CN106356202A - Graphene/tungsten disulfide film flexible super capacitor and manufacturing method and application thereof - Google Patents
Graphene/tungsten disulfide film flexible super capacitor and manufacturing method and application thereof Download PDFInfo
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- CN106356202A CN106356202A CN201610859379.0A CN201610859379A CN106356202A CN 106356202 A CN106356202 A CN 106356202A CN 201610859379 A CN201610859379 A CN 201610859379A CN 106356202 A CN106356202 A CN 106356202A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a graphene/tungsten disulfide film flexible super capacitor and a manufacturing method and an application thereof. The manufacturing method comprises the following specific steps: adding tungsten disulfide into an organic solvent, uniformly stirring and mixing, and performing ultrasonic dispersion to form uniform dispersion liquid; centrifugally separating the dispersion liquid to remove bottom sediment in order to obtain tungsten disulfide/organic solvent supernatant; preparing a graphene oxide aqueous solution, mixing the graphene oxide aqueous solution and the organic solvent supernatant, performing uniform ultrasonic dispersion, performing suction filtration to obtain a graphene oxide/tungsten disulfide composite film, and performing a reduction reaction, washing and vacuum drying to obtain the graphene/tungsten disulfide film flexible super capacitor. Compared with the prior art, the manufactured graphene/tungsten disulfide film flexible super capacitor has higher electric capacity, flexibility and stability, is simple, feasible and environmental-friendly in the manufacturing method, and has a very good application prospect on the aspect of flexible electronic devices.
Description
Technical field
The invention belongs to technical field of function materials, it is related to a kind of Graphene/tungsten disulfide thin film flexible ultracapacitor
And preparation method and application.
Background technology
With the aggravation consumption of non-renewable energy resources, the storage of energy and conversion seem more and more important, along with science and technology
Progress, the generation of wearable portable, rollable Novel electronic devices in a large number, such as Electronic Paper, collapsible display with
And others multimedia, greatly facilitate daily life.In order to meet wearing and the demand folding, these super electricity
Container must have the advantages that flexibility, lightweight, high-performance.But, the research great majority about ultracapacitor are to be based at present
Some harder, heavier tabular materials, therefore, select suitable material to design and prepare high-performance flexible super capacitor
Device, has become one of key factor of impact flexible electronic device performance.
Graphene, as one of the Typical Representative of material with carbon element, has high specific surface area and electrical conductivity, numerous research works
Person is as good matrix material.For example, flexible super capacitor technical elements are being prepared using Graphene, application
Number disclose a kind of structure side of graphene-based thin film flexible ultracapacitor for 201610250256.7 Chinese invention patent
Method, polyaniline fiber is mixed with deionized water, mixes with graphite oxide after supersound process, and supersound process obtains graphite oxide
Alkene and the mixing homogeneous phase solution of polyaniline；Standing, until solution surface forms answering of complete graphene oxide/polyaniline fiber
Close thin film；Using fexible film as matrix, the laminated film of graphene oxide/polyaniline fiber is deposited on matrix, also
Former, the laminated film of the graphene/polyaniline fiber on flexible substrate must be deposited on after cleaning, directly as membrane electrode material
Material, cut, using solid electrolyte, it is applied between the cut of thin film, obtains final product.However, due to Graphene itself theoretical capacity value
Not high, still there is the relatively low technological deficiency of capacity in the capacitor obtained by therefore above-mentioned art solutions.
For above-mentioned technical problem, graphene-supported fake capacitance material typically to be lifted corresponding electric capacity by prior art
Amount.Transient metal sulfide have with graphite-like as two-dimensional layered structure, the weaker Van der Waals force of its interlayer can make its lead to
Cross and mechanically or chemically peel off into monolayer or minority layer nanometer sheet.And reduce with the disulphide number of plies, its structure has and substantially changes
Become, compound layer structure allows gel electrolyte ion more successfully to embed, abjection molecule lamellar spacing.However, mesh
Front it is combined to prepare the existing report of thin film flexible ultracapacitor using transient metal sulfide and Graphene.
Content of the invention
The purpose of the present invention is exactly to provide to overcome the defect that above-mentioned prior art exists a kind of to have higher matter
Amount specific capacity and the good Graphene/tungsten disulfide thin film flexible of area specific capacity, electrochemical performance, economic and practical are super
Capacitor and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
The preparation method of Graphene/tungsten disulfide thin film flexible ultracapacitor, the method specifically includes following steps:
(1) tungsten disulfide is added in organic solvent, is uniformly mixed, being configured to mass concentration is 0.1-10mg/
The mixed solution of ml, by ultrasonic disperse, forms uniform dispersion liquid；
(2) after the dispersion liquid that step (1) is obtained is centrifuged, remove bottom precipitation, obtain tungsten disulfide/organic molten
Agent supernatant；
(3) graphene oxide water solution that mass concentration is 0.1-100mg/ml, the curing being obtained with step (2) are prepared
Tungsten/organic solvent supernatant mixing, after ultrasonic disperse is uniform, sucking filtration, obtain graphene oxide/tungsten disulfide composite membrane；
(4) graphene oxide/tungsten disulfide composite membrane that step (3) is obtained is added in reducing agent, in 60-90 DEG C of bar
Under part, react 3-8h, use saturated sodium bicarbonate solution, deionized water wash successively, then with glass plate clamping fixed after, vacuum is dry
Dry, that is, Graphene/tungsten disulfide thin film flexible ultracapacitor is obtained.
Organic solvent described in step (1) includes n, n- dimethylformamide, n, n- dimethyl acetylamide, n- methylpyrrole
One or more of alkanone, DMSO or isopropanol.
The temperature of the stirring described in step (1) is 5-90 DEG C, and the time of described ultrasonic disperse is 0.5-200h.
The rotating speed of the centrifugation described in step (2) turns/min for 1000-20000, and the time is 5-60min.
Graphene oxide described in step (3) is the graphene oxide being obtained using hummers method, this graphene oxide
Lamellar spacing is 1nm-1um, and graphene oxide is 1:0.1-10 with the mass ratio of tungsten disulfide.
Reducing agent described in step (4) is selected from one of hydrogen iodide, hydrazine hydrate, vitamin c or sodium borohydride, aoxidizes stone
Black alkene is 1:1-10 with the mass ratio of reducing agent.
The Graphene being prepared from using said method/tungsten disulfide thin film flexible ultracapacitor.
The application of Graphene/tungsten disulfide thin film flexible ultracapacitor, will be super for Graphene/tungsten disulfide thin film flexible
Capacitor, as active material, is assembled into all solid state symmetrical flexible super capacitor together with gel electrolyte, collector.
Described gel electrolyte includes polyvinyl alcohol-phosphoric acid or polyvinyl alcohol-sulphuric acid, and described collector includes foam
One of nickel, carbon cloth, stainless (steel) wire or carbon paper.
The mentality of designing of the inventive method is by adding a certain amount of tungsten disulfide, ultrasonic stripping one in organic solvent
After the section time, centrifugation obtains tungsten disulfide dispersion soln, and after this dispersion soln is mixed with graphene oxide solution, vacuum filtration becomes
Thin film, then through reducing agent reduction, that is, Graphene/tungsten disulfide laminated film is obtained, gel electrolyte will be coated on its surface,
Finally obtain flexible super capacitor with another pole self assembly of same material and structure again.
Compared with prior art, after transient metal sulfide (i.e. tungsten disulfide) is combined by the present invention with Graphene, have
Electrochemical performance, pliability is high, the advantages of good cycling stability, has higher specific discharge capacity and area specific capacity,
Electrochemical performance, after the different angle of bending, capacitance loss is small, can be used to solve to prepare the skill of flexible super capacitor
The technical problem such as art process is loaded down with trivial details, combination property is poor.
Brief description
Fig. 1 is the cross sectional Scanning Electron microscope figure of Graphene/tungsten disulfide laminated film that embodiment 1 is obtained；
Fig. 2 is that Graphene/tungsten disulfide laminated film that embodiment 2 is obtained obtains in flexible super capacitor test
Cyclical stability figure；
Fig. 3 obtains in flexible super capacitor test for Graphene/tungsten disulfide laminated film that embodiment 1-5 is obtained
Electric capacity spirogram.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
The preparation method of the present embodiment Graphene/tungsten disulfide thin film flexible ultracapacitor comprises the following steps:
(1) organic solvent auxiliary liquid phase is adopted to peel off tungsten disulfide
2g tungsten disulfide is added to n, in n- dimethylformamide, stirring and dissolving at temperature is 5～90 DEG C, it is configured to
Concentration is the solution of 0.1～10mg/ml, ultrasonic disperse 0.5～200 hour, forms dispersion liquid；
(2) preparation of Graphene/tungsten disulfide composite membrane
The dispersion liquid that step (1) is obtained centrifugation 5～60 minutes under 1000～20000rpm per minute, remove bottom
Portion is precipitated, and measures tungsten disulfide/n, n- dimethylformamide supernatant 26.3ml, then the 5mg/ml graphene oxide measuring 20ml
Aqueous solution is so that Graphene is 1:1 with the mass ratio of tungsten disulfide, after ultrasonic 5～60 minutes are uniformly dispersed, by sucking filtration
Form graphene oxide/tungsten disulfide composite membrane and take off from filter membrane, be added in reducing agent sodium borohydride, 60～90 DEG C anti-
Answer 3～8 hours, then cleaned 3～8 times with saturated sodium bicarbonate solution and deionized water respectively, then be clamped on it with glass plate
Between, take out after vacuum drying a few hours at 60～90 DEG C；
(3) assembling of flexible super capacitor and test
The composite membrane being obtained using step (2) as active material, using polyvinyl alcohol/phosphoric acid as gel electrolyte, foam
Nickel, as collector and flexible substrates, is assembled into all solid state symmetrical flexible super capacitor.
Graphene/tungsten disulfide composite membrane that the present embodiment is obtained, has good mechanical performance, lightly pliable and tough, uses handss
Show the flexible of composite membrane after clinodactyly, and original state can be reverted back to after removing external force.It is assembled into flexible super electric capacity
After device, because composite membrane and nickel foam have preferable pliability, therefore under bending, flexible device is not broken off or damages
Wound.
Shown in Fig. 1, the observation of ultramicroscope is scanned to the cross section of Graphene/tungsten disulfide composite membrane, due to
Graphene is lamellar structure, and tungsten disulfide is also two-dimensional layer material, still has obvious lamella by compound both it
Structure.
Embodiment 2:
The preparation method of the present embodiment Graphene/tungsten disulfide thin film flexible ultracapacitor comprises the following steps:
(1) organic solvent auxiliary liquid phase is adopted to peel off tungsten disulfide
2g tungsten disulfide is added to n, in n- dimethylformamide, stirring and dissolving at temperature is 5～90 DEG C, it is configured to
Concentration is the solution of 0.1～10mg/ml, ultrasonic disperse 0.5～200 hour, forms dispersion liquid；
(2) preparation of Graphene/tungsten disulfide composite membrane
The dispersion liquid that step (1) is obtained centrifugation 5～60 minutes under 1000～20000rpm per minute, remove bottom
Portion is precipitated, and measures tungsten disulfide/n, n- dimethylformamide supernatant 52.6ml, then the 5mg/ml graphene oxide measuring 20ml
Aqueous solution is so that the mass ratio of Graphene and tungsten disulfide is 1:2, after ultrasonic 5～60 minutes are uniformly dispersed, by sucking filtration
Graphene oxide/tungsten disulfide the composite membrane of formation is simultaneously taken off from filter membrane, is added in reducing agent sodium borohydride, 60～90 DEG C
Reaction 3～8 hours, is then cleaned 3～8 times with saturated sodium bicarbonate solution and deionized water respectively, then is clamped on glass plate
Between, take out after vacuum drying a few hours at 60～90 DEG C；
(3) assembling of flexible super capacitor and test
The composite membrane being obtained using step (2) as active material, using polyvinyl alcohol/phosphoric acid as gel electrolyte, foam
Nickel, as collector and flexible substrates, is assembled into all solid state symmetrical flexible super capacitor.
Shown in Fig. 2, Graphene/tungsten disulfide laminated film that the present embodiment is obtained is self-assembled into flexible super capacitor
Afterwards, there is good circulation conservation rate, after circulating 5000 times, capacity retention rate can also reach 88.1%.
Embodiment 3:
The preparation method of the present embodiment Graphene/tungsten disulfide thin film flexible ultracapacitor comprises the following steps:
(1) organic solvent auxiliary liquid phase is adopted to peel off tungsten disulfide
2g tungsten disulfide is added to n, in n- dimethylformamide, stirring and dissolving at temperature is 5～90 DEG C, it is configured to
Concentration is the solution of 0.1～10mg/ml, ultrasonic disperse 0.5～200 hour, forms dispersion liquid；
(2) preparation of Graphene/tungsten disulfide composite membrane
The dispersion liquid that step (1) is obtained centrifugation 5～60 minutes under 1000～20000rpm per minute, remove bottom
Portion is precipitated, and measures tungsten disulfide/n, n- dimethylformamide supernatant 78.9ml, then the 5mg/ml graphene oxide measuring 20ml
Aqueous solution is so that the mass ratio of Graphene and tungsten disulfide is 1:3, after ultrasonic 5～60 minutes are uniformly dispersed, by sucking filtration
Graphene oxide/tungsten disulfide the composite membrane of formation is simultaneously taken off from filter membrane, is added in reducing agent sodium borohydride, 60～90 DEG C
Reaction 3～8 hours, is then cleaned 3～8 times with saturated sodium bicarbonate solution and deionized water respectively, then is clamped on glass plate
Between, take out after vacuum drying a few hours at 60～90 DEG C；
(3) assembling of flexible super capacitor and test
The composite membrane being obtained using step (2) as active material, using polyvinyl alcohol/phosphoric acid as gel electrolyte, foam
Nickel, as collector and flexible substrates, is assembled into all solid state symmetrical flexible super capacitor.
Embodiment 4:
The preparation method of the present embodiment is same as Example 1, and difference is, the mass ratio of Graphene and tungsten disulfide
It is controlled to 1:0.5.
Embodiment 5:
The preparation method of the present embodiment is same as Example 1, and difference is, the mass ratio of Graphene and tungsten disulfide
It is controlled to 1:0.1.
Fig. 3 show the pass of the prepared capacitance value of Graphene/tungsten disulfide composite membrane of embodiment 1-5 and electric current density
It is curve.Analyzed from Fig. 3, the Graphene/tungsten disulfide composite membrane of different quality ratio has the mass ratio electricity of bigger difference
Hold with area than electric capacity, can be derived that optimal Graphene/tungsten disulfide component ratio is 1:2, this best composition ratio soft
Property ultracapacitor is 1ma/cm in electric current density2When, area can reach 250mf/cm than electric capacity2.When component ratio value increases again
Added-time, capability value can reduce on the contrary.
Embodiment 6:
The preparation method of the present embodiment Graphene/tungsten disulfide thin film flexible ultracapacitor, specifically includes following steps:
(1) tungsten disulfide is added in organic solvent, is uniformly mixed, being configured to mass concentration is 0.1mg/ml's
Mixed solution, by ultrasonic disperse, forms uniform dispersion liquid；
(2) after the dispersion liquid that step (1) is obtained is centrifuged, remove bottom precipitation, obtain tungsten disulfide/organic molten
Agent supernatant；
(3) preparation mass concentration is the graphene oxide water solution of 0.1mg/ml, the tungsten disulfide being obtained with step (2)/
Organic solvent supernatant mixes, after ultrasonic disperse is uniform, sucking filtration, and obtain graphene oxide/tungsten disulfide composite membrane；
(4) graphene oxide/tungsten disulfide composite membrane that step (3) is obtained is added in reducing agent, in 60 DEG C of conditions
Under, react 8h, use saturated sodium bicarbonate solution, deionized water wash successively, then with glass plate clamping fixed after, be vacuum dried, that is,
Prepared Graphene/tungsten disulfide thin film flexible ultracapacitor.
Wherein, step (1) organic solvent is by n, and n- dimethyl acetylamide is pressed with n- methyl pyrrolidone, DMSO
Volume ratio mixes for 1:1:1；The temperature of stirring is 5 DEG C, and the time of described ultrasonic disperse is 0.5h.
In step (2), the rotating speed of centrifugation is 1000 turns/min, and the time is 60min.
In step (3), graphene oxide is the graphene oxide being obtained using hummers method, the piece of this graphene oxide
Thickness degree is 1nm-1um, and graphene oxide is 1:0.1 with the mass ratio of tungsten disulfide.
In step (4), reducing agent is hydrogen iodide, and graphene oxide is 1:1 with the mass ratio of reducing agent.
The application of Graphene/tungsten disulfide thin film flexible ultracapacitor, will be super for Graphene/tungsten disulfide thin film flexible
Capacitor, as active material, is assembled into all solid state symmetrical flexible super capacitor together with gel electrolyte, collector.Its
In, gel electrolyte is polyvinyl alcohol-sulphuric acid, and collector is carbon cloth.
Embodiment 7:
The preparation method of the present embodiment Graphene/tungsten disulfide thin film flexible ultracapacitor, specifically includes following steps:
(1) tungsten disulfide is added in organic solvent, is uniformly mixed, being configured to mass concentration is 10mg/ml's
Mixed solution, by ultrasonic disperse, forms uniform dispersion liquid；
(2) after the dispersion liquid that step (1) is obtained is centrifuged, remove bottom precipitation, obtain tungsten disulfide/organic molten
Agent supernatant；
(3) preparation mass concentration is the graphene oxide water solution of 100mg/ml, the tungsten disulfide being obtained with step (2)/
Organic solvent supernatant mixes, after ultrasonic disperse is uniform, sucking filtration, and obtain graphene oxide/tungsten disulfide composite membrane；
(4) graphene oxide/tungsten disulfide composite membrane that step (3) is obtained is added in reducing agent, in 90 DEG C of conditions
Under, react 3h, use saturated sodium bicarbonate solution, deionized water wash successively, then with glass plate clamping fixed after, be vacuum dried, that is,
Prepared Graphene/tungsten disulfide thin film flexible ultracapacitor.
Wherein, step (1) organic solvent is by n, and n- dimethylformamide with isopropanol, DMSO is by volume
1:1:1 mixes；The temperature of stirring is 90 DEG C, and the time of described ultrasonic disperse is 200h.
In step (2), the rotating speed of centrifugation is 20000 turns/min, time 5min.
In step (3), graphene oxide is the graphene oxide being obtained using hummers method, the piece of this graphene oxide
Thickness degree is 1nm-1um, and graphene oxide is 1:10 with the mass ratio of tungsten disulfide.
In step (4), reducing agent is vitamin c, and graphene oxide is 1:10 with the mass ratio of reducing agent.
The application of Graphene/tungsten disulfide thin film flexible ultracapacitor, will be super for Graphene/tungsten disulfide thin film flexible
Capacitor, as active material, is assembled into all solid state symmetrical flexible super capacitor together with gel electrolyte, collector.Its
In, gel electrolyte is polyvinyl alcohol-sulphuric acid, and collector is stainless (steel) wire.
Embodiment 8:
The preparation method of the present embodiment Graphene/tungsten disulfide thin film flexible ultracapacitor, specifically includes following steps:
(1) tungsten disulfide is added in organic solvent, is uniformly mixed, being configured to mass concentration is the mixed of 7mg/ml
Close solution, by ultrasonic disperse, form uniform dispersion liquid；
(2) after the dispersion liquid that step (1) is obtained is centrifuged, remove bottom precipitation, obtain tungsten disulfide/organic molten
Agent supernatant；
(3) graphene oxide water solution that mass concentration is 70mg/ml, the tungsten disulfide being obtained with step (2)/have are prepared
Machine solvent supernatant mixes, after ultrasonic disperse is uniform, sucking filtration, and obtain graphene oxide/tungsten disulfide composite membrane；
(4) graphene oxide/tungsten disulfide composite membrane that step (3) is obtained is added in reducing agent, in 45 DEG C of conditions
Under, react 6h, use saturated sodium bicarbonate solution, deionized water wash successively, then with glass plate clamping fixed after, be vacuum dried, that is,
Prepared Graphene/tungsten disulfide thin film flexible ultracapacitor.
Wherein, step (1) organic solvent is by n, n- dimethylformamide and n- methyl pyrrolidone, isopropanol, diformazan
Maple mixes for 2:1:1:1 by volume for base Asia；The temperature of stirring is 60 DEG C, and the time of described ultrasonic disperse is 24h.
In step (2), the rotating speed of centrifugation is 10000 turns/min, time 15min.
In step (3), graphene oxide is the graphene oxide being obtained using hummers method, the piece of this graphene oxide
Thickness degree is 1nm-1um, and graphene oxide is 1:4 with the mass ratio of tungsten disulfide.
In step (4), reducing agent is hydrazine hydrate, and graphene oxide is 1:5 with the mass ratio of reducing agent.
The application of Graphene/tungsten disulfide thin film flexible ultracapacitor, will be super for Graphene/tungsten disulfide thin film flexible
Capacitor, as active material, is assembled into all solid state symmetrical flexible super capacitor together with gel electrolyte, collector.Its
In, gel electrolyte is polyvinyl alcohol-sulphuric acid, and collector is carbon paper.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be the present invention's for field technique personnel
Within protection domain.
Claims (10)
1. Graphene/tungsten disulfide thin film flexible ultracapacitor preparation method it is characterised in that the method specifically include with
Lower step:
(1) tungsten disulfide is added in organic solvent, is uniformly mixed, being configured to mass concentration is 0.1-10mg/ml's
Mixed solution, by ultrasonic disperse, forms uniform dispersion liquid；
(2), after the dispersion liquid that step (1) is obtained is centrifuged, removes bottom precipitation, obtain on tungsten disulfide/organic solvent
Clear liquid；
(3) preparation mass concentration is the graphene oxide water solution of 0.1-100mg/ml, the tungsten disulfide being obtained with step (2)/
Organic solvent supernatant mixes, after ultrasonic disperse is uniform, sucking filtration, and obtain graphene oxide/tungsten disulfide composite membrane；
(4) graphene oxide/tungsten disulfide composite membrane that step (3) is obtained is added in reducing agent, in 60-90 DEG C of condition
Under, react 3-8h, use saturated sodium bicarbonate solution, deionized water wash successively, then with glass plate clamping fixed after, be vacuum dried,
Graphene/tungsten disulfide thin film flexible ultracapacitor is obtained.
2. the preparation method of Graphene according to claim 1/tungsten disulfide thin film flexible ultracapacitor, its feature exists
Include n in, the organic solvent described in step (1), n- dimethylformamide, n, n- dimethyl acetylamide, n- methyl pyrrolidone,
One or more of DMSO or isopropanol.
3. the preparation method of Graphene according to claim 1/tungsten disulfide thin film flexible ultracapacitor, its feature exists
In the temperature of the stirring described in step (1) is 5-90 DEG C, and the time of described ultrasonic disperse is 0.5-200h.
4. the preparation method of Graphene according to claim 1/tungsten disulfide thin film flexible ultracapacitor, its feature exists
In the rotating speed of the centrifugation described in step (2) turns/min for 1000-20000, and the time is 5-60min.
5. the preparation method of Graphene according to claim 1/tungsten disulfide thin film flexible ultracapacitor, its feature exists
In the graphene oxide described in step (3) is the graphene oxide being obtained using hummers method, the lamella of this graphene oxide
Thickness is 1nm-1um.
6. the preparation method of Graphene according to claim 5/tungsten disulfide thin film flexible ultracapacitor, its feature exists
In the graphene oxide described in step (3) is 1:0.1-10 with the mass ratio of tungsten disulfide.
7. the preparation method of Graphene according to claim 1/tungsten disulfide thin film flexible ultracapacitor, its feature exists
In the reducing agent described in step (4) is selected from one of hydrogen iodide, hydrazine hydrate, vitamin c or sodium borohydride.
8. the preparation method of Graphene according to claim 1/tungsten disulfide thin film flexible ultracapacitor, its feature exists
In the graphene oxide described in step (4) is 1:1-10 with the mass ratio of reducing agent.
9. the Graphene that the method as described in any one of claim 1 to 8 is prepared from/tungsten disulfide thin film flexible super capacitor
Device.
10. the application of Graphene as claimed in claim 9/tungsten disulfide thin film flexible ultracapacitor is it is characterised in that incite somebody to action
Graphene/tungsten disulfide thin film flexible ultracapacitor, as active material, is assembled together with gel electrolyte, collector and helps
The symmetrical flexible super capacitor of solid-state.
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Cited By (5)
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| CN107492456A (en) * | 2017-07-24 | 2017-12-19 | 上海电力学院 | The preparation method and application of carbon-based transient metal sulfide self-supporting polyaniline composite membrane |
| CN108428565A (en) * | 2017-02-13 | 2018-08-21 | 中国科学院宁波材料技术与工程研究所 | Tungsten disulfide/graphene oxide composite material, preparation method and application |
| CN109181638A (en) * | 2018-09-05 | 2019-01-11 | 南京理工大学 | A kind of tungsten disulfide-redox graphene three-dimensional self-assembled structures absorbing material |
| CN113252738A (en) * | 2021-05-14 | 2021-08-13 | 中国农业科学院农业信息研究所 | Nano heterojunction ethylene sensitive film and preparation method and application thereof |
| CN114150290A (en) * | 2021-10-31 | 2022-03-08 | 山东云海国创云计算装备产业创新中心有限公司 | Two-dimensional nano tungsten disulfide semiconductor film and preparation method thereof |
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| CN107492456B (en) * | 2017-07-24 | 2019-07-19 | 上海电力学院 | The preparation method and application of carbon-based transient metal sulfide self-supporting polyaniline composite membrane |
| CN109181638A (en) * | 2018-09-05 | 2019-01-11 | 南京理工大学 | A kind of tungsten disulfide-redox graphene three-dimensional self-assembled structures absorbing material |
| CN113252738A (en) * | 2021-05-14 | 2021-08-13 | 中国农业科学院农业信息研究所 | Nano heterojunction ethylene sensitive film and preparation method and application thereof |
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| CN114150290B (en) * | 2021-10-31 | 2024-02-02 | 山东云海国创云计算装备产业创新中心有限公司 | Two-dimensional nano tungsten disulfide semiconductor film and preparation method thereof |
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