CN106348283B - A kind of graphene film and the application for preparing all solid state energy storage Electrochromic device - Google Patents
A kind of graphene film and the application for preparing all solid state energy storage Electrochromic device Download PDFInfo
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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Abstract
The invention discloses a kind of graphene film and the application of all solid state energy storage Electrochromic device is prepared, the graphene film is that graphite oxide mix with deionized water, and ferric trichloride is added after ultrasonic disperse formation dispersion liquid, shakes and forms graphene oxide hydrogel；After graphene oxide hydrogel Tu plate film forming, in hydroiodic acid and acetic acid mixed liquor, 75 DEG C of immersions, freeze-drying obtains graphene film；Graphene film material of the present invention has higher toughness, preferable pore size distribution situation, and good chemical property can bear the pulling force of 100g.Its specific capacity that 130F/g is able to maintain in the current density constant current charge-discharge test of 1A/g.The all solid state energy storage Electrochromic device of the present invention had not only had the energy storage effect of energy storage device, but also the colour change function with electrochromic device, and under the current density of 0.00005A, area specific capacity is up to 13.3mF/cm.
Description
(1) technical field
The present invention relates to a kind of Graphene gel film and prepare the application of all solid state energy storage Electrochromic device.
(2) background technique
With the development of the social economy, people are increasing for the demand of the energy, energy supply contradiction is further prominent.Storage
Energy device plays the part of more and more important role in we live.
Lithium ion battery and supercapacitor are current using the two kind energy storage devices more with research.With lithium ion battery
There is its unique advantage compared to supercapacitor, such as supercapacitor has bigger power density, there is longer service life
With preferable high rate performance, especially there is its indispensable effect in following field of traffic.Supercapacitor can be divided into double again
Electric layer supercapacitor and pseudocapacitors.By carried out on the surface of electrolyte ion and bigger serface electrode material absorption with
Desorption is stored and is released energy.And for fake capacitance supercapacitor, mainly pass through the electroactive metal oxidation of tool
Object or conducting polymer store energy by its faraday's oxidation-reduction process.
Nowadays grapheme material uses more and more extensive in terms of electrode of super capacitor preparation, main reason is that stone
The excellent performance of black alkene material, such as its high specific surface area, high conductivity, high-mechanical property etc..
Electrochromism refers to that there is a phenomenon where redox reactions to cause color change under electrochemical action for substance.It is common
Electrochromic material mainly have inorganic electrochromic material and conducting polymer organic electroluminescence based on transition metal oxide
Off-color material.Electrochromic device is the main application of electrochromic material, and electrochromic device is in smart window, anti-glare backsight
Mirror and display screen etc. are widely used.There are chemical stabilities for the electrochromic device being assembled into due to use solution electrolyte
Difference is not easy to encapsulate, in use process the problems such as easy-to-leak liquid, in recent years, with the development of solid polyelectrolyte.To sum up institute
It states, the reasonable utilization energy is the developing direction of future technology, so all solid state energy storage Electrochromic device is reasonable energy utilization
Typical example.It can be by changing the voltage of device two-stage to make device show different colors, while can also store energy
Amount can also can judge the amount of device storage according to the different color of device.This device can be used as one kind
Novel energy storage smart window uses.It can be filled as a kind of energy storage on the basis of indoor light can be changed in traditional smart window
It sets, to reach energy conservation, environmental protection, intelligent purpose.
(3) summary of the invention
It is an object of the present invention to provide a kind of graphene film and its application in all solid state energy storage Electrochromic device is being prepared, is being
The preparation of all solid state energy storage Electrochromic device provides a kind of novel thinking.
The technical solution adopted by the present invention is that:
The present invention provides a kind of graphene film, and the graphene film is that graphite oxide is mixed with deionized water, ultrasound
Ferric trichloride is added after forming dispersion liquid in dispersion, and concussion forms graphene oxide hydrogel；By graphene oxide hydrogel Tu plate
After film forming, in hydroiodic acid (HI) and acetic acid (HAC) mixed liquor, 75 DEG C of immersions, freeze-drying obtains graphene film；It is described
Graphite oxide concentration is 1~50mg/ml in dispersion liquid, and the ferric trichloride and graphite oxide mass ratio are 0.01~0.1:1.
Further, the hydroiodic acid and hydroiodic acid dosage arbitrary proportion in acetic acid mixed liquor, preferred volume ratio 1:
0.1-10, more preferable 1:2.
Further, 1~60min is first stood at room temperature after the graphene oxide hydrogel Tu plate film forming, then put again
Enter in HI and HAC mixed liquor, 75 DEG C of immersion 6h.
Further, the graphene film is prepared as follows: graphite oxide being mixed with deionized water, in power
53KHz, graphene oxide dispersion is made in ultrasonic disperse 3h under conditions of 42 DEG C, and ferric trichloride is added, and concussion forms uniform
Graphene oxide hydrogel；Graphene oxide hydrogel is poured on to one end of hydrophilic glass substrate, it is scraped with scraper
Apply, so that graphene oxide hydrogel is formed uniformly graphene oxide aquagel membrane on glass, together with glass at room temperature, air
Middle standing 1-60min；Graphene oxide hydrogel is put into HI and the HAC mixed liquor that volume ratio is 1:2 together with substrate of glass
2-10h is impregnated, 25-100 DEG C (preferably 75 DEG C) is heated to, is kept for 6 hours；Film is taken out from substrate of glass, clear water washs, then
For 24 hours in < 0 DEG C of freeze-drying, graphene film is obtained；Graphite oxide concentration is 8.59mg/ml in the graphite oxide dispersion,
The ferric trichloride and graphite oxide mass ratio are 0.05~0.1:1.
Further, described graphene oxide aquagel membrane blade coating thickness (i.e. the height of scraper) < 2cm, more preferable 100~
800μm。
Further, the graphene film is with a thickness of 0.1-100 μm.
Further, the hydrophilic glass substrate is prepared as follows: sheet glass is dipped in 98% concentrated sulfuric acid and 30%
In the mixed liquor of dioxygen water volume ratio 7:3, it is heated to 90 DEG C and impregnates 1 hour, taking-up is successively washed with deionized water and dehydrated alcohol
It washs, is dried with nitrogen, obtain hydrophilic glass substrate.
The present invention also provides a kind of graphene films to prepare the application in all solid state energy storage Electrochromic device, described complete
Solid-state energy storage Electrochromic device, including first substrate and the second substrate, are from top to bottom folded between the first substrate and the second substrate
Equipped with electrolyte layer and electrochromic electrode layer, the electrochromic electrode layer includes electrochromic electrode workspace and shading
Area, the shading region is the second graphene film, and is laid out the electrochromism around electrochromic electrode workspace
Electrode working zone is electrochromic layer, is provided between the first substrate and the electrolyte layer and offers the of hollow out window
One graphene film, described hollow out the window's position and the electrochromic electrode workspace overlap；First graphene
Film is identical as the second graphene film size, shape and is overlapped.
Further, the first substrate and the second substrate are ITO electro-conductive glass, long 2.5cm, wide 1.5cm.
Further, the electrolyte layer is PVA/ sulfuric acid solid-state electrolyte layer, is prepared as follows: by polyvinyl alcohol
(PVA), 98% sulfuric acid of mass concentration and deionized water mixing, stirring forms colloid at 85 DEG C, cooling, pours into surface plate certainly
So drying, obtains PVA/ sulfuric acid solid-state electrolyte layer；The polyvinyl alcohol and 98% sulfuric acid mass ratio of mass concentration are 1:1, institute
It states deionized water volumetric usage and 10ml/g is calculated as with 98% sulfuric acid quality of mass concentration.
Further, the electrochromic electrode layer is prepared as follows: taking 4,4 ', 4 "-three [2- (3,4- ethylene dioxies
Thienyl) phenyl)] amine (TEAP) monomer is dissolved in chloroform, and ferric trichloride is added, it is under nitrogen protection, anti-in room temperature (25 DEG C)
Methanol extraction, filtering should be added for 24 hours, after reaction, filter cake is dried in vacuo for 24 hours at 60 DEG C, obtains polymer P TEAP powder
End dissolves polymer P TEAP powder with chloroform, obtains PTEAP/ chloroform dispersion liquid, drop coating or is sprayed at ITO electro-conductive glass
On, drying is prepared into electrochromic electrode layer；The ratio between amount of the monomer and ferric trichloride substance is 1:3.5, the chloroform body
Product dosage is calculated as 250ml/g with monomer mass.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
Prepared graphene film material has higher toughness in the present invention.Material has preferable pore size distribution feelings simultaneously
Condition can express good chemical property, can bear the pulling force of 100g.Its current density constant current charge-discharge in 1A/g is surveyed
The specific capacity of 130F/g is able to maintain in examination.This material is suitable as flexible super capacitor electrode material.The present invention is all solid state
Energy storage Electrochromic device had not only had the energy storage effect of energy storage device (symmetry electrode supercapacitor), but also with electrochromic device
Colour change function.Its device is composed of the basic structure of supercapacitor and electrochromic device, has more succinct knot
Structure, ease of assembly.A kind of novel preparation thinking can be provided for the preparation of following all solid state energy storage Electrochromic device.Its device in
Under the current density of 0.00005A, area specific capacity is up to 13.3mF/cm.
(4) Detailed description of the invention
Fig. 1 is that the structure of all solid state energy storage Electrochromic device splits schematic diagram (a) and the combination of all solid state energy storage Electrochromic device is shown
It is intended to (b).
Fig. 2 is all solid state energy storage Electrochromic device in the case where current density is 0.00005A, 0.0001A, 0.0002A,
Voltage window be -0.8-0.2V under constant current charge-discharge test, with all solid state energy storage Electrochromic device under different potentials color
Variation；A is all solid state energy storage Electrochromic device in the case where current density is 0.00005A, 0.0001A, 0.0002A, voltage window
Mouth is the constant current charge-discharge test under -0.8-0.2V, and arrow A corresponds to c, and arrow B corresponds to b；The all solid state energy storage Electrochromic device of b is in electricity
The state that pressure is -0.8V (its window that changes colour is shown as yellow green)；C is all solid state energy storage Electrochromic device when voltage is 0.2V
(its window that changes colour is shown as navy blue to state.
Fig. 3 is high rate performance test result of all solid state energy storage Electrochromic device under different current densities.
Fig. 4 is the cross-sectional SEM image (b) that the present invention prepares graphene film effect picture (a) and graphene film；
Fig. 5 is graphene film electrochemical property test CV image.
Fig. 6 is graphene film electrochemical property test AC impedance image.
Fig. 7 is the tensile test diagram of graphene film material.
(5) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Percentage concentration of the present invention unless otherwise indicated, refers both to mass percentage concentration.
Embodiment 1
(1) sheet glass is first cut into growth 7cm, wide 3cm.Sheet glass is dipped in 98% concentrated sulfuric acid and 30% dioxygen water volume
In mixed liquor than 7:3,90 DEG C are heated to, and impregnates or so hour at this temperature.Take out successively with deionized water with
Dehydrated alcohol washs it, is dried with nitrogen to obtain hydrophilic glass substrate.
(2) graphite oxide is prepared (referring to Bong Gill Choi, HoSeok Park, Tae using the Hummers method of improvement
Jung Park,Min Ho Yang,Joon Sung Kim,Sung-Yeon Jang,Nam Su Heo,Sang Yup Lee,
Jing Kong, and Won Hi Hong, Nano.2010,4,2910-2918.), and washed repeatedly with deionized water to neutrality,
Obtain graphite oxide.Graphite oxide is mixed, and in ultrasonic pond with deionized water, is surpassed under conditions of power 53KHz, 42 DEG C
Sound 3h, obtaining concentration is 8.59mg/ml graphene oxide deionized water dispersion liquid.Take graphene oxide deionized water dispersion liquid
2.5ml is put into 4ml thread bottle, and 1.5mg ferric trichloride, concussion is added, until liquid forms uniform graphene oxide in bottle
Hydrogel.
(3) will prepare in step (2) graphene oxide hydrogel in step (1) in the hydrophilic glass substrate for preparing
One end scratches it with the scraper for being highly 0.56mm, makes graphene oxide hydrogel homogeneous film formation on glass, thickness
It is 4.82 μm, at room temperature, stands 15min in air.Then it places into the mixed liquor that HI and HAC volume ratio is 1:2 and impregnates
40min is heated to 75 DEG C, is kept for about 6 hours.Graphene oxide obtains being reduced into reduced graphene in the process, obtains
Obtain reduced graphene film substrate.
(4) the reduced graphene film in the reduced graphene film substrate of step (3) preparation is taken out, is put in a large amount of clear water
Washing.- 175 DEG C of freeze-dryings for 24 hours, obtain graphene paper, i.e. graphene film in freeze drier.
The characterization of graphene film macroscopic view and microscopic appearance, as shown in Figure 4, a is stone prepared in step (4) in Fig. 4
The photo of black alkene film.It can be seen that its bendable, and free from flaw in appearance, illustrate the graphite using the method for the present invention preparation
Alkene film has good quality.In Fig. 4 b for graphene film prepared in step (4) institute's table at scanning electron microscope (SEM)
The microscopic appearance revealed.Show the internal morphology that its porous and graphene layer is mutually crosslinked.
Electro-chemical test: the graphene film (2mg) for taking step (4) method to prepare, to be pressed on foam under the pressure of 30Mpa
On nickel, electrode is prepared.Using 6M KOH as electrolyte, Pt piece is to electrode, and mercury/mercury oxide is reference electrode, utilizes electrochemistry work
It stands and carries out electro-chemical test (1) to it with the current density of 1A/g, -0.8-0V is that voltage window carries out constant current charge-discharge test
(as shown in Figure 5).(2) using 0.01Hz to 100kHz be frequency separation 5mV be amplitude carry out ac impedance measurement (such as Fig. 6 institute
Show).
Graphene film tensile test:
Graphene film is hung to the weight (as shown in Figure 7) of about 100g.Test result: existed by graphene film in Fig. 5
Constant current charge-discharge test figure can be seen that under 1A/g, and resolution chart is substantially isosceles triangle, reflect preferable capacitive property.
It can calculate simultaneously, this material is able to maintain the relatively Fabrication of High Specific Capacitance of 130F/g in the current density constant current charge-discharge test of 1A/g
Amount.
This material shows lower ion diffusion and transmitting electricity it can be seen from ac impedance measurement figure in Fig. 6
It hinders with lower electron transmission resistance, illustrates that this material has good electric conductivity, and there is good pore distribution structure,
Facilitate the entrance and abjection of electrochemical process ion.Further illustrate the good chemical property of this material.
(5) 98% concentrated sulfuric acid of 6g is added in 60ml deionized water and dilutes, and 6gPVA is added, and heating makes its plastic at 85 DEG C
Shape body, it is cooling.Gel is poured into surface plate natural drying, obtains PVA/ sulfuric acid solid-state electrolyte layer, long 2cm, wide 1.5cm.
(6) taking 4,4 ', 4 "-three, [2- (3,4- ethene dioxythiophene base) phenyl)] amine (TEAP) monomer 100mg is dissolved in 25mL
In chloroform, the oxidant ferric trichloride (0.009755g) that mole is 3.5 times of monomer is added, under nitrogen protection, in room temperature
(25 DEG C) reactions are for 24 hours.After reaction, a large amount of methanol, which is added, precipitates product, then filters.By obtained filter cake at 60 DEG C
Lower vacuum drying for 24 hours, obtains navy blue polymer P TEAP powder.Polymer P TEAP powder is dissolved with chloroform, is obtained
PTEAP/ chloroform dispersion liquid, drop coating or is sprayed on ITO electro-conductive glass (long 2.5cm, wide 1.5cm), dries, is prepared into electroluminescent change
Color electrode layer, long 1.2cm, wide 0.8cm.
(7) graphene paper prepared in step (4) is cut into a length of 2cm in outside, width 1.5cm with scissors, inner edge is length
" returning " font of 1.2cm, the intermediate hollow out that width is 0.8cm.
(8) ITO electro-conductive glass, the electrochromic layer of step (6) preparation, step (7) are prepared into graphene film, step respectively
Suddenly the PVA/ sulfuric acid solid electrolyte of (5) preparation, step (7) prepare graphene film, ITO electro-conductive glass according to the knot in Fig. 1
Structure is sequentially overlapped combination, i.e., the described all solid state energy storage Electrochromic device, including first substrate and the second substrate, the first substrate and
It is from top to bottom folded between the second substrate and is equipped with electrolyte layer and electrochromic electrode layer, the electrochromic electrode layer includes electroluminescent
Electrochromic electrode workspace and shading region, the shading region is the second graphene film, and is laid out and works in electrochromic electrode
Around area, the electrochromic electrode workspace is electrochromic layer, is set between the first substrate and the electrolyte layer
It is equipped with the first graphene film for offering hollow out window, described hollow out the window's position and the electrochromic electrode work
Area's overlapping；First graphene film is identical as the second graphene film size, and shape is identical and is overlapped.It presses under stress
It is real, all solid state energy storage Electrochromic device is made, ito glass part (i.e. above-mentioned first substrate, the second substrate) is electrode.
Electro-chemical test is tested by Shanghai Chen Hua CHI660e electrochemical workstation.The wherein work of electrochemical workstation
Make the second substrate (covering the pole for having electrochromic layer) of electrode link device.Its reference electrode and the to electrode and device
One substrate is connected (only ITO).
(9) test of device:
All solid state energy storage Electrochromic device is connected with electrochemical workstation, working electrode links electrochromic electrode
(PTEAP electrode), reference electrode with to electrode link device to electrode, respectively 0.00005A, 0.0001A, 0.0002A,
Under the current density of 0.0004A, 0.001A, voltage window is to carry out constant current charge-discharge test to it under -0.8~0.2V,
Charging and discharging curve and device color when current density is 0.00005A, 0.0001A, 0.0002A is in the variation of current potential such as Fig. 2
Shown, high rate performance is as shown in Figure 3.
By the charging and discharging curve at symmetrical triangular form shape represented under different current densities of device in Fig. 2, with
Device charge-discharge magnification test chart in Fig. 3, it can be seen that this all solid state energy storage Electrochromic device has good energy-storage property.This device
Part is under the current density of 0.00005A, and area specific capacity is up to 13.3mF/cm.Meanwhile by can also represent this device in Fig. 2
For part when voltage is respectively 0.2V and -0.8V, the color change interval of hollow out shows navy blue and yellow green respectively among device, and
Color differentiation is obvious, color is sensitive with voltage change, illustrates that this device has good electrochromic property.
In conclusion the present invention has provided a kind of novel, of good performance all solid state energy storage Electrochromic device.It is more important
, can be the research of the following all solid state energy storage Electrochromic device and the brand-new method that preparation provide.
Claims (9)
1. a kind of graphene film is preparing the application in all solid state energy storage Electrochromic device, all solid state energy storage Electrochromic device,
It is folded equipped with electrolyte layer and electroluminescent from top to bottom between the first substrate and the second substrate including first substrate and the second substrate
Electrochromic electrode layer, it is characterised in that the electrochromic electrode layer includes electrochromic electrode workspace and shading region, described
Shading region is the second graphene film, and is laid out around electrochromic electrode workspace, the electrochromic electrode work
Area is electrochromic layer, and the first graphene for offering hollow out window is provided between the first substrate and the electrolyte layer
Film, described hollow out the window's position and the electrochromic electrode workspace overlap；First graphene film is oxygen
Graphite is mixed with deionized water, and ferric trichloride is added after forming dispersion liquid in ultrasonic disperse, and concussion forms graphene oxide water-setting
Glue；After graphene oxide hydrogel Tu plate film forming, in hydroiodic acid and acetic acid mixed liquor, 75 DEG C of immersions are freeze-dried, obtain
First graphene film；Graphite oxide concentration is 5 ~ 10mg/ml, the ferric trichloride and graphite oxide quality in the dispersion liquid
Than for 0.01 ~ 0.1:1；Second graphene film is identical as the first graphene film.
2. application as described in claim 1, it is characterised in that the hydroiodic acid is 1:2 with acetic acid volume ratio.
3. application as described in claim 1, it is characterised in that after the hydrogel Tu plate film forming first be stored at room temperature 1 ~
Then 60min is placed into hydroiodic acid and acetic acid mixed liquor, 75 DEG C of immersion 6h.
4. application as described in claim 1, it is characterised in that first graphene film is prepared as follows: will be aoxidized
Graphite is mixed with deionized water, and graphite oxide dispersion is made in ultrasonic disperse 3h under conditions of power 53KHz, 42 DEG C, is added
Ferric trichloride, concussion form uniform graphene oxide hydrogel；Graphene oxide hydrogel is poured on hydrophilic glass substrate
One end, it is scratched with scraper, graphene oxide hydrogel is made to be formed uniformly graphene oxide water on the glass substrate
Gel mould at room temperature, stands 15min in air；Then it places into the hydroiodic acid and acetic acid mixed liquor that volume ratio is 1:2 and soaks
40min is steeped, 75 DEG C is heated to, is kept for 6 hours；Film is taken out from substrate of glass, clear water washing is freeze-dried then at -175 DEG C
For 24 hours, the first graphene film is obtained；Graphite oxide concentration is 8.59mg/ml, the tri-chlorination in the graphite oxide dispersion
Iron and graphite oxide mass ratio are 0.05 ~ 0.1:1.
5. application as claimed in claim 4, it is characterised in that the graphene oxide aquagel membrane scratches thickness < 2cm.
6. application as claimed in claim 4, it is characterised in that the hydrophilic glass substrate is prepared as follows: by glass
Piece is dipped in the mixed liquor of 98% concentrated sulfuric acid and 30% dioxygen water volume ratio 7:3, is heated to 90 DEG C and is impregnated 1 hour, taking-up is successively used
Deionized water and dehydrated alcohol wash, and are dried with nitrogen, obtain hydrophilic glass substrate.
7. application as described in claim 1, it is characterised in that the first substrate and the second substrate are ITO electro-conductive glass.
8. application as described in claim 1, it is characterised in that the electrolyte layer is PVA/ sulfuric acid solid-state electrolyte layer, by such as
The preparation of lower section method: polyvinyl alcohol is mixed with 98% sulfuric acid of mass concentration and deionized water, and stirring forms colloid at 85 DEG C,
It is cooling, surface plate natural drying is poured into, PVA/ sulfuric acid solid-state electrolyte layer is obtained；The polyvinyl alcohol and 98% sulphur of mass concentration
Sour mass ratio is 1:1, and the deionized water volumetric usage is calculated as 10ml/g with 98% sulfuric acid quality of mass concentration.
9. application as described in claim 1, it is characterised in that the electrochromic electrode workspace of the electrochromic electrode layer
Be prepared as follows: '-three that take 4,4 ', 4 ' [2-(3,4- ethene dioxythiophene base) phenyl)] amine monomers are dissolved in chloroform, add
Enter ferric trichloride, under nitrogen protection, react at room temperature 24 h, after reaction, methanol extraction is added, filtering, filter cake is at 60 DEG C
24 h of lower vacuum drying, obtain polymer P TEAP powder, and polymer P TEAP powder is dissolved with chloroform, obtain PTEAP/ chloroform
Dispersion liquid, drop coating or is sprayed on ITO electro-conductive glass, dries, is prepared into electrochromic electrode workspace；The monomer and trichlorine
Changing the ratio between amount of iron substance is 1:3.5, and the chloroform volumetric usage is calculated as 250ml/g with monomer mass.
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| CN107275114B (en) * | 2017-05-04 | 2019-02-01 | 浙江工业大学 | A kind of preparation method of graphene composite film |
| CN107942572B (en) * | 2017-11-17 | 2020-12-04 | 深圳市华星光电技术有限公司 | Color film substrate and preparation method of black matrix material |
| CN109320920B (en) * | 2018-08-16 | 2021-02-09 | 江西科技师范大学 | Preparation method of Te nanowire/PEDOT/PSS composite film |
| CN110349757A (en) * | 2019-05-21 | 2019-10-18 | 浙江工业大学 | A kind of graphene/poly- (3,4- ethene dioxythiophene) self-supporting film and preparation method thereof |
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