CN109867271A - A kind of preparation method of nitrogen, oxygen, the porous carbon nano-particle of sulphur codope - Google Patents
A kind of preparation method of nitrogen, oxygen, the porous carbon nano-particle of sulphur codope Download PDFInfo
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- CN109867271A CN109867271A CN201910178953.XA CN201910178953A CN109867271A CN 109867271 A CN109867271 A CN 109867271A CN 201910178953 A CN201910178953 A CN 201910178953A CN 109867271 A CN109867271 A CN 109867271A
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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 relates to the preparation methods of a kind of nitrogen, oxygen, the porous carbon nano-particle of sulphur codope.Thiocarbamide, 1,4-benzoquinone and ethyl alcohol are successively weighed by the mass ratio of 1:1.4~5.7:50~210, first thiocarbamide and 1,4-benzoquinone are dissolved in ethyl alcohol and being uniformly mixed, under 300~800 revs/min of mixing speed, in 30~70 DEG C of reaction 120min.It is mixed, is subsequently placed in tube furnace, inert gas shielding, by 2~20 DEG C of min with the mass ratio of 1:0.5~3 with potassium hydroxide after gained amine quinone polymer filtration, ethanol washing, drying‑1Heating rate the polymer is heated to 600~1000 DEG C of carbonizations, 2~3h of constant temperature is naturally cooling to room temperature to get nitrogen, oxygen, the porous carbon nano-particle of sulphur codope.Present invention process is simple, is easy to implement, the reaction time is short；Nitrogen obtained, oxygen, sulphur codope carbon nano-particle have many advantages, such as specific surface area and content of heteroatoms height, hierarchical porous structure, nano particle geometrical morphology, when being used as electrode of super capacitor, have excellent chemical property.
Description
Technical field
The present invention relates to the preparation methods of a kind of nitrogen, oxygen, the porous carbon nano-particle of sulphur codope, belong to material preparation technology
Field.
Background technique
Electrochemical energy storage plays an important role in cleaning and the development of sustainable energy technology.Supercapacitor conduct
A kind of electrochemical device, due to its power density is high, charge/discharge speed is fast, have extended cycle life the features such as, receive the pole of people
Big concern.Electrode is one of critical component of supercapacitor.So far, in the material of various manufacture electrodes, carbon material
It is wide because of its adjustable porous structure, bigger serface, good electron conduction and chemical thermal stability outstanding advantages of
General use.In order to improve the memory capacity of supercapacitor, there are many researchs to be directed to develop advanced carbon electrode material.
Carbon nano-particle has adjustable partial size, good mechanical stability and pattern equal as novel functional material
One many advantages, such as, has broad application prospects in fields such as drug delivery, catalyst carrier, photoelectric device, energy storages.
Entitled " mixing method prepares the carbon nano-particle of graded porous structure and its application in lithium ion battery " (middle promulgated by the State Council
Bright patent, application number CN201810977540) it is exactly application in energy storage field.
Currently, the preparation method of carbon nano-particle mainly has templated synthesis, self-assembly method, hydro-thermal reaction, chemical vapor deposition
Area method.Although templated synthesis can be limited by the specific of template with the carbon nano-particle material of controlled syntheses rule, this method
Size, at high cost, preparation process need it is subsequent remove template step, limit practical application.Self-assembly method and chemical vapor deposition
Method usually requires stringent operating condition.The more demanding temperature and pressure environment of hydro-thermal reaction.In addition, carbon nano-particle surface
Relative inertness result in material wettability it is poor, to affect its surface property.
Summary of the invention
It is an object of the invention to a kind of open new carbon nano-particle preparation methods, specifically disclose one kind and are simple and efficient
Nitrogen, oxygen, the porous carbon nano-particle of sulphur codope preparation method.The porous carbon nano-particle tool prepared with method of the invention
There are specific surface area and content of heteroatoms height, hierarchical porous structure, nano particle geometrical morphology.
In order to achieve the above objectives, with 1,4-benzoquinone and thiocarbamide Michael addition reaction generation quinone amine polymerization occurs for present invention selection
Nitrogen, oxygen, the porous carbon nano-particle of sulphur codope is made after synchronous carbonization/chemical activation in object.The present invention is in carbon nano-particle
Surface introducing hetero-atoms not only facilitate and improve its electric conductivity and wetability, while hetero atom can also provide additional counterfeit electricity
Hold, to significantly improve chemical property.Simple, time saving, without template and complicated harshness the experiment condition of the method preparation process,
Hetero atom can be uniformly introduced in carbon nano-particle material skeleton.When it is as electrode material for super capacitor, have
High specific capacitance and superior cyclical stability.
Specific preparation process carries out as follows:
Weigh thiocarbamide in mass ratio: 1,4-benzoquinone: thiocarbamide and 1,4-benzoquinone are dissolved in second by ethyl alcohol=1:1.4~5.7:50~210
In alcohol, it is uniformly mixed, under 300~800 revs/min of mixing speed, obtains amine quinone polymer in 30~70 DEG C of reaction 120min.It will
Gained amine quinone polymer filtration, ethanol washing, drying, then amine quinone polymer: potassium hydroxide=1:0.5~3 is weighed in mass ratio,
Mixing is placed in tube furnace, under inert gas shielding, by 2~20 DEG C of min-1Heating rate be heated to 600~1000
DEG C carbonization, 2~3h of constant temperature is naturally cooling to room temperature to get nitrogen, oxygen, the porous carbon nano-particle of sulphur codope.
Above-mentioned inert gas selects one of nitrogen, argon gas, helium.
Above-mentioned raw materials are commercial reagent grade product.
The present invention has the advantage that
1. the present invention uses 1,4-benzoquinone and thiocarbamide for monomer material, amine quinone polymer is formed by Michael addition reaction,
By synchronous carbonization-activation processing, carbon nano-particle material is obtained, simple process is time saving, without complicated harsh experiment condition.
2. the amine quinone polymer synthesized in the present invention has the function of " All-in-One ", carbon source, nitrogen source, oxygen source are functioned simultaneously as
And sulphur source, effectively hetero atom can be uniformly introduced in carbon nano-particle material skeleton, improve the surface profit of material
Wet performance, and fake capacitance is provided, to be obviously improved the chemical property of material.
3. surface area (the 1800m that nitrogen prepared by the present invention, oxygen, the porous carbon nano-particle of sulphur codope have superelevation2/ g with
On) and unique ultramicropore-Asia micropore-mesopore hierarchical porous structure, when being used as electrode material for super capacitor, surveyed through analysis
It takes temperature bright, at 1.0A/g when charge and discharge, specific capacitance reaches 300F/g or more, and the capacity after cycle charge-discharge 10000 times is kept
Rate shows high specific capacitance and superior cyclical stability 90% or more.
Specific embodiment
Embodiment 1
First weigh thiocarbamide in mass ratio: 1,4-benzoquinone: thiocarbamide and 1,4-benzoquinone are dissolved in ethyl alcohol and mixing by ethyl alcohol=1:1.4:50
Uniformly, under 300 revs/min of mixing speed, amine quinone polymer is obtained in 30 DEG C of reaction 120min.By gained amine quinone polymer mistake
Then filter, ethanol washing, drying weigh dry amine quinone polymer: potassium hydroxide=1:0.5 in mass ratio, mixing is placed in pipe
In formula furnace, inert gas shielding, by 2 DEG C of min-1Heating rate the polymer is heated to 600 DEG C of carbonizations, constant temperature 3h is natural
Room temperature is cooled to get nitrogen, oxygen, the porous carbon nano-particle of sulphur codope.
Embodiment 2
Thiocarbamide, 1,4-benzoquinone and ethyl alcohol are successively weighed by 1:3:100 mass ratio, thiocarbamide and 1,4-benzoquinone are dissolved in ethyl alcohol and mixed
Uniformly, under 500 revs/min of mixing speed, in 50 DEG C of reaction 120min.By gained amine quinone polymer filtration, ethanol washing, do
After dry, dry amine quinone polymer: potassium hydroxide=1:1 is weighed in mass ratio, mixes, is placed in tube furnace, and inert gas is protected
Shield, by 10 DEG C of min-1Heating rate by the polymer be heated to 800 DEG C carbonization, constant temperature 2h, be naturally cooling to room temperature to get
Nitrogen, oxygen, the porous carbon nano-particle of sulphur codope.
Embodiment 3
Thiocarbamide, 1,4-benzoquinone and ethyl alcohol are successively weighed by 1:5.7:210 mass ratio, thiocarbamide and 1,4-benzoquinone are dissolved in ethyl alcohol and mixed
It closes uniformly, under 800 revs/min of mixing speed, in 70 DEG C of reaction 120min.By gained amine quinone polymer filtration, ethanol washing,
After drying, dry amine quinone polymer: potassium hydroxide=1:3 is weighed in mass ratio, is mixed, is placed in tube furnace, inert gas
Protection, by 20 DEG C of min-1Heating rate the polymer is heated to 1000 DEG C of carbonizations, constant temperature 2h is naturally cooling to room temperature, i.e.,
Obtain nitrogen, oxygen, the porous carbon nano-particle of sulphur codope.
Using full-automatic specific surface area and pore analysis instrument (Micromeritics ASAP 2460), using Brunauer-
The surface area of Emmett-Teller method calculating sample.After measured, the resulting nitrogen of embodiment 1-3, oxygen, sulphur codope porous carbon
Nano particle specific surface area is respectively 1843,2917 and 2376m2/g。
Weigh nitrogen obtained in embodiment 1-3, oxygen, the porous carbon nano-particle of sulphur codope in mass ratio: 60wt%'s is poly-
Tetrafluoroethene lotion (is bought) from Shanghai Sanaifu New Material Co., Ltd: graphite=8:1:1, after mixing, infrared
It is dried under lamp, drying sample is pressed on nickel foam under the pressure of 20MPa and (is purchased from Liyuan New Material Co Ltd, Changsha
Buy) on, for 24 hours in 100 DEG C of vacuum drying, make electrode slice.Using the electrode slice as working electrode, surveyed in 6mol/LKOH solution
Try chemical property.Working electrode at 1.0A/g when charge and discharge, divide by the specific capacitance of electrode made from embodiment 1-3 resulting materials
Not Wei 352,378 and 309F/g, the capacity retention ratio after 10000 charge and discharge cycles is respectively 92,96 and 94%.Always
It, with carbon nano-particle prepared by the present invention make electrode slice, specific capacitance reach 300F/g or more, cycle charge-discharge 10000 times
Capacity retention ratio afterwards shows high specific capacitance and superior cyclical stability 90% or more.
The above raw material is commercial reagent grade product.
Claims (1)
1. the preparation method of a kind of nitrogen, oxygen, the porous carbon nano-particle of sulphur codope, it is characterised in that: first weigh sulphur in mass ratio
Urea: 1,4-benzoquinone: thiocarbamide and 1,4-benzoquinone are dissolved in ethyl alcohol by ethyl alcohol=1:1.4~5.7:50~210, are uniformly mixed, 300~
Under 800 revs/min of mixing speed, in 30~70 DEG C of reaction 120min, amine quinone polymer is obtained；By gained amine quinone polymer mistake
Filter, ethanol washing, drying；Weigh dry amine quinone polymer in mass ratio again: potassium hydroxide=1:0.5~3, mixing are placed on
In tube furnace, under inert gas shielding, by 2~20 DEG C of min-1Heating rate be heated to 600~1000 DEG C of carbonizations, constant temperature
2~3h is naturally cooling to room temperature to get nitrogen, oxygen, the porous carbon nano-particle of sulphur codope；
Above-mentioned inert gas selects one of nitrogen, argon gas, helium；
Above-mentioned raw materials are commercial reagent grade product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867325A (en) * | 2019-11-12 | 2020-03-06 | 温州大学 | Nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere as well as preparation method and application thereof |
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2019
- 2019-03-11 CN CN201910178953.XA patent/CN109867271A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867325A (en) * | 2019-11-12 | 2020-03-06 | 温州大学 | Nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere as well as preparation method and application thereof |
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