CN106971861A - The method for improving ultracapacitor Schiff transition metal polymerization thing electrode specific capacity - Google Patents
The method for improving ultracapacitor Schiff transition metal polymerization thing electrode specific capacity Download PDFInfo
- Publication number
- CN106971861A CN106971861A CN201710321499.XA CN201710321499A CN106971861A CN 106971861 A CN106971861 A CN 106971861A CN 201710321499 A CN201710321499 A CN 201710321499A CN 106971861 A CN106971861 A CN 106971861A
- Authority
- CN
- China
- Prior art keywords
- schiff
- electrode
- transition metal
- polymerization thing
- metal polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 57
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 40
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 229920000767 polyaniline Polymers 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910019785 NBF4 Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims 3
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 19
- 239000002322 conducting polymer Substances 0.000 abstract description 18
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 abstract 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 10
- HXFYGSOGECBSOY-UHFFFAOYSA-N 2-[[2-[(2-hydroxyphenyl)methylideneamino]phenyl]iminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=CC=C1N=CC1=CC=CC=C1O HXFYGSOGECBSOY-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002262 Schiff base Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 Schiff base transition metal Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920005588 metal-containing polymer Polymers 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method 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
- H01G11/48—Conductive polymers
-
- 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
- H01G11/66—Current collectors
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
Abstract
A kind of raising ultracapacitor method of Schiff transition metal polymerization thing electrode specific capacity, belongs to organic system ultracapacitor field.Two kinds of different conducting polymer electro-deposition are directly polymerize by the present invention on a current collector by two-step method.First under organic system by electro-deposition mode by Schiff transition metal polymerization thing monomer electropolymerization in collector titanium sheet, the electrode material that aniline polymerization constitute in a kind of collector titanium sheet of conducting polymer pair conducting polymer Poly [M (Schiff)]/PANI ultracapacitors by aniline (AN) monomer by way of electropolymerization is dissolved under acid system afterwards.Composite material exhibits go out exclusive pattern, and the electrode material embodies more excellent capacitance characteristic when being used alone by the synergy between two kinds of conducting polymers than any of which conducting polymer.The inventive method is simple, this structure and carbon material that can be combined both, and transition metal oxide etc. is further combined the performance for improving it as electrode material for super capacitor.
Description
Technical field
Ultracapacitor Schiff transition metal polymerization thing electrode is improved in organic system the present invention relates to one kind
The method of specific capacity.The invention belongs to the electrode material of electrochemical energy storage, available for organic system ultracapacitor field.
Background technology
21 century economic development be every country weight in it, and to be a cornerstone of the state either transport in national defence the energy
With the guided missile of high and new technology, low technology is still used in, the electric cooker of diet daily life is appeared in, the energy is all be unable to do without.
Therefore it is that must lift the height of strategic position in national planning.Ultracapacitor is provided simultaneously with physical capacitor and battery
Good characteristic, as a kind of more novel energy storage energy source device, can discharge higher as General Physics capacitor
Discharge power, can typically be provided with powerful charge storage as battery again.
Ultracapacitor is with all main by component combinations such as collector, electrolyte, electrode material and barrier films battery
Into a big bottleneck of limitation supercapacitor applications is that the specific capacity of electrode material at present.And conducting polymer is due to it
Excellent performance, material is easy to get, and the characteristic such as with low cost is widely used and electrode material for super capacitor.Schiff base mistake
Metal-containing polymer poly [M (Schiff)] is crossed to have a good application prospect as the new electrode materials of ultracapacitor.With
Conventional conductive polymer is compared, and Schiff base transition metal polymerization thing has obvious advantage, wherein wider potential change
Window and good chemical property make it be expected to reduce current ultracapacitor with secondary cell in terms of energy density is stored
Gap.In addition, Schiff base transition metal polymerization thing preparation technology is simple, cost is relatively low, is just meeting current super electricity
The development trend of field of containers.
Conducting polymer is usually by gripping the polymer of pi bond system institute after chemistry or electrochemical doping altogether with electronics
, doped conducting polymer has the electric conductivity of metalloid.Compared with metallic conductor, conducting polymer is except with close
Outside the characteristics of spending small, light weight, easily shaping, also with some unique properties.American professor MacDiarmid is first in acid
The study hotspot that conductive product polyaniline subsequently becomes conducting polymer field is obtained under the conditions of property.Relative to it
Its conducting polymer materials, is easy to get with its raw material, synthesizes convenient, various structures and excellent physical property and good environment
Stability and the broad interest for causing researcher, the focus made internal disorder or usurp is ground as conducting polymer family.And two kinds different
The compound electrode material as ultracapacitor of conducting polymer improves electrode material using synergy between the two
The mode of specific capacity less mention.At the same time electrochemical polymerization method prepares conducting polymer, passes through control electric current or control
Current potential, makes polymerized monomer that oxidative polymerization occur on anode, forms conducting polymer and forms the high shape of specific surface area
Looks.Simultaneous electrochemical method synthesis conducting polymer has the advantages that reaction condition is simple, easy to control, purity is high.
The content of the invention
The purpose of the present invention is being provided in one kind in organic system by electropolymerization Polyaniline-modified ultracapacitor use
Schiff transition metal polymerization thing electrode is so as to the method for improving electrode material for super capacitor specific capacity.Led using both
Synergy between electric polymer significantly improves Schiff base transition metal polymerization thing as the specific capacity of electrode material.For
Above-mentioned requirement is reached, the technical scheme that the present invention is provided is carried out according to the following steps：
1st, the processing of collector titanium sheet：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；It is put into the sodium carbonate of alkalescence
Water-bath, which is deoiled, in solution is placed into deionized water rinsing in 30wt% HCl, is washed with deionized water after 1.5~2.5h of immersion
Only；Clean titanium sheet one end (1cm × 1cm) is polished smooth with the sand paper of different model, until immaculate occurs.
2nd, it polymerize Schiff transition metal polymerization thing monomer：Lower working electrode is afflux in organic three-electrode system
The work area of one end (1 × 1) in body titanium sheet, reference electrode is Ag/AgCl, and auxiliary electrode is the active carbon cloth of large area.Will
Schiff transition metal polymerization thing monomer is dissolved in the low organic solvent of electron number in solution, and adds a certain amount of
Supporting electrolyte, electrode is aggregated into using electrochemical method.
3rd, the double conductive polymer electrodes materials of polymerization aniline monomer construction：Under inorganic acid system, three electrodes are utilized
System electropolymerization aniline monomer.Working electrode is the electrode that (2) step is aggregated into, and reference electrode is mercury-mercurous sulfate electrode, auxiliary
It is platinum electrode to help electrode.Polymer fluid is that aniline monomer is dissolved in dilution heat of sulfuric acid.
Wherein, described in step 1, the titanium sheet collector after being handled by soda acid will meet the requirement of collector, improve experiment
Repeatability.
The species of Schiff transition metal polymerization thing monomer described in step 2 include Me (Schiff) (Me=Ni, Co,
Mn, Pb, etc.), the concentration of monomer is between 1mmol/L-10mmol/L.The low organic solvent of electron number includes acetonitrile, benzene first
Supporting electrolyte includes tetrabutylammonium perchlorate (TBAP), Et simultaneously for nitrile, vinyl carbonate, propylene carbonate etc.4NBF4,
Et4NPF6(anion radius is followed successively by 0.241,0.333,0.435nm) (Me4N)BF4, (Et4N)BF4, (Bu4N)BF4(cation
Secondary is 0.47,0.56,0.96nm).
The concentration of aniline monomer described in step 3 is between 0.2mol/L-0.5mol/L.The concentration of sulfuric acid is in 0.5mol/
Between L-1.5mol/L.Polyaniline (PANI) polymerization includes constant flow method, constant-voltage method, cyclic voltammetry, impulse method.
Schiff transition metal polymerization thing is electrodeposited into collector by the inventive method using the method for electrochemical polymerization
Certain specific capacity is provided as electrode material in fake capacitance behavior because conducting polymer is pure in organic system in titanium sheet.
The inventive method is in collector titanium sheet in acid body on the basis of electropolymerization Schiff transition metal polymerization thing
System is lower to continue electropolymerization aniline, modifies Schiff transition metal conducting polymer.Double composite conductive polymers are placed on organic
Measured in system its specific capacity show its specific capacity than be used alone Schiff transition metal polymerization thing electrode when lifted it is bright
It is aobvious.And preparation method can simply effectively improve its specific capacity.
Brief description of the drawings
Fig. 1 is electric for the scanning of the ultracapacitor Schiff transition metal polymerization thing electrode material prepared by the present invention
Mirror (SEM) figure
Fig. 2 is the ESEM of the ultracapacitor conductive polymer polyanaline electrode material prepared by the present invention
(SEM) figure
Fig. 3 is the ESEM of ultracapacitor Poly [M (Schiff)]/PANI electrode materials prepared by the present invention
(SEM) figure
Fig. 4 is the cyclic voltammetric of ultracapacitor Poly [M (Schiff)]/PANI electrode materials prepared by the present invention
Curve
Fig. 5 is the constant current charge and discharge of ultracapacitor Poly [M (Schiff)]/PANI electrode materials prepared by the present invention
Electric curve
Fig. 6 is different voltages of the ultracapacitor prepared by the present invention with Poly [M (Schiff)]/PANI electrode materials
The interval chrono-amperometric test of step
Embodiment
The present invention is elaborated with reference to the accompanying drawings and examples.Technical scheme is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Embodiment in invention, the every other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example is applied, the scope of protection of the invention is belonged to.
Embodiment 1
Step one：Titanium sheet is cut into the sheet that specification is 1 × 3；Water-bath in the sodium carbonate liquor of alkalescence is put into go
Oil is placed into deionized water rinsing in 30wt% HCl, is washed with deionized water after immersion 2h net；
Clean titanium sheet one end (1 × 1) is polished smooth with the sand paper of different model, until immaculate occurs.
Step 2：The electrolyte tetrabutylammonium perchlorate (TBAP) that 0.1mol/L is dissolved in acetonitrile solution, 1mmol/L Ni
(salphen) Ag/AgCl reference electrodes, are utilized under three-electrode system, large area active carbon cloth auxiliary electrode is used as auxiliary electricity
Pole, using cyclic voltammetry electropolymerization Schiff transition metal polymerization thing Ni (salphen), wherein scanning current potential is 0-1.3V
Sweep speed is 20mv/s, and the scanning number of turns 20 is enclosed.Chemical property after having polymerize under organic system is as shown in the figure.
Step 3：Completed using Polyaniline-modified Schiff transition metal polymerization thing in three-electrode system inorganic
Under acid system, working electrode is the electrode that second step is aggregated into, and reference electrode is mercury-mercurous sulfate electrode, and auxiliary electrode is
Platinum electrode.Polymer fluid is that aniline monomer is dissolved in dilution heat of sulfuric acid, is afterwards aggregated to aniline monomer using constant flow method
On Schiff transition metal polymerization thing.Wherein electric current is that 0.5mA polymerization times are 10min.
Embodiment 2
Step one：Titanium sheet is cut into the sheet that specification is 1 × 3；Water-bath in the sodium carbonate liquor of alkalescence is put into deoil use
Deionized water rinsing is placed into 30wt% HCl, is washed with deionized water after immersion 2h net；By clean titanium sheet one end (1 × 1)
Polished smooth with the sand paper of different model, until immaculate occurs.
Step 2：The electrolyte tetrabutylammonium perchlorate (TBAP) that 0.1mol/L is dissolved in acetonitrile solution, 5mmol/L Ni
(salphen) Ag/AgCl reference electrodes, are utilized under three-electrode system, large area active carbon cloth auxiliary electrode is used as auxiliary electricity
Pole, using cyclic voltammetry electropolymerization Schiff transition metal polymerization thing Ni (salphen), wherein scanning current potential is 0-1.3V
Sweep speed is 20mv/s, and the scanning number of turns 10 is enclosed.Chemical property after having polymerize under organic system is as shown in the figure.
Step 3：Completed using Polyaniline-modified Schiff transition metal polymerization thing in three-electrode system inorganic
Under acid system, working electrode is the electrode that second step is aggregated into, and reference electrode is mercury-mercurous sulfate electrode, and auxiliary electrode is
Platinum electrode.Polymer fluid is that aniline monomer is dissolved in dilution heat of sulfuric acid, is afterwards aggregated to aniline monomer using constant flow method
On Schiff transition metal polymerization thing.Wherein electric current is that 0.5mA polymerization times are 10min.
Embodiment 3
Step one：Titanium sheet is cut into the sheet that specification is 1 × 3；Water-bath in the sodium carbonate liquor of alkalescence is put into deoil use
Deionized water rinsing is placed into 30wt% HCl, is washed with deionized water after immersion 2h net；By clean titanium sheet one end (1 × 1)
Polished smooth with the sand paper of different model, until immaculate occurs.
Step 2：The electrolyte tetrabutylammonium perchlorate (TBAP) that 0.1mol/L is dissolved in acetonitrile solution, 5mmol/L Ni
(salphen) Ag/AgCl reference electrodes, are utilized under three-electrode system, large area active carbon cloth auxiliary electrode is used as auxiliary electricity
Pole, using potentiostatic method electropolymerization Schiff transition metal polymerization thing Ni (salphen), wherein the 0.85V polymerizations of polymerization current potential
Time 20min.Chemical property after having polymerize under organic system is as shown in the figure.
Step 3：Completed using Polyaniline-modified Schiff transition metal polymerization thing in three-electrode system inorganic
Under acid system, working electrode is the electrode that second step is aggregated into, and reference electrode is mercury-mercurous sulfate electrode, and auxiliary electrode is
Platinum electrode.Polymer fluid is that aniline monomer is dissolved in dilution heat of sulfuric acid, is afterwards aggregated to aniline monomer using constant flow method
On Schiff transition metal polymerization thing.Wherein electric current is that 0.5mA polymerization times are 10min.
Embodiment 4
Step one：Titanium sheet is cut into the sheet that specification is 1 × 3；Water-bath in the sodium carbonate liquor of alkalescence is put into deoil use
Deionized water rinsing is placed into 30wt% HCl, is washed with deionized water after immersion 2h net；By clean titanium sheet one end (1 × 1)
Polished smooth with the sand paper of different model, until immaculate occurs.
Step 2：The electrolyte tetrabutylammonium perchlorate (TBAP) that 0.1mol/L is dissolved in acetonitrile solution, 5mmol/L Ni
(salphen) Ag/AgCl reference electrodes, are utilized under three-electrode system, large area active carbon cloth auxiliary electrode is used as auxiliary electricity
Pole, using potentiostatic method electropolymerization Schiff transition metal polymerization thing Ni (salphen), wherein the 0.85V polymerizations of polymerization current potential
Time 20min.Chemical property after having polymerize under organic system is as shown in the figure.
Step 3：Completed using Polyaniline-modified Schiff transition metal polymerization thing in three-electrode system inorganic
Under acid system, working electrode is the electrode that second step is aggregated into, and reference electrode is mercury-mercurous sulfate electrode, and auxiliary electrode is
Platinum electrode.Polymer fluid is that aniline monomer is dissolved in dilution heat of sulfuric acid, is afterwards aggregated to aniline monomer using cyclic voltammetry
On Schiff transition metal polymerization thing.Wherein polymerization potential range is that -0.4V-0.6V polymerizations the number of turns 5 is enclosed.Sweep speed is
20mv/s。
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the common skill of art
Art personnel should be appreciated that can modify or equivalent substitution with reference to above-described embodiment to the embodiment of the present invention,
These any modifications or equivalent substitution without departing from spirit and scope of the invention are applying for that pending claim protects model
Within enclosing.
Claims (8)
1. a kind of method for improving ultracapacitor Schiff transition metal polymerization thing electrode specific capacity, it is characterised in that
Comprise the following steps：
(1) processing of collector titanium sheet：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；It is put into the sodium carbonate liquor of alkalescence
Middle water-bath, which is deoiled, to be placed into deionized water rinsing in 30wt% HCl, is washed with deionized water after 1.5~2.5h of immersion net；Will
Clean titanium sheet one end is polished smooth with the sand paper of different model, until immaculate occurs；
(2) it polymerize Schiff transition metal polymerization thing monomer：Under in organic three-electrode system, working electrode is collector
The work area of one end in titanium sheet, reference electrode is Ag/AgCl, and auxiliary electrode is the active carbon cloth of large area；By Schiff
Transition metal polymerization thing monomer is dissolved in the low organic solvent of electron number in solution, and adds a certain amount of support electrolysis
Matter, electrode is aggregated into using electrochemical method；
(3) the double conductive polymer electrodes materials of polymerization aniline monomer construction：Under inorganic acid system, three-electrode system is utilized
Electropolymerization aniline monomer；Working electrode is the electrode that (2) step is aggregated into, and reference electrode is mercury-mercurous sulfate electrode, auxiliary electricity
Extremely platinum electrode；Polymer fluid is that aniline monomer is dissolved in dilution heat of sulfuric acid.
2. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (1), by soda acid handle certain specification titanium sheet make the requirement that it meets collector, carry
The repeatability of height experiment.
3. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (2), the species of Schiff transition metal polymerization thing monomer includes Me (Schiff) (Me
=Ni, Co, Mn, Pb, etc.), the concentration of monomer is between 1mmol/L-10mmol/L.
4. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (2), the low organic solvent of electron number include acetonitrile, benzonitrile, vinyl carbonate, propylene
Carbonic ester.
5. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (2), supporting electrolyte include TBAP, Et4NBF4, Et4NPF6(anion radius is successively
For 0.241,0.333,0.435nm) (Me4N)BF4, (Et4N)BF4, (Bu4N)BF4(cation time is 0.47,0.56,
0.96nm)。
6. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (2), the method for electrochemical polymerization includes cyclic voltammetry, potentiostatic method, impulse method.
7. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (3), the concentration of aniline monomer is between 0.2mol/L-0.5mol/L.The concentration of sulfuric acid
Between 0.5mol/L-1.5mol/L.
8. a kind of raising ultracapacitor Schiff transition metal polymerization thing electrode specific capacity according to claim 1
Method, it is characterised in that in step (3), polyaniline (PANI) polymerization include constant flow method, constant-voltage method.Cyclic voltammetry,
Impulse method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710321499.XA CN106971861B (en) | 2017-05-09 | 2017-05-09 | The method for improving supercapacitor Schiff transition metal polymerization object electrode specific capacity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710321499.XA CN106971861B (en) | 2017-05-09 | 2017-05-09 | The method for improving supercapacitor Schiff transition metal polymerization object electrode specific capacity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106971861A true CN106971861A (en) | 2017-07-21 |
| CN106971861B CN106971861B (en) | 2019-03-29 |
Family
ID=59331294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710321499.XA Active CN106971861B (en) | 2017-05-09 | 2017-05-09 | The method for improving supercapacitor Schiff transition metal polymerization object electrode specific capacity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106971861B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083259A (en) * | 1992-07-23 | 1994-03-02 | 松下电器产业株式会社 | A kind of ion conducting polymer electrolyte |
| US20070065719A1 (en) * | 2003-10-14 | 2007-03-22 | Alexander Timonov | Electrode for energy storage devices and electrochemical supercapacitor based on said electrode |
-
2017
- 2017-05-09 CN CN201710321499.XA patent/CN106971861B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083259A (en) * | 1992-07-23 | 1994-03-02 | 松下电器产业株式会社 | A kind of ion conducting polymer electrolyte |
| US20070065719A1 (en) * | 2003-10-14 | 2007-03-22 | Alexander Timonov | Electrode for energy storage devices and electrochemical supercapacitor based on said electrode |
Non-Patent Citations (3)
| Title |
|---|
| CHENG CHEN, XINPING LI, FUHAI DENG AND JIANLING LI: ""Electropolymerization and electrochemical behavior of nickel Schiff base complexes with different groups between imine linkages"", 《RSC ADVANCES》 * |
| LI JIANLING, GAO FEI, ZHANG YAKUN, KANG FEIYU,ET AL.: ""Electropolymerization of Ni(salen) on carbon nanotube carrier as a capacitive material by pulse potentiostatic method"", 《SCIENCE CHINA-CHEMISTRY》 * |
| YAKUN ZHANG, JIANLING LI, FEIYU KANG, XINDONG WANG,ET AL.: ""Growth and Electrochemical Behavior of Poly[Ni(saldMp)] on Carbon Nanotubes as Potential Supercapacitor Materials"", 《BULLETIN OF THE KOREAN CHEMICAL SOCIETY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106971861B (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100882503B1 (en) | Highly Efficient Counter Electrodes for Dye-sensitized Solar Cells and Method for Manufacturing Thereof | |
| Yan et al. | Electroactive organic compounds as anode-active materials for solar rechargeable redox flow battery in dual-phase electrolytes | |
| Shih et al. | Electropolymerized polyaniline/graphene nanoplatelet/multi-walled carbon nanotube composites as counter electrodes for high performance dye-sensitized solar cells | |
| CN104465102A (en) | Dye-sensitized solar cell photo-anode and preparing method and application thereof | |
| CN108630449B (en) | Flexible asymmetric super capacitor with ultrahigh energy density and preparation method thereof | |
| CN101488400A (en) | Production method for conductive polymer modified active carbon electrode material of super capacitor | |
| CN108447696A (en) | A kind of preparation method and applications of polypyrrole/conduction carbon cloth combination electrode | |
| CN107794600A (en) | A kind of preparation method of polyaniline/polythiophene composite nano tube | |
| CN102757611A (en) | Conductive polymer solution and preparation method thereof | |
| CN110526299B (en) | Core-shell structure Fe2O3Preparation method of @ PPy composite material and application of @ PPy composite material in supercapacitor | |
| CN105448536A (en) | Nickel oxide/titanium oxide nanocomposite and preparation method and energy storage application therefor | |
| Kurokawa et al. | Controlling the electrocatalytic activities of conducting polymer thin films toward suitability as cost-effective counter electrodes of dye-sensitized solar cells | |
| CN106252099A (en) | A kind of ultracapacitor | |
| CN106971861B (en) | The method for improving supercapacitor Schiff transition metal polymerization object electrode specific capacity | |
| CN109346337A (en) | A kind of preparation method of combination electrode material | |
| CN105957731B (en) | A kind of all solid state asymmetric capacitor and preparation method thereof | |
| CN102157266B (en) | Flexible film super capacitor and preparation method thereof | |
| US20140124025A1 (en) | Metal oxide semiconductor electrode having porous thin film, dye-sensitized solar cell using same, and method for manufacturing same | |
| CN109280178A (en) | A kind of transition metal ions coordination conducting polymer and its preparation method and application | |
| CN112103093B (en) | Application of quinacridone-based polymer as supercapacitor material | |
| CN103578780B (en) | A kind of DSSC to electrode and its preparation method and application | |
| CN104134551A (en) | Electrolyte solute, electrolyte and high-voltage supercapacitor | |
| CN107799324A (en) | Polyselenophenes derivative film electrode applied to ultracapacitor and preparation method thereof | |
| CN105914052B (en) | polymer electrode membrane and preparation method thereof | |
| CN105513826A (en) | Preparation method of pyrrole-o-toluidine copolymer with porous structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |