CN106653387B - Three-diemsnional electrode material and preparation method thereof, solid supercapacitor - Google Patents
Three-diemsnional electrode material and preparation method thereof, solid supercapacitor Download PDFInfo
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- CN106653387B CN106653387B CN201510408772.3A CN201510408772A CN106653387B CN 106653387 B CN106653387 B CN 106653387B CN 201510408772 A CN201510408772 A CN 201510408772A CN 106653387 B CN106653387 B CN 106653387B
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Abstract
The invention discloses a kind of three-diemsnional electrode materials characterized by comprising the Al nano-nail array formed on aluminium foil；The nickel layer formed on the Al nano-nail array；The MnO formed on the nickel layerxNano-nail array.Preparation method is included: S101, is grown Al nano-nail array on aluminium foil using anode oxidation process and etching technics；S102, using magnetron sputtering technique in one nickel layer of Al nano-nail array growth；S103, MnO is grown on the nickel layer using three electrode electrodeposition technologiesxNano-nail array obtains three-diemsnional electrode material.The invention also discloses a kind of solid supercapacitors comprising three-diemsnional electrode material as described above prepares the electrode to be formed.The electrode material is applied in solid supercapacitor, improves the area specific capacitance of capacitor, also improves the multiplying power property and cycle performance of capacitor.
Description
Technical field
The present invention relates to supercapacitor technologies fields more particularly to a kind of three-diemsnional electrode material and preparation method thereof, also
It is related to a kind of solid supercapacitor.
Background technique
Supercapacitor is called electrochemical capacitor, double-layer capacitor, is developed in recent years a kind of based on electricity
Pole/solution interface electrochemical process, dedicated for the extraordinary capacitor of energy storage.Supercapacitor specific power with higher, function
The high hundreds of times of the traditional electrolytic capacitor of rate density ratio.Supercapacitor has longer cycle life, charge and discharge circulation life
Up to 500,000 times or more.Therefore supercapacitor is a kind of ideal secondary power supply, in mobile communication, information technology, electronic
Automobile, aerospace and science and techniques of defence etc. suffer from application prospect of crucial importance and wide.
Solid supercapacitor is with solid electrolyte instead of liquid electrolyte, compared with liquid supercapacitor, Gu
Body supercapacitor battery have many advantages, such as can thin type, arbitrary areaization and arbitrary shape, leakage and combustion will not be generated
The problems for security such as decrepitate is fried.
The performance of supercapacitor and electrode material, electrolyte and its diaphragm that uses are related, and electrode material is wherein
Most important factor, because it is the important base of supercapacitor, the quality of electrode material performance directly influences capacitor
The quality of performance.Mainly there are three classes currently used as the material of electrode of super capacitor: carbon material, metal oxide materials and conduction
Polymer material.Wherein, initial metal oxide materials mainly use the metal oxide containing precious metals such as ruthenium-oxide or yttrium oxide, RuO2
It is most representational electrode material.Although metal oxide containing precious metals have preferable electric conductivity, there are higher specific capacity and ratio
Power, but it is expensive and has larger pollution to environment, aerospace and military industry field is mainly used at present, in industry
Upper large-scale application still can not achieve.Nanoscale Mn oxide, such as nano-manganese dioxide, money higher with specific capacitance
Abundant, the cheap and environmental-friendly feature in source also becomes and is used to mention one of candidate materials of noble metal.It is existing to receive
The method that rice manganese dioxide is used to prepare the electrode of supercapacitor, mainly by nano-manganese dioxide, active carbon and bonding
Example is mixed to form pasty mixture according to a certain mass ratio for agent (such as polytetrafluoroethylene (PTFE)), then pasty mixture is applied to foam
In nickel set fluid and tabletting forms the electrode of supercapacitor.The nano-manganese dioxide electrode that this method is prepared, although
With relatively good electric conductivity and energy density (requirement for being able to satisfy the performance of supercapacitor), but formed by tabletting
The contact area of the structure of nano-manganese dioxide electrode, active material is also smaller.Therefore, if nanometer titanium dioxide can be improved
The structure of manganese electrode increases the contact area of its active material, then the energy density of nano-manganese dioxide electrode should there are also compared with
Big room for promotion.
Summary of the invention
In view of this, the electrode material has larger the present invention provides a kind of three-diemsnional electrode material and preparation method thereof
Active material contact area, improve the energy density of electrode；The electrode material is applied in solid supercapacitor, mentions
The high area specific capacitance of capacitor, also improves the multiplying power property and cycle performance of capacitor.
In order to achieve the above object, present invention employs the following technical solutions:
A kind of three-diemsnional electrode material, wherein include: the Al nano-nail array formed on aluminium foil；In the Al nano-nail
The nickel layer formed on array；The MnO formed on the nickel layerxNano-nail array, x=1~2.
Further, the length of the Al nano-nail is 1~3 μm, and diameter is 300~500nm, two neighboring Al nano-nail
Spacing be 1~1.2 μm；The MnOxThe length of nano-nail is 1~3.5 μm, and diameter is 400~600nm, two neighboring MnOx
The spacing of nano-nail is 1~1.2 μm.
Further, the specific surface area of the three-diemsnional electrode material is 100~200m2/g。
Further, the nickel layer with a thickness of 100~500nm.
The preparation method of three-diemsnional electrode material as described above, wherein comprising steps of S101, using anodic oxygen chemical industry
The Al nano-nail array that skill and etching technics are grown on aluminium foil；S102, using magnetron sputtering technique in the Al nano-nail battle array
Column one nickel layer of growth；S103, MnO is grown on the nickel layer using three electrode electrodeposition technologiesxNano-nail array, described in acquisition
Three-diemsnional electrode material.
Wherein, step S101 is specifically included: firstly, using aluminium foil be anode, carbon-point as cathode be put into electrolyte carry out sun
Pole oxidation；Wherein, the electrolyte is the citric acid solution and second two that the mass fraction that volume ratio is 1:1~1.5 is 3~5%
The mixed solution of alcohol, the voltage of anodic oxidation are the direct current of 350~400V, and the temperature of electrolyte is 25~28 DEG C, anodic oxygen
The time of change is 7~13h；Then, the aluminium foil after anodic oxidation is immersed in containing 5.8~6.4wt% phosphoric acid and 1.6~
In the mixed solution of 2.0wt% chromic acid, 60~90min is etched under conditions of temperature is 63~90 DEG C, is obtained Al nanometers described
Follow closely array.
Wherein, step S101 further includes successively cleaning the aluminium foil using acetone and isopropanol.
Wherein, step S103 is specifically included: growing the aluminium foil for completing nickel layer as working electrode, using three electricity using step S102
Pole electrodeposition technology is to electrode, with 0.5~1M MnSO using saturated calomel electrode as reference electrode, with Pt4With 0.5~1M
CH3The aqueous solution of COONa is electrolyte, is 0.3~0.5mA cm in areal electric current-2Under conditions of react 5~20min, in institute
It states and obtains the MnO on nickel layerxNano-nail array.
The present invention also provides a kind of solid supercapacitor, which includes poly- pair of the successively metal spraying of lamination setting
Ethylene terephthalate film, first electrode, second electrode, first electrode and metal spraying polyethylene terephthalate
Film；Wherein, the first electrode is to prepare the electrode formed by three-diemsnional electrode material as described above, and the second electrode is
CCG electrode is stained with gel electrolyte in the first electrode and second electrode.
Further, the gel electrolyte is that sodium sulphate that mass ratio is 1:0.8~1.2 and polyvinyl alcohol are dissolved in water
Middle preparation is formed.
Three-diemsnional electrode material provided in an embodiment of the present invention is prepared by aluminum oxide template fabricated in situ containing MnOx
The three-diemsnional electrode material of nano-nail array improves electrode conductivuty, increases active contacts area, to promote energy
Density.The electrode material is applied in solid supercapacitor, improves the area specific capacitance of capacitor, also improves capacitor
Multiplying power property and cycle performance.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of three-diemsnional electrode material in the embodiment of the present invention 1.
Fig. 2 is the electrode and conventional one-dimensional manganese oxide that the three-diemsnional electrode material that the embodiment of the present invention 1 is prepared is formed
The specific discharge capacity of nickel plane electrode and the curve graph of volume and capacity ratio.
Fig. 3 is the electrode and conventional one-dimensional manganese oxide that the three-diemsnional electrode material that the embodiment of the present invention 1 is prepared is formed
The CV curve graph of nickel plane electrode.
Fig. 4 is the structural schematic diagram of the solid supercapacitor of the embodiment of the present invention 2.
Fig. 5 is CV curve graph of the supercapacitor of the embodiment of the present invention 2 under different potential windows.
Fig. 6 is the energy density of the supercapacitor of the embodiment of the present invention 2 and the graph of relation of potential window.
Fig. 7 is CV curve graph of the supercapacitor of the embodiment of the present invention 2 under different voltages scanning speed.
Fig. 8 is specific discharge capacity curve of the supercapacitor of the embodiment of the present invention 2 under different voltage scan rates
Figure.
Fig. 9 is charging and discharging curve of the supercapacitor of the embodiment of the present invention 2 under different current densities.
Figure 10 is the supercapacitor of the embodiment of the present invention 2 in different current densities and corresponding specific discharge capacity curve
Figure.
Figure 11 is the supercapacitor power density of the embodiment of the present invention 2 and the graph of relation of energy density.
The supercapacitor cycle-index of Figure 12 embodiment of the present invention 2 and the graph of relation of capacity retention ratio.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention is retouched in detail
It states, it is clear that described embodiment is only a part of example of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's every other embodiment obtained without making creative work,
Belong to the scope of the present invention.
Embodiment 1
The present embodiment provides firstly a kind of three-diemsnional electrode material, specifically includes that the Al nano-nail formed on aluminium foil
Array；The nickel layer formed on the Al nano-nail array；The MnO formed on the nickel layerxNano-nail array.Further
Ground, the nickel layer with a thickness of 100~500nm.Wherein, MnOxRefer to Mn oxide, in general, x=1~2, such as can be with
It is manganese oxide (MnO), manganese dioxide (MnO2), manganese sesquioxide managnic oxide (Mn2O3) etc., it can be a kind of Mn oxide, it can also be with
Being includes two or more Mn oxides, such as can be while including MnO and MnO2.In the present embodiment, MnOxIt is to select
MnO2It is described in detail as specific example.
As shown in Figure 1, the preparation method of three-diemsnional electrode material as described above comprising steps of
S101, the Al nano-nail array grown on aluminium foil using anode oxidation process and etching technics.Specifically, first
Aluminium foil is successively cleaned using acetone and isopropanol；Then using aluminium foil be anode, carbon-point as cathode be put into electrolyte carry out sun
Pole oxidation；Wherein, the electrolyte is the citric acid solution and second two that the mass fraction that volume ratio is 1:1~1.5 is 3~5%
The mixed solution of alcohol, the voltage of anodic oxidation are the direct current of 350~400V, and the temperature of electrolyte is 25~28 DEG C, anodic oxygen
The time of change is 7~13h；Further, the aluminium foil after anodic oxidation is immersed in containing 5.8~6.4wt% phosphoric acid and 1.6~
In the mixed solution of 2.0wt% chromic acid, 60~90min is etched under conditions of temperature is 63~90 DEG C, is obtained Al nanometers described
Follow closely array.More specifically, in the Al nano-nail array being prepared, the length of Al nano-nail is 1~3 μm, diameter is 300~
500nm, the spacing of two neighboring Al nano-nail are 1~1.2 μm.
S102, using magnetron sputtering technique in one nickel layer of Al nano-nail array growth.Specifically, the nickel being prepared
Layer with a thickness of 100~500nm.
S103, MnO is grown on the nickel layer using three electrode electrodeposition technologies2Nano-nail array obtains the three-dimensional
Electrode material.The step specifically includes: growing the aluminium foil for completing nickel layer as working electrode using step S102, is sunk using three electrode electricity
Product technique, is to electrode, with 0.5~1M MnSO using saturated calomel electrode as reference electrode, with Pt4With 0.5~1M CH3COONa
Aqueous solution be electrolyte, areal electric current be 0.3~0.5mA cm-2Under conditions of react 5~20min, on the nickel layer
Obtain the MnO2Nano-nail array finally obtains the three-diemsnional electrode material.Wherein, the MnO being prepared2Nano-nail array
In, MnO2The length of nano-nail is 1~3.5 μm, and diameter is 400~600nm, two neighboring MnO2The spacing of nano-nail be 1~
1.2μm.The specific surface area of the three-diemsnional electrode material finally obtained is 100~200m2/g。
Three-diemsnional electrode material as above is prepared by aluminum oxide template fabricated in situ containing MnO2Nano-nail array
Three-diemsnional electrode material improves electrode conductivuty, increases active contacts area, to promote energy density.
Fig. 2 shows electrodes and conventional one-dimensional manganese oxide nickel that the three-diemsnional electrode material that the present embodiment is prepared is formed
The specific discharge capacity of plane electrode and the curve graph of volume and capacity ratio.It is as shown in Figure 2, wherein be marked with filled symbols is
(circular mark is three-diemsnional electrode to the graph of relation of specific discharge capacity and electrodeposition time, and square marks are one-dimensional oxidation
Manganese nickel plane electrode), be marked with open symbols is the graph of relation (circular mark of volume and capacity ratio and electrodeposition time
For the electrode that three-diemsnional electrode material is formed, square marks are one-dimensional plane electrode).From fig. 2 it can be seen that compared to one-dimensional
Plane electrode, what the present embodiment was prepared contains MnO2The three-diemsnional electrode material of nano-nail array, in identical electro-deposition
Under the conditions of, no matter all having superior performance in terms of volumetric capacitance or quality capacitor.As the time of electro-deposition increases,
More and more manganese oxide active materials are electrodeposited on three-dimensional nano-nail electrode and one-dimensional manganese oxide nickel plane electrode, this
Sample can obtain higher volumetric capacitance and lower quality specific capacitance.When electrodeposition time is 1min, the present embodiment preparation
What is obtained contains MnO2The quality capacitor for the electrode that the three-diemsnional electrode material of nano-nail array is formed is up to 942.2F g-1, it is one
1.62 times on a planar base of deposition for tieing up manganese oxide nickel plane electrode.After electrodeposition time increases to 10min, this implementation
The volumetric capacitance of the three-dimensional manganese oxide nano-nail electrode of example preparation can achieve 4.22F cm-3.Based on three-dimensional manganese oxide nano-nail
Electrode and gradually decreasing for the quality capacitor of one-dimensional manganese oxide nickel plane electrode are because the time with electro-deposition increases oxidation
The conductivity of manganese is gradually reduced, and electrolyte is caused to be restricted in the diffusion of certain space, still, comparatively, the present embodiment
The three-dimensional manganese oxide nano-nail electrode of preparation all has more superior performance than one-dimensional manganese oxide nickel plane electrode.
Fig. 3 shows the electrode and conventional one-dimensional manganese oxide nickel that the three-diemsnional electrode material that the present embodiment is prepared is formed
The CV curve graph of plane electrode, wherein the scanning speed of voltage is 50mV s-1.The CV curve of two kinds of electrodes is all presented closely in figure
Rectangle shows it with ideal capacitance characteristic.But the integral of the three-dimensional manganese oxide nano-nail electrode CV curve of the present embodiment
Integral area of the area obviously than one-dimensional manganese oxide nickel plane electrode is big, illustrates the three-dimensional manganese oxide nano-nail electrode of the present embodiment
Specific capacitance it is bigger.
Embodiment 2
Present embodiments provide a kind of solid supercapacitor.As described in Figure 4, the capacitor include successively lamination be arranged
The pet film 1 of metal spraying, first electrode 2, second electrode 3, first electrode 2 and metal spraying it is poly- to benzene
Naphthalate film 1.Wherein, the first electrode is to prepare shape by the three-diemsnional electrode material provided in such as embodiment 1
At electrode, the second electrode be CCG (chemical convert graphene, chemical conversion graphene) electrode, it is described
Gel electrolyte is stained in first electrode and second electrode.
Wherein, method of the preparation of first electrode 2 refering to the offer in embodiment 1.
The preparation of second electrode 3 specifically includes: the GO (graphite for being 0.5mg/mL by 100~110mL concentration
Oxide, graphite oxide) solution, the hydrazine hydrate and 0.35~0.5mL concentration that addition 0.2~0.5mL concentration is 35wt% are 28%
Ammonium hydroxide, temperature be 95~100 DEG C at 3~5h of heating water bath, CCG solution is prepared.30~35mL is measured to be prepared
CCG solution, suction filtration obtains filter cake, then by filter cake be soaked in water it is overnight remove remaining ammonia and hydrazine hydrate, obtain CCG electricity
Pole.
The preparation of gel electrolyte specifically includes: 6g sodium sulphate and 6g polyvinyl alcohol being dissolved into 60mL water, under 80 degree
1h is stirred, gel electrolyte is prepared.Wherein, as long as sodium sulphate and polyvinyl alcohol meet the range that mass ratio is 1:0.8~1.2
Interior, the dosage of water can be increased or decreased according to the dosage of sodium sulphate and polyvinyl alcohol.
The first electrode 2 being prepared and second electrode 3 are dipped into 5min in gel electrolyte above-mentioned, so that first
Electrode 2 and second electrode 3 are stained with gel electrolyte, then dry 12h at room temperature.Again by the poly terephthalic acid second of metal spraying
Terephthalate films 1, first electrode 2, second electrode 3 assemble asymmetric solid supercapacitor as shown in Figure 2, finally right
The supercapacitor carries out electro-chemical test, and test structure shows that the supercapacitor has superior performance.
Fig. 5 shows CV curve graph of the supercapacitor of the present embodiment at different potential windows (1.0~1.8V),
In, the scanning speed of voltage is 50mV s-1.Contain MnO using what such as embodiment 1 was prepared2The three-dimensional electricity of nano-nail array
The advantage of the electrode that pole material the is formed potential difference range different with CCG electrode, the potential window of the supercapacitor of the present embodiment
1.8V (stable potential window: voltage range 0.0V~0.8V, the CCG electrode of three-dimensional manganese oxide nano-nail electrode can be reached
Voltage range 0.0V~-1.0V).Due to supercapacitor energy density and voltage it is square directly proportional,
Therefore the supercapacitor of the present embodiment has biggish potential window, is conducive to increase energy density.
Fig. 6 shows the energy density of the supercapacitor of the present embodiment and the graph of relation of potential window.Such as Fig. 6 institute
Show, as voltage range increases to 1.8V from 1V, energy density is accordingly from 3.82Wh Kg-1Increase to 20.01Wh Kg-1, energy
Metric density can increase to 424%.And high operating voltage means to reach after only needing less supercapacitor combination
To required output voltage.
Fig. 7 shows CV curve graph of the supercapacitor of the present embodiment under different voltage scan rates.Wherein, electric
Press 10~100 mV s of scanning speed-1, operating voltage window is 0~1.8 V.As can see from Figure 7, all CV curves with
Sweep the increase of speed and still maintain nearly rectangular shape (even if increasing to 100 mV s when sweep speed-1), this illustrates the super capacitor
Device has quick charge-discharge characteristic and high energy density.
Fig. 8 shows specific discharge capacity curve of the supercapacitor of the present embodiment under different voltage scan rates
Figure.As shown in figure 8, when voltage scan rate is respectively 10,20,50,80 and 100 mV S-1When, the supercapacitor is corresponding
Specific discharge capacity be 58.78,52.41,44.47,41 and 39.91 F g-1.The reduction of specific discharge capacity is because sweeping in height
It retouches under speed, electrolyte ion, which is diffused into, to be obstructed so that the electrode material on only surface is used to charge and discharge at the trough of nano-nail
Caused by electricity.But the supercapacitor of the present embodiment, in 100 mV s of voltage scan rate-1, specific discharge capacity also it is poor not
Up to 40 F g-1, this also illustrates that the supercapacitor has superior performance.
Fig. 9 shows charging and discharging curve figure of the supercapacitor of the present embodiment under different current densities, wherein work
Make voltage window be 0~1.8 V when.As it can be seen in figure 9 that all charging curves and discharge curve all almost show phase
With trend and be all the time linear function, it is good that these results all illustrate that the supercapacitor of the present embodiment is shown
Chemical property, small equivalent resistance and ideal capacitance characteristic.
Figure 10 shows the supercapacitor of the present embodiment in different current densities and corresponding specific discharge capacity curve
Figure.As shown in Figure 10, when current density is 1 Ag-1When, the specific discharge capacity of the supercapacitor is about 53F g-1It is (corresponding
Energy density is about 23.02 Wh Kg-1), even if when current density increases to 40 A g-1When, the mass ratio of the supercapacitor
Capacity is still able to maintain higher level, about 14F g-1(corresponding energy density is about 6.57 Wh Kg-1)。
Figure 11 shows the power density of the supercapacitor of the present embodiment and the graph of relation of energy density.From Figure 11
In it can be seen that, the supercapacitor can obtain higher energy density and power density decline it is slower.For example, as worked as function
Rate density is 59130 W Kg-1When, energy density still can reach 6.57 WhKg-1.And when power density is 947.11 W Kg-1(current density is 1 A g-1) when, energy density reaches 23.02 Wh Kg of maximum value-1, it is far longer than power vapour of new generation
Energy density needed for vehicle, this shows that it can meet the application of hybrid vehicle.
Figure 12 shows the cycle-index of the supercapacitor of the present embodiment and the graph of relation of capacity retention ratio,
In, the current density of charge and discharge is 2 A g-1.As can see from Figure 12, the supercapacitor is after circulation 10000 times, capacitor
Amount is almost without decaying.Good cyclical stability is measurement index important in supercapacitor practical application.
In conclusion three-diemsnional electrode material provided in an embodiment of the present invention is prepared by aluminum oxide template fabricated in situ
Contain MnO2The three-diemsnional electrode material of nano-nail array improves electrode conductivuty, increases active contacts area, thus
Promote energy density.The electrode material is applied in solid supercapacitor, improves the area specific capacitance of capacitor, also improves
The multiplying power property and cycle performance of capacitor.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
For member, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications are also answered
It is considered as the protection scope of the application.
Claims (10)
1. a kind of three-diemsnional electrode material characterized by comprising successively use anode oxidation process and etching technics on aluminium foil
The Al nano-nail array that growth in situ is formed；The nickel layer formed on the Al nano-nail array；It is formed on the nickel layer
MnOx nano-nail array, wherein x=1~2.
2. three-diemsnional electrode material according to claim 1, which is characterized in that the length of the Al nano-nail is 1~3 μm,
Diameter is 300~500nm, and the spacing of two neighboring Al nano-nail is 1~1.2 μm；The MnOxThe length of nano-nail be 1~
3.5 μm, diameter is 400~600nm, two neighboring MnOxThe spacing of nano-nail is 1~1.2 μm.
3. three-diemsnional electrode material according to claim 1, which is characterized in that the specific surface area of the three-diemsnional electrode material is
100~200m2/g。
4. three-diemsnional electrode material according to claim 1, which is characterized in that the nickel layer with a thickness of 100~500nm.
5. the preparation method of the three-diemsnional electrode material as described in claim 1-4 is any, which is characterized in that comprising steps of
S101, the Al nano-nail array grown on aluminium foil using anode oxidation process and etching technics；
S102, using magnetron sputtering technique in one nickel layer of Al nano-nail array growth；
S103, MnO is grown on the nickel layer using three electrode electrodeposition technologiesxNano-nail array obtains the three-diemsnional electrode material
Material.
6. the preparation method of three-diemsnional electrode material according to claim 5, which is characterized in that step S101 is specifically included:
Firstly, using aluminium foil be anode, carbon-point is put into electrolyte as cathode and carries out anodic oxidation；Wherein, the electrolyte is body
Product ratio is the mixed solution of citric acid solution and ethylene glycol that the mass fraction of 1:1~1.5 is 3~5%, the voltage of anodic oxidation
For the direct current of 350~400V, the temperature of electrolyte is 25~28 DEG C, and the time of anodic oxidation is 7~13h；
Then, the aluminium foil after anodic oxidation is immersed in the mixing containing 5.8~6.4wt% phosphoric acid and 1.6~2.0wt% chromic acid
In solution, 60~90min is etched under conditions of temperature is 63~90 DEG C, obtains the Al nano-nail array.
7. the preparation method of three-diemsnional electrode material according to claim 5 or 6, which is characterized in that step S101 further includes
The aluminium foil is successively cleaned using acetone and isopropanol.
8. the preparation method of three-diemsnional electrode material according to claim 5, which is characterized in that step S103 is specifically included:
The aluminium foil for completing nickel layer is grown as working electrode using step S102, using three electrode electrodeposition technologies, is with saturated calomel electrode
Reference electrode, with Pt be to electrode, with 0.5~1M MnSO4With 0.5~1MCH3The aqueous solution of COONa is electrolyte, in area
Electric current is 0.3~0.5mA cm-2Under conditions of react 5~20min, the MnO is obtained on the nickel layerxNano-nail array.
9. a kind of solid supercapacitor, which is characterized in that the poly terephthalic acid second two of the metal spraying including the setting of successively lamination
Alcohol ester film, first electrode, second electrode, first electrode and metal spraying pet film；Wherein, institute
Stating first electrode is to prepare the electrode formed by any three-diemsnional electrode material of claim 1-4, and the second electrode is
CCG electrode is stained with gel electrolyte in the first electrode and second electrode.
10. solid supercapacitor according to claim 9, which is characterized in that the gel electrolyte is that mass ratio is
The sodium sulphate and polyvinyl alcohol of 1:0.8~1.2 are dissolved in the water to prepare and be formed.
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| CN101618854A (en) * | 2009-05-22 | 2010-01-06 | 哈尔滨工程大学 | Preparation method of one-dimensional MnO2 nanometer array structure |
| CN102903532A (en) * | 2012-11-06 | 2013-01-30 | 东华大学 | Method for preparing super capacitor material with hierarchical hetero-structure of growing MnO2 nanorod on Co3O4-Au nanosheet |
| CN103426644A (en) * | 2012-12-10 | 2013-12-04 | 中国石油大学(华东) | ZnO-based three-dimensional ordered-structure conductive substrate and preparation method thereof |
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