CN108962629A - A kind of preparation method of flexible super capacitor - Google Patents
A kind of preparation method of flexible super capacitor Download PDFInfo
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- CN108962629A CN108962629A CN201810787022.5A CN201810787022A CN108962629A CN 108962629 A CN108962629 A CN 108962629A CN 201810787022 A CN201810787022 A CN 201810787022A CN 108962629 A CN108962629 A CN 108962629A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of preparation method of flexible super capacitor contains cellulose fibre, graphene oxide and silver ammonia complex (Ag (NH by the high speed rotation preparation of cooking machine rotor first using filter paper as fibrous raw material3)2OH mixed slurry), heats thereafter, and silver ammonia complex is reduced into silver nano-grain using the reproducibility of graphene oxide itself, at the same induced oxidation graphene, silver nano-grain, cellulose fibre three it is compound.Product forms cellulose/graphene oxide/silver nano-grain laminated film after Suction filtration device filters and is dehydrated and sufficiently washes, and then graphene oxide therein is reduced into graphene using hydrazine steam as reducing agent, cellulose/graphene/silver nano-grain fexible film with excellent electric conductivity and excellent electrochemical property can be obtained, then assembles the symmetrical all-solid-state flexible supercapacitor of high-energy density with it directly as positive and negative anodes and using polyvinyl alcohol/potassium chloride gel mould as electrolyte and diaphragm.
Description
Technical field
The invention belongs to the technical fields of advanced energy storage, and in particular to a kind of its preparation side of flexible super capacitor
Method.
Background technique
Electronic product such as wearable device, rollable display, foldable intelligent hand of the market to flexible portable of new generation
Machine, implantable medical chip, electronic skin etc. have urgent demand and expectation, and current energy supply and energy storage electronic equipment seem
It is heavy, blocked up, excessive to cross, and has been difficult to meet the requirement of this emerging field, is event, develops light and portable high-performance flexible storage
Energy system is imperative.In existing various energy storage systems, all-solid-state flexible supercapacitor because its fast charge/discharge speed,
High power density, wide operating temperature, good stability, the service life of length and outstanding safety and be concerned,
Especially graphene-based all-solid-state flexible supercapacitor develops rapidly in recent years, before having good development space and application
Scape.Regrettably, the energy storage characteristic of currently developed most all-solid-state flexible supercapacitors is still difficult to make us full
Meaning, for example specific capacitance is still smaller, energy density is not still high, high rate performance is also relatively poor.For this purpose, how by simply passing through
The method magnanimity preparation of Ji has the self-supporting fexible film of satisfactory electrical conductivity, and then constructs and provide excellent electrochemical behavior
All-solid-state flexible supercapacitor becomes where the difficulties and emphasis in current supercapacitor field.
Summary of the invention
It is an object of that present invention to provide a kind of preparation methods of the all-solid-state flexible supercapacitor of high-energy density.
The present invention is achieved by the following technical solutions:
A kind of preparation method of flexible super capacitor, first using filter paper as fibrous raw material, by cooking machine rotor
High speed rotation preparation contains cellulose fibre, graphene oxide and silver ammonia complex (Ag (NH3)2OH mixed slurry), thereafter plus
Heat treatment, is reduced into silver nano-grain, while induced oxidation stone for silver ammonia complex using the reproducibility of graphene oxide itself
Black alkene, silver nano-grain, cellulose fibre three it is compound.Product forms fine after Suction filtration device filters and is dehydrated and sufficiently washes
Element/graphene oxide/silver nano-grain laminated film is tieed up, and then using hydrazine steam as reducing agent by graphite oxide therein
Alkene is reduced into graphene, can obtain cellulose/graphene/silver nanoparticle with excellent electric conductivity and excellent electrochemical property
Grain fexible film, then assembled with it directly as positive and negative anodes and using polyvinyl alcohol/potassium chloride gel mould as electrolyte and diaphragm
The symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite of high-energy density out
Alkene/silver nano-grain].Specifically includes the following steps:
(1) filter paper is cut into after fragment and is added in cooking machine together with graphene oxide aqueous dispersions, turned using cooking machine
The high speed rotation of son smashes filter paper, and cellulose fibre+graphene oxide slurry is made.
(2) mixed slurry of step (1) is transferred in beaker, excessive concentration is added under quick magnetic agitation is
The silver ammino solution of 0.1-0.5M then heats to 70-90 DEG C and reacts 20-40min.In the process, silver ammonia complex is by oxygen
Graphite alkene is reduced into silver nano-grain, while it is compound to induce each component, and then generates cellulose/graphene oxide/silver nanoparticle
Particle composites.
(3) product of step (2) is filtered into funnel dehydration, forms cellulose/oxidation in Suction filtration device filter membrane surface
Graphene/silver nano-grain laminated film；Add water repeatedly after washes clean, by it under moisture state from filter membrane surface gently
Entirety is torn, and is transferred in reaction kettle, hanging to place；Then hydrazine hydrate is added in inner liner of reaction kettle bottom, postposition is sealed
8-24h is kept in 80-110 DEG C of baking oven, graphene oxide therein is thoroughly reduced into graphene using hydrazine steam.
(4) polyvinyl alcohol is added in water, heating stirring is allowed to dissolve, and the water of potassium chloride is then slowly added dropwise under stiring
Solution, cooled to room temperature, obtains polyvinyl alcohol/potassium chloride gel electrolyte of clear later.
(5) cellulose/graphene/silver nano-grain laminated film in step (3) is cut into rectangular slat, is placed in load
On slide, the polyvinyl alcohol in step (4)/potassium chloride gel electrolyte is then poured into its surface, leaving a blank region is used
It is connected in electrode holder, then allows in gel electrolyte excessive moisture slowly to volatilize and final gelatine at room temperature, formed
Gel mould.
(6) cellulose/graphene/silver nanometer particle film that gel mould is covered in identical two panels step (5) is direct
It is stacked together as flexible electrode, overlapping area is to be covered with the region of gel mould, forms the symmetrical of a high-energy density
All-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphene/silver nano-grain].
Preferably, in above-mentioned steps (1), graphene oxide: the mass ratio 5:95-70:30 of filter paper fibre cellulose fiber.
Preferably, silver nano-grain account for cellulose/graphene/silver nano-grain laminated film quality 10%-60%, into
One step preferably accounts for 50%.
It is further preferred that in above-mentioned steps (3), hydrazine hydrate and cellulose/graphene oxide/silver nano-grain THIN COMPOSITE
The mass ratio of film is 1:1.5-2.5.
Still more preferably, in above-mentioned steps (2), when the reaction temperature after silver ammino solution is added is preferably 85 DEG C, reaction
Between preferably 30min；In above-mentioned steps (3), the reaction temperature that hydrazine hydrate is added is preferably 90 DEG C, the reaction time is preferably 12h.
Further, the filter membrane in above-mentioned steps (3) in Suction filtration device is hydrophilic teflon membrane filter, a diameter of
11cm.Polyvinyl alcohol used is 1799 types in above-mentioned steps (4), i.e., the degree of polymerization is 1700, alcoholysis degree 99%.
Specifically, a kind of preparation method of flexible super capacitor, which is characterized in that it as follows:
(1) filter paper is cut into after fragment and is added in cooking machine together with graphene oxide aqueous dispersions, turned using cooking machine
The high speed rotation of son smashes filter paper, and cellulose fibre+graphene oxide slurry is made；The graphene oxide: filter paper fibre
The mass ratio 5:95-70:30 of cellulose fiber；
(2) mixed slurry of step (1) is transferred in beaker, 60mL concentration is added under quick magnetic agitation is
The brand-new silver ammino solution of 0.15M then heats to 85 DEG C and reacts 30min；
(3) by the product of step (2) in funnel rapid filtration under suction be dehydrated, in Suction filtration device filter membrane surface formed cellulose/
Graphene oxide/silver nano-grain laminated film.Add water repeatedly after washes clean, it is delayed under moisture state from filter membrane surface
Slow ground is whole to tear, and is transferred in the reaction kettle of 1000mL, hanging to place.Then 4mL water is added in inner liner of reaction kettle bottom
Hydrazine is closed, is sealed in the baking oven for be placed on 90 DEG C and keeps 12h, graphene oxide therein is thoroughly reduced into stone using hydrazine steam
Black alkene can synthesize cellulose/graphene with excellent electric conductivity/silver nano-grain self-supporting flexible composite film；
(4) 5g polyvinyl alcohol is added in 50mL water, is warming up to 90 DEG C, while stirring is allowed to dissolve.Then under stiring
2mL 1g mL is slowly added dropwise-1Potassium chloride aqueous solution, cooled to room temperature later, obtain the polyvinyl alcohol of clear/
Potassium chloride gel electrolyte；
(5) cellulose/graphene/silver nano-grain laminated film in step (3) is cut into rectangular slat, is placed in load
On slide, the polyvinyl alcohol in a small amount of step (4)/potassium chloride gel electrolyte is then poured into its surface, leaves a little sky
White region then allows excessive moisture in gel electrolyte slowly to volatilize and be finally gelled at room temperature for being connected with electrode holder
Change, forms gel mould；
(6) cellulose/graphene/silver nanometer particle film that gel mould is covered in identical two panels step (5) is direct
It being stacked together as flexible electrode, overlapping area is to be covered with the region of gel mould, the device finally is wound with preservative film,
Form the symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // fiber an of high-energy density
Element/graphene/silver nano-grain].
All-solid-state flexible supercapacitor [cellulose/graphite in order to prevent when the effect of preservative film in step (6) of the present invention
Alkene/silver nano-grain // cellulose/graphene/silver nano-grain] in the too fast volatilization of polyvinyl alcohol/potassium chloride gel mould moisture
And influence its chemical property.
The capacitor element carries out group as its positive and negative anodes using cellulose/graphene/silver nano-grain flexible composite film
Dress, using polyvinyl alcohol/potassium chloride gel mould as electrolyte and the effect of have both diaphragm, there is enough flexibilities, category
The energy storage mechnism of electric double layer capacitance characteristic, bending state do not influence its electrochemical behavior substantially, have high energy density
And high rate performance, it can be used using series and parallel and can be used to that miniaturized electronics be driven to work as power supply.
Self-supporting composite conductive thin film surface layer structure of the present invention is that silver nano-grain mutually tightly stacks the continuous of formation
Silver nano-grain film, inner layer is cellulose-graphene-silver nano-grain ingredient and cellulose fibre acts as skeleton, inside
Silver nano-grain by graphene wind and coat.Uniform component distribution, without clustering phenomena, good dispersion, film is opened without any
Split phenomenon；Silver nano-grain continuity is good, electric conductivity is excellent.
The invention has the following advantages:
1, the cellulose/graphene/silver nano-grain laminated film sheet resistance developed in the present invention is only 0.17 Ω sq-1, far below sheet resistance (the 1.46 Ω sq for the commercialization carbon cloth for being commonly used for flexible electrode collector-1) and other reports of disclosing
Being directly used as the sheet resistance of the graphene-based of flexible electrode, carbon nanotube base and conducting polymer based coextruded film, (these are compound
The sheet resistance of film is typically larger than 5 Ω sq-1), therefore conductive sexual clorminance is fairly obvious, being more suitable directly makes as flexible electrode
With.
2, previous in report, the electrochemical properties that most flexible electrodes measure under three-electrode system are difficult to enable
People is satisfied.For example its maximum area specific capacitance is often less than 1000mF cm-2, area ratio capacitance fade at higher current densities
Comparatively fast, high rate performance is poor, and 10% capacitance loss is also often had more than in the case where repeated charge is less than 5000 times.Phase
Than under, cellulose/graphene/silver nano-grain laminated film its maximum area specific capacitance developed in the present invention is up to
1242.7mFcm-2, possess good high rate performance, and in 60mAcm-2High current density under it is several after repeated charge 6000 times
Do not have capacitance loss (capacity retention is still up to 99.7%), illustrates the stability of fabulous cycle charge-discharge, thus
There is outstanding electrochemical performance.
3, symmetrical all-solid-state flexible supercapacitor constructed in the present invention [cellulose/graphene/silver nano-grain //
Cellulose/graphene/silver nano-grain] maximum area specific capacitance be 683.8mF cm-2, maximum energy-density is 95 μ Wh
cm-2, and its electrochemical behavior is had substantially no effect in the bent state, and the reported all-solid-state flexible super capacitor of the overwhelming majority
The maximum area specific capacitance of device is no more than 500mF cm-2, maximum energy-density is lower than 60 μ Wh cm-2, which reflects in the present invention
All-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphene/silver nano-grain] tool
There is apparent energy storage advantage.
4, symmetrical all-solid-state flexible supercapacitor constructed in the present invention [cellulose/graphene/silver nano-grain //
Cellulose/graphene/silver nano-grain] can be together in series or parallel use, for example several devices connected are fully charged
After can drive miniaturized electronics such as LED lamp bead, hand-held calculator, electronic watch etc. work normally.
5, cellulose/graphene/silver nano-grain laminated film synthetic method and corresponding symmetrical complete in the present invention
The assembling process of solid flexible supercapacitor is relatively simple to be easy, therefore, for its large scale preparation, development and application ten
Divide advantageous.
Detailed description of the invention
Fig. 1 is that electronics of the cellulose/graphene/silver nano-grain laminated film under nature and bending state shines
Piece.
Fig. 2 is cellulose/graphene/silver nano-grain laminated film X-ray diffractogram.
Fig. 3 is cellulose/graphene under different multiplying/silver nano-grain laminated film outer surface stereoscan photograph.
Fig. 4 is the stereoscan photograph under different multiplying inside cellulose/graphene/silver nano-grain laminated film.
Fig. 5 is the circulation volt that cellulose/graphene/silver nano-grain laminated film sweeps under speed in difference under three-electrode system
Antu.
Fig. 6 is cellulose/graphene under three-electrode system/perseverance of the silver nano-grain laminated film under different current densities
Current charge-discharge electrograph.
Fig. 7 is change of cellulose/graphene/silver nano-grain laminated film capacity retention with repeated charge number
Change relational graph.
Fig. 8 is symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite
Alkene/silver nano-grain] electronic photo under nature and bending state.
Fig. 9 is symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite
Alkene/silver nano-grain] in the different cyclic voltammograms swept under speed.
Figure 10 is symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite
Alkene/silver nano-grain] constant current charge-discharge figure under different current densities.
Figure 11 is symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite
Alkene/silver nano-grain] in 50mV s-1Constant sweep is bent cyclic voltammogram measured by different angle under speed.
Figure 12 is symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite
Alkene/silver nano-grain] in 20mAcm-2Constant current charge-discharge figure measured by different angle is bent under constant current density.
Figure 13 is symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphite
Alkene/silver nano-grain] energy density and saturation effect figure.
Figure 14 be three symmetrical all-solid-state flexible supercapacitors [cellulose/graphene/silver nano-grain // cellulose/
Graphene/silver nano-grain] be together in series the electronics to work as power supply to lightening LED lamp pearl and driving hand-held calculator
Photo.
Specific embodiment
The present invention is further described in detail by way of example and in conjunction with the accompanying drawings.
Embodiment 1
Method provided by the invention is used to prepare cellulose/graphene/silver nano-grain laminated film:
(1) 180mg filter paper is cut into after fragment and 300mL 0.6mg mL-1Graphene oxide aqueous dispersions add to material together
In reason machine, starts cooking machine, make its rotor strength Stirring 4min under about 30000 revs/min of revolving speed, and then filter paper is beaten
It is broken, cellulose fibre+graphene oxide slurry is made.
(2) mixed slurry of step (1) is transferred in beaker, 60mL concentration is added under quick magnetic agitation is
The brand-new silver ammino solution of 0.15M then heats to 85 DEG C and reacts 30min.In the process, silver ammonia complex is oxidized graphite
Alkene is reduced into silver nano-grain, while it is compound to induce each component, and then it is multiple to generate cellulose/graphene oxide/silver nano-grain
Close object.
(3) by the product of step (2) in funnel rapid filtration under suction be dehydrated, in Suction filtration device filter membrane surface formed cellulose/
Graphene oxide/silver nano-grain laminated film.Add water repeatedly after washes clean, it is delayed under moisture state from filter membrane surface
Slow ground is whole to tear, and is transferred in the reaction kettle of 1000mL, hanging to place.Then 4mL water is added in inner liner of reaction kettle bottom
Hydrazine is closed, is sealed in the baking oven for be placed on 90 DEG C and keeps 12h, graphene oxide therein is thoroughly reduced into stone using hydrazine steam
Black alkene can synthesize cellulose/graphene/silver nano-grain flexible composite film of self-supporting.
(4) cellulose/graphene/silver nano-grain laminated film in step (3) is cut into 0.5cm × 3cm rectangle
Strip and directly as working electrode, Ag/AgCl electrode is as auxiliary electrode and with concentration as reference electrode, Pt plate electrode
The potassium chloride solution of 2M is taken three-electrode system to carry out electrochemical properties to it and is tested as electrolyte.
The cellulose of self-supporting prepared by the present embodiment/graphene/silver nano-grain flexible composite film as shown in Figure 1,
For complete uniform film, can arbitrarily be bent, flexibility is splendid.Its X-ray diffraction spectrogram (Fig. 2) has one at 2 θ=23.2 °
Wide weak diffraction maximum, has corresponded to (002) crystal face of graphene, and other strong diffraction maximums be then located at 2 θ=38.1 °, 44.2 °,
At 64.4 °, 77.4 ° and 81.4 °, (111), (200), (220), (311) and (222) of Face-centred Cubic Metals silver have been respectively corresponded
Crystal face.Its electric conductivity is quite outstanding, and sheet resistance is only 0.17 Ω sq-1, far below the commercialization carbon for being commonly used for flexible electrode collector
Sheet resistance (the 1.46 Ω sq of cloth-1) and it is other disclose report be directly used as the graphene-based of flexible electrode, carbon nanotube base with
And (sheet resistance of these laminated films is typically larger than 5 Ω sq to the sheet resistance of conducting polymer based coextruded film-1).Its surface is silver nanoparticle
Particulate component, and be mutually tightly to be stacked to form continuous silver nano-grain film (Fig. 3) by many silver nano-grains, this is
It generates the reason of outstanding electric conductivity, and inside then includes cellulose fibre, graphene and silver nano-grain ingredient, and fine
Cellulose fiber acts as skeleton, with flexibility and keeps certain mechanical strength, internal silver nano-grain is by graphene
Winding and cladding, thus just avoid the aggregation of graphene well, are conducive to the migration of electrolyte ion inside it
And infiltration, and then promote its electrochemical properties (Fig. 4).Fig. 5 is its different cyclic voltammogram swept under speed in three-electrode system,
It can be seen that all curves show approximate rectangular and symmetrical shape, illustrate for the electrode of electric double layer capacitance characteristic.
Fig. 6 be its in three-electrode system different current densities under constant current charge-discharge figure, can therefrom extrapolate
In 2,5,10,20,40,60,80mA cm-2Under current density, area specific capacitance is respectively 1242.7,1135.5,1037.2,
918.1、800.3、705.5、622.9mF cm-2.That is its specific capacitance is kept at very high current density (80mA cm-2)
Rate has still been more than 50%, has reflected good high rate performance.In addition, in minimum electrical current density 2mA cm-2Under, largest face
Product specific capacitance (1242.7mF cm-2) it has been significantly higher than the maximum area specific capacitance of most flexible electrodes reported at present
(often less than 1000mF cm-2)。
Fig. 7 is its 60mA cm in three-electrode system-2Current density under capacity retention with repeated charge number become
The relational graph of change, therefrom it can be seen that its capacitor is almost unchanged during the whole test, and in repeated charge 6000
Capacity retention after secondary is still up to 99.7%, is equally apparently higher than most of flexible electrode reported at present and is filling repeatedly
Capacity retention (often less than 90%) after electric discharge (being often lower than 5000 times), has shown outstanding repeated charge stability.
These results illustrate that cellulose/graphene/silver nano-grain laminated film prepared by the present embodiment has excellent electrochemistry
Property and wide application prospect.
Embodiment 2
Method provided by the invention is used to construct symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/Yin Na
Rice grain // cellulose/graphene/silver nano-grain]:
(1) 5g polyvinyl alcohol is added in 50mL water, is warming up to 90 DEG C, while stirring is allowed to dissolve.Then under stiring
2mL 1g mL is slowly added dropwise-1Potassium chloride aqueous solution, cooled to room temperature later, obtain the polyvinyl alcohol of clear/
Potassium chloride gel electrolyte.
(2) cellulose/graphene/silver nano-grain laminated film synthesized by embodiment 1 is cut into 0.5cm × 3cm
Rectangular slat is placed on glass slide, and the polyvinyl alcohol in a small amount of step (1)/potassium chloride gel electrolyte is then poured into it
Surface, area coverage are 0.5cm × 2cm, namely the white space for leaving 0.5cm × 1cm then exists for being connected with electrode holder
It allows in gel electrolyte excessive moisture slowly to volatilize and final gelatine at room temperature, forms gel mould.
(3) cellulose/graphene/silver nanometer particle film that gel mould is covered in identical two panels step (2) is direct
It is stacked together as flexible electrode, overlapping area is the region 0.5cm × 2cm for being covered with gel mould, is finally twined with preservative film
Wind the device, formed a symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // cellulose/
Graphene/silver nano-grain].
(4) the symmetrical all-solid-state flexible supercapacitor assembled in direct testing procedure (3) under two electrode systems
The electrochemical behavior of [cellulose/graphene/silver nano-grain // cellulose/graphene/silver nano-grain].
(5) by the symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nanoparticle in three steps (3)
Grain // cellulose/graphene/silver nano-grain] be cascaded and be fully charged after as power supply for lightening LED lamp pearl and drive
Dynamic hand-held calculator work.
Symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // fibre prepared by the present embodiment
Tie up element/graphene/silver nano-grain] as shown in figure 8, equally can arbitrarily be bent, flexibility is good.Fig. 9 is it in two electrode bodies
The different cyclic voltammograms swept under speed in system, it can be seen that all curves also show approximate rectangular and symmetrical shape
Shape illustrates for the supercapacitor of electric double layer capacitance characteristic energy storage mechnism.
Figure 10 be its in two electrode systems different current densities under constant current charge-discharge figure, can therefrom extrapolate
In 5,10,20,30,40mA cm-2Under current density, area specific capacitance is respectively 683.8,609.2,504.1,415.5,
347.9mF cm-2.That is its specific capacitance conservation rate has also exceeded 50% at higher current density (40mA cm-2), instead
Satisfactory high rate performance is mirrored.Minimum electrical current density 5mA cm shown in the figure-2Under, maximum area specific capacitance
(683.8mF cm-2) maximum area specific capacitance equally obviously beyond most flexible super capacitors reported at present
(often less than 500mF cm-2)。
In addition, its electrochemical performance is had little influence under bending state, because measured by under different bending angle
A plurality of cyclic voltammetry curve (Figure 11) and a plurality of constant current charge-discharge curve (Figure 12) can almost be overlapped, confirmed it again
Good flexibility and stable electrochemical behavior.Figure 13 is the relational graph of its energy density and power density, is computed, most
Big energy density is 95 μ Wh cm-2, equally most much higher than most all-solid-state flexible supercapacitors reported at present
Big energy density (often less than 60 μ Wh cm-2).It is noted that the symmetrical all-solid-state flexible that three the present embodiment are assembled
Be cascaded is full of supercapacitor [cellulose/graphene/silver nano-grain // cellulose/graphene/silver nano-grain]
It can be used as power supply use after electricity, and can lightening LED lamp pearl and driving hand-held calculator work (Figure 14) well.These are true
Sufficiently show symmetrical all-solid-state flexible supercapacitor [cellulose/graphene/silver nano-grain // fibre prepared by the present embodiment
Dimension element/graphene/silver nano-grain] to possess outstanding chemical property, apparent energy storage advantage and preferable practical application latent
It can be with value.
Embodiment 3-5: the step of pressing following table 1 and parameter carry out, other same as Example 1.
By laminated film made from above embodiments 3-5 and flexible capacitor, still there is the technology effect that the present invention is above-mentioned
Fruit.
Claims (4)
1. a kind of preparation method of flexible capacitor, which comprises the following steps:
(1) filter paper is cut into after fragment and is added in cooking machine together with graphene oxide aqueous dispersions, utilize cooking machine rotor
High speed rotation smashes filter paper, and cellulose fibre+graphene oxide slurry is made；
(2) mixed slurry of step (1) is transferred in beaker, excessive concentration is added under quick magnetic agitation is about
The silver ammino solution of 0.1-0.5M, then heats to 70-90oC simultaneously reacts 20-40 min；
(3) product of step (2) is filtered into funnel dehydration, forms cellulose/graphite oxide in Suction filtration device filter membrane surface
Alkene/silver nano-grain laminated film；Add water repeatedly after washes clean, it is gently whole from filter membrane surface under moisture state
It tears, and is transferred in reaction kettle, it is hanging to place；Then hydrazine hydrate is added in inner liner of reaction kettle bottom, is sealed and is placed on 80-
110o8-24 h is kept in the baking oven of C；
(4) polyvinyl alcohol is added in water, heating stirring is allowed to dissolve, and the water-soluble of potassium chloride is then slowly added dropwise under stiring
Liquid, cooled to room temperature, obtains polyvinyl alcohol/potassium chloride gel electrolyte of clear later；
(5) cellulose/graphene/silver nano-grain laminated film in step (3) is cut into rectangular slat, is placed in load glass
On piece, is then poured into its surface for the polyvinyl alcohol in step (4)/potassium chloride gel electrolyte, and leaving a blank region is used for
It is connected with electrode holder, then allows in gel electrolyte excessive moisture slowly to volatilize and final gelatine at room temperature, formed solidifying
Glue film；
(6) will be covered in identical two panels step (5) cellulose/graphene/silver nanometer particle film of gel mould directly as
Flexible electrode is stacked together, and overlapping area is to be covered with the region of gel mould, forms the symmetrical complete solid of a high-energy density
State flexible super capacitor (cellulose/graphene/silver nano-grain // cellulose/graphene/silver nano-grain).
2. the preparation method of flexible capacitor as described in claim 1, it is characterised in that: in the step (1), aoxidize stone
Black alkene: the mass ratio 5:95-70:30 of filter paper fibre cellulose fiber.
3. the preparation method of flexible capacitor as claimed in claim 1 or 2, it is characterised in that: in the step (3), hydration
Hydrazine and cellulose/graphene oxide/silver nano-grain laminated film mass ratio are 1:1.5-2.5.
4. the preparation method of flexible capacitor as claimed in claim 1,2 or 3, it is characterised in that: state in step (2), add
Reaction temperature after entering silver ammino solution is 85oC, the reaction time is 30 min；In the step (3), the anti-of hydrazine hydrate is added
Answering temperature is 90oC, the reaction time is 12h.
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