CN108439364A - A kind of preparation method of situ Nitrogen Doping porous carbon microsphere - Google Patents
A kind of preparation method of situ Nitrogen Doping porous carbon microsphere Download PDFInfo
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- CN108439364A CN108439364A CN201810424345.8A CN201810424345A CN108439364A CN 108439364 A CN108439364 A CN 108439364A CN 201810424345 A CN201810424345 A CN 201810424345A CN 108439364 A CN108439364 A CN 108439364A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The present invention relates to a kind of preparation methods of situ Nitrogen Doping porous carbon microsphere.Ammonium hydroxide, water and ethyl alcohol are mixed, resorcinol is added, is added with stirring 2 formaldehyde of pyridine；60min is stirred at 50 DEG C, for 24 hours in 100 DEG C of hydro-thermal reactions, polymer with nitrogen microballoon is made.After microballoon drying, in an inert gas atmosphere, is carbonized from room temperature to 700 900 DEG C with the heating rate of 5 10 DEG C/min, obtain N doping porous carbon microsphere.Present invention process is simple, when gained N doping porous carbon microsphere is as electrode material for super capacitor, shows higher specific capacity and preferable cyclical stability.
Description
Technical field
The present invention relates to a kind of preparation methods of situ Nitrogen Doping porous carbon microsphere, belong to technical field of material.
Background technology
Ultracapacitor is a kind of new type of energy storage device between battery and traditional capacitor, has power density
Greatly, the advantages that having extended cycle life has broad application prospects in the fields such as electric vehicle and electronic product.Carbon material is as double
Electric layer capacitor electrode material shows good physics and chemical stability and cyclical stability, there is wider operating temperature model
It encloses.For carbosphere because of its unique nanostructure and pattern, not only itself has abundant hole, but also can be by between sphere
Accumulation formed accumulation hole, these accumulation holes can be used as " ion reservoir " reduction electrolyte ion enter ball interior duct
Transmission path is conducive to improve chemical property of the carbosphere as electrode material for super capacitor.However, prepared by carbon material
It needs to undergo high temperature carbonization process in the process, leads to its surface carbon atom relative inertness so that its wettability of the surface is poor, limit
The fast transferring of electrolyte ion is made.Nitrogen atom doping can not only improve carbon material surface wetability, and can provide
Additional fake capacitance, therefore by the extensive concern of researcher.For example, Zhang Jianan etc. is reported, " a kind of nitrogen-doped nanometer is porous
The preparation method of hollow carbon balls " (Chinese invention patent, application number：201710655676.8), it is single with styrene, acrylonitrile
Polystyrene/polyacrylonitrile nucleocapsid structure composite microballoon is made by mini-emulsion polymerization in body；Silane coupling agent is added dropwise again, continues
Polymerization forms polystyrene/polyacrylonitrile/polysilane coupling agent bilayer nucleocapsid complex microsphere；Then pass through pre-oxidation, charing and
Nitrogen-doped nanometer Porous hollow carbon ball is made after the removal of shell silica；A kind of " hollow mesoporous Nano carbon balls of nitrogen functionalization
Preparation method " (Chinese invention patent, application number：201710320031.9) in using tetrapropoxysilane as silica template
Raw material, using resorcinol and formaldehyde as raw material, prepared by solvent-thermal method and under inert gas atmosphere charing contains silica nanometer
The polymer Nano carbon balls of particle, by going template, then using ionic liquid as nitrogen source, after being mixed with carbon material charing obtain nitrogen work(
The hollow mesoporous Nano carbon balls of energyization.However there are preparation method complexity for these methods, or needed using template in preparation process,
The shortcomings of time-consuming.
Invention content
It is an object of the invention to disclose a kind of preparation method of situ Nitrogen Doping porous carbon microsphere.It is molten with water and ethyl alcohol
Agent, ammonium hydroxide are catalyst, and resorcinol and pyridine-2-formaldehyde are carried out hydro-thermal reaction, obtain polymer with nitrogen microballoon, by its
N doping porous carbon microsphere can be obtained after being carbonized in inert atmosphere.This method simple and effective, it is raw materials used cheap, to forerunner
Body does not need any template or activation process without pretreatment yet.
Specific preparation process carries out as follows：
By 1：44：13.8：1.1-2.2：The mass fraction of 1.3-2.6 measure successively ammonium hydroxide, water, ethyl alcohol, resorcinol and
Pyridine-2-formaldehyde.Ammonium hydroxide, water and ethyl alcohol are uniformly mixed, resorcinol is then added, pyridine-2-formaldehyde is added under stirring；
60min is stirred at 50 DEG C, for 24 hours in 100 DEG C of hydro-thermal reactions, polymer with nitrogen microballoon is made.After microballoon drying, in inert gas
In atmosphere, with the heating rate of 5-10 DEG C/min, DEG C charing from room temperature to 700-900, obtains N doping porous carbon microsphere.
Above-mentioned inert gas selects one kind in nitrogen, argon gas, helium；
The above raw material is commercially available technical grade product.
The invention has the advantages that：
1. the present invention need not be using any template or activation process, gained without pre-processing, also to carbon matrix precursor
Material morphology rule, preparation method are simple and direct efficiently.
2. N doping porous carbon microsphere prepared by the present invention is uniform in size, good dispersion, diameter about 900nm, specific surface area
600m2/ g or more, nitrogen content reach 4-7wt%.
3. N doping porous carbon microsphere prepared by the present invention is as electrode material for super capacitor, table is tested through analysis
Bright, in current density 1A/g, electrode specific capacitance is 220F/g or more, and the capacity retention ratio after cycle charge-discharge 5000 times exists
89% or more, show height ratio capacity and excellent cyclical stability.
Specific implementation mode
Embodiment 1
By 1：44：13.8：1.1：1.3 mass fraction measures ammonium hydroxide, water, ethyl alcohol, resorcinol and pyridine-2-formaldehyde.
Ammonium hydroxide, water and ethyl alcohol are uniformly mixed, resorcinol is added, is added with stirring pyridine-2-formaldehyde；60min is stirred at 50 DEG C, in
For 24 hours, polymer with nitrogen microballoon is made in 100 DEG C of hydro-thermal reactions.After microballoon drying, in an inert gas atmosphere, with 5 DEG C/min's
Heating rate is carbonized from room temperature to 700 DEG C, obtains N doping porous carbon microsphere.
Embodiment 2
By 1：44：13.8：1.5：2 mass fraction measures ammonium hydroxide, water, ethyl alcohol, resorcinol and pyridine-2-formaldehyde.It will
Ammonium hydroxide, water and ethyl alcohol are uniformly mixed, and resorcinol is added, is added with stirring pyridine-2-formaldehyde；60min is stirred at 50 DEG C, in
For 24 hours, polymer with nitrogen microballoon is made in 100 DEG C of hydro-thermal reactions.After microballoon drying, in an inert gas atmosphere, with 7 DEG C/min's
Heating rate is carbonized from room temperature to 800 DEG C, obtains N doping porous carbon microsphere.
Embodiment 3
By 1：44：13.8：2.2：2.6 mass fraction measures ammonium hydroxide, water, ethyl alcohol, resorcinol and pyridine-2-formaldehyde.
Ammonium hydroxide, water and ethyl alcohol are uniformly mixed, resorcinol is added, is added with stirring pyridine-2-formaldehyde；60min is stirred at 50 DEG C, in
For 24 hours, polymer with nitrogen microballoon is made in 100 DEG C of hydro-thermal reactions.After microballoon drying, in an inert gas atmosphere, with 10 DEG C/min
Heating rate from room temperature to 900 DEG C carbonize, obtain N doping porous carbon microsphere.
Analysis test result shows that the N doping porous carbon microsphere that embodiment 1-3 is obtained is uniform in size, good dispersion, directly
Diameter about 900nm, specific surface area 600m2/ g or more, nitrogen content reach 4-7wt%.The N doping porous carbon that embodiment 1-3 is obtained is micro-
Ball presses 8 with graphite and polytetrafluoroethylene (PTFE) (PTFE)：1：1 mass ratio measures, and is dissolved in ethanol solution after ground and mixed is uniform, surpasses
Sound oscillation 1h forms slurry.After the slurry is dried, covered in nickel foam with the pressure of 20MPa, and in 60 DEG C of dryings
12h obtains N doping porous carbon microsphere electrode material for super capacitor.Using N doping porous carbon microsphere as working electrode, nickel foam
For to electrode, Hg/HgO electrodes are reference electrode.With electrochemical workstation (CHI 660D) in the KOH electrolyte of 6mol/L,
It is electrical in 25 DEG C of specific capacity values and cycle charge discharge in potential window -1.0-0V test N doping porous carbon microsphere electrode materials
Energy.Test result shows gained N doping porous carbon microsphere as electrode material for super capacitor, in current density 1A/g,
Electrode specific capacitance is 220F/g or more, and the capacity retention ratio after cycle charge-discharge 5000 times shows Fabrication of High Specific Capacitance 89% or more
Amount and excellent cyclical stability.
The above raw material is commercially available technical grade product.
Above-mentioned hydro-thermal reaction refers to：Reactant is fitted into the stainless steel water heating kettle of inner liner polytetrafluoroethylene and is carried out at hydro-thermal
Reason reaction.
Claims (1)
1. a kind of preparation method of situ Nitrogen Doping porous carbon microsphere, it is characterised in that：
By 1：44：13.8：1.1-2.2：The mass fraction of 1.3-2.6 measures ammonium hydroxide, water, ethyl alcohol, resorcinol and pyridine-successively
2- formaldehyde；Ammonium hydroxide, water and ethyl alcohol are uniformly mixed, resorcinol is then added, pyridine-2-formaldehyde is added under stirring；50℃
For 24 hours in 100 DEG C of hydro-thermal reactions polymer with nitrogen microballoon is made, after microballoon drying, in inert gas atmosphere in lower stirring 60min
In, with the heating rate of 5-10 DEG C/min, DEG C charing from room temperature to 700-900, obtains N doping porous carbon microsphere；
Above-mentioned inert gas selects one kind in nitrogen, argon gas, helium；
The above raw material is commercially available technical grade product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378485A (en) * | 2018-11-03 | 2019-02-22 | 东华大学 | A kind of nonmetallic pyridine nitrogen-doped carbon composite material and preparation method and application based on nano wire |
| CN113443625A (en) * | 2021-06-30 | 2021-09-28 | 华东理工大学 | Preparation method of polystyrene resin-based spherical activated carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103871756A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院兰州化学物理研究所 | Preparation method of submicron porous carbon bead |
| CN105152160A (en) * | 2015-10-21 | 2015-12-16 | 哈尔滨工业大学 | Preparation method of nitrogen-doped carbon microspheres |
-
2018
- 2018-05-07 CN CN201810424345.8A patent/CN108439364A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103871756A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院兰州化学物理研究所 | Preparation method of submicron porous carbon bead |
| CN105152160A (en) * | 2015-10-21 | 2015-12-16 | 哈尔滨工业大学 | Preparation method of nitrogen-doped carbon microspheres |
Non-Patent Citations (1)
| Title |
|---|
| 陈毅等: "含氮多孔碳微球的制备及其电化学性能研究", 《中国化学会第十六届胶体与界面化学会议论文摘要集-第二分会：功能微纳米材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378485A (en) * | 2018-11-03 | 2019-02-22 | 东华大学 | A kind of nonmetallic pyridine nitrogen-doped carbon composite material and preparation method and application based on nano wire |
| CN109378485B (en) * | 2018-11-03 | 2022-07-12 | 东华大学 | Nanowire-based nonmetal pyridine nitrogen-doped carbon composite material and preparation method and application thereof |
| CN113443625A (en) * | 2021-06-30 | 2021-09-28 | 华东理工大学 | Preparation method of polystyrene resin-based spherical activated carbon |
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