CN207009293U - A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array - Google Patents
A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array Download PDFInfo
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- CN207009293U CN207009293U CN201720501139.3U CN201720501139U CN207009293U CN 207009293 U CN207009293 U CN 207009293U CN 201720501139 U CN201720501139 U CN 201720501139U CN 207009293 U CN207009293 U CN 207009293U
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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 utility model discloses a kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array, the negative pole includes conductive substrates, N doped carbon microplates, the conductive substrates are in cellular, the N doped carbons microplate is in foliaceous and array vertical distribution is in conductive substrates, and the N doped carbons microplate includes equally distributed Co nano-particles.The negative pole structure nitrogen-doped carbon cobalt compound microplate array of disclosure of the invention is grown directly upon in conductive substrates, it has very high electron mobility, it is advantageously implemented fast charging and discharging, the negative pole is subjected to electrochemical properties test, swept in different under speed, the cyclic voltammetric of the electrode shows similar rectangular shape, and charging and discharging curve shows linear feature under different current densities, and it is demonstrated by carbon material electric double layer feature.When increasing current density, the specific discharge capacity change of the electrode is smaller, shows that it has preferable multiplying power property as ultra-capacitor negative pole.
Description
Technical field
The utility model belongs to new energy electrode material field, and in particular to one kind is mixed based on conductive substrates direct growth nitrogen
The super capacitor anode of miscellaneous carbon-cobalt compound microplate array.
Background technology
Worldwide all suffers from serious energy crisis at present, and to solve this problem, researcher develops greatly
Measure the energy storage device based on electrochemical storage.Ultracapacitor is because of its high power density, fast charging and discharging and stable circulation
The characteristics of property, not only in consumption electronic products field, and in new-energy automobile, solar energy generating, intelligent grid, electricity
The fields such as power, railway, communication, national defence, which all exist, to be widely applied.Not only in consumption electronic products field, and in new energy
The fields such as automobile, solar energy generating, intelligent grid, electric power, railway, communication, national defence, which all exist, to be widely applied.Electrode material
The exploitation of material is the main method of current supercapacitor technologies research, and its electrode material charge storage directly determines super
The capacitance of electric capacity.Carbons material often has high electrical conductivity, high-ratio surface and good chemical stability, and it is as electrode
Material can obtain high power density.However, in actual applications, due to carbon material surface hydrophobicity, electric double layer storage electric charge
Special card cause its relatively low actual ions to can contact area and small energy density, due to the presence of these defects, make it very
Hardly possible meets application requirement higher in reality.Therefore the carbon material of N doping type not only has high conductivity, and the doping of nitrogen
Carbon surface can be modified, increase its specific capacity, it has larger application prospect.
The operation principle of the doped carbon increase capacity of nitrogen is that may participate in bath surface by the nitrogen-atoms of doping quickly may be used
Inverse redox reaction, and then increase extra energy stores point to realize higher charge storage, in addition carbon material
It is supported directly in conductive substrates, not only synthesis is simple, and can increase the contact area with base, increases medium and electric charge
Transport speed, and promote capacity to increase.
Document [Y.Qin, Adv.Mater., 2015,27,5171] has reported the carbon electrode of the porous N doped graphenes of 3D, should
Then text is interconnected to form carbon precursor by previously prepared graphene oxide under hydrothermal conditions with melamine, formaldehyde, then
High-temperature calcination, the last porous N doped graphenes of 3D, because 3D frame structures prevent graphene in N doping and calcination process
Stacking its is kept porosity, provide extra electricity so as to provide the doping of passage while N of the ion quickly needed for conduction
The contribution of lotus storage point increase fake capacitance.But it is this by the porous N doped graphenes of 3D, synthesis step is various, and cost is higher；This
Outside, this powder carbon material usually requires to add extra non-reactive additives in electrode production process, and adds contact
Resistance.Preparation technology is complicated, cost increase, without practical value.
Document [J.Zhao, Adv.Mater., 2015,27,3541] has reported N doping nano cages, the passing through of technology
Vapour deposition process is learned, using MgO as catalyst and template, pyridine is carbon and nitrogen source, is reacted on high temperature, and last acid removes template system
It is standby go out N doping nano cages, in view of the high electrical conductivity of carbon material, N doping increase hydrophilies make it have more in aqueous phase electrolyte
Wetability well, beneficial to the active area of increase ion, play the effect for increasing capacity.But high temperature vapour deposition method into
This is higher, and it is generally necessary to which addition simultaneously is additionally nonactive to be adhered reagent and conductive agent in electrode production process.Prepare
Complex process, cost increase, without practical value.
Document [T.Lin, Science, 2015,350,1508.] was reported prepares what N was adulterated using high temperature vapour deposition
Mesoporous carbon, by the way that using mesopore silicon oxide as template, Ni is catalyst, methane is carbon source, and ammonia is nitrogen source, and vapour deposition obtains N
Few layer of mesoporous carbon of doping, the porosity between this carbon using mesoporous silicon as its few layer of the method for template is stable, can be favourable
Increase wetability in the doping of the fast transferring of electrolyte ion, and N and greatly improve its contribution as fake capacitance part,
There is high specific capacity as electrochemical capacitance electrode material.But this technology needs the template of mesoporous silicon, subsequent treatment needs to use
Toxicity HF, and the synthesis of multistep pretreatment such as mesoporous silicon, the deposition of catalyst are needed during high temperature is vapor-deposited, it is multiple
Miscellaneous preparation technology, higher production cost is result in, without practical value.
In summary, a kind of ultracapacitor based on substrate direct growth N doping porous carbon-Co compound microplate arrays
The exploitation of negative pole is still the research emphasis of those skilled in the art.
The content of the invention
In view of this, the purpose of this utility model is that providing one kind is based on conductive substrates direct growth nitrogen-doped carbon-cobalt
The super capacitor anode of compound microplate array.
To reach above-mentioned purpose, the utility model provides following technical scheme：
1st, a kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array,
The negative pole includes conductive substrates, N doped carbon microplates, and the conductive substrates are in cellular, and the N doped carbons microplate is in foliaceous
And array vertical distribution, in conductive substrates, the N doped carbons microplate includes equally distributed Co nano-particles.
Preferably, the N doped carbons microplate thickness is 200-400nm, and the Co nano particle diameters are 5-10nm.
Preferably, the conductive substrates are carbon cloth, nickel foam or foam copper.
The beneficial effects of the utility model are：Mixed the utility model discloses one kind based on conductive substrates direct growth nitrogen
The super capacitor anode of miscellaneous carbon-cobalt compound microplate array, negative pole structure nitrogen-doped carbon-cobalt is multiple disclosed in the utility model
Compound microplate array is grown directly upon in conductive substrates, makes it have very high electron mobility, is advantageously implemented quick charge and discharge
Electricity, the negative pole is subjected to electrochemical properties test, it is different sweep speed under, the cyclic voltammetric of the electrode shows similar
Rectangular shape, charging and discharging curve shows linear feature under different current densities, and it is demonstrated by carbon material electric double layer feature.
When increasing current density, the specific discharge capacity change of the electrode is smaller, shows that it has preferably again as ultra-capacitor negative pole
Rate characteristic.
Brief description of the drawings
In order that the purpose of this utility model, technical scheme and beneficial effect are clearer, the utility model provides as follows
Accompanying drawing illustrates：
Fig. 1 is Co- zeolite imidazole ester frame structure material precursor schematic diagrames；
Fig. 2 is the nitrogen-doped carbon perpendicular to the conductive substrates-cobalt compound microplate array schematic diagram obtained after calcining；
Fig. 3 is scanning electron microscope (SEM) photograph (scanning when A expression scales are 1 μm of Co- zeolite imidazole ester frame structure material precursors
Electron microscope；B represents scanning electron microscope (SEM) photograph when scale is 500nm)；
A is the electricity of the nitrogen-doped carbon perpendicular to the conductive substrates-cobalt compound microplate array obtained after calcining in Fig. 4
Scarnning mirror figure, B are power spectrum phenogram；
A is cyclic voltammetry curve of the microplate array as capacitor anode in Fig. 5, and B is constant current charge-discharge curve；
Fig. 6 be microplate array as capacitor anode the different current density vs electrode qualities ratios under the conditions of constant current charge-discharge
The test curve of capacity.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present utility model is described in detail.It is unreceipted in embodiment
The experimental method of actual conditions, generally according to normal condition or according to the condition proposed by manufacturer.
A kind of super electricity based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array of embodiment 1~3
As shown in Figure 1, 2, wherein Fig. 1 is Co- zeolite imidazole ester frame structure material precursor schematic diagrames to container negative pole structure；Fig. 2 is warp
The obtained nitrogen-doped carbon perpendicular to conductive substrates-cobalt compound microplate array schematic diagram is crossed after calcining；The negative pole includes leading
Electric substrate, N doped carbon microplates, the conductive substrates are in cellular, and the N doped carbons microplate is in array vertical distribution in conduction
In substrate, the N doped carbons microplate includes equally distributed Co nano-particles；The N doped carbons microplate thickness is 200-
400nm, the Co nano particle diameters are 5-10nm；The conductive substrates are carbon cloth, nickel foam or foam copper.
Embodiment 1
A kind of super capacitor based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array of the present embodiment
Device negative pole is made as follows：
1) carbon cloth is removed into surface grease with acetone, ethanol and water washing respectively；
2) in molar ratio 1：1：60 weigh Co (NO3)2·6H2O, 2-methylimidazole is added to the water obtained mixed liquor, by step
1) conductive substrates of processing, which are put into mixed liquor, is made Co- zeolite imidazole ester frame structure material precursors, then dries；
3) by obtained Co- zeolite imidazoles ester frame structure material precursor, in the case where Ar atmosphere is enclosed, 500-800 DEG C of condition calcining
30min, that is, the nitrogen-doped carbon cobalt compound microplate array perpendicular to conductive substrates is made；
4) the nitrogen-doped carbon cobalt compound microplate array perpendicular to conductive substrates for being obtained step 3) is in HCl solution
Immersion 6 hours, remove part unstable Co and its oxide, you can obtain the super capacitor anode.
Embodiment 2
A kind of super capacitor based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array of the present embodiment
Device negative pole is made as follows：
1) nickel foam is removed into surface grease with acetone, ethanol and water washing respectively；
2) in molar ratio 1：2：60 weigh Co (NO3)2·6H2O, 2-methylimidazole is added to the water obtained mixed liquor, by step
1) conductive substrates of processing, which are put into mixed liquor, is made Co- zeolite imidazole ester frame structure material precursors, then dries；
3) by obtained Co- zeolite imidazoles ester frame structure material precursor, in the case where Ar atmosphere is enclosed, 500-800 DEG C of condition calcining 3
Hour, that is, the nitrogen-doped carbon cobalt compound microplate array perpendicular to conductive substrates is made；
4) the nitrogen-doped carbon cobalt compound microplate array perpendicular to conductive substrates for being obtained step 3) is in HCl solution
Immersion 12 hours, remove part unstable Co and its oxide, you can obtain the super capacitor anode.
Embodiment 3
A kind of super capacitor based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array of the present embodiment
Device negative pole is made as follows：
1) foam copper is removed into surface grease with acetone, ethanol and water washing respectively；
2) in molar ratio 1：2：60 weigh Co (NO3)2·6H2O, 2-methylimidazole is added to the water obtained mixed liquor, by step
1) conductive substrates of processing, which are put into mixed liquor, is made Co- zeolite imidazole ester frame structure material precursors, then dries；
3) by obtained Co- zeolite imidazoles ester frame structure material precursor, in the case where Ar atmosphere is enclosed, 500-800 DEG C of condition calcining 6
Hour, that is, the nitrogen-doped carbon cobalt compound microplate array perpendicular to conductive substrates is made；
4) the nitrogen-doped carbon cobalt compound microplate array perpendicular to conductive substrates for being obtained step 3) is in HCl solution
Immersion 24 hours, remove part unstable Co and its oxide, you can obtain the super capacitor anode.
Co- zeolite imidazole ester frame structure materials precursor after further being dried to embodiment 1 carries out electron microscope and swept
Retouch, obtain such as A in Fig. 3 and the scanning electron microscope (SEM) photograph shown in B, it can be seen that metal framework compound (Co-ZIFs) microplate foliaceous
Array precursor is equably grown in substrate, and surface is smooth.Further to being obtained after calcining perpendicular to conductive substrates
Nitrogen-doped carbon-cobalt compound microplate array carry out electron-microscope scanning, the electron-microscope scanning figure as shown in A in Fig. 4 is obtained, by calcining
N doped carbons-Co compound microplates array still keeps original foliaceous pattern afterwards, but surface is substantially coarse, the particle on surface
Shape particle is Co metals and its oxide, and power spectrum is further carried out to it and characterizes to obtain power spectrum phenogram as shown in B in Fig. 4,
Power spectrum sign, which also indicates that, contains N in sample, be N doped carbons.
A is cyclic voltammetry curve of the microplate array as capacitor anode in Fig. 5, and B is constant current charge-discharge curve；Can
Find out it is different sweep speed under, the cyclic voltammetric of N doped carbon-Co compound microplate array electrodes shows similar rectangle shape
Shape；A small amount of peak shows the fake capacitance capacity contribution of N doping；Charging and discharging curve shows linear spy under different current densities
Point, it is carbon material electric double layer feature.
Fig. 6 be microplate array as capacitor anode the different current density vs electrode qualities ratios under the conditions of constant current charge-discharge
The test curve of capacity.It can be seen that when increasing current density, the quality specific volume of N doped carbon-Co compound microplate array electrodes
Amount change is smaller, shows it as the good multiplying power property of electrochemical capacitance negative pole.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (3)
1. a kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array, it is special
Sign is, the negative pole includes conductive substrates, N doped carbon microplates, and the conductive substrates are in cellular, the N doped carbons microplate
In foliaceous and array vertical distribution is in conductive substrates, and the N doped carbons microplate includes equally distributed Co nano-particles.
It is 2. a kind of super based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array according to claim 1
Level capacitor anode, it is characterised in that the N doped carbons microplate thickness is 200-400nm, and the Co nano particle diameters are 5-
10nm。
It is 3. a kind of super based on conductive substrates direct growth nitrogen-doped carbon-cobalt compound microplate array according to claim 1
Level capacitor anode, it is characterised in that the conductive substrates are carbon cloth, nickel foam or foam copper.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201720501139.3U CN207009293U (en) | 2017-05-04 | 2017-05-04 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array |
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| CN201720501139.3U CN207009293U (en) | 2017-05-04 | 2017-05-04 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107045945A (en) * | 2017-05-04 | 2017-08-15 | 重庆石墨烯研究院有限公司 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array and preparation method thereof |
| CN113044840A (en) * | 2021-03-09 | 2021-06-29 | 陕西科技大学 | Activated carbon loaded molybdenum and nitrogen double-doped carbon nanosheet array composite material and preparation method and application thereof |
-
2017
- 2017-05-04 CN CN201720501139.3U patent/CN207009293U/en not_active Withdrawn - After Issue
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107045945A (en) * | 2017-05-04 | 2017-08-15 | 重庆石墨烯研究院有限公司 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array and preparation method thereof |
| CN113044840A (en) * | 2021-03-09 | 2021-06-29 | 陕西科技大学 | Activated carbon loaded molybdenum and nitrogen double-doped carbon nanosheet array composite material and preparation method and application thereof |
| CN113044840B (en) * | 2021-03-09 | 2023-11-21 | 陕西科技大学 | Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof |
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| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181019 Address after: 400000 No. 15, Fung Sheng Road, Kowloon Po District, Chongqing, 6 Patentee after: Chongqing Zhongke super capacity Technology Co., Ltd. Address before: 400714 No. 266 Fangzheng Road, Beibei District, Chongqing. Patentee before: Chongqing graphene Research Institute Co., Ltd. |
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| TR01 | Transfer of patent right | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20180213 Effective date of abandoning: 20181221 |
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| AV01 | Patent right actively abandoned |