CN105460915A - A heteroelement doped porous carbon material, a preparing method thereof and applications of the heteroatom doped porous carbon material - Google Patents
A heteroelement doped porous carbon material, a preparing method thereof and applications of the heteroatom doped porous carbon material Download PDFInfo
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- CN105460915A CN105460915A CN201510808363.2A CN201510808363A CN105460915A CN 105460915 A CN105460915 A CN 105460915A CN 201510808363 A CN201510808363 A CN 201510808363A CN 105460915 A CN105460915 A CN 105460915A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title abstract description 10
- 125000005842 heteroatom Chemical group 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 79
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 14
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 10
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 10
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 10
- 229960004853 betadex Drugs 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012467 final product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 2
- 229960003805 amantadine Drugs 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 108010025880 Cyclomaltodextrin glucanotransferase Proteins 0.000 description 1
- 125000003535 D-glucopyranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@@]([H])(O[H])[C@]1([H])O[H] 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- -1 cyclic oligosaccharide Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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)
- Carbon And Carbon Compounds (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
Abstract
The invention relates to a heteroelement doped porous carbon material, a preparing method thereof and applications of the heteroelement doped porous carbon material. The heteroelement doped porous carbon material is prepared by subjecting a main material and an object material to a hydrothermal reaction and then calcinating. The main material is beta-cyclodextrin. Molecules of the object material can be sleeved with holes of molecules of the main material. The heteroelement doped porous carbon material is prepared by subjecting the main material and the object material to the hydrothermal reaction and calcinating, so that the molecules of the object material can be sleeved with the holes of beta-cyclodextrin molecules. The carbon yield is increased and hetero elements can be introduced to form a porous structure, thus improving properties of the carbon material.
Description
Technical field
The invention belongs to field of nanometer material technology, relate to a kind of element doping porous carbon materials, be specifically related to a kind of assorted element doping porous carbon materials, preparation method and application thereof.
Background technology
Heteroatom doping can improve the surface wettability, electroconductibility etc. of carbon material, makes it in electrochemistry, have better application.The carbon material of porous Heteroatom doping is owing to having high conductivity, high specific surface area, high chemical stability, regulatable aperture, can be widely used in gas adsorption separation storage, catalyzer, stored energy, sensor field, in material science, have good prospect.
Beta-cyclodextrin (β-CD) is the cyclic oligosaccharide containing 7 D-glucopyranose units that amylose starch generates under the cyclomaltodextrin glucanotransferase effect produced by genus bacillus, and it has the characteristic such as abundance, low price.In addition, beta-cyclodextrin is not only a member of main body in supramolecular chemistry, and accounts for one seat in the precursor of carbon material.But existing organic molecule and ionic liquid, in carbonization process, substantially volatilize or are broken down into gas, carbon productive rate is extremely low, so can not be widely used in the preparation of carbon material.Need to prepare the high presoma of carbon productive rate, to improve its practical ranges.
Summary of the invention
The present invention seeks to provide a kind of assorted element doping porous carbon materials to overcome the deficiencies in the prior art.
For achieving the above object, the technical solution used in the present invention is: a kind of assorted element doping porous carbon materials, after it carries out hydro-thermal reaction by material of main part and guest materials, carry out calcining again to obtain, described material of main part is beta-cyclodextrin, and described guest materials molecule can be inserted in the hole of described host material molecules.
Optimally, described guest materials is the mixture of one or more compositions in the following chemical structure formula:
,
,
with
, in formula, n is the integer of 1 ~ 12, and m, o are the integer of 1 ~ 6 independently, and X is Cl, Br, I, PF
6or BF
4.
Further, described guest materials is the mixture of one or more compositions in the following chemical structure formula:
,
,
,
with
.
Optimally, the mol ratio of described material of main part and described guest materials is 1:1 ~ 3:1.
Another object of the present invention is the preparation method providing a kind of above-mentioned assorted element doping porous carbon materials, and it comprises the following steps:
A described guest materials molecule is inserted in the hole of described host material molecules and obtains mixing material by ();
B () adds deionized water in described mixing material, carry out hydro-thermal reaction obtain black solid with being placed in reactor;
C () is undertaken calcining by after described black solid grinding.
Optimally, described step (a) is: be dissolved in solvent by described guest materials and described material of main part, and 40 ~ 60 DEG C of reactions 5 ~ 20 hours, rotary evaporation removed desolventizing and obtains described mixing material subsequently.
Optimally, in step (b), described hydro-thermal reaction is 150 ~ 200 DEG C of reactions 15 ~ 25 hours.
Optimally, in step (c), described calcining is be warming up to 700 ~ 1000 DEG C of insulations 0.5 ~ 2 hour with the speed of 5 ~ 15 DEG C/min.
Optimally, it also comprises the black solid after step (d) grinding calcining, with dilute hydrochloric acid washing, then with deionized water wash to neutral, dries.
Another object of the present invention is to provide the application of a kind of above-mentioned assorted element doping porous carbon materials in electrode of super capacitor.
Because technique scheme is used, the present invention compared with prior art has following advantages: the present invention mixes element doping porous carbon materials, after material of main part and guest materials are carried out hydro-thermal reaction, carry out calcining again to obtain, make guest materials molecule can be inserted in the hole of beta-cyclodextrin molecule, not only effectively can put forward high carbon yield, assorted element can also be introduced and form vesicular structure, thus improve the performance of carbon material.
Accompanying drawing explanation
Accompanying drawing 1 is the SEM figure of assorted element doping porous carbon materials in embodiment 1;
Accompanying drawing 2 is the TEM figure of assorted element doping porous carbon materials in embodiment 1;
Fig. 3 is thermogravimetric analysis (TGA) figure of guest materials;
Fig. 4 is thermogravimetric analysis (TGA) figure of material of main part and guest materials mixture.
Embodiment
The present invention mixes element doping porous carbon materials, and after it carries out hydro-thermal reaction by material of main part and guest materials, then carry out calcining and obtain, described material of main part is beta-cyclodextrin, and described guest materials molecule can be inserted in the hole of described host material molecules.After material of main part and guest materials are carried out hydro-thermal reaction, carry out calcining again to obtain, make guest materials molecule can be inserted in the hole of beta-cyclodextrin molecule, not only effectively can put forward high carbon yield, assorted element can also be introduced and form vesicular structure, thus improving the performance of carbon material.
Described guest materials is preferably the mixture of one or more compositions in the following chemical structure formula:
,
,
with
, in formula, n is the integer of 1 ~ 12, and m, o are the integer of 1 ~ 6 independently, and X is Cl, Br, I, PF
6or BF
4, containing higher N content in these materials, thus improve the performance of carbon material further.These guest materialss are preferably the mixture of one or more compositions in the following chemical structure formula:
,
,
,
with
, the bonding force of these materials and beta-cyclodextrin is best, is conducive to the yield improving carbon material.The mol ratio of described material of main part and described guest materials is preferably 1:1 ~ 3:1, and it is excessive that material of main part needs, thus cost-saving.
The preparation method of above-mentioned assorted element doping porous carbon materials, it comprises the following steps: described guest materials molecule is inserted in the hole of described host material molecules and obtains mixing material by (a); B () adds deionized water in described mixing material, carry out hydro-thermal reaction obtain black solid with being placed in reactor; C () is undertaken calcining by after described black solid grinding.The method is calcined after now mixing material being carried out hydro-thermal reaction again, guest materials and material of main part can either be made so accurate evenly can combine and carry out pre-carbonization, thus guarantee the even of carbon material; And technique is simple, cost is low, is suitable for scale operation.Described step (a) is: be dissolved in solvent by described guest materials and described material of main part, and 40 ~ 60 DEG C of reactions 5 ~ 20 hours, rotary evaporation removed desolventizing and obtains described mixing material subsequently.In step (b), described hydro-thermal reaction is 150 ~ 200 DEG C of reactions 15 ~ 25 hours.In step (c), described calcining is be warming up to 700 ~ 1000 DEG C of insulations 0.5 ~ 2 hour with the speed of 5 ~ 15 DEG C/min.It also comprises the black solid after step (d) grinding calcining, with dilute hydrochloric acid washing, then with deionized water wash to neutral, dries.The application of above-mentioned assorted element doping porous carbon materials in electrode of super capacitor, specifically with reference to prior art, mainly can be made into electrode of super capacitor by obtained carbon material and binding agent, carbon black etc.
Below in conjunction with accompanying drawing embodiment, the present invention is further described.
Embodiment 1
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, and it comprises the following steps:
A () is by 2g β-CD(1.8mmol) be dissolved in 5mlDMF with 0.35g P-aminoazobenzene (P-AZO) (1.8mmol), dissolve to obtain mixing material 40 DEG C of heated and stirred; Add 100ml water wherein, separate out precipitation, filter to obtain solid;
B solid that step (a) obtains by () and 10g water to add in hydrothermal reaction kettle and seal, and 180 DEG C of reactions 24 hours, reaction terminated rear centrifugal black solid;
C step (d) black solid and KOH are that 1:2 fully grinds with mass ratio by (), be placed in inert gas atmosphere in 800 DEG C of (temperature rise rate is 5 DEG C/min) carbonizations 1 hour, the product obtained is pulverized, wash with the hydrochloric acid soln of 1mol/L, extremely neutral with deionized water wash again, centrifugal final vacuum is dry; The specific surface area of final product is 989.4m
2/ g, nitrogen content is 4.16%, and carries out Electronic Speculum test (SEM and TEM), as depicted in figs. 1 and 2.
Embodiment 2
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, basically identical in its detailed process and embodiment 1, unlike: in step (a), DMF is removed to obtain solid by Rotary Evaporators.
Embodiment 3
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, and it comprises the following steps:
A () is by 2g β-CD(1.8mmol) and 0.267g amantadine (Ad-NH
2) (1.8mmol) be dissolved in 10g deionized water, dissolves to obtain mixing material 60 DEG C of heated and stirred;
B mixing solutions to add in hydrothermal reaction kettle and seals by (), 150 DEG C of reactions 25 hours, reaction terminated rear centrifugal black solid;
C product that step (b) obtains by () is placed in inert gas atmosphere in 1000 DEG C of (temperature rise rate 15 DEG C/min) carbonizations 0.5 hour, product is pulverized, first wash with the hydrochloric acid soln of 0.5mol/L, extremely neutral with deionized water wash again, centrifugal final vacuum is dry, and final product nitrogen content is 4.7%.
Embodiment 4
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, and it comprises the following steps:
A () is by 6g β-CD(5.4mmol) and 0.267g amantadine (Ad-NH
2) (1.8mmol) be dissolved in 20g deionized water, dissolves to obtain mixing material 50 DEG C of heated and stirred;
B mixing solutions to add in hydrothermal reaction kettle and seals by (), 200 DEG C of reactions 15 hours, reaction terminated rear centrifugal black solid;
C product that step (b) obtains by () is placed in inert gas atmosphere in 700 DEG C of (temperature rise rate 10 DEG C/min) carbonizations 2 hours, product is pulverized, first wash with the hydrochloric acid soln of 2mol/L, extremely neutral with deionized water wash again, centrifugal final vacuum is dry, and final product nitrogen content is 6.7%.
Embodiment 5
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, basically identical in its step and embodiment 1, unlike: that add is 0.417g1-dodecyl imidazole (DIM) (1.8mmol), and final product nitrogen content is 5.7%.
Embodiment 6
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, basically identical in its step and embodiment 1, unlike: that add is 0.5g1 – Ding Ji – 3 – Methylimidazole hexafluorophosphate (BMIPF
6), final product nitrogen content is 5.1%, phosphorus content 0.6%, fluorine content 0.2%.
Embodiment 7
The present embodiment provides a kind of preparation method of nitrogen-doped porous carbon material, basically identical in its step and embodiment 1, unlike: that add is 0.398g1 – Ding Ji – 3 – methyl imidazolium tetrafluoroborate (BMIBF
4), the final product nitrogen content obtained is 2.6%, boron-containing quantity 12.4%, fluorine content 0.3%.
Comparative example 1
The guest materials used in embodiment 1, embodiment 3, embodiment 5, embodiment 6, embodiment 7 is carried out thermal weight loss test (TGA) separately, as shown in Figure 3; And the mixing material of the guest materials in embodiment 1, embodiment 3, embodiment 5, embodiment 6, embodiment 7 and material of main part reaction is carried out thermal weight loss test (TGA) separately, as shown in Figure 4; Carbon productive rate that can be final is significantly increased to more than 10%.
Embodiment 6
The present embodiment provides the application of the nitrogen-doped porous carbon material of preparation in a kind of embodiment 1, be prepared into electrode material for super capacitor, concrete making method is consistent with existing method, can referenced patent number be specifically method in the Chinese invention patent embodiment 12 of 201310060380.3; Then this electrode being dipped in concentration is carry out conventional electro-chemical test in the KOH solution of 6mol/L, it is 1A/g that the ratio capacitance value recording it is respectively 345F/g(current density) and 216F/g(current density be 30A/g), and cycle charge-discharge 5000 times, still can retain the ratio capacitance of 95%, there is high stability and excellent electrochemical properties.
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. an assorted element doping porous carbon materials, it is characterized in that: after it carries out hydro-thermal reaction by material of main part and guest materials, carry out calcining again to obtain, described material of main part is beta-cyclodextrin, and described guest materials molecule can be inserted in the hole of described host material molecules.
2. assorted element doping porous carbon materials according to claim 1, is characterized in that, described guest materials is the mixture of one or more compositions in the following chemical structure formula:
,
,
with
, in formula, n is the integer of 1 ~ 12, and m, o are the integer of 1 ~ 6 independently, and X is Cl, Br, I, PF
6or BF
4.
3. assorted element doping porous carbon materials according to claim 2, is characterized in that, described guest materials is the mixture of one or more compositions in the following chemical structure formula:
,
,
,
with
.
4. assorted element doping porous carbon materials according to claim 1, is characterized in that: the mol ratio of described material of main part and described guest materials is 1:1 ~ 3:1.
5. the preparation method of arbitrary described assorted element doping porous carbon materials in Claims 1-4, it is characterized in that, it comprises the following steps:
A described guest materials molecule is inserted in the hole of described host material molecules and obtains mixing material by ();
B () adds deionized water in described mixing material, carry out hydro-thermal reaction obtain black solid with being placed in reactor;
C () is undertaken calcining by after described black solid grinding.
6. the preparation method of assorted element doping porous carbon materials according to claim 5, it is characterized in that, described step (a) is: be dissolved in solvent by described guest materials and described material of main part, and 40 ~ 60 DEG C of reactions 5 ~ 20 hours, rotary evaporation removed desolventizing and obtains described mixing material subsequently.
7. the preparation method of assorted element doping porous carbon materials according to claim 5, it is characterized in that: in step (b), described hydro-thermal reaction be react 15 ~ 25 hours at 150 ~ 200 DEG C.
8. the preparation method of assorted element doping porous carbon materials according to claim 5, it is characterized in that: in step (c), described calcining be warming up to 700 ~ 1000 DEG C with the speed of 5 ~ 15 DEG C/min to be incubated 0.5 ~ 2 hour.
9. the preparation method of assorted element doping porous carbon materials according to claim 5, is characterized in that: it also comprises the black solid after step (d) grinding calcining, with dilute hydrochloric acid washing, then with deionized water wash to neutral, dries.
10. the application of arbitrary described assorted element doping porous carbon materials in electrode of super capacitor in Claims 1-4.
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| CN107487766A (en) * | 2017-08-29 | 2017-12-19 | 东华理工大学 | A kind of three-dimensional porous carbon material of Heteroatom doping and preparation method thereof |
| CN108470643A (en) * | 2018-03-29 | 2018-08-31 | 渤海大学 | A kind of preparation method of adamantane amine electrolytic solution for super capacitor |
| CN110911697A (en) * | 2019-11-22 | 2020-03-24 | 深圳大学 | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof |
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| CN103406096A (en) * | 2013-07-17 | 2013-11-27 | 国家纳米科学中心 | Nitrogen-doped porous carbon material, preparation method and use thereof |
| CN104056556A (en) * | 2014-06-27 | 2014-09-24 | 南京大学 | Modification method for etching surface of membrane-type artificial lung and bonding beta-cyclodextrin by using low-temperature plasma |
| CN104743540A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN104979105A (en) * | 2015-07-13 | 2015-10-14 | 苏州大学 | Nitrogen-doped porous carbon material, preparation method and applications |
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- 2015-11-20 CN CN201510808363.2A patent/CN105460915B/en active Active
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| CN103406096A (en) * | 2013-07-17 | 2013-11-27 | 国家纳米科学中心 | Nitrogen-doped porous carbon material, preparation method and use thereof |
| CN104743540A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN104056556A (en) * | 2014-06-27 | 2014-09-24 | 南京大学 | Modification method for etching surface of membrane-type artificial lung and bonding beta-cyclodextrin by using low-temperature plasma |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107487766A (en) * | 2017-08-29 | 2017-12-19 | 东华理工大学 | A kind of three-dimensional porous carbon material of Heteroatom doping and preparation method thereof |
| CN108470643A (en) * | 2018-03-29 | 2018-08-31 | 渤海大学 | A kind of preparation method of adamantane amine electrolytic solution for super capacitor |
| CN110911697A (en) * | 2019-11-22 | 2020-03-24 | 深圳大学 | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof |
| CN110911697B (en) * | 2019-11-22 | 2022-06-07 | 深圳大学 | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof |
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| CN105460915B (en) | 2017-09-05 |
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