CN105355463A - Flexible supercapacitor electrode and device preparation method - Google Patents
Flexible supercapacitor electrode and device preparation method Download PDFInfo
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- CN105355463A CN105355463A CN201510755898.8A CN201510755898A CN105355463A CN 105355463 A CN105355463 A CN 105355463A CN 201510755898 A CN201510755898 A CN 201510755898A CN 105355463 A CN105355463 A CN 105355463A
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Abstract
The invention provides a flexible supercapacitor electrode and a device preparation method, belonging to the technical field of function device preparation. Firstly, an alkaline buffer liquid, a dilute acid, an organic solvent, an acid liquid, an anhydrous ethanol, and deionized water to orderly used to wash a porous metal sheet, and the drying is carried out. The washed porous metal sheet is subjected to 2 to 5 MPa pressure for 3 to 6 minutes, and the pressed porous metal sheet is immersed in a corresponding reaction solution for use. The porous metal sheet immersed in the reaction solution is taken, an active material is grown on the porous metal sheet, and the drying is carried out to obtain the flexible supercapacitor electrode. According to the invention, the sequence opposite to a traditional method is employed, firstly the washed porous metal sheet is subjected to compression, then the active material is grown on the porous metal sheet, the porosity of the pressed porous metal sheet is reduced, the growth of the active material is only carried out at the surface of the porous metal sheet, thus the flexibility of the porous metal sheet is maintained well, and the porous metal sheet can be widely applied to flexible electronic equipment.
Description
Technical field
The invention belongs to function element preparing technical field, be specifically related to a kind of based on the electrode of super capacitor of perforated metal sheet substrate and the preparation method of device.
Background technology
Ultracapacitor (supercapacitor), be between battery and traditional capacitor, can fast charging and discharging, energy-storage travelling wave tube based on Cathode/Solution Interface electrochemical process.Owing to having high energy density, longer service life cycle, environmental friendliness and fail safe advantages of higher, ultracapacitor has been widely used in the fields such as traffic, mobile communication, information technology, Aero-Space.Along with the generation of more and more wearable Novel electronic devices that maybe can reel, such as Electronic Paper, collapsible display and other multimedia devices etc., demand for flexible energy storage device is also more and more urgent, and thus the research of flexible super capacitor is more and more subject to the attention of researcher.Compared with conventional Super capacitor, flexible super capacitor not only needs electrode material to have good chemical property, the more important thing is the performance that the electrode material that needs to be applied to flexible super capacitor has all kept under the state such as bending or folding.
In order to realize the bend resistance performance of flexible super capacitor, need choose and there is good pliability, conductivity and have the flexible substrate of better adhesion with active material.Perforated metal sheet covers layer of metal by physics or chemical method on porous substrate material surface and inside, then porous substrate material and the poroid metal material of a class that obtains is removed, it has good conductivity and pliability, has been widely used in the preparation of flexible super capacitor.At present, when preparing the electrode of super capacitor based on perforated metal sheet, be elder generation's growth activity material on the perforated metal sheet cleaned up, then compressing tablet obtains electrode of super capacitor.But, owing to there is larger hole in perforated metal sheet, reaction dissolvent in growth activity substance process easily enters hole inside and reacts with metal material, affects the pliability of perforated metal substrate, thus limits the extensive use of poroid sheet metal in flexible energy storage device field.
Summary of the invention
The present invention is directed to the defect that background technology exists, propose a kind of based on the electrode of super capacitor of perforated metal sheet substrate and the preparation method of device.The present invention is by changing the compacting order of poroid sheet metal in electrode production process, before growth activity material, perforated metal sheet is suppressed, reduce aperture and the porosity of perforated metal sheet, avoid the reaction of reaction dissolvent and internal metallic material, make its pliability obtain good maintenance, and the chemical property of the ultracapacitor obtained also have larger lifting.
Technical scheme of the present invention is as follows:
A preparation method for flexible super capacitor electrode, comprises the following steps:
The cleaning of step 1, perforated metal sheet: adopt alkaline buffer to remove in perforated metal sheet surface oxide layer, diluted acid successively and alkaline buffer and remove oxide layer further, organic solvent removes surperficial grease, acid solution and thoroughly removes oxide layer and strengthen surface reaction activity, absolute ethyl alcohol and deionized water and remove surface cleaning agent, then dry;
The compacting of step 2, perforated metal sheet: the perforated metal sheet after cleaning step 1 carries out compression process, and pressure size is 2-5MPa, and pressing time is 3-6min; Perforated metal sheet after compacting is soaked in corresponding reaction dissolvent stand-by;
The growth of step 3, active material: get the perforated metal sheet be soaked in reaction dissolvent, growth activity material on perforated metal sheet, dry, obtain flexible super capacitor electrode of the present invention.
Further, described in step 1, perforated metal sheet is foam metal, filter screen metal etc., and described foam metal is nickel foam, Foam silver etc.
Further, alkaline buffer described in step 1 is NaOH-Na
2cO
3, Na
2cO
3-NaHCO
3deng; Described diluted acid is watery hydrochloric acid, dilute sulfuric acid etc.; Described organic solvent is ethylene glycol, glycerol etc., and described acid solution is hydrochloric acid, sulfuric acid etc.
Further, thoroughly oxide layer is removed described in step 1 and the concentration strengthening the acid solution of surface reaction activity is 2 times of dilute acid concentration.
Further, the solvent adopted when the corresponding reaction dissolvent of step 2 is step 3 growth activity material, is specially ethylene glycol, ethylenediamine etc.
Further, described in step 3, on perforated metal sheet, growth activity material can adopt the methods such as hydro thermal method, solvent-thermal method, galvanoplastic; Described active material is the composite material etc. of the composite material of the composite material of carbon-based material, conducting polymer, transistion metal compound, conducting polymer and material with carbon element, conducting polymer and transition metal oxide, material with carbon element and transition metal oxide, is specially Graphene, MnO
2, PANI etc.
Further, active material perforated metal sheet described in step 3 grown is homogenous material or two or more materials; When preparing the active material be made up of two or more material, the general method of point one-step growth that adopts obtains.
A preparation method for flexible super capacitor, comprises the following steps:
The cleaning of step 1, perforated metal sheet: adopt alkaline buffer to remove in perforated metal sheet surface oxide layer, diluted acid successively and alkaline buffer and remove oxide layer further, organic solvent removes surperficial grease, acid solution and thoroughly removes oxide layer and strengthen surface reaction activity, absolute ethyl alcohol and deionized water and remove surface cleaning agent, then dry;
The compacting of step 2, perforated metal sheet: the perforated metal sheet after cleaning step 1 carries out compression process, and pressure size is 2-5MPa, and pressing time is 3-6min; Perforated metal sheet after compacting is soaked in corresponding reaction dissolvent stand-by;
The growth of step 3, active material: get the perforated metal sheet be soaked in reaction dissolvent, growth activity material on perforated metal sheet, dry, obtain flexible super capacitor electrode of the present invention;
Step 4: growth step 3 obtained has the perforated metal sheet of active material as upper/lower electrode, the perforated metal sheet of active material, barrier film and growth there is is to have the perforated metal sheet of active material to stack growth in accordance with the order from top to bottom, then electrolyte is injected, air locking, namely obtains flexible super capacitor of the present invention.
Further, described in step 1, perforated metal sheet is foam metal, filter screen metal etc., and described foam metal is nickel foam, Foam silver etc.
Further, alkaline buffer described in step 1 is NaOH-Na
2cO
3, Na
2cO
3-NaHCO
3deng; Described diluted acid is watery hydrochloric acid, dilute sulfuric acid etc.; Described organic solvent is ethylene glycol, glycerol etc., and described acid solution is hydrochloric acid, sulfuric acid etc.
Further, thoroughly oxide layer is removed described in step 1 and the concentration strengthening the acid solution of surface reaction activity is 2 times of dilute acid concentration.
Further, the solvent adopted when the corresponding reaction dissolvent of step 2 is step 3 growth activity material, is specially ethylene glycol, ethylenediamine etc.
Further, described in step 3, on perforated metal sheet, growth activity material can adopt the methods such as hydro thermal method, solvent-thermal method, galvanoplastic; Described active material is the composite material etc. of the composite material of the composite material of carbon-based material, conducting polymer, transistion metal compound, conducting polymer and material with carbon element, conducting polymer and transition metal oxide, material with carbon element and transition metal oxide, is specially Graphene, MnO
2, PANI etc.
Further, active material perforated metal sheet described in step 3 grown is homogenous material or two or more materials; When preparing the active material be made up of two or more material, the general method of point one-step growth that adopts obtains.
Further, electrolyte described in step 4 is ultracapacitor common electrolyte, as gel electrolyte, liquid electrolyte or ionic liquid etc., is specially KOH, Na
2sO
4, H
2sO
4, PVA – H
3pO
4deng.
Beneficial effect of the present invention is:
1, the order that employing of the present invention is contrary with conventional method, namely first compression process is carried out to perforated metal sheet, and then growth activity material thereon, perforated metal sheet porosity after compacting reduces, the growth of active material is only carried out on perforated metal sheet surface, make the flexibility of perforated metal sheet obtain good maintenance, can be widely used in flexible electronic devices.And conventional method is when the perforated metal sheet superficial growth active material do not suppressed, because perforated metal sheet has larger porosity and aperture, reaction dissolvent can enter poroid sheet metal inside and react, destroy the structure of perforated metal sheet inside, the perforated metal sheet pliability of the band active material obtained reduces greatly.
2, the present invention had carried out thorough cleaning to perforated metal sheet and has been stored in follow-up reaction dissolvent before growth activity material, and this avoids the oxidation of perforated metal sheet on the one hand, improves the uniformity and adhesion that are grown on active material on perforated metal sheet; On the other hand, adopt the process of vacuum drying chamber drying before it also avoid use, simplify step, reduce cost.
Accompanying drawing explanation
Fig. 1 is the structural representation assembling the ultracapacitor obtained after flexibility provided by the invention poroid sheet metal growth activity material, wherein perforated metal sheet (the long perforated metal part having active material of a representative of the 1 band active material obtained for the inventive method, b represents the perforated metal part of not long acting material), 3 for being soaked with the barrier film of electrolyte;
Fig. 2 is the structural representation assembling the ultracapacitor obtained after conventional flex perforated metal sheet growth activity material, the wherein perforated metal sheet of the 2 band active materials obtained for conventional method, and 3 for being soaked with the barrier film of electrolyte;
Fig. 3 is the cyclic voltammetry curve comparison diagram of the flexible super capacitor electrode that embodiment 1 and comparative example 1 obtain;
Fig. 4 is the cyclic voltammetry curve comparison diagram of the flexible super capacitor electrode that embodiment 2 and comparative example 2 obtain.
Embodiment
Below in conjunction with drawings and Examples in detail, technical scheme of the present invention is described in detail.
Embodiment 1
The poroid sheet metal of the flexibility adopted in the present embodiment is nickel foam, and this nickel foam is commercially available nickel foam, has good conductivity, pliability and reactivity.
A preparation method for flexible super capacitor electrode, comprises the following steps:
The cleaning of step 1, nickel foam: the nickel foam (0.1600g) of getting 2cm × 2cm, adopts mass fraction to be 5%NaOH and 5%Na successively
2cO
3alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethanol, deionized water ultrasonic cleaning is carried out to nickel foam, the ultrasonic time of each cleaning agent is 10min, dries;
The compacting of step 2, nickel foam: the nickel foam after adopting tablet press machine to clean step 1 carries out compression process, and pressure is 2MPa, and pressing time is 4min; Nickel foam after compacting is soaked in ethylene glycol stand-by;
The growth of step 3, active material: get the nickel foam be soaked in ethylene glycol, carries out the growth of active material thereon; Detailed process is: in 8mL ethylene glycol, add 0.0800g selenium powder, stir, and then adds 8mL anhydrous ethylenediamine, stirs 30min, obtains mixed liquor; Be transferred to by mixed liquor in polytetrafluoroethylene reactor, then put into the nickel foam that step 2 is stored in ethylene glycol solution, then hydro-thermal reaction 24h at 140 DEG C, after having reacted, naturally cools to room temperature; After taking out reaction, growth has the nickel foam of active material, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 70 DEG C of dry 6h, namely obtain the nickel foam being with NiSe active material.
A preparation method for flexible super capacitor, comprises the following steps:
The cleaning of step 1, nickel foam: the nickel foam (0.1600g) of getting 2cm × 2cm, adopts mass fraction to be 5%NaOH and 5%Na successively
2cO
3alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethanol, deionized water ultrasonic cleaning is carried out to nickel foam, the ultrasonic time of each cleaning agent is 10min, dries;
The compacting of step 2, nickel foam: the nickel foam after adopting tablet press machine to clean step 1 carries out compression process, and pressure is 2MPa, and pressing time is 4min; Nickel foam after compacting is soaked in ethylene glycol stand-by;
The growth of step 3, active material: get the nickel foam be soaked in ethylene glycol, carries out the growth of active material thereon; Detailed process is: in 8mL ethylene glycol, add 0.0800g selenium powder, stir, and then adds 8mL anhydrous ethylenediamine, stirs 30min, obtains mixed liquor; Be transferred to by mixed liquor in polytetrafluoroethylene reactor, then put into the nickel foam that step 2 is stored in ethylene glycol solution, then hydro-thermal reaction 24h at 140 DEG C, after having reacted, naturally cools to room temperature; After taking out reaction, growth has the nickel foam of active material, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 70 DEG C of dry 6h, namely obtain the nickel foam being with NiSe active material;
Step 4: the nickel foam of band NiSe active material step 3 obtained is as upper/lower electrode, in accordance with the order from top to bottom the nickel foam of the nickel foam of band NiSe active material, filter paper barrier film and band NiSe active material is stacked, then electrolyte is injected, air locking, namely obtains flexible super capacitor of the present invention.
Comparative example 1
Adopt conventional method to be that flexible super capacitor is prepared in substrate with nickel foam, specifically comprise the following steps:
The cleaning of step 1, nickel foam: the nickel foam (0.1600g) of getting 2cm × 2cm, watery hydrochloric acid, acetone, deionized water is adopted to carry out ultrasonic cleaning to nickel foam successively, the ultrasonic time of each cleaning agent is 10min, then dry in vacuum drying chamber;
The growth of step 2, active material: clean growth activity material in also dry nickel foam in step 1; Detailed process is: in 8mL ethylene glycol, add 0.0800g selenium powder, stir, and then adds 8mL anhydrous ethylenediamine, stirs 30min, obtains mixed liquor; Be transferred to by mixed liquor in polytetrafluoroethylene reactor, then put into the nickel foam that step 1 cleans also drying, then hydro-thermal reaction 24h at 140 DEG C, after having reacted, naturally cools to room temperature; After taking out reaction, growth has the nickel foam of active material, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 70 DEG C of dry 6h, namely obtain the flexible super capacitor electrode based on foam nickel base;
Step 3, employing tablet press machine have the nickel foam of active material to carry out compression process to step 2 growth, and pressure is 2MPa, and pressing time is 4min;
Step 4: using the nickel foam of the band active material after step 3 is suppressed as upper/lower electrode, in accordance with the order from top to bottom the nickel foam of the nickel foam of band active material, filter paper barrier film and band active material is stacked, then inject electrolyte, air locking, obtain described flexible super capacitor.
Fig. 3 is the cyclic voltammetry curve comparison diagram of the flexible super capacitor electrode that embodiment 1 and comparative example 1 obtain; The electrode of super capacitor that the electrode of super capacitor obtained using embodiment 1 respectively and comparative example 1 obtain is as work electrode, and in 6MKOH solution, adopt two-probe method to carry out cyclic voltammetry, wherein scanning voltage is 0 ~ 0.8V, and sweep speed is 5mV/s.Due under same scan speed, the graphics area that cyclic voltammetry curve surrounds is larger, and capacitive property is better; As shown in Figure 3, under same scan speed, the area of area ratio comparative example 1 cyclic voltammetry curve of the cyclic voltammetry curve of embodiment 1 electrode is large, shows that the flexible super capacitor that embodiment 1 obtains has better performance.
Embodiment 2
The poroid sheet metal of the flexibility adopted in the present embodiment is nickel foam, and this nickel foam is commercially available nickel foam, has good conductivity, pliability and reactivity.
To prepare NiSe, NiCo in foam nickel base
2s
4for the electrode of super capacitor of active material is example, comprise the following steps:
The cleaning of step 1, nickel foam: the nickel foam (0.1600g) of getting 2cm × 2cm, adopts mass fraction to be 5%NaOH and 5%Na successively
2cO
3alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethanol, deionized water ultrasonic cleaning is carried out to nickel foam, the ultrasonic time of each cleaning agent is 10min, dries;
The compacting of step 2, nickel foam: the nickel foam after adopting tablet press machine to clean step 1 carries out compression process, and pressure is 2MPa, and pressing time is 4min; Nickel foam after compacting is soaked in ethylene glycol stand-by;
The growth of step 3, NiSe active material: get the nickel foam be soaked in ethylene glycol, carries out the growth of active material thereon; Detailed process is: in 8mL ethylene glycol, add 0.0800g selenium powder, stir, and then adds 8mL anhydrous ethylenediamine, stirs 30min, obtains mixed liquor; Be transferred to by mixed liquor in polytetrafluoroethylene reactor, then put into the nickel foam that step 2 is stored in ethylene glycol solution, then hydro-thermal reaction 24h at 140 DEG C, after having reacted, naturally cools to room temperature; After taking out reaction, growth has the nickel foam of active material, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 70 DEG C of dry 6h, namely obtain the nickel foam being with NiSe active material;
Step 4, NiCo
2s
4the growth of active material: the nickel foam of the band NiSe active material obtained in step 3 grows NiCo
2s
4active material, detailed process is: by 54.525mgNi (NO
3)
26H
2o, 109.136mgCo (NO
3)
26H
2o, 157.714mgHMT (ring pregnancy four hexamine) add in 75mL deionized water, stir 30min, obtain mixed liquor; Mixed liquor is transferred in polytetrafluoroethylene reactor, put into the nickel foam of the band NiSe active material that step 3 obtains again, then hydro-thermal reaction 8h at 95 DEG C, after having reacted, naturally cool to room temperature, namely in the nickel foam of band NiSe active material, obtain nickel cobalt precursor, take out, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 60 DEG C of dry 5h; By 45.034mgNa
2s9H
2o is dissolved in 75mL deionized water, stirs 30min, obtains Na
2s solution; By Na
2s solution is transferred in polytetrafluoroethylene reactor, put into the nickel foam of band nickel cobalt precursor obtained above and NiSe active material again, then hydro-thermal reaction 8h at 120 DEG C, after having reacted, naturally cool to room temperature, namely in the nickel foam of band NiSe active material, obtain NiCo
2s
4active material, takes out, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 60 DEG C of dry 5h, namely obtaining growth has NiSe and NiCo
2s
4the nickel foam of two kinds of active materials.
Band NiSe, NiCo
2s
4the nickel foam of active material is the preparation method of the flexible super capacitor of electrode, comprises the following steps:
The cleaning of step 1, nickel foam: the nickel foam (0.1600g) of getting 2cm × 2cm, adopts mass fraction to be 5%NaOH and 5%Na successively
2cO
3alkaline buffer solution, 3M hydrochloric acid, acetone, 6M hydrochloric acid, ethanol, deionized water ultrasonic cleaning is carried out to nickel foam, the ultrasonic time of each cleaning agent is 10min, dries;
The compacting of step 2, nickel foam: the nickel foam after adopting tablet press machine to clean step 1 carries out compression process, and pressure is 2MPa, and pressing time is 4min; Nickel foam after compacting is soaked in ethylene glycol stand-by;
The growth of step 3, NiSe active material: get the nickel foam be soaked in ethylene glycol, carries out the growth of active material thereon; Detailed process is: in 8mL ethylene glycol, add 0.0800g selenium powder, stir, and then adds 8mL anhydrous ethylenediamine, stirs 30min, obtains mixed liquor; Be transferred to by mixed liquor in polytetrafluoroethylene reactor, then put into the nickel foam that step 2 is stored in ethylene glycol solution, then hydro-thermal reaction 24h at 140 DEG C, after having reacted, naturally cools to room temperature; After taking out reaction, growth has the nickel foam of active material, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 70 DEG C of dry 6h, namely obtain the nickel foam being with NiSe active material;
Step 4, NiCo
2s
4the growth of active material: the nickel foam of the band NiSe active material obtained in step 3 grows NiCo
2s
4active material, detailed process is: by 54.525mgNi (NO
3)
26H
2o, 109.136mgCo (NO
3)
26H
2o, 157.714mgHMT (ring pregnancy four hexamine) add in 75mL deionized water, stir 30min, obtain mixed liquor; Mixed liquor is transferred in polytetrafluoroethylene reactor, put into the nickel foam of the band NiSe active material that step 3 obtains again, then hydro-thermal reaction 8h at 95 DEG C, after having reacted, naturally cool to room temperature, namely in the nickel foam of band NiSe active material, obtain nickel cobalt precursor, take out, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 60 DEG C of dry 5h; By 45.034mgNa
2s9H
2o is dissolved in 75mL deionized water, stirs 30min, obtains Na
2s solution; By Na
2s solution is transferred in polytetrafluoroethylene reactor, put into the nickel foam of band nickel cobalt precursor obtained above and NiSe active material again, then hydro-thermal reaction 8h at 120 DEG C, after having reacted, naturally cool to room temperature, namely in the nickel foam of band NiSe active material, obtain NiCo
2s
4active material, takes out, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 60 DEG C of dry 5h, namely obtaining growth has NiSe and NiCo
2s
4the nickel foam of two kinds of active materials;
Step 5: growth step 4 obtained has NiSe and NiCo
2s
4growth, as upper/lower electrode, is had NiSe and NiCo by the nickel foam of two kinds of active materials in accordance with the order from top to bottom
2s
4the nickel foam of two kinds of active materials, filter paper barrier film and growth have NiSe and NiCo
2s
4the nickel foam of two kinds of active materials stacks, and then injects electrolyte, air locking, namely obtains flexible super capacitor of the present invention.
Comparative example 2
Adopt conventional method preparation to be with NiSe, NiCo
2s
4the nickel foam of active material is the flexible super capacitor of electrode, specifically comprises the following steps:
The cleaning of step 1, nickel foam: the nickel foam (0.1600g) of getting 2cm × 2cm, watery hydrochloric acid, acetone, deionized water is adopted to carry out ultrasonic cleaning to nickel foam successively, the ultrasonic time of each cleaning agent is 10min, then dry in vacuum drying chamber;
The growth of step 2, NiSe active material: clean in step 1 and dry nickel foam grows NiSe active material, detailed process is: in 8mL ethylene glycol, add 0.0800g selenium powder, stir, and then adds 8mL anhydrous ethylenediamine, stir 30min, obtain mixed liquor; Be transferred to by mixed liquor in polytetrafluoroethylene reactor, then put into the nickel foam that step 1 cleans also drying, then hydro-thermal reaction 24h at 140 DEG C, after having reacted, naturally cools to room temperature; After taking out reaction, growth has the nickel foam of active material, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 70 DEG C of dry 6h, namely obtain the nickel foam being with NiSe active material;
Step 3, NiCo
2s
4the growth of active material: the nickel foam of the band NiSe active material obtained in step 2 grows NiCo
2s
4active material, detailed process is: by 54.5250mgNi (NO
3)
26H
2o, 109.1360mgCo (NO
3)
26H
2o, 157.714mgHMT (ring pregnancy four hexamine) add in 75mL deionized water, stir 30min, obtain mixed liquor; Mixed liquor is transferred in polytetrafluoroethylene reactor, put into the nickel foam of the band NiSe active material that step 2 obtains again, then hydro-thermal reaction 8h at 95 DEG C, after having reacted, naturally cool to room temperature, namely in the nickel foam of band NiSe active material, obtain nickel cobalt precursor, take out, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 60 DEG C of dry 5h; By 45.0340mgNa
2s9H
2o is dissolved in 75mL deionized water, stirs 30min, obtains Na
2s solution; By Na
2s solution is transferred in polytetrafluoroethylene reactor, put into the nickel foam of band nickel cobalt precursor obtained above and NiSe active material again, then hydro-thermal reaction 8h at 120 DEG C, after having reacted, naturally cool to room temperature, namely in the nickel foam of band NiSe active material, obtain NiCo
2s
4active material, takes out, adopt deionized water and 95% ethanol replace cleaning 5 times after, be placed in drying box 60 DEG C of dry 5h, namely obtaining growth has NiSe and NiCo
2s
4the nickel foam of two kinds of active materials;
Step 4, employing tablet press machine have NiSe and NiCo to the growth that step 3 obtains
2s
4the nickel foam of two kinds of active materials carries out compression process, and pressure is 2MPa, and pressing time is 4min;
Step 5, step 4 is suppressed after band NiSe and NiCo
2s
4the nickel foam of two kinds of active materials as upper/lower electrode, in accordance with the order from top to bottom by compacting after band NiSe and NiCo
2s
4band NiSe and NiCo after the nickel foam of two kinds of active materials, filter paper barrier film and compacting
2s
4the nickel foam of two kinds of active materials stacks, and then injects electrolyte, air locking, obtains described flexible super capacitor.
Fig. 4 is the cyclic voltammetry curve comparison diagram of the flexible super capacitor electrode that embodiment 2 and comparative example 2 obtain; The electrode of super capacitor that the electrode of super capacitor obtained using embodiment 2 respectively and comparative example 2 obtain is as work electrode, and in 6MKOH solution, adopt two-probe method to carry out cyclic voltammetry, wherein scanning voltage is 0 ~ 0.8V, and sweep speed is 5mV/s.Due under same scan speed, the graphics area that cyclic voltammetry curve surrounds is larger, and capacitive property is better; As shown in Figure 4, under same scan speed, the area of area ratio comparative example 2 cyclic voltammetry curve of the cyclic voltammetry curve of embodiment 2 electrode is large, shows that the flexible super capacitor that embodiment 2 obtains has better performance.
Fig. 1 and Fig. 2 is respectively the structural representation of the flexible super capacitor that the present invention and conventional method obtain; From Fig. 1 and Fig. 2, the flexible super capacitor electrode that the present invention obtains, only has active material in the superficial growth of perforated metal sheet, and the flexibility of internal pore sheet metal obtains good maintenance, contributes to improving its pliability; And the flexible super capacitor electrode that conventional method obtains, because perforated metal sheet has larger porosity and aperture, it is inner that reaction dissolvent can enter poroid sheet metal, perforated metal sheet surface and inside are all grown and has active material, destroy the structure of perforated metal sheet inside, the perforated metal sheet pliability of the band active material obtained reduces greatly.
The order that employing of the present invention is contrary with conventional method, namely first compression process is carried out to perforated metal sheet, and then growth activity material thereon, perforated metal sheet porosity after compacting reduces, the growth of active material is only carried out on perforated metal sheet surface, make the pliability of perforated metal sheet obtain good maintenance, can be widely used in flexible electronic devices; Before growth activity material, thorough cleaning carried out to perforated metal sheet and be stored in follow-up reaction dissolvent, the mode adopting solvent to completely cut off air preserves perforated metal sheet, avoid the oxidation of perforated metal sheet, improve the uniformity and adhesion that are grown on active material on perforated metal sheet; The inventive method is simple to operate, and cost is low, easily realizes industrialization large-scale production.
Claims (10)
1. a preparation method for flexible super capacitor electrode, comprises the following steps:
The cleaning of step 1, perforated metal sheet: adopt alkaline buffer to remove in perforated metal sheet surface oxide layer, diluted acid successively and alkaline buffer and remove oxide layer further, organic solvent removes surperficial grease, acid solution and thoroughly removes oxide layer and strengthen surface reaction activity, absolute ethyl alcohol and deionized water and remove surface cleaning agent, then dry;
The compacting of step 2, perforated metal sheet: the perforated metal sheet after cleaning step 1 carries out compression process, and pressure size is 2-5MPa, and pressing time is 3-6min; Perforated metal sheet after compacting is soaked in corresponding reaction dissolvent stand-by;
The growth of step 3, active material: get the perforated metal sheet be soaked in reaction dissolvent, growth activity material on perforated metal sheet, dry, obtain flexible super capacitor electrode of the present invention.
2. the preparation method of flexible super capacitor electrode according to claim 1, is characterized in that, perforated metal sheet described in step 1 is foam metal, filter screen metal.
3. the preparation method of flexible super capacitor electrode according to claim 2, is characterized in that, described foam metal is nickel foam, Foam silver.
4. the preparation method of flexible super capacitor electrode according to claim 1, is characterized in that, alkaline buffer described in step 1 is NaOH-Na
2cO
3, Na
2cO
3-NaHCO
3; Described diluted acid is watery hydrochloric acid, dilute sulfuric acid; Described organic solvent is ethylene glycol, glycerol, and described acid solution is hydrochloric acid, sulfuric acid.
5. the preparation method of flexible super capacitor electrode according to claim 1, is characterized in that, the concentration of acid solution described in step 1 is 2 times of dilute acid concentration.
6. the preparation method of flexible super capacitor electrode according to claim 1, is characterized in that, the solvent adopted when the corresponding reaction dissolvent of step 2 is step 3 growth activity material.
7. the preparation method of flexible super capacitor electrode according to claim 1, is characterized in that, described in step 3, on perforated metal sheet, the method for growth activity material is hydro thermal method, solvent-thermal method, galvanoplastic.
8. the preparation method of flexible super capacitor electrode according to claim 1, it is characterized in that, active material described in step 3 is the composite material of the composite material of the composite material of carbon-based material, conducting polymer, transistion metal compound, conducting polymer and material with carbon element, conducting polymer and transition metal oxide, material with carbon element and transition metal oxide.
9. the preparation method of flexible super capacitor electrode according to claim 1, is characterized in that, the active material that perforated metal sheet described in step 3 grows is homogenous material or two or more materials; When preparing the active material be made up of two or more material, the method for point one-step growth is adopted to obtain.
10. a preparation method for flexible super capacitor, comprises the following steps:
The cleaning of step 1, perforated metal sheet: adopt alkaline buffer to remove in perforated metal sheet surface oxide layer, diluted acid successively and alkaline buffer and remove oxide layer further, organic solvent removes surperficial grease, acid solution and thoroughly removes oxide layer and strengthen surface reaction activity, absolute ethyl alcohol and deionized water and remove surface cleaning agent, then dry;
The compacting of step 2, perforated metal sheet: the perforated metal sheet after cleaning step 1 carries out compression process, and pressure size is 2-5MPa, and pressing time is 3-6min; Perforated metal sheet after compacting is soaked in corresponding reaction dissolvent stand-by;
The growth of step 3, active material: get the perforated metal sheet be soaked in reaction dissolvent, growth activity material on perforated metal sheet, dry, obtain flexible super capacitor electrode of the present invention;
Step 4: growth step 3 obtained has the perforated metal sheet of active material as upper/lower electrode, the perforated metal sheet of active material, barrier film and growth there is is to have the perforated metal sheet of active material to stack growth in accordance with the order from top to bottom, then electrolyte is injected, air locking, namely obtains flexible super capacitor of the present invention.
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