CN107658143A - A kind of ferrocenyl ultracapacitor - Google Patents
A kind of ferrocenyl ultracapacitor Download PDFInfo
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- CN107658143A CN107658143A CN201710878755.5A CN201710878755A CN107658143A CN 107658143 A CN107658143 A CN 107658143A CN 201710878755 A CN201710878755 A CN 201710878755A CN 107658143 A CN107658143 A CN 107658143A
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- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007767 bonding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000010148 water-pollination Effects 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention discloses a kind of ferrocenyl ultracapacitor, and the ferrocenyl ultracapacitor includes working electrode, reference electrode and to electrode, and electrolyte, wherein, the working electrode is prepared using ferrocenyl CNT.Using the splendid redox characteristic of ferrocenyl CNT and hydrophily a kind of Novel super capacitor can be made as the electrode material of ultracapacitor, so as to greatly improve the chemical property of ultracapacitor in it by the present invention.
Description
Technical field
The present invention relates to supercapacitor technologies field, more particularly to a kind of ferrocenyl ultracapacitor.
Background technology
Ultracapacitor (Supercapacitors, abbreviation SCs) is used as a kind of high-power compensation and energy storage device, both has
There are quick charging and discharging capabilities, long circulation life that there is high security again, be a kind of new and effective energy storage device.CNT is made
For a kind of common carbon-based material, it is widely used in ultracapacitor.But the specific surface area of usual CNT is relatively low,
It is generally less than 100Fg as the specific capacitance of electrode material for electric double layer capacitor-1, and efficiency for charge-discharge is not high, exists and puts certainly
Electrical phenomena, easily reunion etc., it is impossible to meet actual demand very well.So needing to carry out modification to CNT, its electricity is improved
Chemical property.
Ferrocene is a kind of metal organic complex with pi bond type interlayer structure, and it has splendid redox special
Property, therefore ferrocene derivatives are often prepared into modified electrode as redox matrix and are used to develop electrochemistry and bio-sensing
Device.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of ferrocenyl ultracapacitor, purport
Existing CNT is being solved as electrode material for super capacitor, the problem of chemical property is relatively low.
Technical scheme is as follows：
A kind of ferrocenyl ultracapacitor, including working electrode, reference electrode and to electrode, and electrolyte, wherein, institute
State working electrode to be prepared using ferrocenyl CNT (CNT-COFc), the chemistry knot of the ferrocenyl CNT
Structure formula is as follows：
Described ferrocenyl ultracapacitor, wherein, the preparation method of the working electrode includes step：Weigh two cyclopentadienyls
Iron-based CNT, bonding agent and conductive agent are added, pasty state is tuned into, is pressed together on carrier, toasted and ferrocenyl carbon nanometer is made
Pipe electrode.
Described ferrocenyl ultracapacitor, wherein, the preparation method of the working electrode specifically includes step：
5mg ferrocenyl CNT is weighed, adds 1mg bonding agent and 1mg conductive agent, is tuned into pasty state, is pressed
10h is toasted on carrier, at 100 DEG C, and ferrocenyl carbon nanotube electrode is made.
Described ferrocenyl ultracapacitor, wherein, the bonding agent is 60wt% polytetrafluoroethyl-ne aqueous solutions.
Described ferrocenyl ultracapacitor, wherein, the conductive agent is acetylene black.
Described ferrocenyl ultracapacitor, wherein, the carrier is foam nickel sheet.
Described ferrocenyl ultracapacitor, wherein, the size of the foam nickel sheet is 1cm × 5cm.
Described ferrocenyl ultracapacitor, wherein, the reference electrode is Ag/AgCl, and described is Pt silks to electrode,
The electrolyte is Na2SO4。
Beneficial effect：Ferrocenyl CNT of the present invention has splendid redox characteristic and hydrophily, its
As electrode material for super capacitor, the chemical property of ultracapacitor can be greatly improved.
Brief description of the drawings
Fig. 1 is the synthetic reaction formula of CNT-COFc in embodiment 1.
Fig. 2 is TG comparison diagrams of the CNT and CNT-COFc in dry air atmosphere in embodiment 1.
Fig. 3 A are the viewgraph of cross-section that the reclaimed water of embodiment 1 is dropped on CNT (A).
Fig. 3 B are the viewgraph of cross-section that the reclaimed water of embodiment 1 is dropped on CNT-COFc (B).
The SEM figures that Fig. 4 A are CNT (A) in embodiment 1.
The SEM figures that Fig. 4 B are CNT-COFc (B) in embodiment 1.
Fig. 5 is CNT and CNT-COFc in embodiment 1 in 10mVs-1CV figure.
Fig. 6 is CNT and CNT-COFc in embodiment 1 in 10mVs-1Specific capacitance comparison diagram.
Fig. 7 is CV figures of the CNT-COFc under different scanning rates in embodiment 1.
Fig. 8 is the specific capacitance of CNT-COFc in embodiment 1 with the changing trend diagram of sweep speed.
The constant current charge-discharge curve that Fig. 9 is CNT-COFc under different current densities in embodiment 1.
Dependence schematic diagram of the specific capacitance to current density that Figure 10 is CNT-COFc in embodiment 1.
Figure 11 is that current density is 2Ag in embodiment 1-1When CNT-COFc specific capacitance conservation rate to cycle-index according to
Rely property schematic diagram.
Embodiment
The present invention provides a kind of ferrocenyl ultracapacitor, to make the purpose of the present invention, technical scheme and effect more
Clear, clear and definite, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein only to
The present invention is explained, is not intended to limit the present invention.
The present invention provides a kind of ferrocenyl ultracapacitor, including working electrode, reference electrode and to electrode, and electrolysis
Matter, wherein, the working electrode is prepared using ferrocenyl CNT, the chemistry knot of the ferrocenyl CNT
Structure formula is as follows：
Ferrocenyl CNT of the present invention has splendid redox characteristic and hydrophily, and it is as super electricity
Container electrode material, the chemical property of ultracapacitor can be greatly improved.
Specifically, the preparation method of the working electrode includes step：Ferrocenyl CNT is weighed, adds bonding agent
And conductive agent, pasty state is tuned into, is pressed together on carrier, toasts and ferrocenyl carbon nanotube electrode is made.
Below by embodiment, the present invention is described in detail.
Embodiment
1st, reagent
Highly conductive multi-walled carbon nanotube CNT is purchased from Suzhou Tan Feng graphenes Science and Technology Ltd., directly uses.Anhydrous chlorination
Aluminium (purity ＞ 99%), oxalyl chloride (purity ＞ 98%), ferrocene (purity ＞ 99%) are purchased from MACKLIN companies, directly make
With.Concentrated nitric acid, potassium permanganate, perchloric acid, citric acid, hydrochloric acid, tetrahydrofuran, analysis is pure, purchased from Guangzhou Chemical Reagent Factory, directly
Use.Dichloromethane, analysis is pure, and purchased from Guangzhou Chemical Reagent Factory, calcium hydride water removal is standby.Nickel foam, ptfe emulsion,
Purchased from the source battery sales department of Taiyuan Yingze District power.All experimental waters are Millipore ultra-pure waters.
2nd, CNT-COFc preparation
The specific synthetic reaction formulas of CNT-COFc are as shown in Figure 1.Carboxylic carbon nano-tube (CNT-COOH) is according to literature method
Synthesize (Chem.Mater.2004,16:2174-2179), highly conductive multi-walled carbon nanotube (CNT) is specifically scattered in dense nitre
In the mixed liquors of acid, potassium permanganate and perchloric acid, ultrasound 7 hours in superpower Ultrasound Instrument are placed in, cleans and dries after taking-up,
Obtain carboxylic carbon nano-tube (CNT-COOH).1.5 grams of carboxylic carbon nano-tubes (CNT-COOH) are weighed, are added to dry three
In mouth bottle, 40 milliliters of anhydrous methylene chlorides are added, under argon gas protection, ice bath adds 1 milliliter of oxalyl chloride to 3 degree, with syringe, low
3 degree of temperature is reacted 1 hour, then is reacted at room temperature 10 hours.Decompression extracts unreacted oxalyl chloride and solvent, under argon gas protection, then adds
Enter 2.3 grams of anhydrous Aluminum chlorides and 50 milliliters of anhydrous methylene chlorides, stir 10 minutes, ice bath adds 1.2 grams of ferrocene to 3 degree, low
3 degree of temperature is reacted 1 hour, and room temperature reaction is reacted 2 hours again under 4 hours, 40 degree.30 milliliters of 5molL are slowly added dropwise-1Hydrochloric acid it is whole
Only react, filter, alternately wash filter cake with tetrahydrofuran and watery hydrochloric acid, remove aluminium chloride and unreacted ferrocene.Product 40
Degree vacuum drying, obtains 1.7 grams of ferrocenyl CNTs (CNT-COFc).
3rd, the preparation of CNT-COFc working electrodes
The preparation method of working electrode：CNT-COFc 5mg are weighed, add 1mg glue (60wt% polytetrafluoroethylene (PTFE) breast
Liquid) and 1mg acetylene black, be tuned into pasty state, be pressed together in foam nickel sheet (being cut into 1cm × 5cm), 100 DEG C baking 10h be made
CNT-COFc working electrodes.
4th, test and sign
Thermogravimetric analysis (TG) is measured using PerkinElmer TGA 8000, and work atmosphere is dry air, heating rate
For 10 degrees/min.The inductively coupled plasma of detection certification limited company is precisely led in iron content analysis using Dongguan
Body Atomic Emission Spectrometer AES (ICP-OES) determines.FFIR (FTIR) uses Thermo companies of the U.S.
The type Fourier turn infrared instrument of Nicolet 6700 determines.Contact angle uses the OCA of German Dataphysics companies
Type contact angle measurement determines, and test temperature is 25 DEG C.SEM (SEM), model JSM-6701F, JEOL
Co., Ltd. (JEOL).
Cyclic voltammetry and constant current charge-discharge test, specific test condition are carried out using CHI 660E electrochemical workstations
For：Using three-electrode system, 1.0M Na2SO4Make electrolyte, CNT-COFc foam nickel sheet positive electrode as working electrode,
Ag/AgCl (3.0M KCl) and Pt silks are respectively as reference and to electrode.
5th, test result：
5.1st, CNT-COFc structural analysis
" grafting rate " of ferrocene group can pass through thermogravimetric analysis (TG) in ferrocenyl CNT (CNT-COFc)
Determined with inductively coupled plasma atomic emission spectrometer (ICP-OES).CNT and ferrocenyl CNT
(CNT-COFc) as shown in Fig. 2 when CNT (CNT) is heated to 800 degree, residual mass accounts for just the TG figures in dry air
The 2.8wt% of prothyl amount, this residual substance are catalyst and impurity.And ferrocenyl CNT (CNT-COFc) is heated to
At 800 degree, residual mass accounts for the 6.4wt% of initial mass, it is assumed that and ferrocenyl is completely converted into iron oxide after air burning,
" grafting rate " for being computed ferrocenyl in CNT-COFc is 8.3wt%.Ferro element in CNT-COFc is measured by ICP-OES
Content is 1.8wt%, and the content for being converted to ferrocenyl is 6.0wt%, and this is basically identical with TG test results.To sum up, two cyclopentadienyl
" grafting rate " of ferrocenyl is about 7.3wt% in iron-based CNT (CNT-COFc).
Sample CNT-COFc wetability is characterized using water contact angle test, in general, if water contact angle is small
In 90 °, it is hydrophily to show sample surfaces；Contact angle is smaller, and hydrophily is stronger.Water droplet is respectively at multi-walled carbon nanotube CNT (A)
With ferrocenyl CNT CNT-COFc (B) upper viewgraph of cross-section as shown in figs.3 a and 3b.CNT is by two cyclopentadienyls
After iron-based modification, surface hydrophilicity significantly improves than unmodified sample, finds that CNT wetability is to electricity according to research before
Capacity has a great influence, and general appropriate hydrophily is advantageous to specific capacitance.
Further CNT CNT and ferrocenyl CNT CNT-COFc pattern are characterized, CNT
CNT and ferrocenyl CNT CNT-COFc SEM scheme as illustrated in figures 4 a and 4b, it can be seen that after ferrocenyl modification,
CNT-COFc remains in that CNT pattern, i.e. chemical modification does not destroy CNT overall rule degree.
5.2nd, electro-chemical test
In order to study the chemical property for the ferrocenyl ultracapacitor that CNT-COFc is constructed, cyclic voltammetric is carried out to it
Method (CV) and constant current charge-discharge test.Fig. 5 is CNT and CNT-COFc in 10mVs-1CV figure, it can be seen that CNT
CV figures with CNT-COFc are rectangle or class rectangle, show that both materials all have good capacitance characteristic.It can also see
Go out CNT-COFc CV curves has a pair of unconspicuous redox peaks between 0.0-0.4V, and this is probably derived from carbon to peak and received
The contribution of the ferrocenyl of nanotube surface modification, original CNT CV scheme no redox peaks.From figure it has also been found that grafting ferrocene
After base, significantly increased in the area of same scan speed lower curve.Specific capacitance, calculation formula are calculated from Fig. 5 integral area：Result of calculation is as shown in Figure 6.As can be seen from Figure 6, in identical sweep speed 10mVs-1Under,
The specific capacitance 27.2Fg of original carbon nanotubes (CNT)-1, specific capacitance is 67.0Fg after being grafted ferrocenyl-1, that is, it is grafted two
After luxuriant iron-based, specific capacitance brings up to 2.46 times, and this may come from the ferrocenyl that good hydrophily and surface introduce after grafting.
CV figures of the CNT-COFc under different scanning rates is further studied, as shown in fig. 7, as can be seen from the figure with sweep speed
From 10,20,50,100,200mVs-1Increase, the area of curve incrementally increase.Specific capacitance, meter are calculated from Fig. 7 integral area
It is as shown in Figure 8 to calculate result.As can be seen from Figure 8 CNT-COFc specific capacitance declines with the increase of sweep speed.In 200mVs-1
When, specific capacitance 9.5Fg-1, specific capacitance conservation rate is 14.2%.
Charging and discharging curves of the CNT-COFc under different current densities is further studied by constant current charge-discharge test, such as
Shown in Fig. 9, curve shows good symmetry and linear character, embodies excellent super capacitor performance.Utilize formulaSpecific capacitance values of the CNT-COFc under different current densities is calculated from Fig. 9 discharge curve, as shown in Figure 10,
Show that current density is followed successively by 0.4,0.8,1.2,1.6,2.0Ag-1When, specific capacitance is respectively 53.6,47.8,42.8,38.3,
34.1F·g-1.The above results show that CNT-COFc has superior super capacitor performance.In addition to can be with fast charging and discharging,
Cycle life is also another key parameter of research.In 2.0Ag-1Lower progress CNT-COFc cycle life tests, 5000
The result of secondary fast charging and discharging is as shown in figure 11, and specific capacitance value only decays 4% after finding 5000 circulations, shows that it has height
Service life.
In summary, a kind of ferrocenyl ultracapacitor provided by the invention.The present invention utilizes ferrocenyl carbon nanometer
Splendid redox characteristic and hydrophily are managed, it can be made a kind of new super as the electrode material of ultracapacitor
Level capacitor, so as to greatly improve the chemical property of ultracapacitor.Pass through the electrochemistry such as cyclic voltammetry, constant current charge-discharge
Characterize, it is found that the ultracapacitor in current density is 0.2Ag-1When, specific capacitance 67.0Fg-1, it is unmodified carbon nanometer
2.46 times of pipe；In 2.0Ag-1Lower progress CNT-COFc cycle life test, specific capacitance value only decays after 5000 circulations
4%, it is a kind of good super capacitor anode material to show CNT-COFc.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (8)
1. a kind of ferrocenyl ultracapacitor, including working electrode, reference electrode and electrode, and electrolyte, its feature are existed
In the working electrode is prepared using ferrocenyl CNT, the chemical structural formula of the ferrocenyl CNT
It is as follows：
2. ferrocenyl ultracapacitor according to claim 1, it is characterised in that the preparation method of the working electrode
Including step：Ferrocenyl CNT is weighed, bonding agent and conductive agent is added, is tuned into pasty state, is pressed together on carrier, baking system
Obtain ferrocenyl carbon nanotube electrode.
3. ferrocenyl ultracapacitor according to claim 2, it is characterised in that the preparation method of the working electrode
Specifically include step：
5mg ferrocenyl CNT is weighed, 1mg bonding agent and 1mg conductive agent is added, is tuned into pasty state, is pressed together on load
10h is toasted on body, at 100 DEG C, and ferrocenyl carbon nanotube electrode is made.
4. according to the ferrocenyl ultracapacitor described in claim any one of 2-3, it is characterised in that the bonding agent is
60wt% polytetrafluoroethyl-ne aqueous solutions.
5. according to the ferrocenyl ultracapacitor described in claim any one of 2-3, it is characterised in that the conductive agent is second
Acetylene black.
6. according to the ferrocenyl ultracapacitor described in claim any one of 2-3, it is characterised in that the carrier is foam
Nickel sheet.
7. ferrocenyl ultracapacitor according to claim 6, it is characterised in that the size of the foam nickel sheet
For 1cm × 5cm.
8. ferrocenyl ultracapacitor according to claim 1, it is characterised in that the reference electrode is Ag/AgCl,
Described is Pt silks to electrode, and the electrolyte is Na2SO4。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109741961A (en) * | 2018-12-27 | 2019-05-10 | 东莞理工学院 | Supercapacitor based on single-walled carbon nanotube bismuth oxide Pt/Polypyrrole composite material |
| CN109786125A (en) * | 2018-12-27 | 2019-05-21 | 东莞理工学院 | A kind of azobenzene supercapacitor |
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| CN103466595A (en) * | 2013-08-29 | 2013-12-25 | 福州大学 | Method for preparing ferrocene functionalized carbon nanotube composite material |
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| CN103466595A (en) * | 2013-08-29 | 2013-12-25 | 福州大学 | Method for preparing ferrocene functionalized carbon nanotube composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109741961A (en) * | 2018-12-27 | 2019-05-10 | 东莞理工学院 | Supercapacitor based on single-walled carbon nanotube bismuth oxide Pt/Polypyrrole composite material |
| CN109786125A (en) * | 2018-12-27 | 2019-05-21 | 东莞理工学院 | A kind of azobenzene supercapacitor |
| CN109741961B (en) * | 2018-12-27 | 2020-11-03 | 东莞理工学院 | Supercapacitor based on single-walled carbon nanotube bismuth oxide polypyrrole composite material |
| CN109786125B (en) * | 2018-12-27 | 2021-07-02 | 东莞理工学院 | Azophenyl super capacitor |
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