CN108630459A - A kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost - Google Patents
A kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost Download PDFInfo
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- CN108630459A CN108630459A CN201810441055.4A CN201810441055A CN108630459A CN 108630459 A CN108630459 A CN 108630459A CN 201810441055 A CN201810441055 A CN 201810441055A CN 108630459 A CN108630459 A CN 108630459A
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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
The present invention is a kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost.This approach includes the following steps：(1) preparation of transparent flexible collector；(2) preparation of rich defect graphene oxide/carbon nanotube base composite dispersion liquid；(3) preparation of rich defect graphene oxide/carbon nanotube piece base coating pole piece；(4) preparation of rich defect graphene/carbon nano-tube nanometer sheet base stage piece；(5) preparation of transparent solid-state electrolyte；(6) preparation of the electric double layer transparent flexible ultracapacitor of " sandwich " structure finally obtained the electric double layer transparent flexible ultracapacitor of " sandwich " structure.Present invention process flow is simple, at low cost, is easy to implement commercialized application.
Description
Technical field：
The present invention relates to field of new material preparation, specially a kind of all solid state super electricity of multilevel hierarchy transparent flexible of low cost
The preparation method of container.
Background technology
With wearable and portable multi-media electronic equipment continuous development, flexible and transparent electronics device is proposed
Higher requirement, " transparent flexible " have been the change directions of a great foreground of Future Consumption electronic product.In order to
Realize the commercialization of the flexible display device of flatscreen, electric power energy supply component is also required to flexibility and transparence, as it
Indispensable important component, transparent flexible electronic device have potential business impact and huge market value, at
For one of research hotspots of scientific domains such as current material, electronics, communication.As a kind of novel energy storage device, transparent flexible
Ultracapacitor causes the concern of numerous researchers with the advantages that its high power, short charging time, high reliability, long-life.So
And due to the stage and limitation of technology development, it sets up a kind of full transparent and soft electronic product and remains prodigious choose
War property.Transparent flexible ultracapacitor is as important one of integrated power supply, its design and research and development is for realizing that all-transparent is soft
Property electronic product plays vital impetus.
Research for transparent flexible ultracapacitor is concentrated mainly on ultra-thin continuous conduction film and reticulated conductive structure two
A aspect.For ultra-thin continuous conduction film, the hot spot of research is how to prepare high quality, the single layer of large area or few layer graphite
On alkene and its transfer techniques.Currently with chemical vapor deposition (Chemical vapor deposition, CVD) technology growth
High quality large-area graphene has been achieved for rapid progress, is the premise for how ensureing not damaging graphene using bottleneck
Under, it carries out large area, be transferred to efficiently at low cost in arbitrary substrate.It is applied to transparent flexible electricity in ultra-thin continuous conduction film
In terms of container, 2013, the dawn research group that wears of U.S.'s Case Western Reserve University was reported for the first time using graphene as electrode
Transparent flexible ultracapacitor is prepared, basic ideas are：Using the copper foil for first passing through fold processing in advance as substrate, grown
Graphene with microcosmic fold morphology, and the preparation of stretchable transparent flexible ultracapacitor is directly used it for, it stretches
Ability can reach 40%, and light transmittance can reach 57%, and area specific capacitance reaches 5.8 μ F/cm2.It is worth noting that this
Unit area energy storage value is far smaller than the ultracapacitor (mF/cm of conventional structure2The order of magnitude).This is because working as film thickness
Its light transmittance can decay rapidly when increase, this greatly limits the quality of the electrode material on unit area, to can not be
Ensure further to promote the energy storage capacity on its unit area while light transmittance.In addition, active material film microstructure list
One, inside does not have open three-dimensional structure, is unfavorable for diffusion of the electrolyte charge inside active material film, increases expansion
Resistance is dissipated, the high-power output performance of ultracapacitor is also influenced.Therefore, develop a low cost and have high flexibility and height
Energy and the transparent flexible ultracapacitor of power density be a project with great challenge and significance.
Invention content
The purpose of the present invention is for transparent substrate material used in transparent flexible ultracapacitor present in current techniques
The problem that brittleness is larger, energy density is relatively low, a kind of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost of proposition
Preparation method.This method uses carbon nanotube and polystyrene microsphere, and preparing metal nano net transparent electrode using spin-coating method makees
For collector, the transparent flexible electrode with open three-dimensional (multistage) structure-activity material is prepared, further reduced simultaneously
Super capacitor system internal resistance keeps making energy and being optimal of power density on the basis of high transparency.Present invention process
Flow is simple, at low cost, is easy to implement commercialized application.
The technical scheme is that：
A kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost, includes the following steps：
(1) preparation of transparent flexible collector：Using metal nanometer line solution as raw material, by film-forming method in transparent flexible
One side surface of base material prepares metal nanometer line coating, is then dried at 100 DEG C -150 DEG C, obtains surface covering metal
The transparent flexible collector of nanometer line network；
The concentration range of the metal nanometer line solution is 0.1-10mg/mL；The thickness range 1nm-1 μ of coating are made
m；
(2) preparation of rich defect graphene oxide/carbon nanotube base composite dispersion liquid：By graphene oxide solution and peroxide
Change hydrogen solution mixing, 3-7h is stirred at 80 DEG C -150 DEG C, is then dialysed, it is molten to obtain rich defect graphene oxide
Liquid；Rich defect graphene oxide solution is mixed with carbon nanotube, polystyrene microsphere, 1-10h is stirred at 25 DEG C -40 DEG C, into
And obtain rich defect graphene oxide/carbon nanotube base composite dispersion liquid；
Wherein, 30-80mL hydrogenperoxide steam generators are corresponded to per 1g graphene oxides；Graphene oxide solution concentration range is
The mass fraction of 0.1-10mg/mL, hydrogenperoxide steam generator are 20%-40%；It is corresponded to per 1g graphene oxides and carbon nanotube is added
Quality be 0.1-20g and 0.1g-20g polystyrene microspheres；The diameter range 20-200nm of polystyrene microsphere；
(3) preparation of rich defect graphene oxide/carbon nanotube piece base coating pole piece：Obtained rich defect is walked above
Graphene oxide/carbon nanotube base composite dispersion liquid is spin coating liquid, drops in the surface covering metal nano gauze that (1) step obtains
On the transparent flexible collector of network, under conditions of rotating speed is thousand revs/min of 0.5-10.0, spin coating 10-600s；It has obtained being covered with richness
The pole piece of defect graphene oxide/carbon nanotube piece base coating；
Wherein, per 1cm2Surface covers dropwise addition 0.01-100ml richnesses on the transparent flexible collector of metal nanometer line network and lacks
Fall into graphene oxide/carbon nanotube base composite dispersion liquid；
(4) preparation of rich defect graphene/carbon nano-tube nanometer sheet base stage piece：It is covered with rich defect oxidation by what upper step obtained
The pole piece of graphene/carbon nano-tube nanometer sheet base coating is placed in sealing container, hydrazine hydrate is added dropwise again in sealing container, later
At 70 DEG C -150 DEG C, confined reaction 5-24h, after reaction, then by above-mentioned pole piece immerse acetone soln in 0.5-12h, it
Remove extra acetone with deionized water again afterwards, the dry 5-12h at 20-60 DEG C has been obtained being covered with rich defect graphene/carbon and received
The pole piece of mitron nanometer sheet base coating；
Wherein, the mass fraction of hydrazine hydrate is 70%-98%, and the mass fraction of acetone is 70%-98%；1cm2It is covered with richness
Defect graphene oxide/carbon nanotube piece base coating corresponds to 0.1-100 μ L hydrazine hydrates；
(5) preparation of transparent solid-state electrolyte：Polyvinyl alcohol (PVA) powder is added in deionized water, at 60 DEG C -100
Stirring adds phosphoric acid to transparent at a temperature of 60 DEG C -100 DEG C at DEG C, continues to stir 3-5h, has obtained transparent solid-state electrolysis
Matter；
Wherein, 1-5g phosphoric acid and 1-10g polyvinyl alcohol (PVA) powder is added in every 10ml deionized waters；The concentration of phosphoric acid
Ranging from 70%-98%；
(6) preparation of the electric double layer transparent flexible ultracapacitor of " sandwich " structure：The phase obtained in selecting step (4)
It is covered with the pole piece of rich defect graphene/carbon nano-tube nanometer sheet base coating with two panels, they are immersed vertically saturating in above-mentioned (5)
In bright solid electrolyte solution, 5-20min is kept, wherein the length for immersing part is the 20~80% of pole piece length；Take out it
After be dried at room temperature for 2-24h, the one side that rich defect graphene/carbon nano-tube nanometer sheet base coating is covered in two pole pieces is opposite
It places, then fitting is suppressed it 5~15 minutes, the electric double layer for having obtained " sandwich " structure is saturating under 1MP-10MP pressure
Bright flexible super capacitor.
Metal nanometer line is preferably gold, silver nano wire in the step (1)；The a diameter of 30-50nm of metal nanometer line,
Length is 30-40 μm；
The film-forming method is preferably spin coating film-forming method；
The non-transparent flexible substrate material is preferably PET (polyethylene terephthalate)；
Dialysis process described in the step (2) is dialysed for bag filter；
Sealing container is preferably drying basin in the step (4)；
The present invention substantive distinguishing features be：
One, metal nano net transparent electrode is prepared as collector using spin-coating method.Metal nano net transparent electrode be
Transparent flexible matrix surface prepares metal nanometer line conductive network (such as nano silver wire), have extremely low sheet resistance (<10Ω/sq)
With~90% light transmittance, it is considered to be the important component of the following transparent flexible electronic device can be widely applied to film
Solar cell, display, touch screen and intelligent glass etc., and about the application study report in transparent flexible ultracapacitor
It is very few.If using metal nano net transparent electrode as collector, the brittleness problems of ITO materials can be fundamentally solved, while very
The contact resistance that active material is reduced in big degree, to reduce ultracapacitor equal series resistance.In addition, due to transparent electricity
Pole reticulates distribution, prepares active material network corresponding with metal nano net, also may be used while so that dressing density is optimized
Ensure high light transmittance, thus can reach keep high transparency on the basis of so that super capacitor energy and power density is optimized
Purpose.Current prepares metal nano net transparent electrode technology, is difficult to realize above-mentioned high-flexibility, high transparency, low
The preparation requirement of the good characteristics such as sheet resistance, high dressing density.
Two, transparent flexible ultracapacitor is prepared using spin coating technique, by controlling the concentration of spin coating liquid, spin coating turns
The parameters such as speed, time, to realize the controllability of spin coating layer thickness, transparency.Current techniques are largely spray coating method, gas phase is heavy
The methods of product.Spray coating method is extremely difficult for preparing transparent graphene/carbon nano-tube layer, is unfavorable for state modulator, and very
It is uneven.And vapour deposition process is complicated for operation relative to the spin coating method of this patent and cost is very high.
Three, active material film is microcosmic shows open three-dimensional multistage structure.Due to carbon nanotube and polystyrene microsphere
Effect, keep structure between the graphene layer of rich defect sturcture more abundant and polynary, there is carbon nanotube between graphene sheet layer
Formation is conductively connected by force, while carbon nanotube and script strut lamella by the space of polystyrene microsphere filling, make piece interlamellar spacing
Increase, spatially there is fold morphology, open three-dimensional structure is presented, compared to utilization gas phase deposition technology only in collector
The upper two-dimentional active material configuration for depositing several layer graphenes and being formed can store more charges and be conducive to electrolyte electricity
Diffusion of the lotus inside active material film, reduces diffusional resistance, improves the high-power output performance of ultracapacitor.
Beneficial effects of the present invention are：
The present invention proposes a kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost, feature
It is that metal nanometer line network conductivity is high, forms conductive network on transparent base.Simultaneously because transparent electrode reticulates
Distribution, is prepared for the active material network with metal nano net relativity, and height is also can guarantee while so that dressing density is optimized
Light transmittance, if light transmittance is up to 76% at wavelength 550nm for Fig. 3 embodiments 5, the flexility of collector is good, also thoroughly
It solves the brittleness problems of ITO materials itself, no longer restricts the development of the following flexible electronic device, such as wearable electronics produces
Product.In addition, due to one group of originally conflicting performance of both light transmittance and energy density, increasing light transmittance certainly will reduce
Energy density, vice versa.And the present invention makes active material film microstructure that diversification be presented, graphene layer is rich defect
Structure, and there is carbon nanotube to be formed between graphene sheet layer and be conductively connected by force, while carbon nanotube and script are micro- by polystyrene
The space of ball filling struts lamella, so that piece interlamellar spacing is increased, spatially there is fold morphology, open three-dimensional structure, phase is presented
It, can be with than in the two-dimentional active material configuration for only depositing several layer graphenes on a current collector using gas phase deposition technology and being formed
It stores more charges and is conducive to diffusion of the electrolyte charge inside active material film, reduce diffusional resistance, carry
The high high-power output performance of ultracapacitor.It is final realize make on the basis of keeping high transparency and high flexibility it is super
The purpose that capacitor energy and power density optimize, while also reducing the internal resistance of super capacitor system.As embodiment 5 compares
Capacity reaches 397 μ F/cm2Left and right, capacity attenuation is only 2.1% after being bent 5000 times.
Description of the drawings
Specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the structural schematic diagram of the electric double layer transparent flexible ultracapacitor of " sandwich " structure.
Fig. 2 is the microstructure stereoscan photograph of transparent flexible pole piece in embodiment 1.
Fig. 3 is the light transmittance comparison diagram for each transparent flexible ultracapacitor completed device that embodiment 1-5 is obtained.
Fig. 4 is cyclic voltammetry curve figure of the embodiment 1 under the conditions of sweep speed is 0.01V/s-1.0V/s.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.The compound or reagent used in following embodiment is commercially available, or can lead to
It crosses conventional method well known by persons skilled in the art to be prepared, used laboratory apparatus can be bought by commercial sources.
It is gold or nano silver wire the present invention relates to metal nanometer line；The a diameter of 30-50nm of metal nanometer line, length are
30-40μm。
Embodiment 1：
(1) the nano-silver thread solution (10ml) that sol evenning machine spin coating 0.5mg/ml is used in 10cm x10cm PET bases, turns
Speed is 4000rpm, spin-coating time 40s, then heats 5min under the conditions of 120 DEG C with electric hot plate, prepares surface covering gold
Belong to the transparent flexible collector of nanometer line network, the thickness of coating is 100nm.
(2) take graphene oxide solution and the 15ml mass fractions of a concentration of 5mg/ml of 50ml molten for 30% hydrogen peroxide
Liquid mixes, and above-mentioned mixed solution later (is poured into mixed solution dialysis in bag filter, then by bag filter by 100 DEG C of stirring 5h
It immerses in deionized water, carries out dialysis 48h, bag filter is specially " MWCO：1500D”.Dialysis step is identical below), then will be saturating
Solution in analysis bag is poured out, and the rich defect graphene oxide solution of PH=7 is obtained (Before and after dialysis liquor capacity is constant).Later again
0.2g carbon nanotubes and 0.1g polystyrene microspheres are added into above-mentioned rich defect graphene oxide solution, and (grain size of microballoon is
30nm), 5h is stirred at room temperature, obtains rich defect graphene oxide/carbon nanotube base composite dispersion liquid.
(3) take rich defect graphene oxide/carbon nanotube base composite dispersion liquid 2ml in above-mentioned (2) as spin coating liquid, drop
On the transparent flexible collector that the surface that (1) step obtains covers metal nanometer line network, current collector sizes size is 4x
5cm, rotary speed are 1,000 revs/min, spin-coating time 100s；It has obtained being covered with rich defect graphene oxide/carbon nanotube
The pole piece of piece base coating, the results are shown in Figure 2 for coating sem test, and coating film forming is good, and continuous very uniform, thick
Degree is about 60nm.
(4) pole piece for being covered with rich defect graphene oxide/carbon nanotube piece base coating that upper step obtains is placed in close
The volume of envelope is the hydrazine hydrate 50 μ L for being added dropwise to that mass fraction is 98% in the drying basin of 2.5L, reacts 12h under the conditions of 120 DEG C,
The pole piece obtained after above-mentioned reaction is immersed into the acetone soln 5h that purity is 98% again, rinse removes repeatedly with deionized water later
Extra acetone, it is dry, obtain the pole piece for being covered with rich defect graphene/carbon nano-tube nanometer sheet base coating.
(5) 6g PVA (molecular mass 80000-98000) powder is added in 60ml deionized waters, later in 85 DEG C of items
Stirring is to transparent under part, is cooled to room temperature and adds 6g phosphoric acid (a concentration of mass fraction 85% of phosphoric acid) and stirs at room temperature
4h obtains solid transparent electrolyte.
(6) identical two pole pieces for being covered with graphene/carbon nano-tube nanometer sheet base coating acquired in (4) are vertical
Being inserted into 15min in the transparent solid-state electrolyte described in (5), (length for wherein, being submerged into the pole piece part of electrolyte is pole piece
The 70% of total length), 85 DEG C of holding is constant, has obtained further adhering on graphene/carbon nano-tube nanometer sheet base coating surface
There is the pole piece of solid electrolyte.Two identical pole pieces are taken out later, and two pole pieces are covered with graphene/carbon nano-tube nanometer sheet
Opposite place of base coating one side fits together, (wherein, it is attached with the pole piece part fitting of solid electrolyte, two pole pieces
Unsubmerged portion is respectively at the both ends of fitting body), the 10min under the pressure of 1Mp, integral by two pole piece compactings later, obtains
Obtain the electric double layer transparent flexible ultracapacitor of " sandwich " structure.Under conditions of constant bending radius is 2mm, it is bent 5000 times
Capacity attenuation is only 1.2% afterwards.Wherein, test condition is to use electrochemical workstation (Ametek, Princeton Applied
Research, Versa STAT 4) in the potential window of -0.5V to 0.5V with various sweep speed (100mV/s-1000mV/
s)。
Device architecture schematic diagram is shown in Fig. 1, and 1 indicates polyethylene terephthalate in figure, and 2 indicate nano silver wires, and 3 indicate poly-
Vinyl alcohol/phosphoric acid solid electrolyte, 4 indicate rich defect graphene/carbon nano-tube base carbon material；Cyclic voltammetric testing result is as schemed
4, test voltage ranging from -0.5V-0.5V, sweep speed from specific capacitance under 0.01-1.0V/s, 0.01V/s sweep speeds be 910
μF/cm2。
Embodiment 2：
(1) the nano-silver thread solution (10ml) that sol evenning machine spin coating 0.5mg/ml is used in 10cm x10cm PET bases, turns
Speed is 4000rpm, spin-coating time 40s, then heats 5min under the conditions of 120 DEG C with electric hot plate, prepares surface covering gold
Belong to the transparent flexible collector of nanometer line network, the thickness of coating is 100nm.
(2) take graphene oxide solution and the 15ml mass fractions of a concentration of 5mg/ml of 50ml molten for 30% hydrogen peroxide
Liquid mixes, and 100 DEG C of stirring 5h later dialyse mixed solution, then the solution in bag filter is poured out, and the richness for obtaining PH=7 lacks
Fall into graphene oxide solution (Before and after dialysis liquor capacity is constant).It is added again into above-mentioned rich defect graphene oxide solution later
0.2g carbon nanotubes and 0.1g polystyrene microspheres (grain size of microballoon is 30nm), stir 5h, obtain rich defect oxidation at room temperature
Graphene/carbon nano-tube base composite dispersion liquid.
(3) take rich defect graphene oxide/carbon nanotube base composite dispersion liquid 2ml in above-mentioned (2) as spin coating liquid, drop
On the transparent flexible collector that the surface that (1) step obtains covers metal nanometer line network, current collector sizes size is 4x
5cm, rotary speed are 3,000 revs/min, spin-coating time 100s；It has obtained being covered with rich defect graphene oxide/carbon nanotube
The pole piece of piece base coating.
(4) pole piece for being covered with rich defect graphene oxide/carbon nanotube piece base coating that upper step obtains is placed in close
The volume of envelope is the hydrazine hydrate 50 μ L for being added dropwise to that mass fraction is 98% in the drying basin of 2.5L, reacts 12h under the conditions of 120 DEG C,
The pole piece obtained after above-mentioned reaction is immersed into the acetone soln 5h that purity is 98% again, rinse removes repeatedly with deionized water later
Extra acetone, it is dry, obtain the pole piece for being covered with rich defect graphene/carbon nano-tube nanometer sheet base coating.
(5) 6g PVA (molecular mass 80000-98000) powder is added in 60ml deionized waters, later in 85 DEG C of items
Stirring is to transparent under part, is cooled to room temperature and adds 6g phosphoric acid (a concentration of mass fraction 85% of phosphoric acid) and stirs at room temperature
4h obtains solid transparent electrolyte.
(6) identical two pole pieces for being covered with graphene/carbon nano-tube nanometer sheet base coating acquired in (4) are vertical
Being inserted into 15min in the transparent solid-state electrolyte described in (5), (length for wherein, being submerged into the pole piece part of electrolyte is pole piece
The 70% of total length), 85 DEG C of holding is constant, has obtained further adhering on graphene/carbon nano-tube nanometer sheet base coating surface
There is the pole piece of solid electrolyte.Two identical pole pieces are taken out later, and two pole pieces are covered with graphene/carbon nano-tube nanometer sheet
Opposite place of base coating one side fits together, (wherein, it is attached with the pole piece part fitting of solid electrolyte, two pole pieces
Unsubmerged portion is respectively at the both ends of fitting body), the 10min under the pressure of 1Mp, integral by two pole piece compactings later, obtains
Obtain the electric double layer transparent flexible ultracapacitor of " sandwich " structure.Under conditions of constant bending radius is 2mm, it is bent 5000 times
Capacity attenuation is only 1.4% afterwards.Wherein, test condition is to use electrochemical workstation (Ametek, Princeton Applied
Research, Versa STAT 4) in the potential window of -0.5V to 0.5V with various sweep speed (100mV/s-1000mV/
s)。
Embodiment 3：
(1) the nano-silver thread solution (10ml) that sol evenning machine spin coating 0.5mg/ml is used in 10cm x10cm PET bases, turns
Speed is 4000rpm, spin-coating time 40s, then heats 5min under the conditions of 120 DEG C with electric hot plate, prepares surface covering gold
Belong to the transparent flexible collector of nanometer line network, the thickness of coating is 100nm.
(2) take graphene oxide solution and the 15ml mass fractions of a concentration of 5mg/ml of 50ml molten for 30% hydrogen peroxide
Liquid mixes, and 100 DEG C of stirring 5h later dialyse mixed solution, then the solution in bag filter is poured out, and the richness for obtaining PH=7 lacks
Fall into graphene oxide solution (Before and after dialysis liquor capacity is constant).It is added again into above-mentioned rich defect graphene oxide solution later
0.2g carbon nanotubes and 0.1g polystyrene microspheres (grain size of microballoon is 30nm), stir 5h, obtain rich defect oxidation at room temperature
Graphene/carbon nano-tube base composite dispersion liquid.
(3) take rich defect graphene oxide/carbon nanotube base composite dispersion liquid 2ml in above-mentioned (2) as spin coating liquid, drop
On the transparent flexible collector that the surface that (1) step obtains covers metal nanometer line network, current collector sizes size is 4x
5cm, rotary speed are 5,000 revs/min, spin-coating time 100s；It has obtained being covered with rich defect graphene oxide/carbon nanotube
The pole piece of piece base coating.
(4) pole piece for being covered with rich defect graphene oxide/carbon nanotube piece base coating that upper step obtains is placed in close
The volume of envelope is the hydrazine hydrate 50 μ L for being added dropwise to that mass fraction is 98% in the drying basin of 2.5L, reacts 12h under the conditions of 120 DEG C,
The pole piece obtained after above-mentioned reaction is immersed into the acetone soln 5h that purity is 98% again, rinse removes repeatedly with deionized water later
Extra acetone, it is dry, obtain the pole piece for being covered with rich defect graphene/carbon nano-tube nanometer sheet base coating.
(5) 6g PVA (molecular mass 80000-98000) powder is added in 60ml deionized waters, later in 85 DEG C of items
Stirring is to transparent under part, is cooled to room temperature and adds 6g phosphoric acid (a concentration of mass fraction 85% of phosphoric acid) and stirs at room temperature
4h obtains solid transparent electrolyte.
(6) identical two pole pieces for being covered with graphene/carbon nano-tube nanometer sheet base coating acquired in (4) are vertical
Being inserted into 15min in the transparent solid-state electrolyte described in (5), (length for wherein, being submerged into the pole piece part of electrolyte is pole piece
The 70% of total length), 85 DEG C of holding is constant, has obtained further adhering on graphene/carbon nano-tube nanometer sheet base coating surface
There is the pole piece of solid electrolyte.Two identical pole pieces are taken out later, and two pole pieces are covered with graphene/carbon nano-tube nanometer sheet
Opposite place of base coating one side fits together, (wherein, it is attached with the pole piece part fitting of solid electrolyte, two pole pieces
Unsubmerged portion is respectively at the both ends of fitting body), the 10min under the pressure of 1Mp, integral by two pole piece compactings later, obtains
Obtain the electric double layer transparent flexible ultracapacitor of " sandwich " structure.Under conditions of constant bending radius is 2mm, it is bent 5000 times
Capacity attenuation is only 1.8% afterwards.Wherein, test condition is to use electrochemical workstation (Ametek, Princeton Applied
Research, Versa STAT 4) in the potential window of -0.5V to 0.5V with various sweep speed (100mV/s-1000mV/
s)。
Embodiment 4：
(1) the nano-silver thread solution (10ml) that sol evenning machine spin coating 0.5mg/ml is used in 10cm x10cm PET bases, turns
Speed is 4000rpm, spin-coating time 40s, then heats 5min under the conditions of 120 DEG C with electric hot plate, prepares surface covering gold
Belong to the transparent flexible collector of nanometer line network, the thickness of coating is 100nm.
(2) take graphene oxide solution and the 15ml mass fractions of a concentration of 5mg/ml of 50ml molten for 30% hydrogen peroxide
Liquid mixes, and 100 DEG C of stirring 5h later dialyse mixed solution, then the solution in bag filter is poured out, and the richness for obtaining PH=7 lacks
Fall into graphene oxide solution (Before and after dialysis liquor capacity is constant).It is added again into above-mentioned rich defect graphene oxide solution later
0.2g carbon nanotubes and 0.1g polystyrene microspheres (grain size of microballoon is 30nm), stir 5h, obtain rich defect oxidation at room temperature
Graphene/carbon nano-tube base composite dispersion liquid.
(3) take rich defect graphene oxide/carbon nanotube base composite dispersion liquid 2ml in above-mentioned (2) as spin coating liquid, drop
On the transparent flexible collector that the surface that (1) step obtains covers metal nanometer line network, current collector sizes size is 4x
5cm, rotary speed are 7,000 revs/min, spin-coating time 100s；It has obtained being covered with rich defect graphene oxide/carbon nanotube
The pole piece of piece base coating.
(4) pole piece for being covered with rich defect graphene oxide/carbon nanotube piece base coating that upper step obtains is placed in close
The volume of envelope is the hydrazine hydrate 50 μ L for being added dropwise to that mass fraction is 98% in the drying basin of 2.5L, reacts 12h under the conditions of 120 DEG C,
The pole piece obtained after above-mentioned reaction is immersed into the acetone soln 5h that purity is 98% again, rinse removes repeatedly with deionized water later
Extra acetone, it is dry, obtain the pole piece for being covered with rich defect graphene/carbon nano-tube nanometer sheet base coating.
(5) 6g PVA (molecular mass 80000-98000) powder is added in 60ml deionized waters, later in 85 DEG C of items
Stirring is to transparent under part, is cooled to room temperature and adds 6g phosphoric acid (a concentration of mass fraction 85% of phosphoric acid) and stirs at room temperature
4h obtains solid transparent electrolyte.
(6) identical two pole pieces for being covered with graphene/carbon nano-tube nanometer sheet base coating acquired in (4) are vertical
Being inserted into 15min in the transparent solid-state electrolyte described in (5), (length for wherein, being submerged into the pole piece part of electrolyte is pole piece
The 70% of total length), 85 DEG C of holding is constant, has obtained further adhering on graphene/carbon nano-tube nanometer sheet base coating surface
There is the pole piece of solid electrolyte.Two identical pole pieces are taken out later, and two pole pieces are covered with graphene/carbon nano-tube nanometer sheet
Opposite place of base coating one side fits together, (wherein, it is attached with the pole piece part fitting of solid electrolyte, two pole pieces
Unsubmerged portion is respectively at the both ends of fitting body), the 10min under the pressure of 1Mp, integral by two pole piece compactings later, obtains
Obtain the electric double layer transparent flexible ultracapacitor of " sandwich " structure.Under conditions of constant bending radius is 2mm, it is bent 5000 times
Capacity attenuation is only 1.9% afterwards.Wherein, test condition is to use electrochemical workstation (Ametek, Princeton Applied
Research, Versa STAT 4) in the potential window of -0.5V to 0.5V with various sweep speed (100mV/s-1000mV/
s)。
Embodiment 5：
(1) the nano-silver thread solution (10ml) that sol evenning machine spin coating 0.5mg/ml is used in 10cm x10cm PET bases, turns
Speed is 4000rpm, spin-coating time 40s, then heats 5min under the conditions of 120 DEG C with electric hot plate, prepares surface covering gold
Belong to the transparent flexible collector of nanometer line network, the thickness of coating is 100nm.
(2) take graphene oxide solution and the 15ml mass fractions of a concentration of 5mg/ml of 50ml molten for 30% hydrogen peroxide
Liquid mixes, and 100 DEG C of stirring 5h later dialyse mixed solution, then the solution in bag filter is poured out, and the richness for obtaining PH=7 lacks
Fall into graphene oxide solution (Before and after dialysis liquor capacity is constant).It is added again into above-mentioned rich defect graphene oxide solution later
0.2g carbon nanotubes and 0.1g polystyrene microspheres (grain size of microballoon is 30nm), stir 5h, obtain rich defect oxidation at room temperature
Graphene/carbon nano-tube base composite dispersion liquid.
(3) take rich defect graphene oxide/carbon nanotube base composite dispersion liquid 2ml in above-mentioned (2) as spin coating liquid, drop
On the transparent flexible collector that the surface that (1) step obtains covers metal nanometer line network, current collector sizes size is 4x
5cm, rotary speed are 10,000 revs/min, spin-coating time 100s；It has obtained being covered with rich defect graphene oxide/carbon nanotube and receive
The pole piece of rice piece base coating.
(4) pole piece for being covered with rich defect graphene oxide/carbon nanotube piece base coating that upper step obtains is placed in close
The volume of envelope is the hydrazine hydrate 50 μ L for being added dropwise to that mass fraction is 98% in the drying basin of 2.5L, reacts 12h under the conditions of 120 DEG C,
The pole piece obtained after above-mentioned reaction is immersed into the acetone soln 5h that purity is 98% again, rinse removes repeatedly with deionized water later
Extra acetone, it is dry, obtain the pole piece for being covered with rich defect graphene/carbon nano-tube nanometer sheet base coating.
(5) 6g PVA (molecular mass 80000-98000) powder is added in 60ml deionized waters, later in 85 DEG C of items
Stirring is to transparent under part, is cooled to room temperature and adds 6g phosphoric acid (a concentration of mass fraction 85% of phosphoric acid) and stirs at room temperature
4h obtains solid transparent electrolyte.
(6) identical two pole pieces for being covered with graphene/carbon nano-tube nanometer sheet base coating acquired in (4) are vertical
Being inserted into 15min in the transparent solid-state electrolyte described in (5), (length for wherein, being submerged into the pole piece part of electrolyte is pole piece
The 70% of total length), 85 DEG C of holding is constant, has obtained further adhering on graphene/carbon nano-tube nanometer sheet base coating surface
There is the pole piece of solid electrolyte.Two identical pole pieces are taken out later, and two pole pieces are covered with graphene/carbon nano-tube nanometer sheet
Opposite place of base coating one side fits together, (wherein, it is attached with the pole piece part fitting of solid electrolyte, two pole pieces
Unsubmerged portion is respectively at the both ends of fitting body), the 10min under the pressure of 1Mp, integral by two pole piece compactings later, obtains
Obtain the electric double layer transparent flexible ultracapacitor of " sandwich " structure.Under conditions of constant bending radius is 2mm, it is bent 5000 times
Capacity attenuation only 2.1% afterwards.Wherein, test condition is to use electrochemical workstation (Ametek, Princeton Applied
Research, Versa STAT 4) in the potential window of -0.5V to 0.5V with various sweep speed (100mV/s-1000mV/
s)。
Table 1 is capacity attenuation after each embodiment sample light transmittance (at wavelength 550nm) and specific capacitance and 5000 bendings
Test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Light transmittance | 41% | 51% | 60% | 73% | 76% |
| Specific capacitance (μ F/cm2) | 910 | 715 | 496 | 421 | 397 |
| Capacity attenuation | 1.2% | 1.4% | 1.8% | 1.9% | 2.1% |
Although specific embodiment has been combined to be illustrated the present invention, those skilled in the art will recognize that
, without departing from spirit and scope of the present invention, the embodiment can be changed or be improved, model of the present invention
It encloses and is limited by the appended claims.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. a kind of preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost, it is characterized in that this method includes
Following steps：
(1) preparation of transparent flexible collector：Using metal nanometer line solution as raw material, by film-forming method in non-transparent flexible substrate
One side surface of material prepares metal nanometer line coating, is then dried at 100 DEG C -150 DEG C, obtains surface covering metal nano
The transparent flexible collector of gauze network；
The concentration range of the metal nanometer line solution is 0.1-10mg/mL；1nm-1 μm of the thickness range of coating is made；
(2) preparation of rich defect graphene oxide/carbon nanotube base composite dispersion liquid：By graphene oxide solution and hydrogen peroxide
Solution mixes, and 3-7h is stirred at 80 DEG C -150 DEG C, is then dialysed, rich defect graphene oxide solution is obtained；It will
Rich defect graphene oxide solution is mixed with carbon nanotube, polystyrene microsphere, 1-10h is stirred at 25 DEG C -40 DEG C, and then obtain
Rich defect graphene oxide/carbon nanotube base composite dispersion liquid；
Wherein, 30-80mL hydrogenperoxide steam generators are corresponded to per 1g graphene oxides；Graphene oxide solution concentration range is 0.1-
The mass fraction of 10mg/mL, hydrogenperoxide steam generator are 20%-40%；The matter that carbon nanotube is added is corresponded to per 1g graphene oxides
Amount is 0.1-20g and 0.1g-20g polystyrene microspheres；The diameter range 20-200nm of polystyrene microsphere；
(3) preparation of rich defect graphene oxide/carbon nanotube piece base coating pole piece：Obtained rich defect oxidation is walked above
Graphene/carbon nano-tube base composite dispersion liquid is spin coating liquid, drops in the surface covering metal nanometer line network that (1) step obtains
On transparent flexible collector, under conditions of rotating speed is thousand revs/min of 0.5-10.0, spin coating 10-600s；It has obtained being covered with rich defect
The pole piece of graphene oxide/carbon nanotube piece base coating；
Wherein, per 1cm2Surface, which covers, is added dropwise 0.01-100ml richness defect oxygen on the transparent flexible collector of metal nanometer line network
Graphite alkene/carbon nanotube base composite dispersion liquid；
(4) preparation of rich defect graphene/carbon nano-tube nanometer sheet base stage piece：It is covered with rich defect graphite oxide by what upper step obtained
The pole piece of alkene/carbon nanotube piece base coating is placed in sealing container, hydrazine hydrate is added dropwise again in sealing container, later 70
At DEG C -150 DEG C, above-mentioned pole piece after reaction, then is immersed 0.5-12h, Zhi Houzai in acetone soln by confined reaction 5-24h
Extra acetone is removed with deionized water, dry 5-12h, has obtained being covered with rich defect graphene/carbon nano-tube at 20-60 DEG C
The pole piece of nanometer sheet base coating；
Wherein, the mass fraction of hydrazine hydrate is 70%-98%, and the mass fraction of acetone is 70%-98%；1cm2It is covered with rich defect
Graphene oxide/carbon nanotube piece base coating corresponds to 0.1-100 μ L hydrazine hydrates；
(5) preparation of transparent solid-state electrolyte：Polyvinyl alcohol (PVA) powder is added in deionized water, at 60 DEG C -100 DEG C
Stirring adds phosphoric acid to transparent at a temperature of 60 DEG C -100 DEG C, continues to stir 3-5h, has obtained transparent solid-state electrolyte；
Wherein, 1-5g phosphoric acid and 1-10g polyvinyl alcohol (PVA) powder is added in every 10ml deionized waters；The concentration range of phosphoric acid
For 70%-98%；
(6) preparation of the electric double layer transparent flexible ultracapacitor of " sandwich " structure：Identical two obtained in selecting step (4)
Piece is covered with the pole piece of rich defect graphene/carbon nano-tube nanometer sheet base coating, they is immersed vertically transparent solid in above-mentioned (5)
In state electrolyte solution, 5-20min is kept, wherein the length for immersing part is the 20~80% of pole piece length；After taking-up
2-24h is dried at room temperature, and the one side that rich defect graphene/carbon nano-tube nanometer sheet base coating is covered in two pole pieces is put in opposite directions
It sets, is bonded, then it is suppressed 5~15 minutes under 1MP-10MP pressure, the electric double layer for having obtained " sandwich " structure is transparent
Flexible super capacitor.
2. the preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost as described in claim 1, special
Sign is that metal nanometer line is gold, silver nano wire in the step (1)；The a diameter of 30-50nm of metal nanometer line, length are
30-40μm。
3. the preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost as described in claim 1, special
Sign is that the film-forming method is spin coating film-forming method.
4. the preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost as described in claim 1, special
Sign is that the non-transparent flexible substrate material is PET (polyethylene terephthalate).
5. the preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost as described in claim 1, special
Sign is that the dialysis process described in the step (2) is bag filter dialysis.
6. the preparation method of all solid state multilevel hierarchy transparent flexible ultracapacitor of low cost as described in claim 1, special
Sign is that the sealing container volume in the step (4) is 0.01L-1000L.
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