CN105355462B - A kind of δ-MnO2The preparation method and applications of thick film pseudocapacitors electrode - Google Patents

A kind of δ-MnO2The preparation method and applications of thick film pseudocapacitors electrode Download PDF

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CN105355462B
CN105355462B CN201510670124.5A CN201510670124A CN105355462B CN 105355462 B CN105355462 B CN 105355462B CN 201510670124 A CN201510670124 A CN 201510670124A CN 105355462 B CN105355462 B CN 105355462B
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mno
electrode
thick film
pseudocapacitors
deposition
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CN105355462A (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 kind of δ MnO2The preparation method of thick film pseudocapacitors electrode, comprises the following steps：Carbon fiber paper is immersed in liquor potassic permanganate and soaks 0.5 h, then hydrothermal growth GZO nano-wire arrays make three-dimensional framework, and the anodic deposition that different time is finally carried out on the skeleton with good conductivity obtains δ MnO2Thick film.The synthetic method of the present invention is simple, and cost is low, the cyclical stability that obtained pseudocapacitors electrode is become reconciled with high quality and area specific capacitance, higher potential window.

Description

A kind of δ-MnO2The preparation method and applications of thick film pseudocapacitors electrode
Technical field
The present invention relates to the preparation field of ultracapacitor, and in particular to a kind of δ-MnO2The system of thick film pseudocapacitors electrode Preparation Method and its application.
Background technology
The utilization of new energy and cleaning, efficiently utilizing the master for being the current energy of solution and environmental problem for traditional energy Approach is wanted, and to realize grid-connected and traditional fossil energy the clean utilization of the intermittent new energy such as wind energy, solar energy, efficiently, The research and development of environmental-friendly energy stores and supply equipment are crucial.Wherein, ultracapacitor is a most important kind equipment, and The control synthesis of high-performance super capacitor electrode material is the technology of most critical.In carbon-based, metal oxide and conducting polymer In thing three classes electrode material for super capacitor, metal oxide especially Mn oxide is after carbon-based material commercial applications Most there is a kind of high performance electrode material of commercial applications prospect.The crystalline phase of Mn oxide is extremely complex, current synthetic method Concentrate on different structure α-MnO2And its structure of compound, but the device performance that these methods obtain is poor, active material is born Carrying capacity and cycle life is not high, and synthesis technique is complicated.
The content of the invention
The shortcomings that in order to overcome the prior art and deficiency, it is an object of the invention to provide a kind of δ-MnO2Thick film fake capacitance The preparation method of device electrode, the synthetic method is simple, cost is low, and obtained electrode has high specific capacitance, and of a relatively high Load capacity and cyclical stability.
Another object of the present invention is to provide above-mentioned δ-MnO2The commercial applications of electrode of super capacitor.
The purpose of the present invention is achieved through the following technical solutions：
A kind of δ-MnO2The preparation method of thick film pseudocapacitors electrode, modifies three-dimensional porous substrate and skeleton is given birth to Long, then direct growth active material, growth course skeleton gradually dissolve and leave pore passage structure, while have Zn and Ga to enter and live Property material gap or substitute position, realize a secondary growth of the porous thick film of high electronics and ionic transport properties, specifically include with Lower step：
（1）Substrate pretreatment：Business carbon fiber paper is immersed 20 ~ 60 min are soaked in liquor potassic permanganate, it is then natural Dry, fully cleaned with water, re-dry；Received pretreated business carbon fiber paper as substrate grown Ga doping ZnO, that is, GZO Nanowire arrays skeleton, the GZO that pretreated substrate surface is grown are not easy to fall off；
（2）Three-dimensional Ga doping zinc oxide nanometers linear array skeleton growth：The precursor solution of 70 ~ 80 mL is configured first, wherein Include 0.001 ~ 0.015 M Zn (NO3)2, 0.001 ~ 0.015 M urotropines, Ga in solution3+/Zn2+Molar ratio is Ga (the NO of 0.1% ~ 1 %3)3, water and 1 ~ 2 mL NH3H2O, after being sufficiently stirred, soaks pretreated business carbon fiber paper In precursor solution and it is transferred in the reaction kettle with polytetrafluoroethyllining lining, at 80 ~ 120 DEG C after 12 ~ 48 h of constant temperature Obtain growing intensive three-dimensional Ga doping zinc oxide nanometers linear array skeleton on business carbon fiber paper；
（3）MnO2Electrochemical deposition：Precursor solution is configured first, Na in the solution2SO4With Mn (Ac)2Concentration be 0.1 M, solvent are water, and electrochemical deposition is carried out using three-electrode system, and Ag/AgCl makees reference electrode, and platinum guaze is opposed electricity Pole, in business carbon fiber paper（CFP intensive three-dimensional Ga doping zinc oxide nanometers linear array skeleton is grown on) to carry out as working electrode Anodic deposition；Deposition process is divided into two steps, and the first step is to keep 10 ~ 20 s in 0.35 ~ 0.4 V of voltage, then fixed voltage The deposition in 1 ~ 60 min time ranges is carried out in 0.4 ~ 0.45 V, after completing deposition step, to obtained working electrode Fully cleaned with deionized water, finally 3 ~ 5 h of freeze-day with constant temperature obtains δ-MnO at 100 ~ 150 DEG C2Thick film pseudocapacitors Electrode, labeled as MnO2/GZO/CFP；Ga doping ZnO initially can be as highly conductive three-dimensional porous rack, then as deposition The increase of time is gradually corroded, and leaves tunnel-shaped pore passage structure, the Zn and 0 ~ 0.1 wt% Ga finally containing 1 ~ 2 wt% into Enter MnO2Lattice in.
（4）Multiple charge-discharge test activates active material, the MnO of indefinite form2Change the δ-MnO of slabbing2, each piece The only several nanometers of thickness, only several atomic layers thicks, have high specific surface area, are conducive to diffusion and the biography of electrolyte ion It is defeated；
（5）Dry assembling, obtains high performance δ-MnO2Base pseudocapacitors.
Further, Ga in the precursor solution3+/Zn2+When molar ratio is 0.5%, the GZO nanometer linear arrays that grow Row skeleton, electron conduction are optimal；
A kind of δ-MnO2Thick film pseudocapacitors application of electrode is in terms of high-performance pseudocapacitors, that is, ultracapacitor is prepared.
Further, the high-performance pseudocapacitors, specific preparation process are as follows：With 1 M neutrality Na2SO4Aqueous solution makees electricity Xie Zhi, membrane is made with commercialization vitreous carbon fibers or polymer flake, by the carbon support δ-MnO of same area2Thick film makees electricity Container symmetry electrode, the pseudocapacitors of low capacity are assembled into by the use of the shell of button cell as outer packing.
Further, a kind of δ-MnO2The preparation method of thick film pseudocapacitors electrode, comprises the following steps：
（1）Substrate pretreatment
By when immersion 0.5 is small in business carbon fiber paper 0.5 M liquor potassic permanganates of immersion, then dry in the air naturally at room temperature It is dry, then rinsed well with deionized water, most after 70 DEG C of dryings.
（2）Three-dimensional Ga doping ZnO (GZO) skeleton growth
Using pretreated carbon paper as substrate, Ga doping zinc oxide nanometer linear arrays are grown by solvent-thermal method.
Concretely comprise the following steps：The precursor solution of 73 mL is configured first, wherein including 0.015 M Zn (NO3)2 、0.015 M Ga in urotropine, solution3+/Zn2+Molar ratio is 0.5% Ga (NO3)3, water and 2 mL NH3H2O, after being sufficiently stirred, Pretreated carbon paper is immersed in precursor solution and is transferred in the reaction kettle with polytetrafluoroethyllining lining, 90 DEG C of perseverances Temperature keeps 24 h.Finally obtain and intensive three-dimensional Ga doping ZnO skeletons are grown on carbon paper.
（3） MnO2Electrochemical deposition
Carrying out step（2）Afterwards, using substrate as working electrode, sunk in manganese salt solution using anode electrochemical method Product MnO2.With the increase of sedimentation time, ZnO is gradually corroded dissolving, leaves a large amount of pore passage structures.
The deposition process, is specially：Configuration includes 0.1 M Na first2SO4With 0.1 M Mn (Ac)2Presoma Solution；Then electrochemical deposition is carried out using three-electrode system, Ag/AgCl electrodes are reference electrode, and platinum guaze is to electrode, place Carbon paper after reason carries out anodic deposition for working electrode；Deposition process is divided into two steps, and the first step is protected under 0.4 V of fixed voltage 20s is held, then brings the voltage up to the deposition that 0.45 V carries out different time.After completing deposition step, filled with deionized water Distinguish and wash, finally 3 ~ 5 h of constant temperature obtains required sample MnO at 140 DEG C2/GZO/CFP。
Above-mentioned MnO2/ GZO/CFP directly prepares pseudocapacitors as electrode.
The electrode prepares pseudocapacitors, comprises the following steps that：
The standard electrochemical pond purchased using Tianjin Ida, the Na of 1 M2SO4Aqueous solution is as electrolyte, specimen material Working electrode, Ag/AgCl are reference electrode, and platinum guaze is to electrode, is assembled into three-electrode system and carries out electrochemical property test.So Afterwards by the use of an equal amount of disc-shaped sample as symmetry electrode, commercialized glass fibre or polymer flake as membrane, Form symmetrical button capacitor.
Compared with prior art, the present invention has the following advantages and beneficial effect：
（1）The present invention makees substrate using highly conductive porous carbon paper, while is used as current collector, inexpensive Ga-ZnO Nano-wire array makees skeleton, greatly improves the surface area of carbon paper substrate, realizes the high load amount of active material, unit plane Deposition accumulated amount is up to 2.82 mg/cm2。
（2）The present invention adulterates ZnO as expendable three-dimensional framework using Ga, in anodic deposition MnO2During, the bone Frame gradually dissolves, a small amount of Ga3+、 Zn2+Stay in MnO2In lattice, electron conduction is improved.
（3）The present invention, as expendable three-dimensional framework, in the process of skeleton dissolving, is left substantial amounts of using Ga doping ZnO Multibore tunnel so that the MnO of synthesis2With high ratio surface and loose structure, electrolyte ion and active material are added Contact area, shortens ion dilation angle.
（4）Loose structure MnO prepared by the present invention2, with the increase of anodic deposition time, the thickness highest of active material Up to 7 microns, ultracapacitor is assembled them into, there are excellent electrochemical properties.
Brief description of the drawings
Fig. 1 a, Fig. 1 b be respectively in embodiment 1 potassium permanganate processing after CFP under an electron microscope scale be 8 μm and 2 μm SEM figure.
Fig. 2 a, Fig. 2 b are respectively Mn in embodiment 12+On CFP deposit 1min under an electron microscope scale for 1 μm with The SEM figures of 200nm.
Fig. 3 a, Fig. 3 b are respectively electrode CFP@MnO in embodiment 12- 1min is in 2 mV s-1With 50 mV s-1Scanning speed CV figures under rate.
Fig. 4 a, Fig. 4 b be respectively in embodiment 2 electrode basement CFP GZO scales under scanning electron microscope be 4 μm and 1 μm SEM schemes.
Fig. 5 a, Fig. 5 b are respectively electrode CFP@GZO@MnO in embodiment 22- 1min scales under scanning electron microscope are 800nm Scheme with the SEM of 200nm.
Fig. 6 a, Fig. 6 b are respectively electrode CFP@GZO@MnO in embodiment 22The XPS figures of -1min;Wherein abscissa is Bonding Energy（With reference to energy）, ordinate Intensity（Photoelectron intensity）.
Fig. 7 is electrode CFP@GZO@MnO in embodiment 22- 1min figures compared with the CV of substrate；Wherein abscissa is Voltage（Voltage）, ordinate Current（Electric current）.
Fig. 8 a, Fig. 8 b are respectively electrode CFP@GZO@MnO in embodiment 22The voltage-to-current performance test figure of -1min with Sweep speed-specific capacitance performance test figure；Wherein Fig. 8 b abscissas are Scan rate（Sweep speed）, ordinate is Specific capacitance（Specific capacitance）.
Fig. 9 a, Fig. 9 b are respectively electrode CFP@GZO@MnO in embodiment 22- 1min when m- voltage performance test chart with Current density-specific capacitance performance test figure；Wherein Fig. 9 b abscissas are Current density（Current density）.
Figure 10 is electrode CFP@GZO@MnO in embodiment 22The IV curve ratios of -1min after 15000 circulation examinations of experience Compared with figure.
Figure 11 is electrode CFP@GZO@MnO in embodiment 22Ramans of-the 1min after 15000 loop tests are undergone Phenogram；Wherein abscissa is Raman Shift（Raman shift）.
Figure 12 is electrode CFP@GZO@MnO in embodiment 22The EDX after 15000 loop tests are undergone points of -1min Analysis figure.
Figure 13 a, Figure 13 b, Figure 13 c, Figure 13 d are respectively electrode CFP@GZO@MnO in embodiment 22- 1min is being undergone Scale is that 10 μm, 2 μm, 200 μm and 200 μm of SEM schemes under scanning electron microscope after 15000 loop tests.
Figure 14 a, Figure 14 b, Figure 14 c, Figure 14 d are respectively electrode CFP@GZO@MnO in embodiment 32- 5min is in scanning electricity Under mirror scale be 6 μm, 2 μm, 200nm, scheme with the SEM of 100nm.
Figure 15 a, Figure 15 b are respectively electrode CFP@GZO@MnO in embodiment 32The voltage-to-current chemical property of -5min Phenogram and sweep speed-specific capacitance Electrochemical Characterization figure.
Figure 16 a, Figure 16 b are respectively electrode CFP@GZO@MnO in embodiment 32The when m- voltage electrochemical performance of -5min Phenogram and current density-specific capacitance Electrochemical Characterization figure.
Figure 17 a, Figure 17 b are respectively electrode CFP@GZO@MnO in embodiment 42- 30min scales under scanning electron microscope are 4 μ The SEM figures of m and 400nm.
Figure 18 a, Figure 18 b, Figure 18 c, Figure 18 d are respectively electrode CFP@GZO@MnO in embodiment 42- 30min electricity piezo-electrics Stream, sweep speed-specific capacitance, when m- voltage and current density-specific capacitance Electrochemical Characterization figure.
Figure 19 a, Figure 19 b, Figure 19 c, Figure 19 d are respectively electrode CFP@GZO@MnO in embodiment 42- 30min passes through Scale is 6 μm, 1 μm, 5 μm under scanning electron microscope after 10000 loop tests and the SEM of 300nm schemes.
Figure 20 is electrode CFP@GZO@MnO in embodiment 52The SEM figures of -60min.
Figure 21 a, Figure 21 b are respectively electrode CFP@GZO@MnO in embodiment 52M- voltage electrochemical performance during -60min Phenogram and current density-specific capacitance Electrochemical Characterization figure.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) 10x5 centimetres of carbon fiber paper is immersed in liquor potassic permanganate（0.5 M）In, after soaking 0.5 h, take out room Dried under temperature, then pure water, dry at last 70 DEG C, the carbon fiber paper after processing（CFP）Pattern passes through electron microscope （SEM）Characterization, such as Fig. 1 a and Fig. 1 b.
(2) electrochemical process deposition MnO2.Deposition step：Using the precursor solution of 100 mL, wherein containing 0.1 M Na2SO4With 0.1 M Mn (AC)2, solvent is water, and the carbon paper after processing is as working electrode, and Ag/AgCl is reference electrode, Pt Net is to electrode；20 s are kept under 0.4 V first, 1 min is then deposited under 0.45 V, after completing deposition step, to institute The working electrode obtained is fully cleaned with deionized water, and finally 4 h of freeze-day with constant temperature obtains δ-MnO at 140 DEG C2Thick film fake capacitance Device electrode, labeled as CFP@MnO2- 1min samples, deposition are 0.06 mg/cm2.The MnO of deposition2Microscopic appearance passes through electronics Microscope represents, such as Fig. 2 a and Fig. 2 b.
(3) with CFP@MnO manufactured in the present embodiment2- 1min is used as electrode of super capacitor, and electrochemical Characterization is as follows：
In Shanghai Chen Hua electrochemical workstation（CHI 660E）Upper use three-electrode system progress electrochemical property test, 1 M aqueous sodium persulfate solutions are electrolyte, are Pt nets to electrode, and reference electrode uses Ag/AgCl electrodes, CFP@MnO2- 1min conducts Working electrode, measures performance of the supercapacitor, and test result is shown in Fig. 3 a and Fig. 3 b.In the MnO on CFP surfaces when depositing 1 min2 Load capacity compare it is relatively low, be only 0.06 mg cm-2, in 50 mV s-1Sweep speed under, specific capacitance is 323 F g-1, Under relatively low sweep speed, such as 2 mV s-1, its specific capacitance is also only 493 F g-1, it is substantially less than MnO2Theoretical ratio Capacitance.
Embodiment 2
（1）In the present embodiment the processing procedure of substrate with embodiment 1（1）Walk identical, details are not described herein.
（2）Hydrothermal growth Ga-ZnO arrays：The precursor solution of 73 mL is configured, configures the aqueous solution of 71 mL first, should Zn (NO containing 0.015 M in aqueous solution3)2, 0.015 M urotropines and Ga3+/Zn2+Molar ratio is 0.5% Ga (NO3)3, after being sufficiently stirred, the NH of 2 mL is added dropwise again in the aqueous solution3H2O, forms precursor solution（73 mL）, after Continuous stirring, is finally immersed in pretreated business carbon fiber paper in precursor solution and is transferred to in polytetrafluoroethylene (PTFE) In the reaction kettle of lining, the conductive substrates of high-specific surface area are obtained after 90 DEG C of 24 h of constant temperature.By scanning electron microscope it can be seen that ZnO receives Surface vertical-growth of the rice noodles along carbon fiber, uniform fold carbon surface, is distributed in sea urchin shape, and diameter is in 200 nm or so, length 5 ~ 6 μm, such as Fig. 4 a and Fig. 4 b.
（3）MnO2Deposit, MnO in the present embodiment2Electrochemical deposition method and embodiment 1 in the（2）Walk it is identical, herein Repeat no more undefined structure.The sample of 1 min is deposited, load capacity is 0.12 mg cm- 2, sample is denoted as CFP@GZO@MnO2- 1min.It can be seen that when having ZnO skeletons, surface area is larger, and identical sedimentary condition, deposition doubles.Pass through scanning electron microscope（Figure 5a and Fig. 5 b）It can be seen that MnO2Granular size is in 50 nm or so, and uniform fold is on Ga-ZnO surfaces.XPS analysis can be seen that Mn is tetravalence, and there is a small amount of trivalent MnOOH on surface, such as Fig. 6 a and Fig. 6 b.
（4）Electrochemical property test：Using three-dimensional porous structure manufactured in the present embodiment as electrode of super capacitor, electricity Chemical characterization is as follows：Using the electrochemical workstation of three-electrode system, 1 M aqueous sodium persulfate solutions are electrolyte, are Pt to electrode Net, reference electrode use Ag/AgCl electrodes, CFP/GZO/MnO2- 1min is used as working electrode, measures performance of the supercapacitor, Test result is shown in Fig. 7（A, B, C and D are respectively the substrate GZO/CFP grown after Ga-ZnO nano wires in figure, directly fine in carbon Tie up paper deposition MnO2Sample MnO2/ CFP, MnO is deposited on the nano-wire array of ZnO for not mixing Ga2Sample CFP/ZnO/ MnO2, and deposit MnO on the nano-wire array of the ZnO after mixing Ga2Sample CFP/GZO/MnO2）.In same sweep speed Under, mixing the sample of Ga substantially has the electric current of bigger.
（5）CFP/GZO/MnO manufactured in the present embodiment2- 1min electrodes, in 0.1 mA/cm2Charging and discharging currents under, its compare Capacity is up to 1154 F/g, and potential window is 0 ~ 1.0 V vs Ag/AgCl reference electrodes, higher than water decomposition potential window and MnO2Theoretical specific capacity；Under the sweep speed of 2 mV/s, area specific capacitance is 0.12 F/cm2, quality specific capacitance is 975 F/ G, is significantly higher than the sample that no GZO skeletons make substrate.Change scan round velocity test electrode specific capacitance, obtain the result is shown in Fig. 8 a and Fig. 8 b, when sweep speed increases to 200 mV/s from 2, quality specific capacitance is reduced to 519 F/g by 975.Change is filled Discharge current density, obtained discharge and recharge is the result is shown in Fig. 9 a and Fig. 9 b, in 0.1 to 5 mA/cm2Perseverance electricity in current density range Stream charging and discharging curve display quality specific capacitance is reduced to 780 F/g from 1154.Figure 10 cyclical stability test results, in 5mA/ cm2High current density under, more than the discharge and recharge of 15000 circulations, capacitance only shows small change, is reduced to from 785.7 580.5 F/g (73.8% capacitance is remaining), show that the electrode has very high cyclical stability, far above common α-MnO2（2 After ~ 3 thousand circulations more than drop by half）.
（6）After long-term cycle life test, by Raman spectrograms 11 as can be seen that undefined structure be changed into stratiform δ- MnO2.After long-term circulation, ZnO skeletons come off, but still containing trace Zn, Ga elements in active material（Can by the EDX analyses of Figure 12 Know）.Initial nano particle becomes the thin slice that thickness is several nanometers, these nanometer sheets form three-dimensional netted loose structure, such as SEM Figure 13 a, Figure 13 b, shown in Figure 13 c and Figure 13 d.It can be seen that pass through long-term electrochemistry loop test, unbodied MnO2Nanometer Line becomes the δ-MnO with lamellar structure2, it is seen that active material experienced dissolving and then the process to regrow.Here, GZO The structure of skeleton structure, greatly improves load capacity, electric conductivity and porosity of active material etc..
Embodiment 3
The substrate treating method, hydrothermal growth Ga-ZnO arrays, MnO of the present embodiment2Electrochemical deposition method and electrification Learn the step in performance test, with embodiment 2（1）,（2）,（3）,（4）Identical, details are not described herein.By sedimentation time by 1min Increase to 5min.Deposition increases to 0.41 mg/cm2, MnO2Nano wire is gradually grown up into by nano particle, and is formed porous thin Film, GZO base parts are corroded, such as Figure 14 a, Figure 14 b, Figure 14 c and Figure 14 d.
With CFP@GZO@MnO manufactured in the present embodiment2- 5min is used as electrode of super capacitor, in the scanning speed of 2 mV/s Under rate, specific capacitance is 613 F/g, 0.25 F/cm of area specific capacitance2.Change the specific capacitance of scan round velocity test electrode, obtain The result is shown in Figure 1 5a arrived and Figure 15 b, when sweep speed increases to 200 mV/s from 2, specific capacitance is reduced to 299 by 613 F/g F/g.Change charging and discharging currents density, obtained discharge and recharge is as a result, be shown in figure Figure 16 a and Figure 16 b, in 0.5 to 20 mA/cm2Electric current Constant current charge-discharge curve in density range shows that specific capacitance is reduced to 442 F/g from 631 F/g.
Compared with Example 2, the increase of the electronics caused by the increase of deposit thickness and ion transmission resistance, in scanning speed When rate is 2 mV/s, biggest quality specific capacitance is reduced to 631 F/g by 1154, but area specific capacitance increases to 0.25 by 0.12 F/cm2。
Embodiment 4
The substrate treating method, hydrothermal growth Ga-ZnO arrays, MnO of the present embodiment2Electrochemical deposition method and electrification Learn the step in performance test, with embodiment 2（1）,（2）,（3）,（4）Identical, details are not described herein.Only sedimentation time is increased to 30min, deposition increase to 1.67 mg/cm2, MnO2The porous membrane of nano wire composition is grown to serve as, zno-based bottom is completely rotten Erosion, Figure 17 a and Figure 17 b.Chemical property is similar with embodiment 3, in 0.5 mA/cm2Constant current is carried out under current density to fill Put, which remains to reach higher 394 F/g of quality specific capacitance, while area specific capacitance has also reached 0.66 F/cm2, see Figure 18 a, Figure 18 b, Figure 18 c and Figure 18 d.After long-term circulation, from disconnected section it can be seen that active material, δ-MnO2Thickness be 3.43 Micron, while can see MnO2The inside of thick-layer is also to be made of thin slice, and has high porosity（Figure Figure 19 a, Figure 19 b, Figure 19 c and Figure 19 d）, it is thus possible to preserve higher capacitance.
Embodiment 5
The substrate treating method, hydrothermal growth Ga-ZnO arrays, MnO of the present embodiment2Electrochemical deposition method and electrification Learn the step in performance test, with embodiment 2（1）,（2）,（3）,（4）Identical, details are not described herein.Sedimentation time increases to 60min, deposition increase to 2.82 mg/cm2, active material is still the film of porous nano wire composition, zno-based bottom quilt completely Corrosion（Figure 20）, from disconnected section it can be seen that active material δ-MnO2Deposit thickness be up to 5.33 ~ 7.15 microns.In 0.5 mA/ cm2Constant current charge-discharge is carried out under current density, which remains to reach higher quality specific capacitance, 384 F/g, while area Specific capacitance has reached 1.08 F/cm2, such as Figure 21 a and Figure 21 b.In MnO2ZnO is gradually corroded and leaves duct while growth, Even therefore very thick film, sample remains to keep three-dimensional porous structure, and can obtain the quality specific capacitance of relative ideal Higher area specific capacitance.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from the embodiment Limitation, it is other any without departing from the substrate change made under Spirit Essences and principle of the invention, method of modifying, replacement, group Close, simplify, should be equivalent substitute mode, be included within protection scope of the present invention.

Claims (4)

  1. A kind of 1. δ-MnO2The preparation method of thick film pseudocapacitors electrode, it is characterised in that pre-processed to substrate and skeleton is given birth to Long, then direct growth active material, growth course skeleton gradually dissolve and leave pore passage structure, while have Zn and Ga to enter and live Property material gap or substitute position, realize the δ-MnO of high electronics and ionic transport properties2The one of thick film pseudocapacitors electrode is secondary It is long, specifically include following steps：
    （1）Substrate pretreatment：Business carbon fiber paper is immersed 20 ~ 60 min is soaked in liquor potassic permanganate, then naturally dry, Fully cleaned with water, it is dry；GZO nanometers are obtained using pretreated business carbon fiber paper as substrate grown Ga doping ZnO Linear array skeleton；
    （2）Three-dimensional Ga doping zinc oxide nanometers linear array skeleton growth：The precursor solution of 70 ~ 80 mL is configured first, wherein including 0.001~0.015 M Zn(NO3)2, 0.001 ~ 0.015 M urotropines, make Ga in solution3+/Zn2+Molar ratio is Ga (the NO of 0.1% ~ 1 %3)3, water and 1 ~ 2 mL NH3H2O, after being sufficiently stirred, soaks pretreated business carbon fiber paper In precursor solution and it is transferred in the reaction kettle with polytetrafluoroethyllining lining, 12 ~ 48 h of constant temperature at 80 ~ 120 DEG C, Obtain growing intensive three-dimensional Ga doping zinc oxide nanometers linear array skeleton on business carbon fiber paper afterwards；
    （3）Active material MnO2Electrochemical deposition：Precursor solution is configured first, Na in the solution2SO4With Mn (Ac)2Concentration It is 0.1 M, solvent is water, carries out electrochemical deposition using three-electrode system, Ag/AgCl makees reference electrode, and platinum guaze is opposed Electrode, intensive three-dimensional Ga doping zinc oxide nanometers linear array skeleton is grown on business carbon fiber paper and carries out sun as working electrode Pole deposits；Deposition process is divided into two steps, and the first step is to keep 10 ~ 20 s in 0.35 ~ 0.4 V of voltage, and then fixed voltage exists 0.4 ~ 0.45 V is deposited in the range of the different time of 1 ~ 60 min, after completing deposition step, the work electricity to gained Pole is fully cleaned with deionized water, and finally 3 ~ 5 h of freeze-day with constant temperature obtains δ-MnO at 100 ~ 150 DEG C2Thick film pseudocapacitors Electrode, labeled as MnO2/GZO/CFP；Ga doping ZnO initially can be as highly conductive three-dimensional porous rack, then as deposition The increase of time is gradually corroded, and leaves tunnel-shaped pore passage structure, and the Zn and 0 ~ 0.1 wt% Ga for finally having 1 ~ 2 wt% enter MnO2Lattice in.
  2. A kind of 2. δ-MnO according to claim 12The preparation method of thick film pseudocapacitors electrode, it is characterised in that step （2）Ga in the precursor solution3+/Zn2+Molar ratio be 0.5%.
  3. A kind of 3. δ-MnO that the preparation method as described in claim 1 obtains2Thick film pseudocapacitors electrode is preparing pseudocapacitors Using.
  4. 4. application according to claim 3, it is characterised in that the specific preparation process of pseudocapacitors is as follows：With in 1 M Property Na2SO4Aqueous solution makees electrolyte, membrane is made with commercialization vitreous carbon fibers or polymer flake, by the carbon branch of same area Support δ-MnO2Thick film makees capacitor symmetry electrode, and the fake capacitance of low capacity is assembled into by the use of the shell of button cell as outer packing Device.
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