CN110349756A - A kind of self-supporting film and preparation method thereof - Google Patents

A kind of self-supporting film and preparation method thereof Download PDF

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Publication number
CN110349756A
CN110349756A CN201910423322.XA CN201910423322A CN110349756A CN 110349756 A CN110349756 A CN 110349756A CN 201910423322 A CN201910423322 A CN 201910423322A CN 110349756 A CN110349756 A CN 110349756A
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preparation
film
self
graphene
electrode
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张�诚
许若腾
刘军磊
张凯立
罗俊涛
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Zhejiang University of Technology ZJUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • 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
    • 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
    • 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

Abstract

The invention discloses a kind of self-supporting films and preparation method thereof.The preparation method of self-supporting film of the invention includes the following steps: that (1) prepares graphene film；(2) 3 are prepared, the dichloromethane solution of the double fluoroform sulfonamide electrolyte of 4- ethene dioxythiophene (EDOT), 1- butyl -3- methylimidazole, in this, as electrolyte, in the case where not using collector, using graphene film as working electrode, Pt piece is to electrode, and Ag/AgCl electrode is reference electrode, general/poly- (3,4-rthylene dioxythiophene) (PEDOT) electrochemical polymerization is on graphene film material；(3) thin-film material after polymerization is cleaned with dichloromethane solvent, to remove remaining electrolyte and EDOT monomer on material, is dried to get self-supporting film is arrived.Self-supporting film of the invention, which can not only be thrown, to be used except collector directly as electrode, but also specific capacity with higher and cyclical stability.

Description

A kind of self-supporting film and preparation method thereof
Technical field
The invention belongs to self-supporting film technical fields, more particularly to a kind of self-supporting film and preparation method thereof.
Background technique
In recent years, the development of wearable flexible electronic devices, wherein being also required to providing the energy storage device of the energy for soft Property carry out developmental research.Wherein flexible super capacitor receives more concerns.And how to prepare with certain mechanical strength Flexible electrode material one of have become a hot topic of research, furthermore the specific capacity and stability of electrode material are still restriction super capacitor The a great problem of device development.
Graphene (Graphene) makes graphene due to its unique two-dimensional structure and the performances such as outstanding mechanics and electricity Electronics, the energy and in terms of obtain very extensive research and application.People utilize different methods at present The Graphene electrodes material of a variety of different structures has been prepared.Wherein the grapheme material of three-dimensional structure not only maintains original Cellular structure abundant is also obtained in conductive network, is convenient for ion-transfer and diffusion, has huge mention to its chemical property It rises.The material of report generallys use the methods of CVD, suction filtration, hydrothermal synthesis and is prepared, but these methods have higher cost or work The disadvantages of skill is complicated difficult.It needs collector to be used in combination again as electrode active material simultaneously, increases its cost and entirety Quality limits the application of flexible super capacitor.Research shows that polyvalent metal ion and polymer answer grapheme material It closes, the available flexible self-supporting electrode material with some strength.
The present invention utilizes Fe3+The method that ion makes graphene oxide aqueous dispersions generate cross-linking reaction prepares graphene oxide Hydrogel passes through above-mentioned graphene film material by a series of post-processings to prepare a kind of graphene film material The method of in-situ electrochemical polymerization is compounded in the PEDOT with nanowire structure on film, and a kind of new E- is prepared PEDOT/f-rGO composite film material, by the sandwich structure of formation to improve its chemical property.
Summary of the invention
It is being applied to supercapacitor flexible electrical to solve composite material composed by existing graphene and conducting polymer There are collectors in the material of pole it is at high cost, specific capacity is poor and cyclical stability is poor the problems such as, it is an object of the invention to mention A kind of graphene/poly- (3,4-rthylene dioxythiophene) self-supporting film E-PEDOT/f-rGO has been supplied, and has found the composite material not It can only throw and be used except collector directly as electrode, and specific capacity with higher and cyclical stability.
To achieve the above object, the present invention takes following technical scheme:
A kind of preparation method of self-supporting film, includes the following steps:
(1) graphene film is prepared；
(2) 3,4- ethene dioxythiophene (EDOT), the double fluoroform sulfonamide electrolyte of 1- butyl -3- methylimidazole are prepared Dichloromethane solution, it is electric using graphene film as work in the case where not using collector in this, as electrolyte Pole, Pt piece are to electrode, Ag/AgCl (1molL-1KCl) electrode is reference electrode, uses voltage for the perseverance electricity of 1.4~1.8V Pressure mode polymerize 800~1000s, and general/poly- (3,4-rthylene dioxythiophene) (PEDOT) electrochemical polymerization is in graphene film material On material；
(3) thin-film material after polymerization is cleaned with dichloromethane solvent, to remove remaining electrolyte on material It is dry to get to self-supporting film, (E-PEDOT/f-rGO, E indicate Electrochemical method with EDOT monomer；f Indicate film, film；RGO indicates redox graphene).
Further, in the above preparation method, the graphene film is prepared via a method which: in 3~4mL Concentration be 5~10mgmL-1Graphene oxide aqueous dispersions in be added 2~3mg FeCl3, shake and form it into oxidation stone Black alkene hydrogel；Using by graphene oxide hydrogel by the method for blade coating in hydrophilic group substrate of glass, homogeneous film formation, and Stand 15min；Be in the mixed liquor of 1:1~2 by the volume ratio that the material of homogeneous film formation is put into hydroiodic acid and acetic acid impregnate 2~ 3h, graphene oxide are restored, film gradually blackening；Mixed liquor is heated to 75~85 DEG C again, reacts 6~8h；It will be black The oxidation graphene film and substrate of glass of color are detached from, and are washed repeatedly several times with deionized water and ethyl alcohol respectively, removal Remaining hydroiodic acid and other impurities in material, material is being freeze-dried, and finally obtains graphene film material (f-rGO).
Preferably, the graphene oxide aqueous dispersions the preparation method is as follows: H is added in crystalline graphite powder2SO4In, delay It is slow that potassium peroxydisulfate and phosphorus pentoxide is added, and stirred at 70~90 DEG C, the mixed liquor that reaction is obtained uses deionized water Filtration washing, drying obtain pre-oxidation product；It will pre-oxidation product and sodium nitrate addition H2SO4In, it is added under ice-water bath KMnO4, 2~3h under stirring at 30~50 DEG C takes out and is put into 50~100mL is added in ice-water bath deionized water and 4~5mL H2O2, using deionized water centrifuge washing, a certain amount of deionized water is added and obtains graphene oxide aqueous dispersions.
Preferably, the graphene oxide and FeCl3Mass ratio be 1:0.1~0.2.
Preferably, the height of the scraper is 520 μm.
Preferably, the preparation process flow of the hydrophilic group substrate of glass are as follows: common glass sheet is dipped in dense sulphur completely With the mixed liquor of dioxygen water volume ratio 7:3~5, reaction temperature is 80~100 DEG C and reacts 1~2h acid, is then successively spent Ionized water and dehydrated alcohol wash several times, are dried with nitrogen, that stays is spare.
Further, in the above preparation method, the double fluoroform sulfonamides of the EDOT and 1- butyl -3- methylimidazole The mass ratio of the material is 1:20~30.
Further, in the above preparation method, the methylene chloride additional amount by the amount of EODT substance be in terms of 1:5~ 10L/mmol。
The present invention also provides a kind of self-supporting films that above-mentioned preparation method is prepared.
Composite material of the present invention passes through scanning electron microscope (SEM) composite material to obtained by by infrared spectrum characterization Pattern characterized, it was demonstrated that graphene can be made to be formed with conducting polymer PEDOT by the method for electrochemical polymerization special Pattern influence.Electro-chemical test is carried out to composite material by using electrochemical workstation, composite material is obtained and is applied to surpass Grade capacitor flexible electrode material has good specific capacity and cyclical stability.
Compared with prior art, the beneficial effects of the present invention are:
(1) composite material is prepared into self-supporting film by the method for the invention, throws except collector uses, reduces cost.
(2) by the method for electrochemical polymerization, PEDOT is supported on graphene self-supported membrane, Sanming City has been prepared The E-PEDOT/f-rGO composite film material of structure is controlled, and has in film surface and has acicular sea by what nano wire PEDOT was formed Gallbladder cluster structure.
(3) find that E-PEDOT/f-rGO self-supporting film is compared to f- by the chemical property analysis to composite material RGO material has better electrochemical energy storage performance.
Detailed description of the invention
Fig. 1 is the SEM figure of the f-rGO and E-PEDOT/f-rGO that prepare in embodiment 1, and (a) and (b) is respectively f-rGO film Plane and section SEM figure；(c) and (d) is respectively that the plane of E-PEDOT/f-rGO composite membrane and section SEM scheme.
Fig. 2 is the infrared spectrogram of the f-rGO and E-PEDOT/f-rGO that prepare in embodiment 1.
Fig. 3 be the f-rGO prepared in embodiment 1 and E-PEDOT/f-rGO sweeping speed be (a) 25mVs-1(b) 500mV·s-1Under cyclic voltammogram.
Fig. 4 be the f-rGO prepared in embodiment 1 and E-PEDOT/f-rGO current density be (a) 0.5Ag-1With (b)5A·g-1Under constant current charge-discharge diagram.
It in current density is 5Ag that Fig. 5, which is the f-rGO prepared in embodiment 1 and E-PEDOT/f-rGO,-1Shi Hengliu fills Discharge cycles 1000 enclose cyclical stability figure.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be to the embodiment of the present invention Technical solution carries out clear, complete description.Obviously, described embodiment is a part of the embodiments of the present invention, rather than Whole embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art are without creative work Under the premise of every other embodiment obtained, belong to protection scope of the present invention.
Unless otherwise defined, technical term or scientific term used in the disclosure are should be in fields of the present invention The ordinary meaning for thering is the personage of general technical ability to be understood.
Embodiment 1
(1) preparation of graphene film
2mg FeCl is added in the graphene oxide aqueous dispersions that the concentration of 3mL is 10mgmL-13, shaking makes its shape At graphene oxide hydrogel.Graphene oxide hydrogel is passed through into the method for blade coating in parent for 520 μm of scraper using height In water base substrate of glass, homogeneous film formation, and stand 15min.Then, the material of above-mentioned homogeneous film formation is put into hydroiodic acid and acetic acid Volume ratio be to impregnate 2h in the mixed liquor of 1:2, graphene oxide restored, film gradually blackening.Mixed liquor is added again Heat reacts 6h to 75 DEG C.The oxidation graphene film of black and substrate of glass are detached from, use deionized water and ethyl alcohol respectively It washs repeatedly several times, removes remaining hydroiodic acid and other impurities in material, freeze-drying finally obtains graphene film material, It is named as f-rGO.
The wherein preparation process flow of hydrophilic group substrate of glass are as follows: common glass sheet is dipped in the concentrated sulfuric acid and hydrogen peroxide completely In the mixed liquor of volume ratio 7:3, reaction temperature is 90 DEG C and reacts 1h, if then successively being washed with deionized water and dehydrated alcohol It dry time, is dried with nitrogen, that stays is spare.
(2) preparation of the compound self-supported membrane material of E-PEDOT/f-rGO
Preparation 3,4- ethene dioxythiophene (EDOT) concentration is 5mmolL-1, the double trifluoro methylsulphurs of 1- butyl -3- methylimidazole Amidic-salt electrolyte concentration is 0.1molL-1Dichloromethane solution, in this, as electrolyte.In the feelings for not using collector Under condition, the above-mentioned f-rGO graphene film material being prepared is without any processing, and as working electrode, Pt piece is To electrode, Ag/AgCl (1molL-1KCl) electrode is reference electrode, uses voltage for the constant voltage mode of 1.4V, is polymerize 800s.By PEDOT electrochemical polymerization on f-rGO graphene film material.Film is taken out, is carried out clearly with dichloromethane solvent It washes several times, to remove remaining electrolyte and EDOT monomer on material, is dried to obtain composite film material, is named as E- PEDOT/f-rGO。
The compound self-supported membrane of graphene film f-rGO and E-PEDOT/f-rGO SEM figure and infrared spectrogram respectively referring to Fig. 1 and Fig. 2.
Electro-chemical test is all made of CHI660E (Shanghai, occasion China) electrochemical workstation and carries out.Electro-chemical test is three electrodes System (active material is working electrode, is platinum electrode to electrode, and reference electrode is Ag/AgCl electrode), test electrolyte is 1M KCl.Cyclic voltammetric and constant current charge-discharge test are carried out under the voltage window of -0.4~0.6V.
F-rGO and E-PEDOT/f-rGO self-supporting film is (a) 25mVs sweeping speed-1(b) under 500mVs-1 Cyclic voltammetry curve figure is referring to Fig. 3；F-rGO and E-PEDOT/f-rGO self-supporting film is (a) 0.5Ag in current density-1With (b)5A·g-1Under constant current charge-discharge curve graph referring to fig. 4；F-rGO and E-PEDOT/f-rGO composite self-supporting thin film material exists Current density is 5Ag-1When constant current charge-discharge circulation 1000 circle cyclical stability test chart referring to Fig. 5.
By the testing result of Fig. 3-5 it can be seen that the specific capacity and cyclical stability of E-PEDOT/f-rGO all compare f-rGO It is obviously improved.
Embodiment 2
(1) preparation of graphene film
3mg FeCl is added in the graphene oxide aqueous dispersions that the concentration of 4mL is 5mgmL-13, shaking makes its shape At graphene oxide hydrogel.Graphene oxide hydrogel is passed through into the method for blade coating in parent for 520 μm of scraper using height In water base substrate of glass, homogeneous film formation, and stand 15min.Then, the material of above-mentioned homogeneous film formation is put into hydroiodic acid and acetic acid Volume ratio be to impregnate 3h in the mixed liquor of 1:1, graphene oxide restored, film gradually blackening.Mixed liquor is added again Heat reacts 8h to 85 DEG C.The oxidation graphene film of black and substrate of glass are detached from, use deionized water and ethyl alcohol respectively It washs repeatedly several times, removes remaining hydroiodic acid and other impurities in material, freeze-drying finally obtains graphene film material, It is named as f-rGO.
The wherein preparation process flow of hydrophilic group substrate of glass are as follows: common glass sheet is dipped in the concentrated sulfuric acid and hydrogen peroxide completely In the mixed liquor of volume ratio 7:3, reaction temperature is 90 DEG C and reacts 1h, if then successively being washed with deionized water and dehydrated alcohol It dry time, is dried with nitrogen, that stays is spare.
(2) preparation of the compound self-supported membrane material of E-PEDOT/f-rGO
Preparation 3,4- ethene dioxythiophene (EDOT) concentration is 5mmolL-1, the double trifluoro methylsulphurs of 1- butyl -3- methylimidazole Amidic-salt electrolyte concentration is 0.15molL-1Dichloromethane solution, in this, as electrolyte.In the feelings for not using collector Under condition, the above-mentioned f-rGO graphene film material being prepared is without any processing, and as working electrode, Pt piece is To electrode, Ag/AgCl (1molL-1KCl) electrode is reference electrode, uses voltage for the constant voltage mode of 1.8V, is polymerize 1000s.By PEDOT electrochemical polymerization on f-rGO graphene film material.Film is taken out, is carried out with dichloromethane solvent Cleaning several times, to remove remaining electrolyte and EDOT monomer on material, is dried to obtain composite film material, is named as E- PEDOT/f-rGO。
Electro-chemical test is all made of CHI660E (Shanghai, occasion China) electrochemical workstation and carries out.Electro-chemical test is three electrodes System (active material is working electrode, is platinum electrode to electrode, and reference electrode is Ag/AgCl electrode), test electrolyte is 1M KCl.Cyclic voltammetric and constant current charge-discharge test are carried out under the voltage window of -0.4~0.6V.
Through detecting, the specific capacity and cyclical stability of E-PEDOT/f-rGO is all obviously improved than f-rGO.
The method of the present invention that the above embodiments are only used to help understand and its core concept.It should be pointed out that for For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention Dry improvement and modification, these improvement and modification are also fallen into the claims in the present invention protection scope.

Claims (9)

1. a kind of preparation method of self-supporting film, which comprises the steps of:
(1) graphene film is prepared；
(2) prepare 3,4- ethene dioxythiophene (EDOT), the double fluoroform sulfonamide electrolyte of 1- butyl -3- methylimidazole two Chloromethanes solution, in this, as electrolyte, in the case where not using collector, using graphene film as working electrode, Pt Piece is to electrode, and Ag/AgCl electrode is reference electrode, uses voltage for the constant voltage mode of 1.4~1.8V, polymerization 800~ 1000s, general/poly- (3,4-rthylene dioxythiophene) (PEDOT) electrochemical polymerization is on graphene film material；
(3) thin-film material after polymerization is cleaned with dichloromethane solvent, with remove on material remaining electrolyte with EDOT monomer is dried to get self-supporting film (E-PEDOT/f-rGO) is arrived.
2. preparation method according to claim 1, which is characterized in that the graphene film be prepared via a method which and At: it is 5~10mgmL in the concentration of 3~4mL-1Graphene oxide aqueous dispersions in be added 2~3mg FeCl3, concussion makes It forms graphene oxide hydrogel；Pass through the method scratched in hydrophilic group substrate of glass using by graphene oxide hydrogel On, homogeneous film formation, and stand 15min；It is the mixed of 1:1~2 by the volume ratio that the material of homogeneous film formation is put into hydroiodic acid and acetic acid It closes in liquid, impregnates 2~3h, graphene oxide is restored, film gradually blackening；Mixed liquor is heated to 75~85 DEG C again, React 6~8h；The oxidation graphene film of black and substrate of glass are detached from, washed repeatedly with deionized water with ethyl alcohol respectively It washs several times, removes remaining hydroiodic acid and other impurities in material, material is being freeze-dried, graphene film is finally obtained Material (f-rGO).
3. preparation method according to claim 2, which is characterized in that the preparation method of the graphene oxide aqueous dispersions It is as follows: H is added in crystalline graphite powder2SO4In, it is slowly added to potassium peroxydisulfate and phosphorus pentoxide, and stir at 70~90 DEG C, The mixed liquor that reaction obtains is obtained into pre-oxidation product using deionized water filtration washing, drying；It will pre-oxidation product and nitric acid H is added in sodium2SO4In, KMnO is added under ice-water bath4, at 30~50 DEG C stir under 2~3h, take out be put into ice-water bath be added 50 The deionized water of~100mL and the H of 4~5mL2O2, using deionized water centrifuge washing, a certain amount of deionized water is added and obtains oxygen Graphite alkene aqueous dispersions.
4. preparation method according to claim 2, which is characterized in that the graphene oxide and FeCl3Mass ratio be 1: 0.1~0.2.
5. preparation method according to claim 2, which is characterized in that the height of the scraper is 520 μm.
6. preparation method according to claim 2, which is characterized in that the preparation process stream of the hydrophilic group substrate of glass Journey are as follows: common glass sheet is dipped in completely in the mixed liquor of the concentrated sulfuric acid and dioxygen water volume ratio 7:3~5, reaction temperature is 80~ It 100 DEG C and 1~2h of reaction, is then successively washed several times, is dried with nitrogen, that stays is spare with deionized water and dehydrated alcohol.
7. preparation method according to claim 1, which is characterized in that EDOT the and 1- butyl -3- methylimidazole double three Fluorine methylsulfonyl amine salt the mass ratio of the material is 1:20~30.
8. preparation method according to claim 1, which is characterized in that the methylene chloride additional amount is with the amount of EODT substance To count 1:5~10L/mmol.
9. a kind of self-supporting film that the described in any item preparation methods of claim 1-8 are prepared.
CN201910423322.XA 2019-05-21 2019-05-21 A kind of self-supporting film and preparation method thereof Pending CN110349756A (en)

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Publication number Priority date Publication date Assignee Title
CN107275114A (en) * 2017-05-04 2017-10-20 浙江工业大学 A kind of preparation method of graphene composite film
WO2018185419A1 (en) * 2017-04-03 2018-10-11 Nawatechnologies Process for manufacturing electrochemical capacitors
CN109192527A (en) * 2018-08-29 2019-01-11 浙江工业大学 It is a kind of using nickel foam as the poly- 3,4- ethene dioxythiophene electrode material for super capacitor of substrate
CN109686582A (en) * 2019-01-11 2019-04-26 中山大学 A method of combination electrode is prepared based on graphene and polyethylene dioxythiophene

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2018185419A1 (en) * 2017-04-03 2018-10-11 Nawatechnologies Process for manufacturing electrochemical capacitors
CN107275114A (en) * 2017-05-04 2017-10-20 浙江工业大学 A kind of preparation method of graphene composite film
CN109192527A (en) * 2018-08-29 2019-01-11 浙江工业大学 It is a kind of using nickel foam as the poly- 3,4- ethene dioxythiophene electrode material for super capacitor of substrate
CN109686582A (en) * 2019-01-11 2019-04-26 中山大学 A method of combination electrode is prepared based on graphene and polyethylene dioxythiophene

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Application publication date: 20191018