CN108439369A - Hollow carbon nanometer micro ball of nitrogen oxygen codope and its preparation method and application - Google Patents
Hollow carbon nanometer micro ball of nitrogen oxygen codope and its preparation method and application Download PDFInfo
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- CN108439369A CN108439369A CN201810328495.9A CN201810328495A CN108439369A CN 108439369 A CN108439369 A CN 108439369A CN 201810328495 A CN201810328495 A CN 201810328495A CN 108439369 A CN108439369 A CN 108439369A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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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 invention discloses a kind of hollow carbon nanometer micro balls of nitrogen oxygen codope and preparation method thereof and electrode of super capacitor, ultracapacitor.The hollow carbon nanometer micro ball preparation method of nitrogen oxygen codope comprises the step of：Pyrroles and aniline are subjected to polymerisation in the aqueous solution containing soft template, obtain hollow carbon nanometer micro ball presoma；The hollow carbon nanometer micro ball presoma is washed, dusting processing, then through charing process and ammonium hydroxide activation process, obtains the hollow carbon nanometer micro ball of nitrogen oxygen codope.The hollow carbon nanometer micro ball of nitrogen oxygen codope prepared by preparation method of the present invention has large specific surface area, good wetability, high specific surface area utilization rate.The electrode of super capacitor, ultracapacitor contain the hollow carbon nanometer micro ball of nitrogen oxygen codope of the method for the present invention preparation.
Description
Technical field
The present invention relates to electrode material technical fields, and in particular to a kind of hollow carbon nanometer micro ball of nitrogen oxygen codope and its system
Preparation Method and application.
Background technology
Currently, the earth faces huge energy challenge, and continuous oil crisis and environmental problem force various countries to begin look for
New clean regenerative resource.It solves these problems, energy storage and managing device play a key role.In recent years,
Ultracapacitor causes people and greatly pays close attention to.As a kind of novel energy storage apparatus, it has fast charging and discharging, power close
Spending high, pollution-free and excellent cyclical stability makes it in communication apparatus, and the fields such as communications and transportation, aerospace have wide
Application prospect.
Carbon material is considered as the ideal material for being best suited for industrial super capacitor device.Carbon-based electrochemical capacitor belongs to
Typical double layer capacitor.Currently, the various carbon materials such as activated carbon, carbon fiber, carbon nanotube and graphene are used extensively
Make ultracapacitor research.Activated carbon is most materials of research, because it is easily prepared, specific surface area is high, but its aperture
It is relatively simple, thus specific surface area utilization rate is extremely limited；Carbon fiber has excellent electric conductivity and can not use binder,
But its apparent density is relatively low, volumetric capacitance is not high, and expensive；Carbon nanotube pore size is easy to control, but specific surface
Product is not high, and cost is generally higher；Graphene is to be considered a kind of very promising material in recent years, it has good
Electric conductivity, larger specific surface area and controllable pore size, but graphene is very easy to reunite, and makes the big discounting of its performance
Button.And hollow carbon nanometer micro ball, not only have many advantages, such as that the low-density of hollow-particle, Surface Permeability is good, total pore volume is big, also has
There are the characteristics such as large specific surface area, stability height, the porosity of carbon nanomaterial, therefore is widely paid close attention in energy storage field.
Traditional method for preparing hollow carbon nanometer micro ball is：First prepare SiO2Equal sphere template, is then wrapped in template
The presoma of carbon material is wrapped, can just be lacked after again being corroded template with the strong corrosives chemicals such as HF acid after presoma carbonization
The hollow carbon nanometer micro ball of amount, and pattern is irregular.It is cumbersome that traditional hard template method prepares hollow carbon nanometer micro ball process, consumption
Shi Jiu, low output, and the chemicals of high risk is also used, in the disclosed another method for preparing hollow carbon balls,
Hollow carbon balls are prepared using containing hazardous chemical such as sulfuric acid and using high temperature, therefore, this method safety is poor, and prepared
Hollow carbon balls size be micron order.And, surface area poor according to hollow carbon nanometer micro ball wetability prepared by existing method
Utilization rate and chemical property are undesirable.
Invention content
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, it is micro- to provide a kind of nitrogen oxygen codope hollow carbon nanometer
Ball and preparation method thereof, with solve process existing for existing hollow carbon nanometer micro ball preparation method it is cumbersome, take long, low output,
Safety is poor, and the hollow carbon nanometer micro ball wetability prepared is poor, surface area utilization rate and the undesirable technology of chemical property
Problem.
Another object of the present invention is to provide a kind of electrode of super capacitor and ultracapacitors, existing super to solve
Capacitor causes specific capacitance, high rate performance low due to its electrode material, the undesirable technical problem of cyclical stability.
In order to achieve the above-mentioned object of the invention, it is micro- to provide a kind of nitrogen oxygen codope hollow carbon nanometer for an aspect of of the present present invention
The preparation method of ball.The hollow carbon nanometer micro ball preparation method of nitrogen oxygen codope includes the following steps：
Pyrroles and aniline are subjected to polymerisation in the aqueous solution containing soft template, obtain hollow carbon nanometer micro ball forerunner
Body；
The hollow carbon nanometer micro ball presoma is washed, dusting processing, then through charing process and ammonium hydroxide activation at
Reason, obtains the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Another aspect of the present invention provides a kind of hollow carbon nanometer micro ball of nitrogen oxygen codope.In the nitrogen oxygen codope
Empty carbon nanometer micro ball is to be prepared by the hollow carbon nanometer micro ball preparation method of nitrogen oxygen codope of the present invention.
Another aspect of the invention provides a kind of electrode of super capacitor.The electrode of super capacitor includes afflux
Body and the electrode material layer being incorporated on the collector, the electrode material layer include electrode material, conductive agent and binder,
Wherein, the electrode material is the hollow carbon nanometer micro ball of nitrogen oxygen codope of the present invention.
Another aspect of the present invention provides a kind of ultracapacitor.The ultracapacitor includes electrode, the electrode
For electrode of super capacitor of the present invention.
Compared with prior art, the hollow carbon nanometer micro ball preparation method of nitrogen oxygen codope of the present invention is directly by pyrroles and aniline
It is dispersed in the aqueous solution containing soft template and carries out polymerisation, directly obtain hollow carbon nanometer micro ball presoma, therefore, this hair
Bright preparation method technique is relatively easy, and condition is easily-controllable, efficient, from and also prepared hollow carbon nanometer micro ball presoma size
Uniformly, shell thickness is controllable, and presoma itself contains abundant nitrogen.Ammonium hydroxide activation process after carrying out charing process
Afterwards so that the hollow carbon nanometer micro ball of nitrogen oxygen codope of preparation has large specific surface area, higher nitrogen content and oxygen content, contains
The introducing of nitrogen functional group and oxygen-containing functional group not only assigns the hollow carbon nanometer micro ball of nitrogen oxygen codope good wetability, and
And increasing specific surface area utilization rate.
The hollow carbon nanometer micro ball of nitrogen oxygen codope of the present invention has porous structure, and surface nitrogen-containing functional group and oxygen-containing
Official.Therefore, with large specific surface area, good wetability, higher specific surface area utilization rate.
Electrode of super capacitor and ultracapacitor of the present invention are micro- due to containing nitrogen oxygen codope hollow carbon nanometer of the present invention
Ball electrode material, therefore, the electrode of super capacitor and ultracapacitor not only have higher specific capacitance, but also also good
Good high rate performance and cyclical stability.
Description of the drawings
Fig. 1 is hollow carbon nanometer micro ball presoma principle schematic prepared by the embodiment of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of hollow carbon nanometer micro ball presoma prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscopic picture (SEM) of the hollow carbon nanometer micro ball of nitrogen oxygen codope prepared by the embodiment of the present invention 1；
Fig. 4 is the hollow carbon nanometer micro ball nitrogen adsorption desorption curve graph of nitrogen oxygen codope prepared by the embodiment of the present invention 1
(BET)；
Fig. 5 is constant current charge-discharge curve graph of the ultracapacitor that provides of the embodiment of the present invention 6 under different current densities；
Fig. 6 is cyclic voltammetry curve figure of the ultracapacitor that provides of the embodiment of the present invention 6 under different scanning rates.
Specific implementation mode
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Unless otherwise defined, otherwise all technical terms and scientific terms used herein have and institute of the embodiment of the present invention
Belong to technical field those of ordinary skill and is generally understood identical meaning.If the definition stated in this part be incorporated by reference
The definition stated in the patent of this paper, patent application, the patent application of announcement and other publications is opposite or other aspects
Inconsistent, the definition listed in this part is prior to the definition in being totally incorporated herein by reference.
In addition, the weight of Related Component noted in the disclosure of the embodiment of the present invention not only may refer to each component
Concrete content can also indicate the proportionate relationship of weight between each component, therefore, as long as according to specification phase of the embodiment of the present invention
The content for closing component is scaled up or is reduced within specification of embodiment of the present invention scope of disclosure.Specifically, this hair
Bright embodiment weight described in the specification can be unit of weight well known to the chemical fields such as μ g, mg, g, kg.
On the one hand, the embodiment of the present invention provides a kind of preparation method of the hollow carbon nanometer micro ball of nitrogen oxygen codope.The nitrogen
The preparation method of the hollow carbon nanometer micro ball of oxygen codope includes the following steps：
Step S01. prepares hollow carbon nanometer micro ball presoma：
Pyrroles and aniline are subjected to polymerisation in the aqueous solution containing soft template, obtain hollow carbon nanometer micro ball forerunner
Body；
Step S02. carries out charing and activation process to hollow carbon nanometer micro ball presoma：
The hollow carbon nanometer micro ball presoma is washed, dusting processing, then through charing process and ammonium hydroxide activation at
Reason, obtains the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Wherein, polymerisation is occurred into the aqueous solution containing soft template for the pyrroles and aniline in step S01
Method can be carried out in accordance with the following steps：
The pyrroles and aniline are added in the aqueous solution containing the soft template, initiator is then added and in 0-5 DEG C
Lower carry out polymerisation.
It is the mass concentration in the aqueous solution containing the soft template by the concentration control of the pyrroles in one is described
For 0.3%-0.6%, mass concentration of the aniline in the aqueous solution containing the soft template is 0.4%-0.8%.Pass through
Control to reactant concentration to effectively improve polymerisation efficiency, and can be controlled and adjusted by the concentration to reactant
Section, effectively can control and adjust the grain size for generating hollow carbon nanometer micro ball presoma.
In a further embodiment, the initiator in the polymerisation is in ammonium persulfate, potassium peroxydisulfate
It is at least one.In addition, mass concentration of the initiator in the aqueous solution containing the soft template is 8%-16%.By right
The control of initiator type and content, to improve the yield of polymerisation efficiency and polymer between reactant.
In polymerization reaction system in the above embodiments, due to the characteristic of soft template, it is added in aqueous solution, molten
Spherical droplets are formed in liquid, the droplet as shown in A in Fig. 1, after aniline and pyrrole monomer is added, since aniline and pyrroles are dredged
Water characteristic, so can enter in the droplet of soft template, as shown in B in Fig. 1, after initiator is further added, aniline and pyrrole
It coughs up monomer and can diffuse to soft template droplet surface and react with the initiator in water, particularly, pyrroles is in initiator
Effect is lower to occur polymerisation generation polypyrrole, and aniline generates polyaniline under the action of initiator, therefore, by polymerisation
Afterwards, the polymer of generation is the mixture polymer of polyaniline and polypyrrole, specifically thus soft template droplet surface
One layer of polymeric clad is formed, i.e., using polyaniline-polypyrrole as the hollow microsphere of protective layer (black portions in figure), such as Fig. 1
Shown in middle C.
In step S01, the mass ratio of an embodiment, soft template and water in reaction solution is (0.5-2)：(70-
99.5), specifically, the soft template is triton x-100.
In addition, the reactant such as aniline and initiator for reaction of polymerisation in the various embodiments described above are very fast, it therefore, will
The temperature of polymerisation is controlled at 0-5 degrees Celsius, by controlling reaction temperature to control the rate of polymerization of polymer monomer, from
And ensure that the polymer generated can effectively coat soft template, to generate the hollow carbon nanometer micro ball presoma of target.
In above-mentioned steps S02, the washing to the hollow carbon nanometer micro ball presoma is to remove unreacted reaction
Object and dissolvent residual, therefore, as long as in the case where not influencing the hollow carbon nanometer micro ball presoma, it is any to remove
The washing methods of reactant and dissolvent residual within the scope of disclosed herein, in a such as embodiment, is received the hollow carbon
Meter Wei Qiu presomas are repeatedly washed, and are filtered, until filtrate close to it is colourless until, then drying and processing.
Dusting processing is carried out to the hollow carbon nanometer micro ball presoma after washing, conventional method progress may be used,
Such as according to the requirement of grain size, the hollow carbon nanometer micro ball presoma is subjected to smashing processing.
In step S02, charing process can be conventional charing process, that is to say by through dusting treated it is described in
Empty carbon nanometer micro ball presoma thermal cracking, to which polymer cracking is generated carbon.In one embodiment, the temperature of the charing process
Degree can be 700-1000 DEG C.In addition charing process should be sufficient, such as in one embodiment, at 700-1000 DEG C at heat
The time of reason is 20-120min so that above-mentioned hollow carbon nanometer micro ball presoma fully carbonizes.In addition, controlling the heat treatment
It is that 2-10 DEG C/min is warming up to 700-1000 DEG C that temperature, which is with heating rate,.In this way, by the control of heating rate, ensure charing
The hollow carbon nanometer micro ball particle generated is complete, and has porous structure.
In one embodiment, the ammonium hydroxide activation process is so that the hollow carbon nanometer micro ball particle that charing generates is being protected
In property atmosphere, it is heat-treated at 700-1000 DEG C；And the protective atmosphere contains the ammonia thermally decomposed to generate by ammonium hydroxide
The mixed gas of gas and vapor.Activation process is carried out to hollow carbon nanometer micro ball particle by ammonia so that generate in charing
Hollow carbon nanometer micro ball particle surface on generate abundant nitrogenous and oxygen-containing functional group, nitrogen-containing functional group and oxygen-containing functional group
In the presence of additional Faraday pseudo-capacitance can be increased, improves the wetability of the hollow carbon nanometer micro ball particle surface, improve its ratio
Surface utilisation reduces diffusional resistance of the electrolyte intermediate ion in material duct, can provide lone pair electrons, increases electronics and exists
Transmission rate in material attracts electrolyte intermediate ion to improve electric double layer concentration, increases the chemical property of material.
In a preferred embodiment, the method for the charing process and ammonium hydroxide activation process is as follows：
It, will be through dusting treated the hollow carbon nanometer micro ball presoma at 700-1000 DEG C in protective atmosphere
It is heat-treated；And the protective atmosphere contains the mixed gas of the ammonia and vapor that are thermally decomposed to generate by ammonium hydroxide.This
Charing process and activation process are arranged and are handled in same atmosphere, charing process can not only be made to generate hollow by sample
Abundant nitrogenous and oxygen-containing functional group is generated on carbon nanometer micro ball particle surface, improves its wetability and related chemical property,；
On the other hand, additionally it is possible to the porous structure on its surface is effectively improved, so that the hole of its porous structure is with gradient pore
Diameter, such as containing micropore, mesoporous and macropore hierarchical porous structure, certainly, the porous structure of this different pore size is random distribution
, the porous structure of this porous pore-size distribution can synergistic effect for promoting the electricity of the hollow carbon nanometer micro ball of nitrogen oxygen codope
Chemical property, such as electrode material for super capacitor when, the property such as specific capacity, high rate performance and cyclical stability can be improved
Energy.
In addition, the protective atmosphere of above-mentioned charing or activation process can be provided by argon gas, into the protective atmosphere
The ammonia and water vapour for being passed through the heated volatilization of ammonia can be imported with argon gas.As in one embodiment, the flow of the argon gas can
To be set as 20-100ml/min, the ammonia and water vapour of the volatilization of ammonia should be enough.
Therefore, the preparation method of the above-mentioned hollow carbon nanometer micro ball of nitrogen oxygen codope is by setting processing step and condition
Fixed, so that preparing, the hollow carbon nanometer micro ball technique of nitrogen oxygen codope is relatively easy, and condition is easily-controllable, efficient, effectively avoids
It is insufficient existing for existing hard template method, and the grain size of the hollow carbon nanometer micro ball of nitrogen oxygen codope of preparation can be controlled
System, surface contains porous structure and is bonded with abundant nitrogen-containing functional group and oxygen-containing functional group, to assign the nitrogen oxygen
The hollow carbon nanometer micro ball of codope has large specific surface area, good wetability and chemical property.
Based on the hollow carbon nanometer micro ball preparation method of nitrogen oxygen codope described above, the embodiment of the present invention additionally provides one
The kind hollow carbon nanometer micro ball of nitrogen oxygen codope, specifically, the nitrogen of the hollow carbon nanometer micro ball of nitrogen oxygen codope by mentioned earlier
The hollow carbon nanometer micro ball preparation method of oxygen codope prepares.Therefore, hollow one side of carbon nanometer micro ball of the nitrogen oxygen codope
Face has porous structure, and porous structure can be the unequal hierarchical porous structure in aperture of random distribution, such as containing micropore,
Mesoporous and macropore hierarchical porous structure；On the other hand, the hollow carbon nanometer micro ball surface bond of the nitrogen oxygen codope has abundant
Nitrogen-containing functional group and oxygen-containing functional group.Just because of the hollow carbon nanometer micro ball of nitrogen oxygen codope has the design feature, therefore,
It is with large specific surface area, higher specific surface area utilization rate, good wetability and chemical property.By measuring, institute
The grain size for stating the hollow carbon nanometer micro ball of nitrogen oxygen codope is 60-150 nanometers.
On the other hand, based on the hollow carbon nanometer micro ball of nitrogen oxygen codope and preparation method thereof described above, the present invention is real
It applies example and additionally provides a kind of electrode of super capacitor.The electrode of super capacitor may include that electrode of super capacitor is necessary
Component, such as the electrode material layer including collector and on collector as described in being incorporated in.
Wherein, collector can be common current collector material such as nickel foam etc..
The electrode material layer may include electrode material, conductive agent and binder.Wherein, electrode material, conductive agent and
Weight of binder ratio can be with but not just for (70-90)：(5-15)：(5-20).The binder can with but not only select
PTFE, the conductive agent can with but not only select acetylene black.The electrode material is nitrogen oxygen codope hollow carbon described above
Nanoparticle.Therefore, such as porous structure is had based on the hollow carbon nanometer micro ball of nitrogen oxygen codope described above and be bonded abundant
Nitrogen-containing functional group and oxygen-containing functional group.The electrode of super capacitor has higher specific capacitance, and also good multiplying power
Performance and cyclical stability.
On the basis of the electrode of super capacitor, the embodiment of the present invention additionally provides a kind of ultracapacitor.It is described
Ultracapacitor includes necessary component, such as including electrode component, wherein the electrode is super capacitor of the embodiment of the present invention
Device electrode.In this way, the ultracapacitor has higher specific capacitance, and also good high rate performance and stable circulation
Property.
Now by taking specific hollow carbon nanometer micro ball of nitrogen oxygen codope and its preparation method and application as an example, to the present invention into traveling
One step is described in detail.
1. the hollow carbon nanometer micro ball of nitrogen oxygen codope and preparation method thereof embodiment
Embodiment 1
The present embodiment provides a kind of hollow carbon nanometer micro balls of nitrogen oxygen codope and preparation method thereof.In the nitrogen oxygen codope
Empty carbon nanometer micro ball preparation method includes the following steps：
S11：The triton x-100 solution that 0.45g temperature is 2 DEG C is added in the deionized water that 450g temperature is 2 DEG C, is used
Magnetic stirrer is uniformly mixed for 60 minutes, forms diluted triton x-100 solution；
S12：It is that dilution prepared by above-mentioned steps is added in 2 DEG C of aniline by pyrroles that 2.2g temperature is 2 DEG C and 2.8g temperature
Triton x-100 solution in, continue stir 30min, so that pyrroles and aniline is evenly distributed in triton x-100 solution；
S13：The ammonium persulfate solution of the new 1M for preparing 60mL is added in step S12 solution, gentle agitation 30s, then
In 0 DEG C of environment temperature, reaction 12h is stood；
S14：Step S13 products therefroms are repeatedly washed, filter, until filtrate close to it is colourless until, then dry,
It is ground to powder and obtains required hollow carbon nanometer micro ball presoma, then carbon nanometer micro ball presoma is sealed and is waited for
With；
S15：It takes the hollow carbon nanometer micro ball presomas of 1.5g to be put in corundum crucible, crucible is put in tube furnace, with stream
The ammonia discord vapor that the ammonium hydroxide (50 DEG C) of heating decomposes is passed through in tube furnace by amount by the argon gas of 50ml/min, is managed at this time
The mixed gas of argon gas, vapor and ammonia is filled in formula stove；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 5 DEG C/min, is heated to 950 DEG C of heat preservation 40min, then
It is cooled to room temperature and can be obtained the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Embodiment 2
The present embodiment provides a kind of hollow carbon nanometer micro balls of nitrogen oxygen codope and preparation method thereof.In the nitrogen oxygen codope
Empty carbon nanometer micro ball preparation method includes the following steps：
S11：The triton x-100 solution that 0.6g temperature is 2 DEG C is added in the deionized water that 500g temperature is 2 DEG C, is used
Magnetic stirrer is uniformly mixed for 60 minutes, forms diluted triton x-100 solution；
S12：It is that dilution prepared by above-mentioned steps is added in 2 DEG C of aniline by pyrroles that 2.0g temperature is 2 DEG C and 2.4g temperature
Triton x-100 solution in, continue stir 30min, so that pyrroles and aniline is evenly distributed in triton x-100 solution；
S13：The ammonium persulfate solution of the new 1M for preparing 50mL is added in step S12 solution, gentle agitation 50s, then
In 3 DEG C of environment temperature, reaction 8h is stood；
S14：By step S13 products therefroms, repeatedly washed, filter, until filtrate close to it is colourless until, then dry
It is dry, it is ground to powder and obtains required hollow carbon nanometer micro ball presoma, then carbon nanometer micro ball presoma is sealed and is protected
It deposits for use；
S15：It takes the hollow carbon nanometer micro ball presomas of 1.0g to be put in corundum crucible, crucible is put in tube furnace, with stream
The ammonia discord vapor that the ammonium hydroxide (60 DEG C) of heating decomposes is passed through in tube furnace by amount by the argon gas of 30ml/min, is managed at this time
The mixed gas of argon gas, vapor and ammonia is filled in formula stove；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 2 DEG C/min, is heated to 800 DEG C of heat preservation 100min, then
It is cooled to room temperature and can be obtained the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Embodiment 3
The present embodiment provides a kind of hollow carbon nanometer micro balls of nitrogen oxygen codope and preparation method thereof.In the nitrogen oxygen codope
Empty carbon nanometer micro ball preparation method includes the following steps：
S11：The triton x-100 solution that 0.4g temperature is 1 DEG C is added in the deionized water that 500g temperature is 0 DEG C, is used
Magnetic stirrer is uniformly mixed for 20 minutes, forms diluted triton x-100 solution；
S12：It is that dilution prepared by above-mentioned steps is added in 2 DEG C of aniline by pyrroles that 2.0g temperature is 2 DEG C and 2.2g temperature
Triton x-100 solution in, continue stir 40min, so that pyrroles and aniline is evenly distributed in triton x-100 solution；
S13：The ammonium persulfate solution of the new 1M for preparing 50mL is added in step S12 solution, gentle agitation 40s, then
In 0 DEG C of environment temperature, reaction 14h is stood；
S14：By step S13 products therefroms, repeatedly washed, filter, until filtrate close to it is colourless until, then dry
It is dry, it is ground to powder and obtains required hollow carbon nanometer micro ball presoma, then carbon nanometer micro ball presoma is sealed and is protected
It deposits for use；
S15：It takes the hollow carbon nanometer micro ball presomas of 1.5g to be put in corundum crucible, crucible is put in tube furnace, with stream
The ammonia discord vapor that the ammonium hydroxide (30 DEG C) of heating decomposes is passed through in tube furnace by amount by the argon gas of 70ml/min, is managed at this time
The mixed gas of argon gas, vapor and ammonia is filled in formula stove；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 4 DEG C/min, is heated to 850 DEG C of heat preservation 60min, then
It is cooled to room temperature and can be obtained the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Embodiment 4
The present embodiment provides a kind of hollow carbon nanometer micro balls of nitrogen oxygen codope and preparation method thereof.In the nitrogen oxygen codope
Empty carbon nanometer micro ball preparation method includes the following steps：
S11：The triton x-100 solution that 0.55g temperature is 1 DEG C is added in the deionized water that 550g temperature is 1 DEG C, is used
Magnetic stirrer is uniformly mixed for 50 minutes, forms diluted triton x-100 solution；
S12：It is that dilution prepared by above-mentioned steps is added in 1 DEG C of aniline by pyrroles that 1.8g temperature is 2 DEG C and 2.0g temperature
Triton x-100 solution in, continue stir 40min, so that pyrroles and aniline is evenly distributed in triton x-100 solution；
S13：The ammonium persulfate solution of the new 1M for preparing 65mL is added in step S12 solution, gentle agitation 50s, then 1
DEG C environment temperature in, stand reaction 9h；
S14：By step S13 products therefroms, repeatedly washed, filter, until filtrate close to it is colourless until, then dry
It is dry, it is ground to powder and obtains required hollow carbon nanometer micro ball presoma, then carbon nanometer micro ball presoma is sealed and is protected
It deposits for use；
S15：It takes the hollow carbon nanometer micro ball presomas of 2.0g to be put in corundum crucible, crucible is put in tube furnace, with stream
The ammonia discord vapor that the ammonium hydroxide (45 DEG C) of heating decomposes is passed through in tube furnace by amount by the argon gas of 55ml/min, is managed at this time
The mixed gas of argon gas, vapor and ammonia is filled in formula stove；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 8 DEG C/min, is heated to 900 DEG C of heat preservation 45min, then
It is cooled to room temperature and can be obtained the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Embodiment 5
The present embodiment provides a kind of hollow carbon nanometer micro balls of nitrogen oxygen codope and preparation method thereof.In the nitrogen oxygen codope
Empty carbon nanometer micro ball preparation method includes the following steps：
S11：The triton x-100 solution that 0.42g temperature is 3 DEG C is added in the deionized water that 450g temperature is 3 DEG C, is used
Magnetic stirrer is uniformly mixed for 50 minutes, forms diluted triton x-100 solution；
S12：It is that dilution prepared by above-mentioned steps is added in 3 DEG C of aniline by pyrroles that 2.2g temperature is 3 DEG C and 2.5g temperature
Triton x-100 solution in, continue stir 35min, so that pyrroles and aniline is evenly distributed in triton x-100 solution；
S13：The ammonium persulfate solution of the new 1M for preparing 55mL is added in S12 solution, gentle agitation 35s, then 0 DEG C
In environment temperature, reaction 15h is stood；
S14：By step S13 products therefroms, repeatedly washed, filter, until filtrate close to it is colourless until, then dry
It is dry, it is ground to powder and obtains required hollow carbon nanometer micro ball presoma, then carbon nanometer micro ball presoma is sealed and is protected
It deposits for use；
S15：It takes the hollow carbon nanometer micro ball presomas of 1.8g to be put in corundum crucible, crucible is put in tube furnace, with stream
The ammonia discord vapor that the ammonium hydroxide (55 DEG C) of heating decomposes is passed through in tube furnace by amount by the argon gas of 45ml/min, is managed at this time
The mixed gas of argon gas, vapor and ammonia is filled in formula stove；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 3 DEG C/min, is heated to 925 DEG C of heat preservation 40min, then
It is cooled to room temperature and can be obtained the hollow carbon nanometer micro ball of nitrogen oxygen codope.
Hollow carbon nanometer micro ball presoma, the hollow carbon nanometer micro ball of nitrogen-doped carbon further prepared by the present embodiment 1-5
It is scanned Electronic Speculum respectively, wherein the scanning electron microscopic picture such as Fig. 2 institutes for the hollow carbon nanometer micro ball presoma that embodiment 1 provides
Show, the scanning electron microscope of the hollow carbon nanometer micro ball of nitrogen-doped carbon is as shown in Figure 3.By Fig. 2 and 3 it is found that the hollow carbon nanometer micro ball
Presoma and the hollow carbon nanometer micro ball of nitrogen-doped carbon are grain structure, and particle size has nanoscale, and size distribution is equal
It is even.The hollow carbon nanometer micro ball presomas of embodiment 2-5, the hollow carbon nanometer micro ball of nitrogen-doped carbon be scanned respectively electron microscopic picture with
Embodiment 1 is approximate.
The hollow carbon nanometer micro ball of nitrogen-doped carbon prepared by embodiment 1-5 further carries out physical adsorption property analysis,
In, the physical absorption curve (BET) of the hollow carbon nanometer micro ball of 1 nitrogen-doped carbon of embodiment is as shown in Figure 4.As shown in Figure 4, the nitrogen
The nitrogen adsorption desorption curve of the hollow carbon nanometer micro ball of doped carbon is typical I/IV types adsorption curve, is all in low relative pressure
Under (P/P0<0.05)N 2Adsorbance, which first steeply rises, is then rapidly reached balance, this illustrates all carbon nanobelts micro-sphere materials
There is a large amount of micropore (＜ 2nm) structures, in P/P0Ranging from 0.9~1 region, the desorption curve of all carbon nanobelts
Adsorption curve is all obviously lagged behind, thus forms a lag winding, this shows that there is also crowds inside hollow carbon nanometer micro ball
More mesoporous (2-50nm) and macropore (＞ 50nm).The physical adsorbability of the hollow carbon nanometer micro ball of nitrogen-doped carbon in embodiment 2-5
It can be approximate with embodiment 1.
2. electrode of super capacitor and ultracapacitor embodiment
Embodiment 6
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and other necessary parts, wherein the electrode is made as follows
It is standby：
By the hollow carbon nanometer micro ball of nitrogen oxygen codope, 5% PTFE solution and acetylene black hollow carbon is co-doped with nitrogen oxygen and is received
Meter Wei Qiu：PTFE:Acetylene black is 8:1:1 ratio is mixed and is ground uniformly, is then coated in nickel foam；It is subsequently placed in true
In empty drying box, then 110 DEG C of hollow dry 12h use tablet press machine, are that thin slice obtains super capacitor electrode by nickel foam pressure
Pole.
Embodiment 7
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
By the hollow carbon nanometer micro ball of nitrogen oxygen codope, 3% PTFE solution and acetylene black hollow carbon is co-doped with nitrogen oxygen and is received
Meter Wei Qiu：PTFE:Acetylene black is 78:10:12 ratio is mixed and is ground uniformly, is then coated in nickel foam；Then it sets
In vacuum drying chamber, then 80 DEG C of hollow dry 16h use tablet press machine, are that thin slice obtains ultracapacitor by nickel foam pressure
Electrode.
Embodiment 8
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
By the hollow carbon nanometer micro ball of nitrogen oxygen codope, 7% PTFE solution and acetylene black hollow carbon is co-doped with nitrogen oxygen and is received
Meter Wei Qiu：PTFE:Acetylene black is 85:7:8 ratio is mixed and is ground uniformly, is then coated in nickel foam；It is subsequently placed in
In vacuum drying chamber, then 120 DEG C of hollow dry 10h use tablet press machine, are that thin slice obtains super capacitor electrode by nickel foam pressure
Pole.
Embodiment 9
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
By the hollow carbon nanometer micro ball of nitrogen oxygen codope, 4% PTFE solution and acetylene black hollow carbon is co-doped with nitrogen oxygen and is received
Meter Wei Qiu：PTFE:Acetylene black is 82:9:9 ratio is mixed and is ground uniformly, is then coated in nickel foam；It is subsequently placed in
In vacuum drying chamber, 70 DEG C of hollow dryings for 24 hours, then use tablet press machine, are that thin slice obtains super capacitor electrode by nickel foam pressure
Pole.
Embodiment 10
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
By the hollow carbon nanometer micro ball of nitrogen oxygen codope, 3% PTFE solution and acetylene black hollow carbon is co-doped with nitrogen oxygen and is received
Meter Wei Qiu：PTFE:Acetylene black is 75:10:15 ratio is mixed and is ground uniformly, is then coated in nickel foam；Then it sets
In vacuum drying chamber, then 95 DEG C of hollow dry 14h use tablet press machine, are that thin slice obtains ultracapacitor by nickel foam pressure
Electrode.
The present embodiment 6-10 ultracapacitors are carried out under different current densities to constant current charge-discharge curve and difference respectively
Cyclic voltammetry curve analysis is carried out under sweep speed.Wherein, the ultracapacitor that embodiment 6 provides is under different current densities
Constant current charge-discharge curve is as shown in figure 5, the cyclic voltammetry curve pore size distribution curve under different scanning rates is as shown in Figure 6.
As shown in Figure 5,6 ultracapacitor of embodiment constant current charge-discharge curve under different current densities is triangle,
There is no apparent IR drops to generate, even if when electric current increases to 20A/g, the GCD curves of the hollow carbon nanometer micro ball of nitrogen oxygen codope are still
It can so keep preferable triangular shaped, this illustrates the charge storage of the hollow carbon nanometer micro ball of nitrogen oxygen codope and having for transmission
High reversible has ideal electric double layer capacitance.And under the current density of 0.25A/g, specific capacitance value is up to
387F/g, even if current density increases to 20A/g, specific capacitance value is still up to 152F/g, and through measuring the electricity in 20A/g
Capacity retention is still above 50% under current density；After being recycled 12000 times under the current density of 5A/g, 95% is still maintained
Capacity.The ultracapacitor that embodiment 7-10 is provided also has the high electrochemical as similar in ultracapacitor in embodiment 6
Energy.
It will be appreciated from fig. 6 that the shape of 6 ultracapacitor of embodiment class rectangle of CV curves under the sweep speed of 10-200Mv
Remain good, all CV curves are all without apparent redox peaks, therefore, illustrate the nitrogen oxygen that embodiment 1 provides
The hollow carbon nanometer micro ball electrode material of codope belongs to ideal electrode material for electric double layer capacitor.And work as scanning voltage direction
When changing, electric current can also quickly reach platform, this explanation, the capacitance good reversibility of prepared hollow carbon nanometer micro ball.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of preparation method of the hollow carbon nanometer micro ball of nitrogen oxygen codope, which is characterized in that include the following steps：
Pyrroles and aniline are subjected to polymerisation in the aqueous solution containing soft template, obtain hollow carbon nanometer micro ball presoma；
The hollow carbon nanometer micro ball presoma is washed, dusting processing, then through charing process and ammonium hydroxide activation process, obtained
To the hollow carbon nanometer micro ball of nitrogen oxygen codope.
2. according to the preparation method described in claim 1, which is characterized in that the pyrroles and aniline are being contained soft template
The method that polymerisation occurs in aqueous solution is as follows：
The pyrroles and aniline are added in the aqueous solution containing the soft template, be then added initiator and at 0-5 DEG C into
Row polymerisation；And/or
Mass concentration of the pyrroles in the aqueous solution containing the soft template be 0.3%-0.6%, the aniline containing
Mass concentration in the aqueous solution of the soft template is 0.4%-0.8%.
3. preparation method according to claim 2, it is characterised in that：The initiator is in ammonium persulfate, potassium peroxydisulfate
At least one；And/or
Mass concentration of the initiator in the aqueous solution containing the soft template is 8%-16%.
4. according to claim 1-3 any one of them preparation methods, it is characterised in that：At the charing process and ammonium hydroxide activation
The method of reason is as follows：
In protective atmosphere, the hollow carbon nanometer micro ball presoma is heat-treated at 700-1000 DEG C；And it is described
Protective atmosphere contains the mixed gas of the ammonia and vapor that are thermally decomposed to generate by ammonium hydroxide.
5. preparation method according to claim 4, it is characterised in that：The time of the heat treatment is 20-120min；With/
Or
It is that 2-10 DEG C/min is warming up to 700-1000 DEG C that the heat treatment temperature, which is with heating rate,.
6. according to claim 1-3,5 any one of them preparation methods, which is characterized in that in the aqueous solution of the soft template
The mass ratio of soft template and water is (0.5-2)：(70-99.5)；And/or
The soft template is triton x-100.
7. a kind of hollow carbon nanometer micro ball of nitrogen oxygen codope, which is characterized in that the hollow carbon nanometer micro ball of nitrogen oxygen codope by
Claim 1-6 any one of them preparation methods prepare.
8. the hollow carbon nanometer micro ball of nitrogen oxygen codope according to claim 7, which is characterized in that in the nitrogen oxygen codope
The grain size of empty carbon nanometer micro ball is 60-150 nanometers；And/or
The hollow carbon nanometer micro ball of nitrogen oxygen codope is porous structure.
9. a kind of electrode of super capacitor, including collector and the electrode material layer that is incorporated on the collector, feature exist
In the electrode material layer includes electrode material, conductive agent and binder, wherein the electrode material is that claim 7-8 appoints
The hollow carbon nanometer micro ball of nitrogen oxygen codope described in one.
10. a kind of ultracapacitor, including electrode, which is characterized in that the electrode is the ultracapacitor described in claim 9
Electrode.
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| CN109065899A (en) * | 2018-09-07 | 2018-12-21 | 黄冈师范学院 | A kind of supported porous C catalyst of cobalt nitride of fuel battery negative pole oxygen reduction reaction and preparation method thereof |
| CN109585860A (en) * | 2018-11-07 | 2019-04-05 | 三峡大学 | A kind of preparation method of sulfur doping cobalt oxide and sulphur, nitrogen, oxygen doping carbon In-situ reaction electrode |
| CN110255999A (en) * | 2019-06-10 | 2019-09-20 | 北京科技大学 | A kind of nitrogen oxygen codope porous hollow bowl-type carbon material and preparation method thereof |
| CN110407194A (en) * | 2019-08-02 | 2019-11-05 | 武汉理工大学 | The hollow Nano carbon balls of three-dimensional porous N doping and its controllable method for preparing and application |
| CN114074936A (en) * | 2020-08-21 | 2022-02-22 | 中国科学院福建物质结构研究所 | Nitrogen-doped carbon nanosphere and preparation method and application thereof |
| CN115240986A (en) * | 2022-07-22 | 2022-10-25 | 燕山大学 | Nitrogen-oxygen co-doped carbon electrode material and preparation method thereof |
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| CN109065899A (en) * | 2018-09-07 | 2018-12-21 | 黄冈师范学院 | A kind of supported porous C catalyst of cobalt nitride of fuel battery negative pole oxygen reduction reaction and preparation method thereof |
| CN109065899B (en) * | 2018-09-07 | 2021-09-03 | 黄冈师范学院 | Cobalt nitride supported porous carbon catalyst for fuel cell cathode oxygen reduction reaction and preparation method thereof |
| CN109585860A (en) * | 2018-11-07 | 2019-04-05 | 三峡大学 | A kind of preparation method of sulfur doping cobalt oxide and sulphur, nitrogen, oxygen doping carbon In-situ reaction electrode |
| CN109585860B (en) * | 2018-11-07 | 2021-11-09 | 三峡大学 | Preparation method of sulfur-doped cobalt oxide and sulfur, nitrogen and oxygen-doped carbon in-situ composite electrode |
| CN110255999A (en) * | 2019-06-10 | 2019-09-20 | 北京科技大学 | A kind of nitrogen oxygen codope porous hollow bowl-type carbon material and preparation method thereof |
| CN110407194A (en) * | 2019-08-02 | 2019-11-05 | 武汉理工大学 | The hollow Nano carbon balls of three-dimensional porous N doping and its controllable method for preparing and application |
| CN114074936A (en) * | 2020-08-21 | 2022-02-22 | 中国科学院福建物质结构研究所 | Nitrogen-doped carbon nanosphere and preparation method and application thereof |
| CN114074936B (en) * | 2020-08-21 | 2023-07-21 | 中国科学院福建物质结构研究所 | Nitrogen-doped carbon nanosphere and preparation method and application thereof |
| CN115240986A (en) * | 2022-07-22 | 2022-10-25 | 燕山大学 | Nitrogen-oxygen co-doped carbon electrode material and preparation method thereof |
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