CN105129767A - Method for preparing two-dimension nitrogen-containing porous carbon material - Google Patents
Method for preparing two-dimension nitrogen-containing porous carbon material Download PDFInfo
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- CN105129767A CN105129767A CN201510500320.8A CN201510500320A CN105129767A CN 105129767 A CN105129767 A CN 105129767A CN 201510500320 A CN201510500320 A CN 201510500320A CN 105129767 A CN105129767 A CN 105129767A
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- carbon material
- porous carbon
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- santochlor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention discloses a method for preparing a two-dimensional nitrogen-containing porous carbon material, dichlorobenzene waste as a carbon source, Mg (OH) 2 as a template and azodicarbonamide as a nitrogen source are mixed in a proper ratio, and at a certain temperature, argon gas is introduced in for template carbonization reaction to obtain a porous carbon material used for a supercapacitor. Through regulation of mass ratio of the dichlorobenzene, the nano flake-shaped Mg (OH) 2 and the azodicarboxamide, carbonization temperature and heating rate and other factors, the two-dimensional nitrogen-containing porous carbon material is synthesized. The prepared two-dimensional nitrogen-containing porous carbon material has high purity, excellent ultra-capacitor performance and other characteristics. In addition, the production process is simple, easy to operate, short in synthetic cycle, and suitable for scale production of a two-dimensional scale nitrogen-doped supercapacitor electrode carbon material.
Description
One, technical field
The present invention relates to the preparation method of the nitrogenous porous carbon material of a kind of two dimension, belong to electrode of super capacitor field of charcoal material.
Two, background technology
Ultracapacitor, as a kind of Novel energy storage apparatus, is a kind of new power type energy storage equipment between traditional capacitor and rechargeable battery with fast charging and discharging, has superpower (10kWkg
– 1), have extended cycle life (more than 100,000 times can be reached), discharge and recharge fast fast and security high, in the automobile etc. of aerospace, power supply supply, storage and backup system and advanced person, have very wide application prospect.
Electrode materials is the key of ultracapacitor, and it decides the main performance index of ultracapacitor.The research that the various porous carbon materials such as activity charcoal powder, activated carbon fiber, carbon gel, template carbon are used as electrode material for super capacitor has report.Aperture is large, hole dimension is adjustable, specific surface area high owing to having for template carbon, and the electrode materials high rate performance as ultracapacitor is given prominence to.After Ruoff equals reported first in 2008 capacitive property of Graphene, this there is two-dimensional nanostructure, the novel charcoal material of high conductivity receives publicity rapidly in the application in ultracapacitor field, become a focus of current research.
In addition, by certain technique means, Carbon Materials can be adulterated the nitrogen impurity of some content, be also necessary.Such nitrogen impurity can produce typical fake capacitance in electrode, in conjunction with the electric double layer capacitance (EDLC) of Carbon Materials self, can significantly improve the performance of ultracapacitor.
Santochlor is white crystal, easy distillation, irritant smell is important organic synthesis raw material, for the synthesis of dyestuff (large red-based g G) and pesticide intermediate, as fumigating insecticide, fabric mothproofing agent, deodorization of air agent, 65% ~ 70% for the manufacture of naphthalene ball, a small amount of for extreme pressure lubricant, corrosion inhibitor.But with regard to santochlor waste material, its degraded at natural environmental condition is comparatively slow, very huge to the harm of environment particularly human body, can produce serial irreversible damage, therefore, how effective recycling santochlor waste material is an important research topic.
Patent of invention CN102956876A provides a kind of pyrolytic hard carbon material and its production and use.This pyrolytic hard carbon material be hard carbon precursor pyrolysis is formed, there is mean thickness 1-200nm, geometrical surface 10-2000m
2the sheeting of the similar two dimensional surface of/g, there is micropore or mesopore in described pyrolytic hard carbon material inside.But the two-dimensional sheet structure that this patent relates to is in micron-scale, fails to reach nano-scale.
Three, summary of the invention
The present invention aims to provide the preparation method of the nitrogenous porous carbon material of a kind of two dimension, be with santochlor waste material be carbon source, nano-sheet Mg (OH)
2for template, Cellmic C 121 are nitrogenous source, by template charring control synthesis two-dimentional nitrogenous porous carbon material, present method is easy and simple to handle, electrochemical capacitance excellent performance, be easy to large-scale industrial produce.
The preparation method of the nitrogenous porous carbon material of the present invention's two dimension comprises the steps:
The ratio of 1:0.5-3:0.5-5 takes santochlor waste material, nano-sheet Mg (OH) in mass ratio
2with Cellmic C 121 powder, obtain mixture after grinding, described mixture is moved in horizontal pipe furnace porcelain boat, pass into argon gas 30min, subsequently horizontal pipe furnace is heated to 700-900 DEG C with the temperature rise rate of 5 ~ 20 DEG C/min, and is incubated 2 ~ 8h in argon gas atmosphere; Products therefrom is put into 1mol/L hydrochloric acid soln to flood, to remove solvable and soluble impurity, extremely neutral with deionized water wash after suction filtration, collect black precipitate, in 120 DEG C of vacuum-drying 12h, obtain two-dimentional nitrogenous porous carbon material.
The making of experimental electrode:
Take ethanol as solvent, tetrafluoroethylene (PTFE) tackiness agent of the Carbon Materials sample of 80 mass parts, the acetylene black of 15 mass parts and 5 mass parts is mixed and obtains mix slurry, under 20MPa pressure, this mix slurry is pressed onto in collector nickel foam subsequently, vacuum-drying 24 hours at 120 DEG C subsequently, obtains carbon material electrode.
Electrochemical property test:
In three-electrode system, with platinum electrode (6cm
2) for supporting electrode, saturated calomel electrode be reference electrode, carbon material electrode is working electrode, utilizes KOH solution (6mol/L) to be electrolytic solution.Electrochemical workstation is adopted to carry out the electro-chemical tests such as cyclic voltammetric, constant current charge-discharge and alternating-current impedance.
The present invention is by regulation and control santochlor, nano-sheet Mg (OH)
2with mass ratio, the factor such as carbonization temperature and temperature rise rate of Cellmic C 121, synthesize two-dimentional nitrogenous porous carbon material.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention is with santochlor waste material for carbon source, can effectively improve its resource utilization degree.
2, the present invention is with nano-sheet Mg (OH)
2for template, its flake nano structure can be kept in carbonization process, thus obtain two-dimentional Carbon Materials.
3, the present invention take Cellmic C 121 as nitrogenous source, can significantly improve the nitrogen content of Carbon Materials.
4, the nitrogenous porous carbon material of two dimension that the present invention obtains has the features such as ratio capacitance is high, good cycle, and under the current density of 1A/g, discharge and recharge ratio capacitance can reach 312.3F/g.Circulate after 5000 times, discharge and recharge ratio capacitance conservation rate is up to 98%.
5, reaction time of the present invention is short, and easy handling is less demanding to reaction conditions, and the large-scale industrial that can realize two-dimentional nitrogenous porous carbon material is produced.
Four, accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of the Carbon Materials sample that embodiment 1 obtains.As can be seen from Figure 1 Carbon Materials sample presents two-dimensional sheet nanostructure.
Fig. 2 is scanning electron microscope (SEM) photo of the Carbon Materials sample that embodiment 2 obtains.As can be seen from Figure 2 Carbon Materials sample presents two-dimensional sheet nanostructure.
Fig. 3 is scanning electron microscope (SEM) photo of the Carbon Materials sample that embodiment 3 obtains.As can be seen from Figure 3 Carbon Materials sample presents two-dimensional sheet nanostructure.
Five, embodiment
Embodiment 1:
1:0.5:1 takes santochlor waste material, Mg (OH) in mass ratio
2with Cellmic C 121 powder, fully obtain mixture after grinding, this mixture is moved in horizontal pipe furnace porcelain boat, passes into argon gas 30min, subsequently horizontal pipe furnace is heated to 800 DEG C with the temperature rise rate of 5 DEG C/min, and is incubated 2h in argon gas atmosphere.Products therefrom is put into 1mol/L dilute hydrochloric acid solution to flood, to remove solvable and soluble impurity, extremely neutral with deionized water wash after suction filtration, collect black precipitate, in 120 DEG C of vacuum-drying 12h, obtain two-dimentional nitrogenous porous carbon material.
Embodiment 2:
First appropriate santochlor waste material, Mg (OH) is taken
2fully grind with Cellmic C 121 powder (mass ratio is 1:1:2), then this mixture is moved in horizontal pipe furnace porcelain boat, pass into argon gas 30min, subsequently horizontal pipe furnace is heated to 700 DEG C with the temperature rise rate of 10 DEG C/min, and is incubated 4h in argon gas atmosphere.Products therefrom is put into 1mol/L dilute hydrochloric acid solution to flood, to remove solvable and soluble impurity, extremely neutral with deionized water wash after suction filtration, collect black precipitate, in 120 DEG C of vacuum-drying 12h, obtain two-dimentional nitrogenous porous carbon material.
Embodiment 3:
First appropriate santochlor waste material, Mg (OH) is taken
2fully grind with Cellmic C 121 powder (mass ratio is 1:0.5:3.5), then this mixture is moved in horizontal pipe furnace porcelain boat, pass into argon gas 30min, subsequently horizontal pipe furnace is heated to 900 DEG C with the temperature rise rate of 15 DEG C/min, and is incubated 8h in argon gas atmosphere.Products therefrom is put into 1mol/L dilute hydrochloric acid solution to flood, to remove solvable and soluble impurity, extremely neutral with deionized water wash after suction filtration, collect black precipitate, in 120 DEG C of vacuum-drying 12h, obtain two-dimentional nitrogenous porous carbon material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. a preparation method for the nitrogenous porous carbon material of two dimension, is characterized in that: be with santochlor waste material be carbon source, nano-sheet Mg (OH)
2for template, Cellmic C 121 are nitrogenous source, control the two-dimentional nitrogenous porous carbon material of synthesis by template charring.
2. preparation method according to claim 1, is characterized in that comprising the steps:
By santochlor waste material, nano-sheet Mg (OH)
2obtain mixture with after the grinding of Cellmic C 121 powder, described mixture is moved in horizontal pipe furnace porcelain boat, passes into argon gas, subsequently horizontal pipe furnace is warming up to 700-900 DEG C, and be incubated 2 ~ 8h in argon gas atmosphere; Products therefrom is put into 1mol/L hydrochloric acid soln to flood, to remove solvable and soluble impurity, extremely neutral with deionized water wash after suction filtration, collect black precipitate, in 120 DEG C of vacuum-drying 12h, obtain two-dimentional nitrogenous porous carbon material.
3. preparation method according to claim 1 and 2, is characterized in that:
Santochlor waste material, nano-sheet Mg (OH)
2be 1:0.5-3:0.5-5 with the mass ratio of Cellmic C 121.
4. preparation method according to claim 2, is characterized in that:
The temperature rise rate of horizontal pipe furnace is set to 5 ~ 20 DEG C/min.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102325721A (en) * | 2009-03-10 | 2012-01-18 | 东洋炭素株式会社 | Porous carbon and process for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102325721A (en) * | 2009-03-10 | 2012-01-18 | 东洋炭素株式会社 | Porous carbon and process for producing same |
Non-Patent Citations (2)
| Title |
|---|
| HAI TAO YI ET AL.: "A simple Mg(OH)2-assisted template carbonization method to N-doped nanoporous carbon material from phenidone and the capacitive improvement with the addition of azobisformamide", 《ELECTROCHIMICA ACTA》 * |
| ZHONG JIE ZHANG ET AL.: "Pronounced improvement of supercapacitor capacitance by using redox active electrolyte of p-phenylenediamine", 《ELECTROCHIMICA ACTA》 * |
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