds of gases is respectively 0~
1000sccm, 0~100sccm, 0-500sccm, 0~50sccm, and at least one gas content is not 0；Preferably
300sccm, 50sccm, 100sccm, 5sccm.
Etching and cleaning.It is cooled to room temperature to sample, using hydrofluoric acid and mixed in hydrochloric acid acid soak sample to remove sample
In silicon-containing compound and zinc metal.It impregnates two days under room temperature, then the sample that cleans repeatedly is until washing lotion pH=7,
Separation is filtered, and solid is dried, obtains the nitrogen-doped carbon material.
In the disclosure, in nitrogen-doped carbon material contain a large amount of micropore, meso-hole structure, micropore size be 0.5~
2nm, mesoporous pore size are 2~20nm, there is the pore-size distribution more concentrated at 8nm, and specific surface area (being measured using BET method) is super
Cross 1500m2/g.The N doping form is mainly that graphite mould nitrogen, pyridine type nitrogen and pyrroles's type nitrogen, nitrogen-atoms percentage composition are more than
5.5%.Above-mentioned nitrogen-doped carbon material can be also used to prepare supercapacitor by the present invention.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
10mL dehydrated alcohol is measured, 0.02mol Zn (NO is sequentially added3)2·6H2O, 2g P-123,2ml pyrroles, the positive silicic acid of 4ml
Ethyl ester and 0.4ml dilute hydrochloric acid (1mol/L).Raw material to be added is completely dissolved to form clear solution after, continue stirring one section when
Between.Prepared colloidal sol is poured into surface plate and is stood, hydrolyzes it slowly 2 days, placing into 50 DEG C of baking ovens makes its gel, when
Between be 2 days.Then it is ground to uniform powder.Sample is heat-treated in tube furnace, temperature is 1000 DEG C.It is heated from room temperature
To 1000 DEG C, heating rate is 5 DEG C/min, needs to protect gas (argon gas, 300sccm, hydrogen, 50sccm) in heating process, when
When in-furnace temperature rises to 600 DEG C, it is passed through ammonia (NH3, 100sccm), methane gas is passed through when temperature reaches 1000 DEG C, and (flow is
5sccm), 1000 DEG C at a temperature of keep the temperature 120min.It is cooled to room temperature to sample, uses hydrofluoric acid and mixed in hydrochloric acid acid soak
Sample is to remove the inorganic matter ingredient in sample.It impregnates two days under room temperature, then the sample cleaned repeatedly is until washing lotion
PH=7 filters separation, and solid is dried, and obtains the nitrogen-doped carbon material.
Embodiment 2
10mL dehydrated alcohol is measured, 0.01mol Zn (NO is sequentially added3)2·6H2O, 2g P-123,2ml pyrroles, the positive silicic acid of 2ml
Ethyl ester and 0.4ml dilute hydrochloric acid (1mol/L).Raw material to be added is completely dissolved to form clear solution after, continue stirring one section when
Between.Prepared colloidal sol is poured into surface plate and is stood, hydrolyzes it slowly 2 days, placing into 50 DEG C of baking ovens makes its gel, when
Between be 2 days.Then it is ground to uniform powder.Sample is heat-treated in tube furnace, temperature is 1000 DEG C.It is heated from room temperature
To 1000 DEG C, heating rate is 5 DEG C/min, needs to protect gas (argon gas, 300sccm, hydrogen, 50sccm) in heating process, when
When in-furnace temperature rises to 600 DEG C, it is passed through ammonia (NH3, 100sccm), methane gas is passed through when temperature reaches 1000 DEG C, and (flow is
5sccm), 1000 DEG C at a temperature of keep the temperature 120min.It is cooled to room temperature to sample, uses hydrofluoric acid and mixed in hydrochloric acid acid soak
Sample is to remove the inorganic matter ingredient in sample.It impregnates two days under room temperature, then the sample cleaned repeatedly is until washing lotion
PH=7 filters separation, and solid is dried, and obtains the nitrogen-doped carbon material.
Comparative example 1
10mL dehydrated alcohol is measured, 2g P-123,2ml pyrroles, 2ml ethyl orthosilicate and 0.4ml dilute hydrochloric acid are sequentially added
(1mol/L).Raw material to be added is completely dissolved to form clear solution after, continue stirring a period of time.Prepared colloidal sol is fallen
Enter in surface plate and stand, hydrolyze it slowly 2 days, placing into 50 DEG C of baking ovens makes its gel, and the time is 2 days.Then it is ground to
Uniform powder.Sample is heat-treated in tube furnace, temperature is 1000 DEG C.1000 DEG C are heated to from room temperature, heating rate
For 5 DEG C/min, need to protect gas (argon gas, 300sccm, hydrogen, 50sccm) in heating process, when in-furnace temperature rises to 600 DEG C
When, it is passed through ammonia (NH3, 100sccm), methane gas (flow 5sccm) is passed through when temperature reaches 1000 DEG C, at 1000 DEG C
At a temperature of keep the temperature 120min.It is cooled to room temperature to sample, using hydrofluoric acid and mixed in hydrochloric acid acid soak sample to remove in sample
Inorganic matter ingredient.Two days samples cleaned repeatedly again are impregnated under room temperature up to washing lotion pH=7, filter separation, and
By solid target material obtained by drying.
Fig. 1 is the stereoscan photograph of three-dimensional grading-hole carbon material prepared by embodiment 1, be can clearly be seen that in figure abundant
Cellular structure.The sample that embodiment 1 and comparative example 1 are prepared shows apparent difference on pore-size distribution, such as Fig. 2 institute
Show.A kind of wider pore-size distribution is all presented in two samples, and distribution is from the micropore of 0.5nm to Jie of aperture 10nm or so
Hole, the sample of embodiment 1 also have the pore-size distribution more concentrated at 8nm, are generated by the template action of Zn simple substance.Two samples
Product have the specific surface area being closer to, and the specific surface area of 1 sample of embodiment reaches 1610m2g-1.Fig. 3 is embodiment 1 and comparison
The infrared spectroscopy for the sample that gel in example 1 obtains after being heat-treated in 300 DEG C of argon gas.For comparative example 1,1100 (vs),
800(mw)、and 450(s)cm-1A set of peak at place represents the vibration of amorphous silica, and 550cm in 1 sample of embodiment-1
Extra peak represents the signal of Zn-N and Zn-O vibration, 965cm-1The strong absworption peak at place often illustrates exotic atom and silica
The combination of network is zinc ion here in conjunction with the oxygen in Si-O-Si network, 1600cm-1The signal at place is in Si-O-Si structure
The signal of water is adsorbed, this is because the nitrogen-atoms of zinc complexing has also entered the parent for increasing material in Si-O-Si network structure
It is aqueous.Fig. 4 is that the N1s that embodiment 1 and comparative example 1 are prepared in the XPS spectrum of nitrogen-doped carbon material is composed.Embodiment 1 is prepared
Sample nitrogen content be more than 5.5at.%, and the ratio of active nitrogen content (N-5+N-6) is more than the 80% of the total nitrogen content of sample.It is right
The nitrogen content 4.7at.% for the sample that ratio 1 is prepared, the ratio of active nitrogen are slightly below 70%.This explanation passes through Si-Zn
It is higher that complex sol can prepare nitrogen content, and also higher carbon material, this material may have very active nitrogen ratio
Good capacitor energy-storage property.Fig. 5 is the nitrogen-doped carbon material for preparing of embodiment 1 and comparative example 1 as electrode of super capacitor
Cyclic voltammetry curve.The capacity of 1 sample of embodiment is 380F/g, and the capacity higher than 1 sample of comparative example is 260F/g.
Claims (11)
1. a kind of preparation method of nitrogen-doped carbon material characterized by comprising
(1) using dehydrated alcohol as solvent, zinc salt, surfactant, pyrroles, ethyl orthosilicate and dilute hydrochloric acid is added and mixes,
Colloidal sol is obtained, the zinc salt is at least one of zinc nitrate and zinc acetate；
(2) it after gained colloidal sol being stood the stipulated time, then is dried, obtains gel；
(3) after gained gel being heat-treated at 700 DEG C~1100 DEG C, then etched and cleaning, obtain the N doping
Carbon material.
2. preparation method according to claim 1, which is characterized in that zinc salt in the colloidal sol, surfactant, pyrroles,
The content of ethyl orthosilicate and dilute hydrochloric acid be respectively 0.001~0.005mol/ml, 0.1~0.5g/ml, 0.05~0.5ml/ml,
0.05~1ml/ml and 0.01~0.1ml/ml, preferably 0.002mol/ml, 0.2g/ml, 0.2ml/ml, 0.4ml/ml and
0.04ml/ml；The concentration of the hydrochloric acid is 1mol/L.
3. preparation method according to claim 1 or 2, which is characterized in that the surfactant is P123.
4. preparation method according to any one of claim 1-3, which is characterized in that the ethyl orthosilicate and pyrroles's
Mass ratio is 1:(0.2~1).
5. preparation method described in any one of -4 according to claim 1, which is characterized in that the temperature of the standing is room temperature,
Time is 1~5 day, preferably 2 days；The temperature of the drying process is 30~50 DEG C, and the time is 1~5 day；Preferably, described
The temperature of drying process is 50 DEG C, and the time is 2 days.
6. preparation method according to any one of claims 1-5, which is characterized in that the temperature of the heat treatment is 800
DEG C~1000 DEG C；It is preferred that before the heat treatment, gained gel is carried out pulverization process.
7. preparation method according to claim 1 to 6, which is characterized in that the time of the heat treatment is not surpass
4 hours are spent, preferably 2 hours.
8. preparation method described in any one of -7 according to claim 1, which is characterized in that be passed through in the heat treatment process
Gas be argon gas, hydrogen, ammonia and methane mixed gas；The argon gas, hydrogen, ammonia and methane mixed gas flow point
Not Wei 10~1000sccm, 0~100sccm, 0~500sccm and 0~50sccm, preferably 300sccm, 50sccm,
100sccm and 5sccm.
9. preparation method according to claim 1 to 8, which is characterized in that etching liquid used in the etching is hydrogen
The mixed acid solution of fluoric acid and hydrochloric acid.
10. a kind of nitrogen-doped carbon material of preparation method preparation according to claim 1 to 9, feature exist
In the nitrogen-doped carbon material contains microcellular structure and meso-hole structure, nitrogen atom content > 5.5at%, and specific surface area is more than
1500m2/g；N doping form is at least one in graphite mould nitrogen, pyridine type nitrogen and pyrroles's type nitrogen in the nitrogen-doped carbon material
Kind.
11. a kind of application of nitrogen-doped carbon material as claimed in claim 10 in preparation supercapacitor.
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