CN104465119B - Based on three-dimensional ZnO@MnO2Ultracapacitor of composite Nano array interdigital electrode and preparation method thereof - Google Patents
Based on three-dimensional ZnO@MnO2Ultracapacitor of composite Nano array interdigital electrode and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- 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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- 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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- H—ELECTRICITY
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- 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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- 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
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- 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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Abstract
Three-dimensional ZnO@MnO are based on the present invention relates to one kind2Ultracapacitor of composite Nano array interdigital electrode and preparation method thereof.The ultracapacitor includes packaging bag and solid electrolyte, also including ZnO@MnO2Composite Nano array interdigital electrode, the solid electrolyte and the ZnO@MnO2Composite Nano array interdigital electrode is placed in the packaging bag, and the solid electrolyte is applied to the ZnO@MnO2In composite Nano array interdigital electrode.The ZnO@MnO2Composite Nano array interdigital electrode utilizes micro-nano technology technology, transparent interdigital colelctor electrode is prepared on flexible and transparent PET substrate, by solwution method on colelctor electrode growing three-dimensional ZnO rod nano-arrays, and one layer of MnO is coated around three-dimensional ZnO nanorod using electrodeposition technology2It is prepared from.The ultracapacitor substantially increases the area specific capacitance of device, and nano-array gap provides the passage for being easy to ion to transmit and exchange, and also improves the multiplying power property and cycle performance of electric capacity.
Description
Technical field
Three-dimensional ZnO@MnO are based on the present invention relates to energy storage technical field, more particularly to one kind2Composite Nano array is pitched
Refer to ultracapacitor of electrode and preparation method thereof.
Background technology
With continuing to develop for wearable and portable multi-media electronic equipment, flexible and transparent electron device is proposed
Higher requirement, such as the commercialization for the flexible display device of realizing flatscreen, its electric power energy supply part are also required to
Flexibility and transparence.The device of conventional offer energy storage is mainly lithium battery and ultracapacitor.Ultracapacitor is made
For a kind of new electric energy storage device, due to there is higher energy density compared to traditional plane-parallel capacitor, and phase
Than there is higher power density and longer life-span in lithium ion battery, and widely studied.
Ultracapacitor is broadly divided into two classes, and a class is referred to as double layer capacitor, another kind of to be referred to as faraday's electric capacity
Device or pseudocapacitors.Double layer capacitor is mainly made up of various carbon materials, such as CNT, graphene, carbon fiber
With carbon black etc..The electrode active material of faraday's capacitor mainly by various transition-metal oxides such as RuO, NiO,
CO3O4、MnO2Constituted Deng with conducting polymer.Faraday's capacitor is for double layer capacitor, and its energy storage mechnism is electricity
The chemical reaction of Rapid reversible can occur during discharge and recharge for pole material, therefore can have higher specific capacity, so at present
It is mainly for high-power and high-energy ultracapacitor research in terms of concentrating on faraday's capacitor.
Three-dimensional manometer electrode structure (3D) has the ion access way of high specific surface area and three dimension scale, by this spy
Different structure is applied to the electrode of high-performance super capacitor, has been demonstrated with extensive prospect.ZnO nano-rod array has
Three-dimensional structure, the electrode as 3D ultracapacitors prepares template, has given play to potential advantage (Yong Zhao, Peng
Jiang.MnO2nanosheets grown on the ZnO-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-like
MnO2nanostructure for supercapacitors,Journal of Power Sources,2013,239,393-
398) having, but not yet is used for ZnO arrays the related report and technology of 3D flexible and transparent ultracapacitor devices.
Lift-Off micro-machining manufacture technologies are a kind of micro-machining manufacture means ripe, simple and easy to apply, and the technology passes through purple
Outer photoetching technique processes photoetching agent pattern on substrate, redeposited required material, then with acetone or other solvents
Photoresist is removed, the pattern of institute's deposition materials is obtained.Interdigital electrode is prepared in flexible transparent substrate using the technology, is one
Highly effective transparent electronics processing mode is planted, such as patent document CN 201210579735.5 discloses a kind of based on flat
Transparent flexible electrochemical device of face comb-like electrode structure and preparation method thereof, uses interdigital electrode to be prepared for one-dimensional carbon film
Material is the transparent ultracapacitor of electric double layer of electrode, but the capacitor specific capacitance is very low, and uses liquid electrolyte, is pacified
Full property is poor, is difficult encapsulation, is difficult to apply to solidstate electronics device, it is difficult to adapt to high-power, high-energy flexible and transparent super
The demand for development of capacitor.
The content of the invention
It is a kind of based on three-dimensional ZnO@MnO it is an object of the invention to propose2The super electricity of composite Nano array interdigital electrode
Container and preparation method thereof, the ultracapacitor pliability is strong, transparency is high, with higher area specific capacitance and power, follows
Ring excellent performance, long lifespan disclosure satisfy that powerful charge-discharge power demand.
For up to this purpose, the present invention uses following technical scheme：
On the one hand, three-dimensional ZnO@MnO are based on the invention provides one kind2The super capacitor of composite Nano array interdigital electrode
Device, including packaging bag and solid electrolyte, also including ZnO@MnO2Composite Nano array interdigital electrode, the solid electrolyte and
The ZnO@MnO2Composite Nano array interdigital electrode is placed in the packaging bag, and the solid electrolyte be applied to it is described
ZnO@MnO2In composite Nano array interdigital electrode.
Described ZnO@MnO2Composite Nano array interdigital electrode is by flexible transparent substrate and in flexible transparent substrate
Three-dimensional ZnO nano-rod array and MnO2Material is constituted, and the length of nanometer rods is micro- for 6-8 in the three-dimensional ZnO nano-rod array
Rice, the MnO2Material is coated on outside the three-dimensional ZnO nano-rod array.
The flexible transparent substrate be PET, PMMA or PDMS, preferably PET, the macromolecular material of other flexible and transparents is all
It can be used.
The ZnO@MnO2The active electrode width and electrode spacing of composite Nano array interdigital electrode are 2-100 microns,
Such 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 described above, comprise the following steps：
1) solid electrolyte is prepared；
2) solid electrolyte is equably applied to ZnO@MnO2In composite Nano array interdigital electrode；
3) the ZnO@MnO of solid electrolyte will have been smeared2Composite Nano array interdigital electrode is encapsulated, and obtains the super electricity
Container.
Step 1) the preparation solid electrolyte is specially according to mass ratio 2 by lithium chloride and PVA:1 is dissolved in appropriate go
Ionized water, in 85 DEG C of -90 DEG C of stirring in water bath 1h, obtains solid electrolyte.
Step 3) packaging bag material be PMMA.
Present invention also offers the ZnO@MnO2The preparation method of composite Nano array interdigital electrode：Utilize micro-nano technology
Technology, prepares interdigital colelctor electrode in flexible transparent substrate, by solwution method on interdigital colelctor electrode growing three-dimensional ZnO nanorod
Array, and one layer of MnO is coated around three-dimensional ZnO nanorod using electrodeposition technology2Active material, prepares 3D flexible and transparents
ZnO@MnO2Composite Nano array interdigital electrode.
The ZnO@MnO2The preparation method of composite Nano array interdigital electrode specifically includes following steps：
1) substrate is selected：Selection flexible transparent substrate is simultaneously surface-treated to it；
2) interdigital electrode pattern is designed：Designed mask plate pattern, using semiconductor devices micro fabrication, in the substrate
On process interdigital electrode pattern；
3) prepared by colelctor electrode and ZnO Seed Layers：Pt films are deposited on the interdigital electrode pattern of the substrate and ZnO is thin
Film；
4) three-dimensional ZnO nano-rod array interdigital electrode is prepared：By step 3) substrate is placed in sealable container, plus
Enter three-dimensional ZnO nano-rod array precursor liquid, sealed after being sufficiently stirred for, then under condition of water bath heating, obtain three-dimensional ZnO nano
Rod array interdigital electrode；
5) MnO is deposited2：In step 4) MnO is coated on obtained three-dimensional ZnO nano-rod array2, obtain MnO2The three of cladding
Tie up ZnO nano-rod array interdigital electrode；
6) Lift-Off techniques：By MnO2Unnecessary photoresist is gone in the three-dimensional ZnO nano-rod array interdigital electrode of cladding
Remove, obtain the ZnO@MnO of flexible and transparent2Composite Nano array interdigital electrode.
Step 1) material of the flexible transparent substrate is PET, PMMA or PDMS, preferably PET, other flexible and transparents are high
Molecular material is equally applicable；The surface treatment instrument is oxygen plasma surface treating machine, and the time of the processing is
2-3min, is surface-treated to remove organic impurities to the backing material, and beneficial to the viscous of later stage photoresist and substrate
Attached property.
Step 2) the making interdigital electrode pattern is using ultraviolet photolithographic technology, and concrete operations condition is：From model
AZ4620 photoresist, spin coating thickness is 3-4 microns, and spin coating speed is 1000-2000 revs/min, and pre-bake temperature is 80-105
DEG C, the time for exposure is 15-25s, and developing time is 65-70s.
Designed interdigital electrode active electrode width and electrode spacing can be according to the requirements of light transmittance at 2-100 microns
Interior selection, preferably electrode width are 100 microns, and electrode spacing is also 100 microns.
Step 3) the Pt films and ZnO film deposited by magnetron sputtering mode, and the thickness of the Pt films is 60-
70nm, such as 62nm, 64nm, 65nm, 66nm, 67nm, 68nm or 69nm, the thickness of the ZnO film is 10-20nm, such as 11nm,
12nm, 14nm, 15nm, 16nm, 17nm, 18nm or 19nm.
Step 4) the three-dimensional ZnO nano-rod array precursor liquid is 0.5-0.55mol/L zinc nitrate solution, 0.1-
0.15mol/L polyethylenimine solution, 0.25-0.3mol/L hexamethylenetetramine solution, mass fraction be 75%
The mixed liquor of ammoniacal liquor and deionized water；The deionized water：Zinc nitrate solution：Polyethylenimine solution：Hexamethylenetetramine
Solution：The volume ratio of ammoniacal liquor is 32:2:4:2:1；The temperature of the heating water bath be 65-70 DEG C, such as 66 DEG C, 67 DEG C, 68 DEG C or
68 DEG C, the time of the heating water bath is 5-13h, such as 6h, 7h, 8h, 9h, 10h, 11h or 12h.The zinc nitrate solution it is dense
Spend for 0.5-0.55mol/L, such as 0.51mol/L, 0.52mol/L, 0.53mol/L or 0.54mol/L, the polyvinyl
The concentration of solution is 0.1-0.15mol/L, such as 0.11mol/L, 0.12mol/L, 0.13mol/L or 0.14mol/L, described six times
The concentration of tetramine solution is 0.25-0.3mol/L, such as 0.26mol/L, 0.27mol/L, 0.28mol/L or 0.29mol/L.
Step 4) the three-dimensional ZnO nano-rod array also coated by magnetron sputtering technique 10-15nm such as 11nm,
12nm, 13nm or 14nm Pt films.
Step 5) the deposition MnO2The side of physical deposition such as magnetron sputtering, electron beam evaporation or electrochemical deposition can be used
Prepared by formula, other active materials such as RuO can be also deposited on three-dimensional ZnO nano-rod array2, NiO or CO3O4.The present invention is used
Three-electrode electro Chemical is deposited, and the operating condition of the three-electrode electro Chemical deposition is：With three-dimensional ZnO nano-rod array interdigital electrode
For working electrode, manganese nitrate and sodium nitrate mixed liquor are electrodeposit liquid, and platinized platinum is that calomel electrode is reference electrode to electrode, electricity
The current density of deposition is 0.5-0.6mA/cm2, such as 0.51mA/cm2、0.52mA/cm2、0.54mA/cm2、0.55mA/cm2、
0.57mA/cm2Or 0.59mA/cm2, electrodeposition time is 25-30min, such as 26min, 27min, 28min or 29min, in three-dimensional
Electro-deposition coats MnO around ZnO nano-rod array interdigital electrode2。
Compared with prior art, beneficial effects of the present invention are：
(1) the solid-state super capacitor device pliability that provides of the present invention is strong, transparency is high；
(2) solid-state super capacitor that the present invention is provided has higher area specific capacitance and power, and cycle performance is excellent,
Long lifespan；
(3) solid-state super capacitor that the present invention is provided disclosure satisfy that powerful charge-discharge power demand, can be applied to aobvious
Show field and wearable electronic product scope, meet demand of the people for modern science and technology product and high-quality green living.
Brief description of the drawings
Fig. 1 is the interdigital electrode mask plate design diagram that the specific embodiment of the invention 1 is provided.
Fig. 2 is the SEM figures for the three-dimensional ZnO nano-rod array interdigital electrode that the specific embodiment of the invention 1 is provided.
Fig. 3 is the ZnO@MnO that the specific embodiment of the invention 1 is provided2The SEM figures of composite Nano array interdigital electrode.
Fig. 4 is the flexible and transparent solid-state 3D ultracapacitors that the specific embodiment of the invention 2 is provided.
Fig. 5 is the cyclic voltammetry curve for the flexible and transparent solid-state 3D ultracapacitors that the specific embodiment of the invention 2 is provided.
Fig. 6 is that the cyclical stability for the flexible and transparent solid-state 3D ultracapacitors that the specific embodiment of the invention 2 is provided is surveyed
Try curve.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
Prepare ZnO@MnO2Composite Nano array interdigital electrode
1st, substrate is selected：Select PET as substrate, 2min is handled with oxygen plasma surface treating machine.
2nd, interdigital electrode is designed：Using semiconductor devices micro fabrication, interdigital electrode pattern is processed on PET substrate.
Interdigital electrode design as ultraviolet photolithographic mask plate is as shown in Figure 1.It can be seen that prepared interdigital electrode
Logarithm be 8 pairs, the spacing and finger beam between the interdigital electrode are 100 microns.The operating condition of photoetching process is：Ultraviolet photolithographic
The photoresist model AZ4620 of use, spin coating thickness is 3 microns, and spin coating speed is 2000 revs/min, and pre-bake temperature is 105
Degree, the time for exposure is 25s, and developing time is 70s, is prepared on PET is sunk to the bottom interdigital to electrode pattern.
3rd, prepared by colelctor electrode and ZnO Seed Layers：Using magnetron sputtering mode, interdigital electricity is carried prepared by above-mentioned 2nd step
70nm Pt films and 20nm ZnO film are deposited on the PET substrate of pole figure case.
4th, ZnO nano-rod array is prepared：PET substrate prepared by above-mentioned 3rd step is inserted in sealable container, according to
32:2:4:2:1 ratio, is separately added into deionized water, 0.5mol/L zinc nitrate solution, 0.1mol/L polyvinyl
Solution, 0.25mol/L hexamethylenetetramine solution and mass fraction are 75% ammoniacal liquor.Sealed after being sufficiently stirred for, Ran Hou
Heating water bath 10 hours at 65 DEG C, obtain the nanometer zinc oxide array of 6 microns, as shown in Figure 2.Figure it is seen that
ZnO nanorod is evenly distributed on interdigital Pt electrode films, and ZnO nanorod arrangement is close, and its length is about 6 microns.To enter one
Step improves the electric conductivity of zinc oxide nano rod, can also use magnetron sputtering mode, 10nm Pt is coated on zinc oxide nano rod
Film；
5th, three-dimensional MnO2It is prepared by array：Coated using three-electrode electro Chemical depositional mode on three-dimensional ZnO nano-rod array
Inexpensively, environment-friendly MnO2Material, the operating condition of electrochemical deposition is：Electrodeposit liquid for 0.02mol/L manganese nitrate and
0.1mol/L sodium nitrate mixed liquor, the three-dimensional ZnO nano-rod array interdigital electrode using the preparation of the 4th step is working electrode, platinized platinum
For to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.5mA/cm2, sedimentation time is 25min, in ZnO
Electro-deposition coats MnO around nanometer rods2Electrode material, obtains MnO2The ZnO nano-rod array of cladding；
6th, Lift-Off techniques.The three-dimensional MnO that 5th step is obtained2Array soaks 2h, ultrasonic 10min in acetone, goes
Except unnecessary photoresist, the ZnO@MnO of flexible and transparent are obtained2Composite Nano array interdigital electrode, as shown in Figure 3.Can from figure
To find out, the MnO2Film is uniformly coated on three-dimensional ZnO nano-rod array, MnO2Film thickness is about 40nm or so.
Embodiment 2
Prepare flexible and transparent solid-state 3D ultracapacitors
By lithium chloride and PVA according to mass ratio 2:1 is dissolved in appropriate deionized water, in 85 DEG C of stirring in water bath 1h, consolidate
Body electrolyte.Solid electrolyte is equably applied in prepared interdigitated capacitors, and encapsulated with PMMA, just obtain flexibility
Transparent solid-state ultracapacitor, as shown in figure 4, it can be seen that described solid-state super capacitor length is about 5cm,
Transparency is high, can bend, with good pliability.Prepared flexible and transparent solid-state super capacitor cyclic voltammetry curve
As shown in figure 5, it can be seen that being swept in different under speed, CV curves are in nearly rectangular configuration, are typical amorphous state MnO2
Capacitance characteristic, in the case where sweeping fast 2mV/s, the area capacitance of the device is up to 167mF/cm-2.Fig. 6 is the device in crossing current charge and discharge
Cycle performance curve in the case of electricity, it can be seen that have passed through after 5000 circulations, the capacity of device remains at 99% left side
The right side, illustrates that the device has good stability.
Embodiment 3
Prepare ZnO@MnO2Composite Nano array interdigital electrode
1st, substrate is selected：Select PDMS as substrate, 2min is handled with oxygen plasma surface treating machine.
2nd, interdigital electrode is designed：Using semiconductor devices micro fabrication, interdigital electrode pattern is processed on PDMS substrates.
The spacing and finger beam of interdigital electrode as ultraviolet photolithographic mask plate are 2 microns.The operating condition of photoetching process is：Ultraviolet photolithographic
The photoresist model AZ4620 of use, spin coating thickness is 4 microns, and spin coating speed is 1000 revs/min, and pre-bake temperature is 80
Degree, the time for exposure is 15s, and developing time is 65s, and interdigital electrode figure is prepared on PDMS substrates.
3rd, prepared by colelctor electrode and ZnO Seed Layers：Using magnetron sputtering mode, interdigital electricity is carried prepared by above-mentioned 2nd step
60nm Pt films and 10nm ZnO film are deposited on the PDMS substrates of pole figure case.
4th, three-dimensional ZnO nano-rod array is prepared：PDMS substrates prepared by above-mentioned 3rd step are inserted in sealable container,
According to 32:2:4:2:1 ratio, is separately added into deionized water, 0.55mol/L zinc nitrate solution, 0.15mol/L polyethylene
Base imide liquor, 0.3mol/L hexamethylenetetramine solution and mass fraction are 75% ammoniacal liquor.Sealed after being sufficiently stirred for, so
Heating water bath 13 hours at 70 DEG C, obtain the nanometer zinc oxide array of 6 microns afterwards；
5th, three-dimensional MnO2It is prepared by array：Coated using three-electrode electro Chemical depositional mode on three-dimensional ZnO nano-rod array
Inexpensively, environment-friendly MnO2Material, the operating condition of electrochemical deposition is：Electrodeposit liquid for 0.02mol/L manganese nitrate and
0.1mol/L sodium nitrate mixed liquor, the three-dimensional ZnO nano-rod array interdigital electrode using the preparation of the 4th step is working electrode, platinized platinum
For to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.6mA/cm2, sedimentation time is 30min, in ZnO
Electro-deposition coats MnO around nanometer rods2Electrode material, obtains MnO2The ZnO nano-rod array of cladding；
6th, Lift-Off techniques.The three-dimensional MnO that 5th step is obtained2Array soaks 2h, ultrasonic 10min in acetone, removes
Unnecessary photoresist, obtains ZnO@MnO2Composite Nano array interdigital electrode.
Embodiment 4
Prepare ZnO@MnO2Composite Nano array interdigital electrode
1st, substrate is selected：Select PMMA as substrate, 2min is handled with oxygen plasma surface treating machine.
2nd, interdigital electrode is designed：Using semiconductor devices micro fabrication, interdigital electrode pattern is processed on PMMA substrates.
The spacing and finger beam of interdigital electrode as ultraviolet photolithographic mask plate are 50 microns.The operating condition of photoetching process is：Ultraviolet light
The photoresist model AZ4620 used is carved, spin coating thickness is 3.5 microns, and spin coating speed is 1500 revs/min, and pre-bake temperature is
90 DEG C, the time for exposure is 20s, and developing time is 68s, and interdigital electrode figure is prepared on PMMA substrates.
3rd, prepared by colelctor electrode and ZnO Seed Layers：Using magnetron sputtering mode, interdigital electricity is carried prepared by above-mentioned 2nd step
65nm Pt films and 15nm ZnO film are deposited on the PMMA substrates of pole figure case.
4th, ZnO nano-rod array is prepared：PMMA substrates prepared by above-mentioned 3rd step are inserted in sealable container, according to
32:2:4:2:1 ratio, is separately added into deionized water, 0.52mol/L zinc nitrate solution, 0.12mol/L polyvinyl Asia
Amine aqueous solution, 0.28mol/L hexamethylenetetramine solution and mass fraction are 75% ammoniacal liquor.Sealed after being sufficiently stirred for, then
Heating water bath 5 hours at 70 DEG C, obtain the nanometer zinc oxide array of 6 microns；
5th, three-dimensional MnO2It is prepared by array：Coated using three-electrode electro Chemical depositional mode on three-dimensional ZnO nano-rod array
Inexpensively, environment-friendly MnO2Material, the operating condition of electrochemical deposition is：Electrodeposit liquid for 0.02mol/L manganese nitrate and
0.1mol/L sodium nitrate mixed liquor, the three-dimensional ZnO nano-rod array interdigital electrode using the preparation of the 4th step is working electrode, platinized platinum
For to electrode, calomel electrode is reference electrode, and the current density of electro-deposition is 0.55mA/cm2, sedimentation time is 28min,
Electro-deposition coats MnO around ZnO nanorod2Electrode material, obtains MnO2The ZnO nano-rod array of cladding；
6th, Lift-Off techniques.The three-dimensional MnO that 5th step is obtained2Array soaks 2h, ultrasonic 10min in acetone, removes
Unnecessary photoresist, obtains ZnO@MnO2Composite Nano array interdigital electrode.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. one kind is based on three-dimensional ZnO@MnO2The preparation method of the ultracapacitor of composite Nano array interdigital electrode, its feature exists
In described to be based on three-dimensional ZnO@MnO2The ultracapacitor of composite Nano array interdigital electrode includes packaging bag and solid electrolytic
Matter, also including ZnO@MnO2Composite Nano array interdigital electrode, the solid electrolyte and the ZnO@MnO2Composite Nano array
Interdigital electrode is placed in the packaging bag, and the solid electrolyte is applied to the ZnO@MnO2The interdigital electricity of composite Nano array
On extremely；
It is described to be based on three-dimensional ZnO@MnO2The preparation method of the ultracapacitor of composite Nano array interdigital electrode includes following step
Suddenly：
1) solid electrolyte is prepared；
2) solid electrolyte is equably applied to ZnO@MnO2In composite Nano array interdigital electrode；The ZnO@MnO2It is compound
The preparation method of nano-array interdigital electrode is：Using micro-nano technology technology, interdigital colelctor electrode is prepared in flexible transparent substrate,
By solwution method on interdigital colelctor electrode growing three-dimensional ZnO nano-rod array, and using electrodeposition technology in three-dimensional ZnO nanorod
Surrounding coats one layer of MnO2Active material, prepares 3D flexible and transparent ZnO@MnO2Composite Nano array interdigital electrode；
3) the ZnO@MnO of solid electrolyte will have been smeared2Composite Nano array interdigital electrode is encapsulated, and obtains the ultracapacitor.
2. preparation method according to claim 1, it is characterised in that described ZnO@MnO2The interdigital electricity of composite Nano array
Three-dimensional ZnO nano-rod array and MnO of the pole by flexible transparent substrate and in flexible transparent substrate2Material is constituted, the MnO2
Material is coated on outside the three-dimensional ZnO nano-rod array.
3. preparation method according to claim 1, it is characterised in that the flexible transparent substrate be PET, PMMA or
PDMS。
4. preparation method according to claim 1, it is characterised in that described ZnO@MnO2The interdigital electricity of composite Nano array
The active electrode width and electrode spacing of pole are 2-100 microns.
5. preparation method according to claim 1, it is characterised in that the ZnO@MnO2Composite Nano array interdigital electrode
Preparation method specifically include following steps：
1) substrate is selected：Selection flexible transparent substrate is simultaneously surface-treated to it；
2) interdigital electrode pattern is designed：Designed mask plate pattern, using semiconductor devices micro fabrication, adds over the substrate
Work goes out interdigital electrode pattern；
3) prepared by colelctor electrode and ZnO Seed Layers：Pt films and ZnO film are deposited on the interdigital electrode pattern of the substrate；
4) three-dimensional ZnO nano-rod array interdigital electrode is prepared：By step 3) substrate is placed in sealable container, adds three
ZnO nano-rod array precursor liquid is tieed up, is sealed after being sufficiently stirred for, then under condition of water bath heating, three-dimensional ZnO nanorod battle array is obtained
Row interdigital electrode；
5) MnO is deposited2：In step 4) MnO is coated on obtained three-dimensional ZnO nano-rod array2, obtain MnO2The three-dimensional ZnO of cladding
Nanometer stick array interdigital electrode；
6) Lift-Off techniques：By MnO2Unnecessary photoresist is removed in the three-dimensional ZnO nano-rod array interdigital electrode of cladding, is obtained
To the ZnO@MnO of flexible and transparent2Composite Nano array interdigital electrode.
6. preparation method according to claim 5, it is characterised in that step 2) the processing interdigital electrode pattern use purple
Outer photoetching technique, concrete operations condition is：From model AZ4620 photoresist, spin coating thickness is 3-4 microns, spin coating speed
For 1000-2000 revs/min, pre-bake temperature is 80-105 DEG C, and the time for exposure is 15-25s, and developing time is 65-70s.
7. preparation method according to claim 5, it is characterised in that step 3) the Pt films and ZnO film pass through magnetic
Control sputtering mode is deposited, and the thickness of the Pt films is 60-70nm, and the thickness of the ZnO film is 10-20nm.
8. preparation method according to claim 5, it is characterised in that step 4) the three-dimensional ZnO nano-rod array forerunner
Liquid is 0.5-0.55mol/L zinc nitrate solution, 0.1-0.15mol/L polyethylenimine solution, 0.25-0.3mol/L's
75% ammoniacal liquor and the mixed liquor of deionized water that hexamethylenetetramine solution, mass fraction are；The deionized water：Zinc nitrate is molten
Liquid：Polyethylenimine solution：Hexamethylenetetramine solution：The volume ratio of ammoniacal liquor is 32:2:4:2:1；The heating water bath
Temperature is 65-70 DEG C, and the time of the heating water bath is 5-13h.
9. preparation method according to claim 5, it is characterised in that in step 4) on the three-dimensional ZnO nano-rod array
10-15nm Pt films have also been coated by magnetron sputtering technique.
10. preparation method according to claim 5, it is characterised in that step 5) the deposition MnO2Using three electrode electrochemicals
Deposition is learned, the operating condition of the three-electrode electro Chemical deposition is：It is electric by work of three-dimensional ZnO nano-rod array interdigital electrode
Pole, manganese nitrate and sodium nitrate mixed liquor are electrodeposit liquid, and platinized platinum is that calomel electrode is reference electrode, the electricity of electro-deposition to electrode
Current density is 0.5-0.6mA/cm2, electrodeposition time is 25-30min, electric around three-dimensional ZnO nano-rod array interdigital electrode
Deposition cladding MnO2。
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| BR112018073886A2 (en) * | 2016-05-23 | 2019-02-26 | Araujo Dayrell Ivan | design and manufacture of graphene supercapacitor |
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| CN109036858B (en) * | 2017-11-28 | 2021-12-21 | 中国科学院大连化学物理研究所 | Flexible all-solid-state planar interdigital lithium ion capacitor and preparation method thereof |
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| CN110148528A (en) * | 2019-05-28 | 2019-08-20 | 吉林师范大学 | MnOx/CoNi-LDH/CFP composite electrode material for super capacitor and preparation method thereof |
| CN110931263B (en) * | 2019-11-21 | 2021-08-03 | 杭州电子科技大学 | Super capacitor electrode structure and reinforcing method |
| CN111261423A (en) * | 2020-01-20 | 2020-06-09 | 佛山科学技术学院 | ZnO @ MnO2Three-dimensional porous electrode and preparation method thereof |
| CN111272819B (en) * | 2020-02-21 | 2022-09-16 | 中山大学 | Interdigital arrangement conductive nanotube sensing device for detecting multi-element activity of myocardial cells |
| CN112951622A (en) * | 2021-01-29 | 2021-06-11 | 西安电子科技大学 | Preparation method of miniature super capacitor capable of being used for kHZ alternating current linear filtering |
| CN113675006A (en) * | 2021-08-11 | 2021-11-19 | 浙江浙能技术研究院有限公司 | Preparation method of manganese-based oxide micro supercapacitor |
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