CN107958792B - A kind of carbon@CoO composite material of core-shell structure and its preparation method and application - Google Patents
A kind of carbon@CoO composite material of core-shell structure and its preparation method and application Download PDFInfo
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- CN107958792B CN107958792B CN201711071728.3A CN201711071728A CN107958792B CN 107958792 B CN107958792 B CN 107958792B CN 201711071728 A CN201711071728 A CN 201711071728A CN 107958792 B CN107958792 B CN 107958792B
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- 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 carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion, are mixed by cobalt carbonate and nitrogen containing polymer resin, are carbonized to obtain through a step, the core-shell structure of the carbon@CoO with carbon nanotube insertion.Preparation method includes: the preparation of 1) melamine resin；2) cobalt carbonate-melamine resin powder preparation；3) preparation of the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion.As the application of electrode material for super capacitor, the charge and discharge in -0.3-0.4V range, when discharge current density is 1 A/g, specific capacitance can achieve 800-900 F/g.The present invention uses one step carbonization, simple process；The carbon of carbon nanotube and N doping generates simultaneously, improves the electric conductivity of material；CoO is covered by carbon material, improves the electric conductivity of material, prevents the volume contraction in the corrosion and charge and discharge process of CoO, shows excellent electrochemical properties and chemical stability, can use the electrode material of supercapacitor.
Description
Technical field
The present invention relates to supercapacitor technologies fields, and in particular to a kind of carbon@CoO of the N doping of carbon nanotube insertion
Composite material of core-shell structure and its preparation method and application.
Background technique
Supercapacitor receives extensive attention in recent years as a kind of novel energy accumulating device, it has the circulation longevity
The advantages that life length, power density is high, light weight, the charge and discharge time is short.The electrode material of supercapacitor is mainly with carbon material
Main, although carbon material has good cyclical stability and high specific surface area, its specific capacitance is low, thus its use is limited
System；Another kind of material is fake capacitance electrode material, such as transition metal oxide.Although transition metal oxide can provide ratio
High 10 times of the specific capacitance of carbon material, but its electric conductivity and stability are poor, and perishable during charge and discharge and volume hair
Changing.
The generally existing following technical problem of supercapacitor preparation method of currently available technology report:
1, the specific capacitance of carbon material is low, generally in 100-300 F/g or so,；
2, the specific surface area of material is smaller, influences the comprehensive performance of supercapacitor；
3, the transition metal oxide electric conductivity loaded is poor；
4, the transition metal oxide loaded is in cyclic process, and stability is poor, perishable and volume change is serious；
5, preparation process is complicated, needs first to prepare the carbon material of specific morphology, then carry out transition metal oxide doping,
Load.
Summary of the invention
The object of the present invention is to provide a kind of carbon nanotube insertion N doping carbon@CoO composite material of core-shell structure and
Preparation method and application in supercapacitor field.
By mixing cobalt carbonate and macromolecule resin, CO2 is generated using during resin carbonation, cobalt carbonate is decomposed
With CoO:CoCO3=CoO+CO2 ↑；The CoO of generation be reduced under the action of carbon Co:CoO+C=Co+ CO ↑；It generates
High activity Co catalytic resin generate carbon nanotube；Co is by the dioxygen oxidation in the oxygen or air that contain in material again later
CoO, therefore, obtained composite material not only show the electric double layer capacitance performance of porous carbon, but also show metal oxidation
Faraday's capacitive property of object, thus there is the superperformance of the electrode material as supercapacitor.One side carbon nanotube,
The carbon of N doping has good electric conductivity, can provide high electric double layer capacitance；Another aspect CoO is covered by carbon material
In, the electric conductivity of oxide is improved, volume of the oxide in the corrosion and charge and discharge process of electrolyte has effectively been restrained and has received
Contracting, effectively increases composite material specific capacitance.And composite material, by step carbonization synthesis, method is simple, and batch is suitble to make
It is standby.
Realization effectively overcomes specific capacitance of the existing technology low and transition metal oxide poorly conductive, stability are poor,
Perishable and the serious technical problem of volume change purpose.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
The carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion, by cobalt carbonate and nitrogen containing polymer resin
Mixing, then carry out high temperature cabonization and obtain, there is carbon@CoO core-shell structure, and in the carbon@CoO core-shell structure of carbon nanotube insertion,
The CoO nuclear diameter wherein formed is 10-20nm, and the nitrogen containing polymer resin is melamine resin, the carbon@CoO core
In shell structure, the carbon shell for coating CoO is N doping, the carbon-coated CoO formation C@CoO nucleocapsid knot of carbon nanotube and N doping
Structure is simultaneously synthesizing by step carbonization.
Carbon nanotube insertion N doping carbon@CoO composite material of core-shell structure preparation method the following steps are included:
The preparation of step 1) melamine resin meets mass ratio for 1:3-5, by formaldehyde and three with formaldehyde and melamine
Wiring solution-forming in there-necked flask is added in poly cyanamid, starts blender, pH value is gradually adjusted to 7.0-9.0 with Na2CO3, is warming up to 70-
90 DEG C, 30-60 min is reacted with this condition, pH value is adjusted to 5.0-7.0 with formic acid, and react 30-60 with this condition
Min, cooling obtain melamine resin；
The preparation of step 2 cobalt carbonate-melamine resin powder, is 1:2:20 with mass ratio, will be three obtained by step 1)
Cymel powder, cobalt carbonate and water are mixed, and 1-2 h is stirred；Then it dries, crush, grinding, obtaining cobalt carbonate-three
Cymel powder；
The preparation of the carbon@CoO composite material of core-shell structure of the N doping of step 3) carbon nanotube insertion, step 2 is obtained
Cobalt carbonate-melamine resin powder with 5 DEG C/min of heating rate, be warming up to 700-900 DEG C of progress under a nitrogen atmosphere
Calcining, then keeps the temperature 3-5h, and the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion can be obtained.
The carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion is as electrode material for super capacitor
Using the charge and discharge in -0.3-0.4V range, when discharge current density is 1 A/g, specific capacitance can achieve 800-900 F/
g。
A kind of carbon@CoO composite material of core-shell structure through experimental tests of the N doping of carbon nanotube insertion of the invention, knot
Fruit is as follows:
The carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion is through transmissioning electric mirror test, CoO nanoparticle
Son is covered by carbon material well.
Carbon nanotube insertion N doping carbon@CoO composite material of core-shell structure electrochemical property test, detection-
Charge and discharge within the scope of 0.3-0.4V, when discharge current density is 1 A/g, the carbon@CoO nucleocapsid of the N doping of carbon nanotube insertion
Structural composite material electrode of super capacitor specific capacitance range is in 800-900 F/g.
And the specific capacitance of the carbon material without CoO of melamine resin preparation is used merely for 100-300 F/g, in phase
With under current density, the discharge time of the carbon@CoO composite material of core-shell structure material of the N doping of carbon nanotube insertion is apparently higher than
Single melamine resin porous carbon electrode material, discharge time improve more than 5 times, show more single more of its specific capacitance
The performance of hole carbon is obviously improved, and it is good to show that the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion has
Good super capacitor performance.
Therefore, the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube of the invention insertion is for existing skill
Art has the advantage that
1. preparation method is simple, the carbon@CoO nucleocapsid of the N doping of carbon nanotube insertion is achieved with using one step carbonization
Structural composite material, and melamine resin be it is commercialized, it is cheap, be suitable for large batch of production；
2. the present invention is mixed using cobalt carbonate and melamine resin, while cobalt carbonate pyrolytic generates CoO, produce
Raw bulk gas advantageously forms the porous carbon of high-specific surface area；
3. the carbon@CoO composite material of core-shell structure of the N doping of resulting carbon nanotube insertion, carbon nanotube and nitrogen are mixed
Miscellaneous carbon generates simultaneously, effectively increases the electric conductivity of material；
4. the carbon@CoO composite material of core-shell structure of the N doping of resulting carbon nanotube insertion, CoO are covered by carbon materials
In material, the electric conductivity of material is on the one hand improved, the volume in the corrosion and charge and discharge process of CoO is on the other hand prevented to receive
Contracting.
Therefore, the present invention has broad application prospects in supercapacitor field.
Detailed description of the invention
Fig. 1 is the carbon@CoO composite material of core-shell structure of the N doping of the carbon nanotube insertion of preparation of the embodiment of the present invention
Scanning electron microscope (SEM) photograph；
Fig. 2 is the carbon@CoO composite material of core-shell structure of the N doping of the carbon nanotube insertion of preparation of the embodiment of the present invention
Transmission electron microscope picture；
Fig. 3 is the carbon@CoO composite material of core-shell structure of the N doping of the carbon nanotube insertion of preparation of the embodiment of the present invention
High-resolution-ration transmission electric-lens figure；
Fig. 4 is the carbon@CoO composite material of core-shell structure of the N doping of the carbon nanotube insertion of preparation of the embodiment of the present invention
The comparison diagram of discharge curve.
Specific embodiment
The present invention is described in further detail the content of present invention in conjunction with Figure of description, but be not pair by embodiment
Restriction of the invention.
Embodiment
A kind of carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion:
The preparation of step 1) melamine resin, the formalin and 30 g melamines that mass ratio is 10g are added three mouthfuls
In bottle, blender is started, pH value is gradually adjusted to 8 with Na2CO3, is warming up to 90 DEG C, 30min is reacted under the conditions of 90 DEG C, uses first
The pH value of reaction solution is adjusted to 5.0 by acid, and reacts 60 min with this condition, dry, and grinding obtains melamine resin powder.
The preparation of step 2 cobalt carbonate-melamine resin powder, melamine resin prepared by 1 g step 1), 2
G cobalt carbonate disperses in 20mL water, stirs 1h, then dries, crushes, grinding, obtaining cobalt carbonate-melamine resin powder；
The preparation of the carbon@CoO composite material of core-shell structure of the N doping of step 3) carbon nanotube insertion, step 2 is obtained
Cobalt carbonate-melamine resin powder be put into tube furnace, calcined under the conditions of 800 DEG C, under condition of nitrogen gas, heating speed
Rate is 5 DEG C/min, keeps the temperature 3h, and the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion can be obtained.
The carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion is through microcosmic shape obtained by sem test
Shown in looks Fig. 1 and transmission electron microscope Fig. 2.As can be seen from the figure carbon nanotube and spherical nanoparticles generate.High-resolution transmission electricity
Mirror Fig. 3 can clearly be seen that CoO nanoparticle is coated by carbon material, form core-shell structure.
In order to verify the remarkable effect that CoO promotes material property, according to the carbon@of the N doping of above-mentioned carbon nanotube insertion
The identical preparation method of CoO composite material of core-shell structure is prepared for the carbon material without CoO, not specified step with it is above-mentioned
Preparation method is identical, the difference is that: the step 2 does not add cobalt carbonate, cannot get the N doping of carbon nanotube insertion
Carbon@CoO composite material of core-shell structure.
The electrochemical property test of the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion, specific method
Are as follows: weigh carbon@CoO composite material of core-shell structure, the 0.01 g acetylene black and 0.01 of the N doping of 0.08 g carbon nanotube insertion
G ptfe micropowder is placed in small agate and grinds in alms bowl, and 0.5 mL ethyl alcohol is added and is ground；It will be ground with the pressure of 10 kPa
The foamed nickel current collector of sample and 1 mm thickness afterwards is suppressed, and is dried in air, at room temperature, is cut into the cm of 2 cm × 2, is made
Electrode of super capacitor tests its specific capacitance.
Testing result is as shown in Figure 4, it is known that: the charge and discharge in -0.3-0.4V range are 1 A/g in discharge current density
When, the carbon@CoO composite material of core-shell structure electrode of super capacitor specific capacitance of the N doping of carbon nanotube insertion can achieve
830 F/g, and the specific capacitance for the porous carbon materials without CoO for using melamine resin to prepare merely is 157 F/g.In phase
With under current density, the discharge time of the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion is apparently higher than list
One carbon electrode material, discharge time improves shows that the performance of the more single porous carbon of its specific capacitance has significantly more 5 times
It improves, shows that the carbon CoO composite material of core-shell structure of the N doping of carbon nanotube insertion has good super capacitor performance.
Claims (5)
1. a kind of carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion, it is characterised in that: by cobalt carbonate and
The mixing of nitrogen containing polymer resin, then carry out high temperature cabonization and obtain, there is carbon@CoO core-shell structure, and the carbon@of carbon nanotube insertion
In CoO core-shell structure, wherein the CoO nuclear diameter formed is 10-20nm, the nitrogen containing polymer resin is melamine tree
Rouge, in the carbon@CoO core-shell structure, the carbon shell for coating CoO is N doping, the carbon coating of carbon nanotube insertion and N doping
CoO formed carbon@CoO core-shell structure be by a step be carbonized it is simultaneously synthesizing.
2. the preparation side of the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion according to claim 1
Method, it is characterised in that the following steps are included:
The preparation of step 1) melamine resin meets certain mass ratio with formaldehyde and melamine, by formaldehyde and melamine
Wiring solution-forming in there-necked flask is added, reaction obtains melamine resin under certain condition；
The mass ratio of the step 1) formaldehyde and melamine is 1:3-5, and the reaction condition of the step 1) is, in stirring condition
Under, gradually use Na2CO3PH value is adjusted to 7.0-9.0, is warming up to 70-90 DEG C, reacts 30-60 min, then with formic acid by pH value
It is adjusted to 5.0-7.0,30-60 min is reacted, is cooled to room temperature after completion of the reaction；
Step 2 cobalt carbonate-melamine resin powder preparation, with certain mass ratio, by melamine resin obtained by step 1)
Powder, cobalt carbonate and water are mixed, and 1-2 h is stirred；Then it dries, crush, grinding, obtaining cobalt carbonate-melamine resin
Powder；
The preparation of the carbon@CoO composite material of core-shell structure of the N doping of step 3) carbon nanotube insertion, the carbon that step 2 is obtained
Sour cobalt-melamine resin powder, is calcined under certain condition, and the carbon@CoO core of the N doping of carbon nanotube insertion can be obtained
Core-shell structure composite material.
3. preparation method according to claim 2, it is characterised in that: melamine resin, the cobalt carbonate of the step 2
Mass ratio with water is 1:2:20.
4. preparation method according to claim 2, it is characterised in that: the calcination condition of the step 3) is in condition of nitrogen gas
Under, with 5 DEG C/min of heating rate, it is warming up to 700-900 DEG C and is calcined, then keep the temperature 3-5h.
5. the carbon@CoO composite material of core-shell structure of the N doping of carbon nanotube insertion is as super electricity according to claim 1
The application of container electrode material, it is characterised in that: the charge and discharge in -0.3-0.4V range are 1 A/g in discharge current density
When, specific capacitance can achieve 800-900 F/g.
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| CN108855184B (en) * | 2018-06-14 | 2020-03-13 | 中南大学 | High-performance oxygen evolution CoO @ Co-NC/C composite catalyst and preparation method and application thereof |
| CN114783785B (en) * | 2022-04-22 | 2024-01-26 | 江苏科技大学 | Electrode material with high electrochemical performance, preparation method and application |
| CN115000432B (en) * | 2022-06-06 | 2023-09-08 | 广东工业大学 | Cobalt oxide-luffa derivative nitrogen-doped carbon composite material and preparation method and application thereof |
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| CN101728526A (en) * | 2009-12-09 | 2010-06-09 | 北京化工大学 | Lithium ion battery cathode material and preparation method thereof |
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