CN108364796A - A kind of heteroatom doped porous carbon material and preparation method thereof - Google Patents
A kind of heteroatom doped porous carbon material and preparation method thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 85
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007772 electrode material Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000010792 warming Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- -1 uniformly mixing Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000003990 capacitor Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000010431 corundum Substances 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000007581 slurry coating method Methods 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 235000012207 sodium gluconate Nutrition 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical group C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- KXXBTYROZQVYLL-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;potassium;hydrate Chemical compound O.[K].OC(=O)CC(O)(C(O)=O)CC(O)=O KXXBTYROZQVYLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 5
- 241000264877 Hippospongia communis Species 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 230000035807 sensation Effects 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002127 nanobelt Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of heteroatom doped porous carbon materials and preparation method thereof；The preparation method includes the following steps：1）Two citrate hydrate hydrochlorates are uniformly ground with urea or thiocarbamide, uniformly mixing, mixture is placed in container, under inert gas protection, certain temperature is warming up in tube furnace in proportion, is kept the temperature, is naturally cooled to room temperature, obtain powder；2）By step 1）In obtained powder grinding it is uniform, be then soaked in deionized water and stir or be ultrasonically treated, be then filtered by vacuum or centrifuge, filter or centrifugation after use deionized water and washes of absolute alcohol powder；Until the close neutrality of filtrate；3）By step 2）In obtained powder is dry, cooling, grinding uniformly to get.Honey comb like porous carbon materials prepared by the present invention have excellent good power density, energy density, high rate performance and cycle performance, and after cycle 20000 weeks, capacity is almost undamped, and the preparation for energy storage device electrode material of new generation provides mentality of designing.
Description
Technical field
The invention belongs to the preparation field of energy storage material more particularly to a kind of heteroatom doped porous carbon material and its systems
Preparation Method.
Background technology
Currently, as consuming excessively for fossil fuel is growing with energy demand, the development and application of sustainable energy
As the focus of social concerns and the emphasis of scientific research.Effective storage of electrochemical energy and by sustainable resource conversion
It is to obtain the most important two ways of sustainable energy so far.Since ultracapacitor can provide high power density, width
Operating temperature range, high stability and safety and possess the superior functions such as longer cycle life than traditional battery, surpasses
Grade capacitor is considered as one of most potential energy storage equipment, and is commonly employed (doi in many fields：
10.1039/b813846j).Therefore, researchers carry out ultracapacitor research work have very big realistic meaning and
Social benefit.Certainly, the performance of ultracapacitor can also be influenced and restriction by some factors, such as electrode material, electrolysis
Liquid and electrical conductance etc..But in all influence factors, electrode material is most important factor, thus develops a kind of energy
The high performance electrode material high, at low cost, that stability is good of metric density is current urgent required.Carbon material is most widely used
Electrode material for super capacitor has high-specific surface area, suitable pore diameter, good electric conductivity and electrolyte infiltration
Performance, however the low feature of its specific capacity limits its further applies (doi：10.1039/c1cs15060j).Therefore, right
Carbon material, which is modified, has become current research hot spot, and wherein heteroatom doping can be modified and be carried to carbon material surface
For energy storage active site, its electric conductivity and energy density (doi can be effectively improved：10.1038/srep09591), which causes
The extensive concern of researcher.
Zhang et al. (doi：Template and potassium hydroxide 10.1016/j.jpowsour.2017.05.031) is used to live
Change, nitrogen sulphur codope is prepared for as raw material using pyrroles and sulfuric acid and has the carbon materials of hierarchical porous structure (micropore, mesoporous and macropore)
Material.Research shows that the carbon material has rational pore structure and shows good electrochemistry in the application of ultracapacitor
Performance.However, in practical applications, this method drawback is apparent, the template employed in preparation process is expensive, Wu Fashi
It now produces in batches, actual application prospect is weak.
Lee et al. (doi：10.1016/j.jpowsour.2017.05.031) use graphene nanobelt as carbon source,
Nitrile ammonia and benzyl disulfide are mixed using liquid phase, are dried and the method being further carbonized is prepared respectively as nitrogen source and sulphur source
Nitrogen sulphur codope graphene nanobelt.Research shows that the nitrogen sulphur codope carbon material can be realized under high working voltage (1.8V)
The high power density of 8.7KW and have good cycle performance.But nitrile ammonia and benzyl disulfide all have larger toxicity,
And graphene nanobelt needs to obtain by cutting carbon nanotubes, carbon nanotube is of high cost, and the process of cutting carbon nanotubes needs
Use the strong acid Strong oxdiative object such as potassium permanganate, sulfuric acid and phosphoric acid, preparation process danger coefficient is high, deficiency in economic performance and is difficult to reality
Now produce in enormous quantities.
Patent application CN 105140050A disclose a kind of nitrogen sulphur codope quasiflake graphite electrode material for super capacitor
Preparation method, natural flake graphite mixes with sodium hydroxide, is then placed into micro-wave oven micro- at 1000 DEG C by this method
Wave handles 2-5min, then natural cooling, and washing is dried to obtain quasiflake graphite electrode material.Thiocarbamide is added in quasiflake graphite
After 1h being stirred in solution strongly, the ultrasonic reaction 2-3h at 30-50 DEG C, after filtration drying under nitrogen protection, with 20 DEG C/min
Heating rate rise to 1000 DEG C, last natural cooling simultaneously washs and is dried to obtain nitrogen sulfur doping quasiflake graphite super capacitor electrode
Pole material, but not only danger coefficient is high for the highly basic sodium hydroxide used in the preparation method, but also not environmentally；Its preparation process walks
It is rapid it is more, process is cumbersome；Need to use micro-wave oven as reactor, this seriously constrains the application of this technology in actual production.
Patent application CN 104795248A disclose a kind of catkin electrode material for super capacitor and preparation method and super
Capacitor.Catkin and potassium hydroxide mixing are first raised to 400 DEG C of lasting 1-2h by it with the heating rate of 5 DEG C/min, then with 10 DEG C/
The heating rate of min is raised to 850 DEG C of lasting 1-2h, then natural cooling, obtained porous silicon carbide catkin electrode material.It will be porous
The catkin that is carbonized is added in thiourea solution, after strong stirring 0.5-1h, is heated at 80-90 DEG C and is evaporated moisture；The object that will be obtained
Matter is raised to 800 DEG C under protection of argon gas, with the heating rate of 10 DEG C/min, natural cooling after continuous heating 2-3h, obtained nitrogen
Sulfur doping carbonization catkin electrode material.But the preparation method of the invention has equally used danger coefficient high and highly basic not environmentally
Sodium hydroxide；And using catkin as carbon source, the uncontrollability of difference limits between the unstability and batch in source
The actual application prospect of the technology.
To sum up, there are still performance is unstable, cost for carbon electrode material of existing ultracapacitor and preparation method thereof
Height, is difficult to the problems such as industrialization at complex process, therefore, it is necessary to develop a kind of carbon electrode material of new ultracapacitor
Material and preparation method thereof.
Invention content
In order to solve the above-mentioned problems of the prior art, the present invention is intended to provide a kind of heteroatom doped porous carbon
Material and preparation method thereof；The present invention preparation method it is simple, the prices of raw materials are cheap, realize industrial mass production and
Practical application in ultracapacitor；Meanwhile carbon material prepared by the present invention is made of a large amount of multistage pore structure, is had
Height ratio capacity, high rate capability and excellent stability, great application prospect.
An object of the present invention is to provide a kind of heteroatom doped porous carbon material and preparation method thereof.
The second object of the present invention is to provide a kind of heteroatom doped porous carbon material to prepare electrode of super capacitor material
The method of material.
The third object of the present invention is to provide above-mentioned heteroatom doped porous carbon material and preparation method thereof and by different
The application of electrode material for super capacitor prepared by the atom doped porous carbon materials of matter.
For achieving the above object, the invention discloses following technical proposals：
First, the invention discloses a kind of preparation methods of heteroatom doped porous carbon material, specifically, the preparation
Method includes the following steps：
1) two citrate hydrate hydrochlorates are uniformly ground with urea or thiocarbamide, uniformly mixing, appearance is placed in by mixture in proportion
In device, under inert gas protection, it is warming up to certain temperature in tube furnace, keeps the temperature, naturally cool to room temperature, obtain powder；
2) powder obtained in step 1) is ground uniformly, is then soaked in deionized water and stirs or be ultrasonically treated, so
It is filtered by vacuum or centrifuges afterwards, filter or use deionized water and washes of absolute alcohol powder after centrifuging；Repeat above-mentioned immersion, stirring,
It filters, the process of cleaning, until the close neutrality of filtrate.
3) powder obtained in step 2) is dry, cooling, grinding is uniformly to get heteroatom doped porous carbon material.
In step 1), the two citrate hydrates hydrochlorate includes trisodium citrate dihydrate, two citric acid monohydrate potassium.
In step 1), the mass ratio of the two citrate hydrates hydrochlorate, urea or thiocarbamide is (1-20)：(1-10).
Preferably, the mass ratio of the two citrate hydrates hydrochlorate, urea or thiocarbamide is (1-10)：1.
In step 1), the container includes corundum boat, nickel boat.
In step 1), the inert gas is argon gas or nitrogen.
In step 1), the rate of the heating is 2-20 DEG C/min.
Preferably, the rate of the heating is 4-10 DEG C/min.
In step 1), the temperature is 400-1000 DEG C, soaking time 0.5-5h.
Preferably, the temperature is 500-800 DEG C；Soaking time is 1-2h.
In step 2), the ratio of the powder and deionized water is 1g：500-1200mL.
Preferably, the ratio of the powder and deionized water is 1g：1000mL.
In step 2), the time of the stirring or supersound process is 6-48h.
In step 2), the immersion, stirring or ultrasound, the number of repetition for filtering, cleaning are 2-5 times.
Preferably, the immersion, stirring or ultrasound, the number of repetition for filtering, cleaning are 3 times.
In step 3), the condition of the drying is：It is dried in vacuo 5-8h at 60-90 DEG C.
Preferably, the condition of the drying is：It is dried in vacuo 6h at 70 DEG C.
In step 1), two citrate hydrate hydrochlorates are substituted with sodium gluconate.
In step 1), thiocarbamide is substituted with ammonium sulfate.
In step 1), urea is substituted with itrogenous organic substances such as hexas.
Secondly, the invention discloses the sides that a kind of heteroatom doped porous carbon material prepares electrode material for super capacitor
Method, specifically, described method includes following steps：
(1) by above-mentioned steps 3) in obtained heteroatom doped porous carbon material in advance with after conductive agent, dispersant,
Magnetic agitation in organic solvent is put into, slurry is obtained；
(2) by the slurry coating in step (1) on electrode holder, drying is to get electrode material for super capacitor.Step
(1) in, the conductive agent includes：Carbon black, graphene, carbon nanotube etc..
In step (1), the dispersant includes polytetrafluoroethylene (PTFE), Kynoar (PVDF) etc..
In step (1), the organic solvent includes ethyl alcohol, N-Methyl pyrrolidone (NMP) etc..
In step (1), the porous carbon materials, conductive agent, dispersant mass ratio be (5-10):1:1.
Preferably, the porous carbon materials, conductive agent, dispersant mass ratio be 8:1:1.
In step (1), the time of the magnetic agitation is 6-10h.
Preferably, the time of the magnetic agitation is 8h.
In step (2), the electrode holder includes collector nickel foam, stainless (steel) wire.
In step (2), the condition of the drying is：60-80 DEG C of vacuum drying 10-14h.
Preferably, the condition of the drying is：70 DEG C of vacuum drying 12h.
Finally, the invention discloses above-mentioned heteroatom doped porous carbon material and preparation method thereof and by heteroatom
The application of ultracapacitor prepared by doped porous carbon material, including (1) heteroatom doped porous carbon material and its preparation side
Application of the method in electrode material for super capacitor preparation.(2) super capacitor prepared by heteroatom doped porous carbon material
Application of the device in energy storage, catalysis, sewage treatment field.
Compared with prior art, the present invention achieves following advantageous effect：
(1) present invention prepares the low in raw material price used in porous carbon materials, derives from a wealth of sources, considerably reduces and be produced into
This.
(2) present invention takes one step carbonization to prepare porous carbon materials, and step is simple, and equipment and operation require low, are easy to
It promotes, has good industrial prospect.
(3) honey comb like porous carbon materials prepared by the present invention have excellent good power density, energy density, multiplying power
Performance and cycle performance, after cycle 20000 weeks, capacity is almost undamped, for the preparation of energy storage device electrode material of new generation
Provide mentality of designing.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the preparation process schematic diagram of 2 heteroatom doped porous carbon material of the embodiment of the present invention.
Fig. 2 is SEM figure of the obtained heteroatom doped porous carbon material of the embodiment of the present invention 2 under low power.
Fig. 3 is SEM figure of the obtained heteroatom doped porous carbon material of the embodiment of the present invention 2 under high power.
Fig. 4 is the distribution map of element in the heteroatom doped porous carbon material that the embodiment of the present invention 2 obtains.
Fig. 5 is the x-ray photoelectron spectroscopy test that the heteroatom that the embodiment of the present invention 2 and comparative example obtain adulterates porous carbon
As a result.
Fig. 6 is the electrode material for the heteroatom doped porous carbon material preparation that the embodiment of the present invention 2 obtains in super electricity
Cycle performance figure in container.
Fig. 7 is the electrode material for the heteroatom doped porous carbon material preparation that the embodiment of the present invention 2 obtains in super electricity
Power density-energy density logarithmic relationship figure in container.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As described in background, carbon electrode material of existing ultracapacitor and preparation method thereof still has performance
Unstable, of high cost, complex process is difficult to the problems such as industrialization, and therefore, it is more that the present invention provides a kind of heteroatom doping
Hole carbon material and preparation method thereof, in conjunction with the drawings and specific embodiments, invention is further explained.
Embodiment 1：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) bis- citric acid monohydrate potassium of 10g and 0.5g urea are weighed, input mortar is uniformly ground, until without apparent granular sensation,
Mixture after grinding is placed in the corundum boat that size is 10cm*4cm*2cm, it is straight that corundum boat is then placed in quartz ampoule
Diameter is under protection of argon gas, to be warming up to 700 DEG C in the tube furnace of 5cm with the rate of 5 DEG C/min, keep the temperature 1h, naturally cool to room
Temperature obtains powder；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 0.1g：Powder is soaked in deionized water by the ratio of 50mL stirs 6h, is then filtered by vacuum, is spent after suction filtration
Ionized water and washes of absolute alcohol powder；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 2 times are repeated, filtrate is neutrality；
3) powder obtained in step 2) at 70 DEG C is dried in vacuo 6h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, carbon black, polytetrafluoroethylene (PTFE) according to
100g：10g：The ratio of 10g mixes, and then mixture is dissolved in ethyl alcohol, magnetic agitation 10h obtains slurry；
(2) by the slurry coating in step (1) in collector nickel foam, vacuum drying 10h is to get super at 80 DEG C
Capacitor electrode material.
Embodiment 2：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) 10g trisodium citrate dihydrates and 1g thiocarbamides are weighed, input mortar is uniformly ground, until without apparent granular sensation, it will
Mixture after grinding is placed in the corundum boat that size is 10cm*4cm*2cm, and corundum boat is then placed in quartz tube
In the tube furnace of 5cm, under nitrogen protection, to be warming up to 700 DEG C with the rate of 4 DEG C/min, keeping the temperature 1h, naturally cool to room
Temperature obtains powder；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 1g：Powder is soaked in deionized water by the ratio of 1000mL is ultrasonically treated 30min, is then filtered by vacuum, and takes out
Deionized water and washes of absolute alcohol powder are used after filter；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 3 times are repeated, during filtrate is
Property；
3) powder obtained in step 2) at 70 DEG C is dried in vacuo 6h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, graphene, Kynoar according to
80g：10g：The ratio of 10g mixes, and then mixture is dissolved in ethyl alcohol, magnetic agitation 8h obtains slurry；
(2) by the slurry coating in step (1) in collector nickel foam, vacuum drying 12h is to get super at 70 DEG C
Capacitor electrode material.
Embodiment 3：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) 10g sodium gluconates and 10g urea are weighed, input mortar uniformly grinds, until without apparent granular sensation, will grind
Mixture afterwards is placed in the nickel boat that size is 10cm*4cm*2cm, and it is 5cm's that nickel boat, which is then placed in quartz tube,
In tube furnace, under nitrogen protection, 400 DEG C is warming up to the rate of 2 DEG C/min, 5h is kept the temperature, naturally cools to room temperature, obtain powder
Body；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 1g：Powder is soaked in deionized water by the ratio of 1200mL stirs 10h, is then filtered by vacuum, is used after suction filtration
Deionized water and washes of absolute alcohol powder；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 4 times are repeated, filtrate is neutrality；
3) powder obtained in step 2) at 60 DEG C is dried in vacuo 8h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, carbon nanometer, polytetrafluoroethylene (PTFE) according to
50g：10g：The ratio of 10g mixes, and then mixture is dissolved in NMP, magnetic agitation 6h obtains slurry；
(2) by the slurry coating in step (1) on stainless (steel) wire, vacuum drying 14h is to get super capacitor at 60 DEG C
Device electrode material.
Embodiment 4：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) 1g sodium gluconates and 10g ammonium sulfate are weighed, input mortar uniformly grinds, until without apparent granular sensation, will grind
Mixture after mill is placed in the nickel boat that size is 10cm*4cm*2cm, and it is 5cm that nickel boat, which is then placed in quartz tube,
Tube furnace in, under nitrogen protection, be warming up to 1000 DEG C with the rate of 20 DEG C/min, keep the temperature 0.5h, naturally cool to room temperature,
Obtain powder；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 1g：Powder is soaked in deionized water by the ratio of 800mL stirs 20h, is then filtered by vacuum, is spent after suction filtration
Ionized water and washes of absolute alcohol powder；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 4 times are repeated, filtrate is neutrality；
3) powder obtained in step 2) at 90 DEG C is dried in vacuo 5h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, graphene, Kynoar according to
60g：10g：The ratio of 10g mixes, and then mixture is dissolved in NMP, magnetic agitation 7h obtains slurry；
(2) by the slurry coating in step (1) in collector nickel foam, vacuum drying 11h is to get super at 70 DEG C
Capacitor electrode material.
Embodiment 5：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) 20g sodium gluconates and 10g hexas are weighed, input mortar is uniformly ground, until without apparent particle
Mixture after grinding is placed in the corundum boat that size is 10cm*4cm*2cm, corundum boat is then placed in quartz by sense
Pipe diameter is under nitrogen protection, 800 DEG C to be warming up to the rate of 10 DEG C/min in the tube furnace of 5cm, keep the temperature 2h, naturally cold
But room temperature is arrived, powder is obtained；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 1g：Powder is soaked in deionized water by the ratio of 600mL stirs 30h, is then filtered by vacuum, is spent after suction filtration
Ionized water and washes of absolute alcohol powder；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 3 times are repeated, filtrate is neutrality；
3) powder obtained in step 2) at 65 DEG C is dried in vacuo 7h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, carbon black, Kynoar is according to 90g：
10g：The ratio of 10g mixes, and then mixture is dissolved in ethyl alcohol, magnetic agitation 9h obtains slurry；
(2) by the slurry coating in step (1) on stainless (steel) wire, vacuum drying 13h is to get super capacitor at 75 DEG C
Device electrode material.
Embodiment 6：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) 15g trisodium citrate dihydrates and 8g hexas are weighed, input mortar is uniformly ground, until without apparent
Mixture after grinding is placed in the corundum boat that size is 10cm*4cm*2cm, corundum boat is then placed in stone by grain sense
English pipe diameter is under nitrogen protection, 500 DEG C to be warming up to the rate of 5 DEG C/min in the tube furnace of 5cm, keep the temperature 1.5h, natural
It is cooled to room temperature, obtains powder；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 1g：Powder is soaked in deionized water by the ratio of 1100mL stirs 48h, is then filtered by vacuum, is used after suction filtration
Deionized water and washes of absolute alcohol powder；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 5 times are repeated, filtrate is neutrality；
3) powder obtained in step 2) at 75 DEG C is dried in vacuo 6h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, carbon nanotube, Kynoar according to
65g：10g：The ratio of 10g mixes, and then mixture is dissolved in ethyl alcohol, magnetic agitation 7h obtains slurry；
(2) by the slurry coating in step (1) in collector nickel foam, vacuum drying 10h is to get super at 80 DEG C
Capacitor electrode material.
Comparative example：
1, a kind of preparation method of heteroatom doped porous carbon material, includes the following steps：
1) 15g trisodium citrate dihydrates are weighed, input mortar is uniformly ground, until without apparent granular sensation, after grinding
Mixture is placed in the corundum boat that size is 10cm*4cm*2cm, and it is 5cm's that corundum boat, which is then placed in quartz tube,
In tube furnace, under protection of argon gas, 700 DEG C is warming up to the rate of 4 DEG C/min, 1h is kept the temperature, naturally cools to room temperature, obtain powder
Body；
2) powder obtained in step 1) is placed in mortar and is ground uniformly to without apparent granular sensation, then according to powder with
Deionized water is 1g：Powder is soaked in deionized water by the ratio of 100mL stirs 6h, is then filtered by vacuum, is spent after suction filtration
Ionized water and washes of absolute alcohol powder；Above-mentioned immersion, ultrasound, suction filtration, cleaning process 5 times are repeated, filtrate is neutrality.
3) powder obtained in step 2) at 70 DEG C is dried in vacuo 6h, removes remaining absolute ethyl alcohol, Temperature fall
After take out and grind uniformly to get heteroatom doped porous carbon material.
2, a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor, including walk as follows
Suddenly：
(1) by above-mentioned steps 3) in obtain heteroatom doped porous carbon material, conductive agent, dispersant is according to 80g：
10g：The ratio of 10g mixes, and then mixture is dissolved in ethyl alcohol, magnetic agitation 8h obtains slurry；
(2) by the slurry coating in step (1) in collector nickel foam, vacuum drying 12h is to get super at 70 DEG C
Capacitor electrode material.
Performance test：
Fig. 1 is the preparation flow schematic diagram of heteroatom doped porous carbon material prepared by embodiment 2；；By sulphur therein
Urea is changed to urea, which can indicate the preparation flow of heteroatom doping porous carbon in embodiment 1.
Fig. 2 is the SEM under different multiples on the heteroatom doped porous carbon material surface that embodiment 2 is prepared
Figure can be seen that from Fig. 2 and 3：Porous carbon materials prepared by embodiment 2 have apparent porous structure, and pore structure is close
Like being hexagon, that is, there is honey comb like feature.
Fig. 4 is the distribution diagram of element on the heteroatom doped porous carbon material surface that embodiment 2 obtains, and can be seen by Fig. 4
Go out：Three kinds of carbon, nitrogen, sulphur elements are evenly distributed in porous carbon base body, it was demonstrated that two kinds of elements of nitrogen sulphur successfully adulterate enter it is porous
Carbon material.
Fig. 5 is the x-ray photoelectron spectroscopy test result for the heteroatom doping porous carbon that embodiment 2 and comparative example obtain,
Wherein, NSPC-1, NSPC-2, NSPC-5, NSPC-10 respectively represent in embodiment 2 sodium citrate and thiocarbamide according to different matter
Amount is than (1:1、1:2、1:5、1:10) preparation-obtained porous carbon materials, in Fig. 5 (e), PC, which is represented, does not add sulphur in comparative example
The porous carbon obtained when urea, other four curves from bottom to top distinguish embodiment 2 in four different quality ratios (from bottom to top successively
It is 1:1、1:2、1:5、1:10) porous carbon materials, Fig. 5 (f), (g), (h) are respectively represented sodium citrate and sulphur in embodiment 2
Urea is according to 1:The high-resolution collection of illustrative plates of carbon in porous carbon materials, nitrogen, element sulphur is obtained prepared by the mass ratio of 5 (NSPC-5)；From Fig. 5
(f), (g), (h) are as can be seen that carbon, nitrogen, element sulphur have successfully been doped into porous carbon materials, and different types of nitrogen
It also all matches with its standard peak position with element sulphur.From Fig. 5 (e) as can be seen that the obtained porous carbon materials of comparative example are in 168eV
(representing element sulphur) and 400eV (representing nitrogen) nearby exist without peak, it is meant that exist without heterogeneous element, and embodiment
There is above-mentioned two peak in the sample obtained according to different proportion in 2, it was demonstrated that nitrogen and element sulphur are successfully doped into
Porous carbon materials.
Fig. 6 is that electrode material prepared by the heteroatom doped porous carbon material that embodiment 2 obtains is electric in three electrode supers
The cyclic lifetime test results in container, as seen from the figure after cycle 20000 weeks, capacity is almost undamped, and this point also may be used
With by cyclic voltammetry curve in Fig. 6 before and after cycle almost unchanged secondary evidence.
Fig. 7 is that electrode material prepared by the heteroatom doped porous carbon material that embodiment 2 obtains is electric in two electrode supers
The logarithmic relationship figure of energy density and power degree in container, passes through the comparison (document 1-4) with similar operation, it can be seen that this
Preparation-obtained electrode material is had excellent performance in invention, and power density and energy density are superior to above-mentioned similar operation.
Document 1：doi：10.1016/j.jpowsour.2013.11.014.
Document 2：doi：10.1039/C7TA00448F.
Document 3：doi：10.1038/ncomms9503.
Document 3：Guo H,Gao Q.Boron and nitrogen co-doped porous carbon and its
enhanced properties as supercapacitor；Journal of Power Sources.2009,186(2):
551-6。
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for those skilled in the art
For member, the application can have various modifications and variations.Any modification made by within the spirit and principles of this application,
Equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of preparation method of heteroatom doped porous carbon material；It is characterized in that：The preparation method includes following step
Suddenly：
1) two citrate hydrate hydrochlorates are uniformly ground with urea or thiocarbamide, uniformly mixing, mixture is placed in container in proportion,
Under inert gas protection, it is warming up to certain temperature in tube furnace, keeps the temperature, naturally cools to room temperature, obtain powder；
2) powder obtained in step 1) is ground uniformly, is then soaked in deionized water and stirs or be ultrasonically treated, then very
Sky filters or centrifugation, filters or uses deionized water and washes of absolute alcohol powder after centrifuging；Repeat above-mentioned immersion, stirring, suction filtration,
The process of cleaning, until the close neutrality of filtrate；
3) powder obtained in step 2) is dry, cooling, grinding is uniformly to get heteroatom doped porous carbon material.
2. preparation method as described in claim 1；It is characterized in that：The two citrate hydrates hydrochlorate includes two citric acid monohydrates
Sodium, two citric acid monohydrate potassium；
Preferably, the mass ratio of the two citrate hydrates hydrochlorate, urea or thiocarbamide is (1-20)：(1-10)；It is further preferred that
The mass ratio of the two citrate hydrates hydrochlorate, urea or thiocarbamide is (1-10)：1；
Preferably, the container includes corundum boat, nickel boat；
Preferably, the inert gas is argon gas or nitrogen；
Preferably, the rate of the heating is 2-20 DEG C/min；It is further preferred that the rate of the heating be 4-10 DEG C/
min。
3. preparation method as described in claim 1；It is characterized in that：In step 2), the ratio of the powder and deionized water
For 1g：500-1200mL；It is further preferred that the ratio of the powder and deionized water is 1g：1000mL；
Preferably, the time of the stirring or supersound process is 6-48h.
4. preparation method as described in claim 1；It is characterized in that：The immersion, stirring or ultrasound filter, the weight of cleaning
Again number is 2-5 times；
Preferably, the immersion, stirring or ultrasound, the number of repetition for filtering, cleaning are 3 times；
Preferably, the condition of the drying is：It is dried in vacuo 5-8h at 60-90 DEG C；It is further preferred that the condition of the drying
For：It is dried in vacuo 6h at 70 DEG C.
5. preparation method according to any one of claims 1-4；It is characterized in that：Two citrate hydrates are substituted with sodium gluconate
Hydrochlorate；Preferably, thiocarbamide is substituted with ammonium sulfate；It is further preferred that substituting urea with hexa.
6. a kind of method that heteroatom doped porous carbon material prepares electrode material for super capacitor；It is characterized in that：It is described
Method includes the following steps：
(1) the heteroatom doped porous carbon material for obtaining any one of claim 1-5 preparation methods and conductive agent, dispersant
After mixing, magnetic agitation in organic solvent is put into, slurry is obtained；
(2) by the slurry coating in step (1) on electrode holder, drying is to get electrode material for super capacitor.
7. method as claimed in claim 6；It is characterized in that：The porous carbon materials, conductive agent, dispersant mass ratio be
(5-10):1:1；
Preferably, the porous carbon materials, conductive agent, dispersant mass ratio be 8:1:1；
Preferably, the conductive agent includes：Carbon black, graphene, carbon nanotube；
Preferably, the dispersant includes polytetrafluoroethylene (PTFE), Kynoar；
Preferably, the organic solvent includes ethyl alcohol, N-Methyl pyrrolidone；
Preferably, the electrode holder includes collector nickel foam, stainless (steel) wire.
8. method as claimed in claim 6；It is characterized in that：The time of the magnetic agitation is 6-10h；Preferably, described
The time of magnetic agitation is 8h.
9. method as claimed in claim 6；It is characterized in that：The condition of the drying is：60-80 DEG C of vacuum drying 10-
14h；Preferably, the condition of the drying is：70 DEG C of vacuum drying 12h.
10. if any one of claim 1-5 preparation methods and its heteroatom doped porous carbon material of preparation are in super capacitor
Application in the preparation of device electrode material；As the ultracapacitor of claim 6-9 any one of them method and its preparation is storing up
It can, be catalyzed, the application in sewage treatment field.
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| CN110577205A (en) * | 2019-09-30 | 2019-12-17 | 南京航空航天大学 | Fe. Preparation method of N-codoped ultrahigh specific surface area hierarchical porous carbon material |
| CN111439739A (en) * | 2019-01-17 | 2020-07-24 | 中国科学院化学研究所 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN111446086A (en) * | 2020-03-09 | 2020-07-24 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanosheet/foamed nickel @ nitrogen-doped carbon electrode material |
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| CN111446086A (en) * | 2020-03-09 | 2020-07-24 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanosheet/foamed nickel @ nitrogen-doped carbon electrode material |
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