CN105355462A - Preparation method and application for delta-MnO2 thick film pseudocapacitor electrode - Google Patents

Preparation method and application for delta-MnO2 thick film pseudocapacitor electrode Download PDF

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CN105355462A
CN105355462A CN201510670124.5A CN201510670124A CN105355462A CN 105355462 A CN105355462 A CN 105355462A CN 201510670124 A CN201510670124 A CN 201510670124A CN 105355462 A CN105355462 A CN 105355462A
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electrode
mno
thick film
pseudocapacitors
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CN105355462B (en
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程爽
杨陆峰
刘美林
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method for a delta-MnO2 thick film pseudocapacitor electrode. The preparation method comprises the following steps of immersing carbon fiber paper into a potassium permanganate solution for 0.5 hour, then performing hydrothermal growth to form a GZO nanowire array to be used as a three-dimensional framework, and finally performing positive electrode disposition in different times on the framework with high conductivity to obtain the delta-MnO2 thick film. The synthetic method provided by the invention is simple, and low in cost; and the obtained pseudocapacitor electrode is high in quality specific capacitance and area specific capacitance, relatively high in potential window and high in the cycling stability.

Description

A kind of δ-MnO 2the preparation method of thick film pseudocapacitors electrode and application thereof
Technical field
The present invention relates to the preparation field of ultracapacitor, be specifically related to a kind of δ-MnO 2the preparation method of thick film pseudocapacitors electrode and application thereof.
Background technology
The exploitation of new forms of energy and clean, the efficiency utilization of traditional energy are the main paties solving the current energy and environmental problem, and the clean utilization of the grid-connected and traditional fossil energy of the intermittent new forms of energy such as wind energy, solar energy will be realized, the research and development of efficient, eco-friendly stored energy and supply equipment are crucial.Wherein, ultracapacitor is a most important kind equipment, and the control of high-performance super capacitor electrode material synthesis is the technology of most critical.At carbon back, metal oxide and conducting polymer three in class electrode material for super capacitor, metal oxide especially Mn oxide is the class high performance electrode material having commercial applications prospect after carbon-based material commercial applications most.The crystalline phase of Mn oxide is very complicated, and current synthetic method concentrates on different structure α-MnO 2and the structure of compound, but the device performance that these methods obtain is poor, active material load capacity and cycle life not high, and synthesis technique is complicated.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the present invention is to provide a kind of δ-MnO 2the preparation method of thick film pseudocapacitors electrode, this synthetic method is simple, cost is low, and the electrode obtained has high specific capacitance, and relatively high load capacity and cyclical stability.
Another object of the present invention is to provide above-mentioned δ-MnO 2the commercial applications of electrode of super capacitor.
Object of the present invention is achieved through the following technical solutions:
A kind of δ-MnO 2the preparation method of thick film pseudocapacitors electrode, three-dimensional porous substrate is modified and skeleton growth, then direct growth active material, growth course skeleton dissolves gradually and leaves pore passage structure, there is Zn and Ga to enter active material space or alternative position simultaneously, achieve a secondary growth of the porous thick film of high electronics and ionic transport properties, specifically comprise the following steps:
(1) substrate pretreatment: business carbon fiber paper is immersed in liquor potassic permanganate and soaks 20 ~ 60min, then naturally dry, fully clean with water, drier; Using pretreated business carbon fiber paper as substrate grown Ga doping ZnO and GZO nano-wire array skeleton, the GZO that pretreated substrate surface grows is not easy to come off;
(2) three-dimensional Ga doped ZnO nano-wire array backbone growth: the precursor solution first configuring 70 ~ 80mL, wherein comprises 0.001 ~ 0.015MZn (NO 3) 2, 0.001 ~ 0.015M urotropine, Ga in solution 3+/ Zn 2+mol ratio is the Ga (NO of 0.1% ~ 1% 3) 3, water and 1 ~ 2mLNH 3h 2o, after abundant stirring, pretreated business carbon fiber paper be immersed in precursor solution and be transferred to in teflon-lined reactor, obtaining after constant temperature 12 ~ 48h on business carbon fiber paper, grow intensive three-dimensional Ga doped ZnO nano-wire array backbone at 80 ~ 120 DEG C;
(3) MnO 2electrochemical deposition: first configure precursor solution, Na in this solution 2sO 4with Mn (Ac) 2concentration be 0.1M, solvent is water, and use three-electrode system to carry out electrochemical deposition, Ag/AgCl makes reference electrode, platinum guaze is done electrode, carries out anodic deposition at the intensive three-dimensional Ga doped ZnO nano-wire array backbone of the upper growth of business carbon fiber paper (CFP) as work electrode; Deposition process is divided into two steps, the first step keeps 10 ~ 20s at voltage 0.35 ~ 0.4V, then fixed voltage carries out the deposition in 1 ~ 60min time range at 0.4 ~ 0.45V, after completing deposition step, fully clean obtained work electrode deionized water, finally at 100 ~ 150 DEG C, freeze-day with constant temperature 3 ~ 5h obtains δ-MnO 2thick film pseudocapacitors electrode, is labeled as MnO 2/ GZO/CFP; Ga doping ZnO can be used as the three-dimensional porous rack of high connductivity at first, then along with the increase of sedimentation time is corroded gradually, leaves tunnel-shaped pore passage structure, finally containing 1 ~ 2wt% Zn and 0 ~ 0.1wt%Ga enters MnO 2lattice in.
(4) repeatedly active material activates by charge-discharge test, the MnO of indefinite form 2be transformed into the δ-MnO of sheet 2, thickness only several nanometer of each, only several atomic layers thick, has high specific area, is conducive to diffusion and the transmission of electrolyte ion;
(5) dry assembling, obtains high performance δ-MnO 2base pseudocapacitors.
Further, Ga in described precursor solution 3+/ Zn 2+when mol ratio is 0.5%, the GZO nano-wire array skeleton grown, electron conduction is best;
A kind of δ-MnO 2thick film pseudocapacitors application of electrode is in preparation high-performance pseudocapacitors and ultracapacitor.
Further, described high-performance pseudocapacitors, concrete preparation process is as follows: with the neutral Na of 1M 2sO 4the aqueous solution makes electrolyte, makees barrier film with commercialization vitreous carbon fibers or polymer flake, and the carbon of same area is supported δ-MnO 2thick film makes capacitor symmetry electrode, is assembled into the pseudocapacitors of low capacity with the shell of button cell as external packing.
Further, a kind of δ-MnO 2the preparation method of thick film pseudocapacitors electrode, comprises the following steps:
(1) substrate pretreatment
Business carbon fiber paper is immersed in 0.5M liquor potassic permanganate and soaks 0.5 hour, then at room temperature naturally dry, cleaner with deionized water rinsing, finally in 70 DEG C of dryings.
(2) three-dimensional Ga doping ZnO (GZO) skeleton growth
Using pretreated carbon paper as substrate, by solvent-thermal method growth Ga doping zinc oxide nanometer linear array.
Concrete steps are: the precursor solution first configuring 73mL, wherein comprise 0.015MZn (NO 3) 2, 0.015M urotropine, Ga in solution 3+/ Zn 2+mol ratio is the Ga (NO of 0.5% 3) 3, water and 2mLNH 3h 2o, after fully stirring, pretreated carbon paper is immersed in precursor solution and is transferred to in teflon-lined reactor, 90 DEG C of constant temperature keep 24h.Finally obtain on carbon paper, grow intensive three-dimensional Ga doping ZnO skeleton.
(3) MnO 2electrochemical deposition
After carrying out step (2), using substrate as work electrode, in manganese salt solution, anode electrochemical method is adopted to deposit MnO 2.Along with the increase of sedimentation time, ZnO is corroded dissolving gradually, leaves a large amount of pore passage structure.
Described deposition process, is specially: first configuration packet is containing 0.1MNa 2sO 4with 0.1MMn (Ac) 2precursor solution; Then use three-electrode system to carry out electrochemical deposition, Ag/AgCl electrode is reference electrode, and platinum guaze is to electrode, and the carbon paper after process is that work electrode carries out anodic deposition; Deposition process is divided into two steps, and the first step keeps 20s under fixed voltage 0.4V, then brings the voltage up to the deposition that 0.45V carries out different time.After completing deposition step, fully clean with deionized water, finally at 140 DEG C, constant temperature 3 ~ 5h obtains required sample MnO 2/ GZO/CFP.
Above-mentioned MnO 2/ GZO/CFP directly prepares pseudocapacitors as electrode.
Described electrode prepares pseudocapacitors, and concrete steps are as follows:
Use the standard electrochemical pond that Tianjin Ida is purchased, the Na of 1M 2sO 4the aqueous solution is as electrolyte, and specimen material is work electrode, and Ag/AgCl is reference electrode, and platinum guaze is to electrode, is assembled into three-electrode system and carries out electrochemical property test.Then with onesize disc-shaped sample as symmetry electrode, business-like glass fibre or polymer flake as barrier film, the button capacitor that composition is symmetrical.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention adopts the porous carbon paper of high connductivity to do substrate, simultaneously as current collector, the Ga-ZnO nano-wire array of low cost makes skeleton, greatly improves the surface area of carbon paper substrate, achieve the high capacity amount of active material, deposited per area unit amount is up to 2.82mg/cm 2.
(2) the present invention adopts Ga doping ZnO as expendable three-dimensional framework, at anodic deposition MnO 2process in, this skeleton dissolves gradually, a small amount of Ga 3+, Zn 2+stay MnO 2in lattice, improve electron conduction.
(3) the present invention adopts Ga doping ZnO as expendable three-dimensional framework, in the process that skeleton dissolves, leaves a large amount of multibore tunnels, makes the MnO synthesized 2there is high specific surface and loose structure, add the contact area of electrolyte ion and active material, shorten ion diffuse radius.
(4) the loose structure MnO for preparing of the present invention 2, along with the increase of anodic deposition time, the thickness of active material reaches as high as 7 microns, is assembled into ultracapacitor, has excellent electrochemical properties.
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b be respectively CFP in embodiment 1 after potassium permanganate process under an electron microscope scale be 8 μm and scheme with the SEM of 2 μm.
Fig. 2 a, Fig. 2 b are respectively Mn in embodiment 1 2+cFP deposits 1min under an electron microscope scale be 1 μm and scheme with the SEM of 200nm.
Fig. 3 a, Fig. 3 b are respectively electrode CFPMnO in embodiment 1 2-1min is at 2mVs -1with 50mVs -1sweep speed under CV figure.
Fig. 4 a, Fig. 4 b are respectively electrode basement CFPGZO scale under ESEM in embodiment 2 and are 4 μm and scheme with the SEM of 1 μm.
Fig. 5 a, Fig. 5 b are respectively electrode CFPGZOMnO in embodiment 2 2-1min scale under ESEM is the SEM figure of 800nm and 200nm.
Fig. 6 a, Fig. 6 b are respectively electrode CFPGZOMnO in embodiment 2 2the XPS figure of-1min; Wherein abscissa is that BondingEnergy(combines energy), ordinate is Intensity(photoelectron intensity).
Fig. 7 is electrode CFPGZOMnO in embodiment 2 2the CV comparison diagram of-1min and substrate; Wherein abscissa is Voltage(voltage), ordinate is Current(electric current).
Fig. 8 a, Fig. 8 b are respectively electrode CFPGZOMnO in embodiment 2 2the voltage-to-current performance test figure of-1min and sweep speed-ratio capacitance performance test figure; Wherein Fig. 8 b abscissa is Scanrate(sweep speed), ordinate is Specificcapacitance(ratio capacitance).
Fig. 9 a, Fig. 9 b are respectively electrode CFPGZOMnO in embodiment 2 2the time m-voltage performance resolution chart and current density-ratio capacitance performance test figure of-1min; Wherein Fig. 9 b abscissa is Currentdensity(current density).
Figure 10 is electrode CFPGZOMnO in embodiment 2 2the IV curve comparison diagram of-1min after experience 15000 circulation examinations.
Figure 11 is electrode CFPGZOMnO in embodiment 2 2the Raman phenogram of-1min after experience 15000 loop tests; Wherein abscissa is RamanShift(Raman shift).
Figure 12 is electrode CFPGZOMnO in embodiment 2 2the EDX analysis chart of-1min after experience 15000 loop tests.
Figure 13 a, Figure 13 b, Figure 13 c, Figure 13 d are respectively electrode CFPGZOMnO in embodiment 2 2-1min after experience 15000 loop tests under ESEM scale be 10 μm, 2 μm, 200 μm, scheme with the SEM of 200 μm.
Figure 14 a, Figure 14 b, Figure 14 c, Figure 14 d are respectively electrode CFPGZOMnO in embodiment 3 2-5min scale under ESEM is 6 μm, 2 μm, 200nm, scheme with the SEM of 100nm.
Figure 15 a, Figure 15 b are respectively electrode CFPGZOMnO in embodiment 3 2the voltage-to-current Electrochemical Characterization figure of-5min and sweep speed-ratio capacitance Electrochemical Characterization figure.
Figure 16 a, Figure 16 b are respectively electrode CFPGZOMnO in embodiment 3 2the time m-voltage electrochemical performance characterization figure and current density-ratio capacitance Electrochemical Characterization figure of-5min.
Figure 17 a, Figure 17 b are respectively electrode CFPGZOMnO in embodiment 4 2-30min scale under ESEM is 4 μm schemes with the SEM of 400nm.
Figure 18 a, Figure 18 b, Figure 18 c, Figure 18 d are respectively electrode CFPGZOMnO in embodiment 4 2-30min voltage-to-current, sweep speed-ratio capacitance, time m-voltage and current density-ratio capacitance Electrochemical Characterization figure.
Figure 19 a, Figure 19 b, Figure 19 c, Figure 19 d are respectively electrode CFPGZOMnO in embodiment 4 2-30min after 10000 loop tests under ESEM scale be 6 μm, 1 μm, 5 μm, scheme with the SEM of 300nm.
Figure 20 is electrode CFPGZOMnO in embodiment 5 2the SEM figure of-60min.
Figure 21 a, Figure 21 b are respectively electrode CFPGZOMnO in embodiment 5 2m-voltage electrochemical performance characterization figure and current density-ratio capacitance Electrochemical Characterization figure during-60min.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) carbon fiber paper of 10x5 centimetre is immersed in liquor potassic permanganate (0.5M), after soaking 0.5h, dries under taking out room temperature, then pure water, dry at last 70 DEG C, carbon fiber paper (CFP) pattern after process is characterized, as Fig. 1 a and Fig. 1 b by electron microscope (SEM).
(2) electrochemical process deposition MnO 2.Deposition step: the precursor solution using 100mL, wherein containing 0.1MNa 2sO 4with 0.1MMn (AC) 2, solvent is water, and the carbon paper after process is as work electrode, and Ag/AgCl is reference electrode, and Pt net is to electrode; First under 0.4V, keep 20s, then under 0.45V, deposit 1min, after completing deposition step, fully clean the work electrode deionized water of gained, finally at 140 DEG C, freeze-day with constant temperature 4h obtains δ-MnO 2thick film pseudocapacitors electrode, is labeled as CFPMnO 2-1min sample, deposition is 0.06mg/cm 2.The MnO of deposition 2microscopic appearance is represented by electron microscope, as Fig. 2 a and Fig. 2 b.
(3) with CFPMnO prepared by the present embodiment 2-1min is as electrode of super capacitor, and electrochemical Characterization is as follows:
Carry out electrochemical property test at the upper three-electrode system that adopts of Shanghai occasion China's electrochemical workstation (CHI660E), 1M aqueous sodium persulfate solution is electrolyte, is Pt net to electrode, and reference electrode adopts Ag/AgCl electrode, CFPMnO 2-1min is as work electrode, and measure ultracapacitor performance, test result is shown in Fig. 3 a and Fig. 3 b.MnO on CFP surface during deposition 1min 2load capacity relatively low, be only 0.06mgcm -2, at 50mVs -1sweep speed under, ratio capacitance is 323Fg -1even if, under lower sweep speed, as 2mVs -1, its ratio capacitance is also only 493Fg -1, significantly lower than MnO 2theoretical ratio capacitance.
Embodiment 2
(1) processing procedure of substrate in the present embodiment is identical with (1) step of embodiment 1, does not repeat them here.
(2) hydrothermal growth Ga-ZnO array: the precursor solution of configuration 73mL, first configures the aqueous solution of 71mL, the Zn (NO containing 0.015M in this aqueous solution 3) 2, 0.015M urotropine and Ga 3+/ Zn 2+mol ratio is the Ga (NO of 0.5% 3) 3, after fully stirring, in this aqueous solution, drip the NH of 2mL again 3h 2o, forms precursor solution (73mL), continues to stir, and finally pretreated business carbon fiber paper is immersed in precursor solution and is transferred to in teflon-lined reactor, obtaining the conductive substrates of high-specific surface area after 90 DEG C of constant temperature 24h.Can see the surperficial vertical-growth of ZnO nano-wire along carbon fiber by ESEM, uniform fold carbon surface, distribute in sea urchin shape, diameter is at about 200nm, and length 5 ~ 6 μm, as Fig. 4 a and Fig. 4 b.
(3) MnO 2deposition, MnO in the present embodiment 2electrochemical deposition method identical with (2) step in embodiment 1, do not repeat them here undefined structure.The sample of deposition 1min, load capacity is 0.12mgcm -2, sample is designated as CFPGZOMnO 2-1min.Visible when having a ZnO skeleton, surface area is comparatively large, and identical sedimentary condition, deposition doubles.MnO can be seen by ESEM (Fig. 5 a and Fig. 5 b) 2granular size is at about 50nm, and uniform fold is on Ga-ZnO surface.XPS analysis can find out that Mn is tetravalence, and there are 3 a small amount of valency MnOOH on surface, as Fig. 6 a and Fig. 6 b.
(4) electrochemical property test: the three-dimensional porous structure prepared using the present embodiment is as electrode of super capacitor, electrochemical Characterization is as follows: the electrochemical workstation adopting three-electrode system, 1M aqueous sodium persulfate solution is electrolyte, Pt net to electrode, reference electrode adopts Ag/AgCl electrode, CFP/GZO/MnO 2-1min, as work electrode, measures ultracapacitor performance, and test result is shown in Fig. 7, and (in figure, A, B, C and D are respectively the substrate GZO/CFP after growth Ga-ZnO nano wire, directly at carbon fiber paper deposition MnO 2sample MnO 2/ CFP, the nano-wire array of ZnO not mixing Ga deposits MnO 2sample CFP/ZnO/MnO 2, and the nano-wire array of ZnO after mixing Ga deposits MnO 2sample CFP/GZO/MnO 2).Under same sweep speed, the sample mixing Ga obviously has larger electric current.
(5) CFP/GZO/MnO for preparing of the present embodiment 2-1min electrode, at 0.1mA/cm 2charging and discharging currents under, its specific capacity is up to 1154F/g, and potential window is 0 ~ 1.0VvsAg/AgCl reference electrode, higher than potential window and the MnO of water decomposition 2theoretical specific capacity; Under the sweep speed of 2mV/s, area ratio electric capacity is 0.12F/cm 2, quality is 975F/g than electric capacity, is significantly higher than the sample doing substrate without GZO skeleton.Change the ratio capacitance of scan round velocity test electrode, what obtain the results are shown in Figure 8a and Fig. 8 b, and when sweep speed is increased to 200mV/s from 2, quality is reduced to 519F/g than electric capacity by 975.Change charging and discharging currents density, the discharge and recharge obtained the results are shown in Figure 9a and Fig. 9 b, 0.1 to 5mA/cm 2constant current charge-discharge curve display quality ratio capacitance in current density range is reduced to 780F/g from 1154.Figure 10 cyclical stability test result, at 5mA/cm 2high current density under, more than the discharge and recharge of 15000 circulations, electric capacity only shows small change, reduces to 580.5F/g (73.8% electric capacity residue), show that this electrode has very high cyclical stability, far above common α-MnO from 785.7 2(after 2 ~ 3,000 circulations more than drop by half).
(6), after long-term cycle life test, can be found out by Raman spectrogram 11, undefined structure becomes stratiform δ-MnO 2.After long-term circulation, ZnO skeleton comes off, but still containing trace Zn, Ga element (being analyzed from the EDX of Figure 12) in active material.Initial nano particle becomes the thin slice that thickness is several nanometer, and these nanometer sheet form three-dimensional netted loose structure, as shown in SEM Figure 13 a, Figure 13 b, Figure 13 c and Figure 13 d.Visible by long-term electrochemistry loop test, unbodied MnO 2nano wire becomes the δ-MnO with lamellar structure 2, visible active material experienced by the process that then dissolving regrows.At this, the structure of GZO skeleton structure, greatly improves the load capacity of active material, conductivity and porousness etc.
Embodiment 3
The substrate treating method of the present embodiment, hydrothermal growth Ga-ZnO array, MnO 2electrochemical deposition method and electrochemical property test, with the step (1) in embodiment 2, (2), (3), (4) are identical, do not repeat them here.Sedimentation time is increased to 5min by 1min.Deposition increases to 0.41mg/cm 2, MnO 2grow up into nano wire gradually by nano particle, and form the film of porous, GZO base part is corroded, as Figure 14 a, Figure 14 b, Figure 14 c and Figure 14 d.
With CFPGZOMnO prepared by the present embodiment 2-5min is as electrode of super capacitor, and under the sweep speed of 2mV/s, ratio capacitance is 613F/g, area ratio electric capacity 0.25F/cm 2.Change the ratio capacitance of scan round velocity test electrode, what obtain the results are shown in Figure 15a and Figure 15 b, and when sweep speed is increased to 200mV/s from 2, ratio capacitance is reduced to 299F/g by 613F/g.Change charging and discharging currents density, the discharge and recharge result obtained, is shown in figure Figure 16 a and Figure 16 b, 0.5 to 20mA/cm 2constant current charge-discharge curve display ratio capacitance in current density range is reduced to 442F/g from 631F/g.
Compared with embodiment 2, the increase of the electronics that the increase because of deposit thickness causes and ion transfer resistance, when sweep speed is 2mV/s, biggest quality ratio capacitance is reduced to 631F/g by 1154, but area ratio electric capacity is increased to 0.25F/cm by 0.12 2.
Embodiment 4
The substrate treating method of the present embodiment, hydrothermal growth Ga-ZnO array, MnO 2electrochemical deposition method and electrochemical property test, with the step (1) in embodiment 2, (2), (3), (4) are identical, do not repeat them here.Only sedimentation time is increased to 30min, deposition increases to 1.67mg/cm 2, MnO 2be grown to serve as the porous membrane of nano wire composition, be corroded completely at the bottom of zno-based, Figure 17 a and Figure 17 b.Similar in chemical property and embodiment 3, at 0.5mA/cm 2carry out constant current charge and discharge under current density, this electrode still can reach higher quality than electric capacity 394F/g, and area ratio electric capacity also reaches 0.66F/cm simultaneously 2, see Figure 18 a, Figure 18 b, Figure 18 c and Figure 18 d.After long-term circulation, active material can be seen from disconnected cross section, δ-MnO 2thickness be 3.43 microns, simultaneously can see MnO 2the inside of thick-layer is also made up of thin slice, and has much higher permeability (figure Figure 19 a, Figure 19 b, Figure 19 c and Figure 19 d), thus can preserve higher capacitance.
Embodiment 5
The substrate treating method of the present embodiment, hydrothermal growth Ga-ZnO array, MnO 2electrochemical deposition method and electrochemical property test, with the step (1) in embodiment 2, (2), (3), (4) are identical, do not repeat them here.Sedimentation time increases to 60min, and deposition increases to 2.82mg/cm 2, active material is still the film of the nano wire composition of porous, and be corroded at the bottom of zno-based (Figure 20) completely, can see active material δ-MnO from disconnected cross section 2deposit thickness up to 5.33 ~ 7.15 microns.At 0.5mA/cm 2carry out constant current charge-discharge under current density, this electrode still can reach higher quality than electric capacity, 384F/g, and area ratio electric capacity reaches 1.08F/cm simultaneously 2, as Figure 21 a and Figure 21 b.At MnO 2while growth, ZnO is corroded gradually and leaves duct, even therefore very thick film, sample still can keep three-dimensional porous structure, and the quality that can obtain relative ideal is than electric capacity and higher area ratio electric capacity.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not limited by the examples; substrate change, the method for modifying done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (4)

1. a δ-MnO 2the preparation method of thick film pseudocapacitors electrode, it is characterized in that, preliminary treatment and skeleton growth are carried out to substrate, then direct growth active material, growth course skeleton dissolves gradually and leaves pore passage structure, there is Zn and Ga to enter active material space or alternative position simultaneously, achieve the δ-MnO of high electronics and ionic transport properties 2one secondary growth of thick film pseudocapacitors electrode, specifically comprises the following steps:
(1) substrate pretreatment: business carbon fiber paper is immersed in liquor potassic permanganate and soaks 20 ~ 60min, then naturally dry, fully clean with water, dry; Using pretreated business carbon fiber paper as substrate grown Ga doping ZnO and GZO nano-wire array skeleton;
(2) three-dimensional Ga doped ZnO nano-wire array backbone growth: the precursor solution first configuring 70 ~ 80mL, wherein comprises 0.001 ~ 0.015MZn (NO 3) 2, 0.001 ~ 0.015M urotropine, Ga in solution 3+/ Zn 2+mol ratio is the Ga (NO of 0.1% ~ 1% 3) 3, water and 1 ~ 2mLNH 3h 2o, after abundant stirring, pretreated business carbon fiber paper is immersed in precursor solution and is transferred to in teflon-lined reactor, constant temperature 12 ~ 48h at 80 ~ 120 DEG C, after obtain on business carbon fiber paper, grow intensive three-dimensional Ga doped ZnO nano-wire array backbone;
(3) active material MnO 2electrochemical deposition: first configure precursor solution, Na in this solution 2sO 4with Mn (Ac) 2concentration be 0.1M, solvent is water, and use three-electrode system to carry out electrochemical deposition, Ag/AgCl makes reference electrode, platinum guaze is done electrode, business carbon fiber paper grows intensive three-dimensional Ga doped ZnO nano-wire array backbone and carries out anodic deposition as work electrode; Deposition process is divided into two steps, the first step keeps 10 ~ 20s at voltage 0.35 ~ 0.4V, then fixed voltage deposits within the scope of the different time of 1 ~ 60min at 0.4 ~ 0.45V, after completing deposition step, fully clean the work electrode deionized water of gained, finally at 100 ~ 150 DEG C, freeze-day with constant temperature 3 ~ 5h obtains δ-MnO 2thick film pseudocapacitors electrode, is labeled as MnO 2/ GZO/CFP; Ga doping ZnO can be used as the three-dimensional porous rack of high connductivity at first, then along with the increase of sedimentation time is corroded gradually, leaves tunnel-shaped pore passage structure, finally has 1 ~ 2wt%zn and 0 ~ 0.1wt%Ga enters MnO 2lattice in.
2. a kind of δ-MnO according to claim 1 2the preparation method of thick film pseudocapacitors electrode, is characterized in that, Ga in the described precursor solution of step (2) 3+/ Zn 2+mol ratio be 0.5%.
3. a kind of δ-MnO obtained by preparation method described in claim 1 2the application of thick film pseudocapacitors electrode in preparation high-performance pseudocapacitors and ultracapacitor.
4. a kind of δ-MnO according to claim 3 2the application of thick film pseudocapacitors electrode, is characterized in that, described high-performance pseudocapacitors, and concrete preparation process is as follows: with the neutral Na of 1M 2sO 4the aqueous solution makes electrolyte, makees barrier film with commercialization vitreous carbon fibers or polymer flake, and the carbon of same area is supported δ-MnO 2thick film makes capacitor symmetry electrode, is assembled into the pseudocapacitors of low capacity with the shell of button cell as external packing.
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CN110931263A (en) * 2019-11-21 2020-03-27 杭州电子科技大学 Super capacitor electrode structure and reinforcing method
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CN111318179A (en) * 2020-03-09 2020-06-23 西南石油大学 MnO with superstrong oil stain resistance2/carbon fiber cloth composite filtering membrane and preparation method thereof

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