CN104465119A - Super capacitor based on three-dimensional ZnO@MnO2 composite nano array interdigital electrode and manufacturing method thereof - Google Patents
Super capacitor based on three-dimensional ZnO@MnO2 composite nano array interdigital electrode and manufacturing method thereof Download PDFInfo
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- CN104465119A CN104465119A CN201410713658.7A CN201410713658A CN104465119A CN 104465119 A CN104465119 A CN 104465119A CN 201410713658 A CN201410713658 A CN 201410713658A CN 104465119 A CN104465119 A CN 104465119A
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a super capacitor based on a three-dimensional ZnO@MnO2 composite nano array interdigital electrode and a manufacturing method of the super capacitor. The super capacitor comprises a packaging bag and a solid electrolyte, and further comprises the ZnO@MnO2 composite nano array interdigital electrode, the solid electrolyte and the ZnO@MnO2 composite nano array interdigital electrode are arranged in the packaging bag, and the ZnO@MnO2 composite nano array interdigital electrode is smeared with the solid electrolyte. The micro-nano machining technology is adopted in the ZnO@MnO2 composite nano array interdigital electrode, a transparent interdigital collector electrode is manufactured on a flexible and transparent PET substrate, a three-dimensional ZnO bar nano array is grown on the collector electrode through a solution method, and three-dimensional ZnO bars are coated with a layer of MnO2 based on an electro-deposition technology. According to the super capacitor, the area ratio capacitance of a device is greatly improved, a nano array clearance is adopted as a channel facilitating ion transmission and exchange, and the rate capacity and circulating performance of the capacitor are improved.
Description
Technical field
The present invention relates to energy storage technical field, particularly relate to a kind of based on three-dimensional ZnO@MnO
2ultracapacitor of composite Nano array interdigital electrode and preparation method thereof.
Background technology
Along with wearable and development that is portable multi-media electronic equipment, flexible and transparent electron device are had higher requirement, such as in order to realize the commercialization of the flexible display device of flatscreen, its electric power energy supply parts also need flexibility and transparence.Conventional device mainly lithium battery and the ultracapacitor that energy storage is provided.Ultracapacitor, as a kind of novel electric energy storage device, owing to having higher energy density compared to traditional plane-parallel capacitor, and has higher power density and longer life-span compared to lithium ion battery, and is studied widely.
Ultracapacitor is mainly divided into two classes, and a class is called as double electric layer capacitor, is another kind ofly called as Faradic electricity container or pseudocapacitors.Double electric layer capacitor is mainly made up of various material with carbon element, such as carbon nano-tube, Graphene, carbon fiber and carbon black etc.The electrode active material of Faradic electricity container mainly by various transition-metal oxide as RuO, NiO, CO
3o
4, MnO
2form Deng with conducting polymer.Faradic electricity container is relative to double electric layer capacitor, its energy storage mechnism is the chemical reaction that Rapid reversible can occur electrode material in the process of discharge and recharge, therefore higher specific capacity can be had, so at present Faradic electricity container aspect is mainly concentrated on for high-power and research that is high-energy ultracapacitor.
Three-dimensional manometer electrode structure (3D) has the ion access way of high specific area and three dimension scale, this special structure is applied to the electrode of high-performance super capacitor, has been proved to be and has had prospect widely.ZnO nano-rod array has three-dimensional structure, and the electrode as 3D ultracapacitor prepares template, has given play to potential advantage (Yong Zhao, Peng Jiang.MnO
2nanosheets grown on theZnO-nanorod-modified carbon fiber paper for supercapacitor electrode materials, Colloids and SurfacesA:Physicochem.Eng.Aspects, 2014,444,232-239; Yong Zhao, Peng Jiang, Sishen Xie.Template-mediated synthesis of three-dimensional coral-likeMnO
2nanostructure for supercapacitors, Journal of Power Sources, 2013,239,393-398), but not yet there are the relevant report and technology that ZnO array are used for 3D flexible and transparent ultracapacitor device.
Lift-Off micro-machining manufacture technology is a kind of maturation, simple micro-machining manufacture means, this technology processes photoetching agent pattern by ultraviolet photolithographic technology on substrate, deposit required material again, then being removed by photoresist with acetone or other solvent, the pattern of institute's deposition materials is obtained.This technology is utilized to prepare interdigital electrode in flexible transparent substrate, it is a kind of highly effective transparent electronics processing mode, as patent documentation CN 201210579735.5 discloses a kind of transparent flexible electrochemical device based on plane comb-like electrode structure and preparation method thereof, the transparent ultracapacitor of electric double layer that it is electrode that employing interdigital electrode has been prepared with one dimension carbon film material, but this capacitor ratio capacitance is very low, and employing liquid electrolyte, fail safe is poor, not easily encapsulate, be difficult to be applied to solidstate electronics device, be difficult to adaptation high-power, the demand for development of high-energy flexible and transparent ultracapacitor.
Summary of the invention
The object of the invention is to propose one based on three-dimensional ZnO@MnO
2ultracapacitor of composite Nano array interdigital electrode and preparation method thereof, this ultracapacitor pliability is strong, transparency is high, has higher area ratio electric capacity and power, and cycle performance is excellent, and the life-span is long, can meet powerful charge-discharge power demand.
For reaching this object, the present invention by the following technical solutions:
On the one hand, the invention provides one based on three-dimensional ZnO@MnO
2the ultracapacitor of composite Nano array interdigital electrode, comprises packaging bag and solid electrolyte, also comprises ZnO@MnO
2composite Nano array interdigital electrode, described solid electrolyte and described ZnO@MnO
2composite Nano array interdigital electrode is placed in described packaging bag, and described solid electrolyte spreads upon described ZnO@MnO
2in composite Nano array interdigital electrode.
Described ZnO@MnO
2composite Nano array interdigital electrode is by flexible transparent substrate and the three-dimensional ZnO nano-rod array be positioned in flexible transparent substrate and MnO
2material forms, and in described three-dimensional ZnO nano-rod array, the length of nanometer rods is 6-8 micron, described MnO
2it is outside that material is coated on described three-dimensional ZnO nano-rod array.
Described flexible transparent substrate is PET, PMMA or PDMS, and be preferably PET, the macromolecular material of other flexible and transparents all can use.
Described ZnO@MnO
2the active electrode width of composite Nano array interdigital electrode and electrode spacing are 2-100 micron, as 5 microns, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns or 90 microns.
On the other hand, the invention provides the preparation method of ultracapacitor as above, comprise the following steps:
1) solid electrolyte is prepared;
2) solid electrolyte is applied to equably ZnO@MnO
2in composite Nano array interdigital electrode;
3) the ZnO@MnO of solid electrolyte will have been smeared
2composite Nano array interdigital electrode encapsulates, and obtains described ultracapacitor.
Step 1) described preparation solid electrolyte, be specially and lithium chloride and PVA are dissolved in appropriate deionized water according to mass ratio 2:1, at 85 DEG C of-90 DEG C of stirring in water bath 1h, obtain solid electrolyte.
Step 3) material of described packaging bag is PMMA.
Present invention also offers described ZnO@MnO
2the preparation method of composite Nano array interdigital electrode: utilize micro-nano technology technology, flexible transparent substrate is prepared interdigital collector electrode, by solwution method growing three-dimensional ZnO nano-rod array on interdigital collector electrode, and utilize electrodeposition technology coated one deck MnO around three-dimensional ZnO nanorod
2active material, prepares 3D flexible and transparent ZnO@MnO
2composite Nano array interdigital electrode.
Described ZnO@MnO
2the preparation method of composite Nano array interdigital electrode specifically comprises the following steps:
1) substrate is selected: select flexible transparent substrate and surface treatment is carried out to it;
2) design interdigital electrode pattern: designed mask plate pattern, adopt semiconductor device micro fabrication, process interdigital electrode pattern over the substrate;
3) collector electrode and the preparation of ZnO Seed Layer: deposit Pt film and ZnO film on the interdigital electrode pattern of described substrate;
4) three-dimensional ZnO nano-rod array interdigital electrode is prepared: by step 3) described substrate is placed in sealable container, add three-dimensional ZnO nano-rod array precursor liquid, seal after abundant stirring, then under condition of water bath heating, obtain three-dimensional ZnO nano-rod array interdigital electrode;
5) MnO is deposited
2: in step 4) coated MnO on the three-dimensional ZnO nano-rod array that obtains
2, obtain MnO
2coated three-dimensional ZnO nano-rod array interdigital electrode;
6) Lift-Off technique: by MnO
2photoresist unnecessary in coated three-dimensional ZnO nano-rod array interdigital electrode is removed, and obtains the ZnO@MnO of flexible and transparent
2composite Nano array interdigital electrode.
Step 1) material of described flexible transparent substrate is PET, PMMA or PDMS, be preferably PET, other flexible and transparent macromolecular materials are applicable equally; Described surface treatment instrument is oxygen plasma surface treating machine, and the time of described process is 2-3min, carries out surface treatment to remove organic impurities, and be beneficial to the adhesiveness of later stage photoresist and substrate to described backing material.
Step 2) described making interdigital electrode pattern employing ultraviolet photolithographic technology, concrete operations condition is: select model to be the photoresist of AZ4620, even glue thickness is 3-4 micron, even glue speed is 1000-2000 rev/min, pre-bake temperature is 80-105 DEG C, time for exposure is 15-25s, and developing time is 65-70s.
Designed interdigital electrode active electrode width and electrode spacing can be selected in 2-100 micron according to the requirement of light transmittance, and being preferably electrode width is 100 microns, and electrode spacing is also 100 microns.
Step 3) described Pt film and ZnO film deposited by magnetron sputtering mode, the thickness of described Pt film is 60-70nm, as 62nm, 64nm, 65nm, 66nm, 67nm, 68nm or 69nm, the thickness of described ZnO film is 10-20nm, as 11nm, 12nm, 14nm, 15nm, 16nm, 17nm, 18nm or 19nm.
Step 4) described three-dimensional ZnO nano-rod array precursor liquid is the zinc nitrate solution of 0.5-0.55mol/L, the polyethylenimine solution of 0.1-0.15mol/L, the mixed liquor of the hexamethylenetetramine solution of 0.25-0.3mol/L, 75% ammoniacal liquor that mass fraction is and deionized water; Described deionized water: zinc nitrate solution: polyethylenimine solution: hexamethylenetetramine solution: the volume ratio of ammoniacal liquor is 32:2:4:2:1; The temperature of described heating water bath is 65-70 DEG C, and as 66 DEG C, 67 DEG C, 68 DEG C or 68 DEG C, the time of described heating water bath is 5-13h, as 6h, 7h, 8h, 9h, 10h, 11h or 12h.The concentration of described zinc nitrate solution is 0.5-0.55mol/L, as 0.51mol/L, 0.52mol/L, 0.53mol/L or 0.54mol/L, the concentration of described polyethylenimine solution is 0.1-0.15mol/L, as 0.11mol/L, 0.12mol/L, 0.13mol/L or 0.14mol/L, the concentration of described hexamethylenetetramine solution is 0.25-0.3mol/L, as 0.26mol/L, 0.27mol/L, 0.28mol/L or 0.29mol/L.
Step 4) described three-dimensional ZnO nano-rod array is by the also coated Pt film of 10-15nm as 11nm, 12nm, 13nm or 14nm of magnetron sputtering technique.
Step 5) described deposition MnO
2the mode of physical deposition as magnetron sputtering, electron beam evaporation or electrochemical deposition can be adopted to prepare, also can deposit other active material as RuO on three-dimensional ZnO nano-rod array
2, NiO or CO
3o
4.The present invention adopts three-electrode electro Chemical to deposit, the operating condition of described three-electrode electro Chemical deposition is: with three-dimensional ZnO nano-rod array interdigital electrode for work electrode, manganese nitrate and sodium nitrate mixed liquor are electrodeposit liquid, platinized platinum is to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.5-0.6mA/cm
2, as 0.51mA/cm
2, 0.52mA/cm
2, 0.54mA/cm
2, 0.55mA/cm
2, 0.57mA/cm
2or 0.59mA/cm
2, electrodeposition time is 25-30min, as 26min, 27min, 28min or 29min, and the coated MnO of electro-deposition around three-dimensional ZnO nano-rod array interdigital electrode
2.
Compared with prior art, beneficial effect of the present invention is:
(1) solid-state super capacitor device pliability provided by the invention is strong, transparency is high;
(2) solid-state super capacitor provided by the invention has higher area ratio electric capacity and power, and cycle performance is excellent, and the life-span is long;
(3) solid-state super capacitor provided by the invention can meet powerful charge-discharge power demand, can be applied to display field and wearable electronic product scope, meets the demand of people for modern science and technology product and high-quality green living.
Accompanying drawing explanation
Fig. 1 is the interdigital electrode mask plate design diagram that the specific embodiment of the invention 1 provides.
Fig. 2 is the SEM figure of the three-dimensional ZnO nano-rod array interdigital electrode that the specific embodiment of the invention 1 provides.
Fig. 3 is the ZnO@MnO that the specific embodiment of the invention 1 provides
2the SEM figure of composite Nano array interdigital electrode.
Fig. 4 is the solid-state 3D ultracapacitor of flexible and transparent that the specific embodiment of the invention 2 provides.
Fig. 5 is the cyclic voltammetry curve of the solid-state 3D ultracapacitor of flexible and transparent that the specific embodiment of the invention 2 provides.
Fig. 6 is the cyclical stability test curve of the solid-state 3D ultracapacitor of flexible and transparent that the specific embodiment of the invention 2 provides.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment 1
Making ZnO@MnO
2composite Nano array interdigital electrode
1, substrate is selected: select PET as substrate, with oxygen plasma surface treating machine process 2min.
2, interdigital electrode design: adopt semiconductor device micro fabrication, PET substrate is processed interdigital electrode pattern.As ultraviolet photolithographic mask plate interdigital electrode design as shown in Figure 1.As can be seen from the figure, the logarithm of prepared interdigital electrode is 8 right, and the spacing between described interdigital electrode and finger beam are 100 microns.The operating condition of photoetching process is: the photoresist model that ultraviolet photolithographic adopts is AZ4620, and even glue thickness is 3 microns, and even glue speed is 2000 revs/min, pre-bake temperature is 105 degree, time for exposure is 25s, and developing time is 70s, prepares interdigital to electrode pattern on PET sinks to the bottom.
3, collector electrode and the preparation of ZnO Seed Layer: adopt magnetron sputtering mode, the Pt film of PET deposited on substrates 70nm with interdigital electrode pattern prepared in above-mentioned 2nd step and the ZnO film of 20nm.
4, making ZnO nanometer stick array: PET substrate prepared by above-mentioned 3rd step is inserted in sealable container, according to the ratio of 32:2:4:2:1, adding deionized water, the zinc nitrate solution of 0.5mol/L, the polyethylenimine solution of 0.1mol/L, the hexamethylenetetramine solution of 0.25mol/L and mass fraction is respectively the ammoniacal liquor of 75%.Seal after abundant stirring, then heating water bath 10 hours at 65 DEG C, obtains the nanometer zinc oxide array of 6 microns, as shown in Figure 2.As can be seen from Figure 2, ZnO nanorod is evenly distributed on interdigital Pt electrode film, and closely, its length is about 6 microns in ZnO nanorod arrangement.For improving the conductivity of zinc oxide nano rod further, also can adopt magnetron sputtering mode, the Pt film of coated 10nm on zinc oxide nano rod;
5, three-dimensional MnO
2prepared by array: adopt three-electrode electro Chemical depositional mode coated cheapness, eco-friendly MnO on three-dimensional ZnO nano-rod array
2material, the operating condition of electrochemical deposition is: electrodeposit liquid is the manganese nitrate of 0.02mol/L and the sodium nitrate mixed liquor of 0.1mol/L, the three-dimensional ZnO nano-rod array interdigital electrode prepared with the 4th step is for work electrode, platinized platinum is to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.5mA/cm
2, sedimentation time is 25min, the coated MnO of electro-deposition around ZnO nanorod
2electrode material, obtains MnO
2coated ZnO nano-rod array;
6, Lift-Off technique.By the three-dimensional MnO that the 5th step obtains
2array soaks 2h in acetone, ultrasonic 10min, removes unnecessary photoresist, obtains the ZnO@MnO of flexible and transparent
2composite Nano array interdigital electrode, as shown in Figure 3.As can be seen from the figure, described MnO
2film is coated on three-dimensional ZnO nano-rod array equably, MnO
2film thickness is approximately about 40nm.
Embodiment 2
Prepare the solid-state 3D ultracapacitor of flexible and transparent
Lithium chloride and PVA are dissolved in appropriate deionized water according to mass ratio 2:1, at 85 DEG C of stirring in water bath 1h, obtain solid electrolyte.Solid electrolyte is applied to equably in prepared interdigitated capacitors, and encapsulate with PMMA, just flexible and transparent solid-state super capacitor is obtained, as shown in Figure 4, as can be seen from the figure, described solid-state super capacitor length is about 5cm, and transparency is high, can bend, there is good pliability.Prepared flexible and transparent solid-state super capacitor cyclic voltammetry curve as shown in Figure 5, as can be seen from the figure, different sweep speed under, CV curve is nearly rectangular configuration, is typical amorphous state MnO
2capacitance characteristic, sweeping under fast 2mV/s, the area capacitance of this device can reach 167mF/cm
-2.Fig. 6 is the cycle performance curve of this device under crossing current charge status, can find out, after have passed through 5000 circulations, the capacity of device still remains on about 99%, illustrates that this device has good stability.
Embodiment 3
Making ZnO@MnO
2composite Nano array interdigital electrode
1, substrate is selected: select PDMS as substrate, with oxygen plasma surface treating machine process 2min.
2, interdigital electrode design: adopt semiconductor device micro fabrication, PDMS substrate is processed interdigital electrode pattern.It is 2 microns as the spacing of the interdigital electrode of ultraviolet photolithographic mask plate and finger beam.The operating condition of photoetching process is: the photoresist model that ultraviolet photolithographic adopts is AZ4620, and even glue thickness is 4 microns, and even glue speed is 1000 revs/min, pre-bake temperature is 80 degree, time for exposure is 15s, and developing time is 65s, and PDMS substrate is prepared interdigital electrode figure.
3, collector electrode and the preparation of ZnO Seed Layer: adopt magnetron sputtering mode, the Pt film of PDMS deposited on substrates 60nm with interdigital electrode pattern prepared in above-mentioned 2nd step and the ZnO film of 10nm.
4, three-dimensional ZnO nano-rod array is prepared: insert in sealable container by PDMS substrate prepared by above-mentioned 3rd step, according to the ratio of 32:2:4:2:1, adding deionized water, the zinc nitrate solution of 0.55mol/L, the polyethylenimine solution of 0.15mol/L, the hexamethylenetetramine solution of 0.3mol/L and mass fraction is respectively the ammoniacal liquor of 75%.Seal after abundant stirring, then heating water bath 13 hours at 70 DEG C, obtains the nanometer zinc oxide array of 6 microns;
5, three-dimensional MnO
2prepared by array: adopt three-electrode electro Chemical depositional mode coated cheapness, eco-friendly MnO on three-dimensional ZnO nano-rod array
2material, the operating condition of electrochemical deposition is: electrodeposit liquid is the manganese nitrate of 0.02mol/L and the sodium nitrate mixed liquor of 0.1mol/L, the three-dimensional ZnO nano-rod array interdigital electrode prepared with the 4th step is for work electrode, platinized platinum is to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.6mA/cm
2, sedimentation time is 30min, the coated MnO of electro-deposition around ZnO nanorod
2electrode material, obtains MnO
2coated ZnO nano-rod array;
6, Lift-Off technique.By the three-dimensional MnO that the 5th step obtains
2array soaks 2h in acetone, ultrasonic 10min, removes unnecessary photoresist, obtains ZnO@MnO
2composite Nano array interdigital electrode.
Embodiment 4
Making ZnO@MnO
2composite Nano array interdigital electrode
1, substrate is selected: select PMMA as substrate, with oxygen plasma surface treating machine process 2min.
2, interdigital electrode design: adopt semiconductor device micro fabrication, PMMA substrate is processed interdigital electrode pattern.It is 50 microns as the spacing of the interdigital electrode of ultraviolet photolithographic mask plate and finger beam.The operating condition of photoetching process is: the photoresist model that ultraviolet photolithographic adopts is AZ4620, and even glue thickness is 3.5 microns, and even glue speed is 1500 revs/min, pre-bake temperature is 90 DEG C, time for exposure is 20s, and developing time is 68s, and PMMA substrate is prepared interdigital electrode figure.
3, collector electrode and the preparation of ZnO Seed Layer: adopt magnetron sputtering mode, the Pt film of PMMA deposited on substrates 65nm with interdigital electrode pattern prepared in above-mentioned 2nd step and the ZnO film of 15nm.
4, making ZnO nanometer stick array: PMMA substrate prepared by above-mentioned 3rd step is inserted in sealable container, according to the ratio of 32:2:4:2:1, adding deionized water, the zinc nitrate solution of 0.52mol/L, the polyethylenimine solution of 0.12mol/L, the hexamethylenetetramine solution of 0.28mol/L and mass fraction is respectively the ammoniacal liquor of 75%.Seal after abundant stirring, then heating water bath 5 hours at 70 DEG C, obtains the nanometer zinc oxide array of 6 microns;
5, three-dimensional MnO
2prepared by array: adopt three-electrode electro Chemical depositional mode coated cheapness, eco-friendly MnO on three-dimensional ZnO nano-rod array
2material, the operating condition of electrochemical deposition is: electrodeposit liquid is the manganese nitrate of 0.02mol/L and the sodium nitrate mixed liquor of 0.1mol/L, the three-dimensional ZnO nano-rod array interdigital electrode prepared with the 4th step is for work electrode, platinized platinum is to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.55mA/cm
2, sedimentation time is 28min, the coated MnO of electro-deposition around ZnO nanorod
2electrode material, obtains MnO
2coated ZnO nano-rod array;
6, Lift-Off technique.By the three-dimensional MnO that the 5th step obtains
2array soaks 2h in acetone, ultrasonic 10min, removes unnecessary photoresist, obtains ZnO@MnO
2composite Nano array interdigital electrode.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. one kind based on three-dimensional ZnO MnO
2the ultracapacitor of composite Nano array interdigital electrode, comprises packaging bag and solid electrolyte, it is characterized in that, also comprises ZnO@MnO
2composite Nano array interdigital electrode, described solid electrolyte and described ZnO@MnO
2composite Nano array interdigital electrode is placed in described packaging bag, and described solid electrolyte spreads upon described ZnO@MnO
2in composite Nano array interdigital electrode.
2. ultracapacitor according to claim 1, is characterized in that, described ZnO@MnO
2composite Nano array interdigital electrode is by flexible transparent substrate and the three-dimensional ZnO nano-rod array be positioned in flexible transparent substrate and MnO
2material forms, described MnO
2it is outside that material is coated on described three-dimensional ZnO nano-rod array.
3. ultracapacitor according to claim 2, is characterized in that, described flexible transparent substrate is PET, PMMA or PDMS, is preferably PET.
4. according to the ultracapacitor one of claim 1-3 Suo Shu, it is characterized in that, described ZnO@MnO
2the active electrode width of composite Nano array interdigital electrode and electrode spacing are 2-100 micron.
5. a preparation method for the ultracapacitor as described in one of claim 1-4, is characterized in that, comprises the following steps:
1) solid electrolyte is prepared;
2) solid electrolyte is applied to equably ZnO@MnO
2in composite Nano array interdigital electrode;
3) the ZnO@MnO of solid electrolyte will have been smeared
2composite Nano array interdigital electrode encapsulates, and obtains described ultracapacitor.
6. a preparation method for the ultracapacitor as described in one of claim 1-4, is characterized in that, described ZnO MnO
2the preparation method of composite Nano array interdigital electrode is: utilize micro-nano technology technology, flexible transparent substrate is prepared interdigital collector electrode, by solwution method growing three-dimensional ZnO nano-rod array on interdigital collector electrode, and utilize electrodeposition technology coated one deck MnO around three-dimensional ZnO nanorod
2active material, prepares 3D flexible and transparent ZnO@MnO
2composite Nano array interdigital electrode.
7. preparation method according to claim 6, is characterized in that, described ZnO@MnO
2the preparation method of composite Nano array interdigital electrode specifically comprises the following steps:
1) substrate is selected: select flexible transparent substrate and surface treatment is carried out to it;
2) design interdigital electrode pattern: designed mask plate pattern, adopt semiconductor device micro fabrication, process interdigital electrode pattern over the substrate;
3) collector electrode and the preparation of ZnO Seed Layer: deposit Pt film and ZnO film on the interdigital electrode pattern of described substrate;
4) three-dimensional ZnO nano-rod array interdigital electrode is prepared: by step 3) described substrate is placed in sealable container, add three-dimensional ZnO nano-rod array precursor liquid, seal after abundant stirring, then under condition of water bath heating, obtain three-dimensional ZnO nano-rod array interdigital electrode;
5) MnO is deposited
2: in step 4) coated MnO on the three-dimensional ZnO nano-rod array that obtains
2, obtain MnO
2coated three-dimensional ZnO nano-rod array interdigital electrode;
6) Lift-Off technique: by MnO
2unnecessary in coated three-dimensional ZnO nano-rod array interdigital electrode
Photoresist is removed, and obtains the ZnO@MnO of flexible and transparent
2composite Nano array interdigital electrode.
8. preparation method according to claim 7, it is characterized in that, step 2) described making interdigital electrode pattern employing ultraviolet photolithographic technology, concrete operations condition is: select model to be the photoresist of AZ4620, even glue thickness is 3-4 micron, and even glue speed is 1000-2000 rev/min, and pre-bake temperature is 80-105 DEG C, time for exposure is 15-25s, and developing time is 65-70s;
Preferably, step 3) described Pt film and ZnO film deposited by magnetron sputtering mode, and the thickness of described Pt film is 60-70nm, and the thickness of described ZnO film is 10-20nm.
9. the preparation method according to claim 7 or 8, it is characterized in that, step 4) described three-dimensional ZnO nano-rod array precursor liquid is the zinc nitrate solution of 0.5-0.55mol/L, the polyethylenimine solution of 0.1-0.15mol/L, dense, 75% ammoniacal liquor that mass fraction is of the hexamethylenetetramine solution of 0.25-0.3mol/L and the mixed liquor of deionized water; Described deionized water: zinc nitrate solution: polyethylenimine solution: hexamethylenetetramine solution: the volume ratio of ammoniacal liquor is 32:2:4:2:1; The temperature of described heating water bath is 65-70 DEG C, and the time of described heating water bath is 5-13h;
Preferably, step 4) described three-dimensional ZnO nano-rod array is by the also coated Pt film of 10-15nm of magnetron sputtering technique.
10., according to the preparation method one of claim 7-9 Suo Shu, it is characterized in that, step 5) described deposition MnO
2employing three-electrode electro Chemical deposits, the operating condition of described three-electrode electro Chemical deposition is: with three-dimensional ZnO nano-rod array interdigital electrode for work electrode, manganese nitrate and sodium nitrate mixed liquor are electrodeposit liquid, platinized platinum is to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.5-0.6mA/cm
2, electrodeposition time is 25-30min, the coated MnO of electro-deposition around three-dimensional ZnO nano-rod array interdigital electrode
2.
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