CN108172414A - A kind of preparation method and applications of the graphene film of Polyaniline-modified - Google Patents
A kind of preparation method and applications of the graphene film of Polyaniline-modified Download PDFInfo
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- CN108172414A CN108172414A CN201711421772.2A CN201711421772A CN108172414A CN 108172414 A CN108172414 A CN 108172414A CN 201711421772 A CN201711421772 A CN 201711421772A CN 108172414 A CN108172414 A CN 108172414A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 152
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920000767 polyaniline Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 19
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 230000005518 electrochemistry Effects 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 47
- 229910021641 deionized water Inorganic materials 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000005357 flat glass Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- -1 Graphite alkene Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Microelectronics & Electronic Packaging (AREA)
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- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses a kind of preparation method and applications of the graphene film of Polyaniline-modified.The preparation method includes the following steps：(a) preparation of graphene oxide film：Graphene oxide film is prepared using the method for solvent volatilization self assembly；(b) reduction of graphene oxide film：The graphene oxide film that step (a) is prepared is reduced into graphene film using hydrazine hydrate steam in autoclave；(c) preparation of the graphene film of Polyaniline-modified：Polyaniline is polymerize in step (b) graphene film material surface using the method for electrochemistry, obtains the graphene film of Polyaniline-modified.The advantages of graphene film for the Polyaniline-modified that the present invention is prepared has large area self-supporting, and electric property is excellent, and preparation method is easy, quick, at low cost, is suitble to large-scale production.
Description
Technical field
The invention belongs to electrode for capacitors technical fields, are related to a kind of preparation method of the graphene film of Polyaniline-modified
And its application.
Background technology
Graphene is a kind of new material of individual layer laminated structure being made of carbon atom, is that one kind forms hexagonal by carbon atom
Shape is in the flat film of honeycomb lattice, and only there are one the two-dimensional materials of carbon atom thickness.Graphene is that known world is most thin, most
Hard material, it is almost fully transparent, only absorbs 2.3% light, and thermal conductivity factor is up to 5300W/mK, is received higher than carbon
Mitron and diamond, electron mobility is more than 15000cm under room temperature2/ VS, it is higher than carbon nanotubes or silicon crystal, and resistivity
Only about 10-8 Ω m, it is lower than copper or silver, it is the material of world resistivity minimum.Graphene is zero gap semiconductor, is carried
It is 100 times higher than silicon to flow transport factor, is the ideal of nanometric circuit at room temperature with micron order free path and big coherence length
Material.In addition, graphene also has a series of properties such as perfect quantum tunneling effect and the quantum hall effect of half-integer.This
A little excellent performances cause graphene in terms of nano electron device, gas sensor, battery, ultracapacitor and hydrogen storage and receive
There is bright application prospect in the fields such as nano composite material.
The method that graphene film is prepared using graphene aqueous solution as raw material is versatile and flexible, graphene film can deposit or
It is transferred in different substrates, such as SiO2/ Si, glass, quartz, polyethylene terephthalate, polymethyl methacrylate
Deng.It is prepared, and there is good dispersion in water since graphene oxide has been carried out magnanimity.Therefore, many researchs at present
Mostly graphene film is prepared using graphene oxide as raw material.
The preparation method of common graphene film includes：Spin coating method, vacuum filtration method, spray deposition, liquid phase
Gentle liquid level self assembly of electrophoretic deposition etc..Niu et al. (Niu Z.Q., Chen J., Hng H.H., Ma J., Chen X.D.,
Adv.Mater., 2012,24 (30), 4144-4150) graphene oxide dispersion that supersound process obtains is passed through into vacuum first
It filters and paper material is made, then the thin film of graphite is prepared with the reduction of hydrazine hydrate steam.Although it is filtered by vacuum to prepare graphene
The research of film is more, but this method is there are suction filtration process high energy consumption, the period is long and product area is smaller, is not suitable for industrialization
Production, it is difficult to prepare the graphene film of large area.Chinese patent discloses CN104961124A and discloses a kind of graphene film
Preparation method, will be covered with the substrate of graphene oxide film, it is by the method for electrochemical reduction that graphene oxide is thin
Film is reduced into graphene film, but this method is high using electrochemical reduction cost, and graphene film and the separating step of substrate
It is cumbersome, it is unfavorable for mass producing.
In addition, simple grapheme material is used for there is a situation where that specific capacity is not high during electrode material for super capacitor.And
With conjugation group on polyaniline backbone, electrostatic, π-pi-conjugated and hydrogen bond action, by graphene table can occur with graphene
Face functional group type and number are regulated and controled, and further increase the specific capacitance of graphene.
To sum up, based on deficiency of the prior art, the present invention develops a kind of system of the graphene film of Polyaniline-modified
Preparation Method, and the film is further used for electrode material.The graphene film of the present invention has large area self-supporting, and electricity
The advantages of function admirable.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of the graphene film of Polyaniline-modified.The present invention is prepared into
The advantages of graphene film of the Polyaniline-modified arrived has large area self-supporting, and electric property is excellent, and preparation method
It is easy, quick, at low cost, it is suitble to large-scale production.
To achieve these goals, the present invention provides a kind of preparation method of the graphene film of Polyaniline-modified, packets
Include following steps：
(a) preparation of graphene oxide film：Graphene oxide film is prepared using the method for solvent volatilization self assembly；
(b) reduction of graphene oxide film：Step (a) is prepared using hydrazine hydrate steam in autoclave
Graphene oxide film be reduced into graphene film；
(c) preparation of the graphene film of Polyaniline-modified：Polyaniline is polymerize in step (b) using the method for electrochemistry
Graphene film material surface obtains the graphene film of Polyaniline-modified.
In the above-mentioned methods, the preparation of step (a) graphene oxide film is as follows：
Graphite oxide is added in deionization, ultrasound stripping 2-3h obtains graphene oxide deionized water dispersion liquid, by institute
Graphene oxide deionized water dispersion liquid addition bottom is obtained to be covered in the container of substrate, and the container is placed in temperature range and is
12-48h in 30-120 DEG C of baking oven until the deionized water in graphene oxide deionized water dispersion liquid is volatilized completely, that is, exists
Substrate surface in container forms one layer of graphene oxide film；Graphite oxide in the graphene oxide deionized water dispersion liquid
A concentration of 1-5g/L of alkene.
In step (a), a concentration of 2g/L of the graphene oxide.
In step (a), the power of the ultrasound is 54KHz.
In step (a), the substrate is one or more in sheet glass, Pt pieces, PET sheet.Preferred glass in the present invention
Glass piece is as substrate.
In step (a), the glass chip bottom is cleaned sheet glass, wherein, the method for the cleaning is：By glass
Piece is cleaned by ultrasonic 10min, and dried up with nitrogen successively with deionized water, ethyl alcohol, acetone respectively.
In step (a), the container is preferably 25ml small beakers.
In the above-mentioned methods, the reduction of step (b) graphene oxide film is as follows：Step (a) is taken to obtain
Substrate of the surface arrived covered with graphene oxide film, substrate is put into an autoclave, is added in autoclave
Enter the filter paper of a piece of certain density hydrazine hydrate aqueous solution containing 0.5-5ml, then this autoclave is put into temperature as 50-
It is heated in 150 DEG C of baking oven, to form hydrazine hydrate steam, reacts 4-48h, be washed out, dry and obtain graphene film.Pass through
The restoring method, graphene film can be detached with substrate of glass automatically, and method is simpler easy.
In step (b), deionized water is respectively adopted, the graphene film after reduction reaction is washed with alcohol solvent.
In step (b), the autoclave is 20ml.
In step (b), the size of the filter paper is adapted with autoclave liner floor space size.
In step (b), the mass concentration of the hydrazine hydrate aqueous solution is 80%.In step (b), the hydrazine hydrate aqueous solution
Volume be 1ml.
In step (b), the oven temperature is 95 DEG C.
In step (b), the heating time is 12h.
In the above-mentioned methods, the preparation of the graphene film of step (c) Polyaniline-modified is as follows：It utilizes
As working electrode, Ag/AgCl, as to electrode, immerses graphene film prepared by step (b) as reference electrode, Pt
In the aqueous electrolyte that concentration of aniline is 0.01-0.1mol/L, sulfuric acid concentration is 0.1-1mol/L, and electrode is respectively connected to electricity
Chem workstation is 0-1V in voltage, carries out electrochemical polymerization 60-900s under conditions of constant voltage, then take working electrode
Go out, cleaned with deionized water to get to the graphene film of Polyaniline-modified.
In step (c), the graphene film is as the method for working electrode：Electrode holder is pressed from both sides into middle institute in step (b)
One side of the graphene film of preparation is immersed in solution.
In step (c), the concentration of aniline is 0.05mol/L.
In step (c), the sulfuric acid concentration is 0.5mol/L.
In step (c), the voltage is 0.75V.
It is another object of the present invention to provide a kind of graphene film of Polyaniline-modified answering in electrode material
With.
Compared with prior art, the present invention has following technical characterstic：
1) present invention directly restores the graphene oxide film of substrate surface using hydrazine hydrate steam, and graphene is thin
Film can be detached with substrate of glass automatically, simple process, quick.
2) graphene film of Polyaniline-modified of the present invention has higher specific capacity compared to simple graphene film,
Experiment proves specific capacity 450-500F/g, there is very big prospect in terms of energy storage.
Description of the drawings
Fig. 1 is the cross-sectional SEM image of polyaniline/Graphene composite thin film material prepared by the present invention.
Fig. 2 is the graphene film of (a) simple graphene film and (b) Polyaniline-modified in sweep speed
Cyclic voltammetric contrast images during ranging from 0.002-0.02V/s.
Fig. 3 is that the graphene film material of (a) simple graphene film, simple polyaniline electrode and Polyaniline-modified is being swept
Cyclic voltammetric contrast images when retouching speed as 0.002V/s, (b) pure graphene film, simple polyaniline electrode and polyaniline are repaiied
Constant current charge-discharge contrast images of the graphene film of decorations when current density is 0.1A/g.
Specific embodiment
Specific examples below is the further explanation to method provided by the invention and technical solution, but is not construed as
Limitation of the present invention.
Embodiment 1
(1) graphite oxide being added in deionized water, ultrasound stripping 2h obtains graphene oxide deionized water dispersion liquid,
Gained graphene oxide deionized water dispersion liquid addition bottom is covered in the container of substrate, and the container is placed in 60 DEG C of baking ovens
In for 24 hours, until the deionized water in graphene oxide deionized water dispersion liquid is volatilized completely, i.e., glass chip bottom in a reservoir
Surface forms one layer of graphene oxide film；Graphene oxide is a concentration of in the graphene oxide deionized water dispersion liquid
2g/L；
(2) substrate of the surface covered with graphene oxide film that step (1) obtains is taken, substrate is put into a reaction under high pressure
In kettle, it is identical with reaction kettle liner bottom size and containing 1ml mass concentrations that a piece of size is added in this autoclave liner
Filter paper for 80% hydrazine hydrate aqueous solution.This autoclave is put into the baking oven that temperature is 95 DEG C again and heats 12h, it can be complete
It is put into the electronation of graphene oxide film therein in pairs.
It opens reaction kettle to take out the graphene film restored, it is carried out with alcohol solvent with deionized water respectively
Washing, drying, can obtain graphene film.
(3) it is clipped on one side as working electrode, Ag/AgCl conducts by the use of above-mentioned prepared graphene film electrode holder
Reference electrode, Pt are used as to electrode, and immersion concentration of aniline is 0.05mol/L, the aqueous electrolysis that sulfuric acid concentration is 0.5mol/L
In liquid, and electrode is respectively connected to electrochemical workstation.It is 0.75V in voltage, electrochemical polymerization is carried out under conditions of constant voltage
300s polymerize polyaniline in graphene film surface electrochemistry.Finally working electrode is taken out, is cleaned with deionized water, with system
The graphene film composite material of standby Polyaniline-modified, will prepare electrode and is named as c-RGO/PANI.
Embodiment 2
(1) graphite oxide being added in deionized water, ultrasound stripping 2h obtains graphene oxide deionized water dispersion liquid,
Gained graphene oxide deionized water dispersion liquid addition bottom is covered in the container at glass chip bottom, and the container is placed in 60
In DEG C baking oven for 24 hours, until the solvent deionized water in graphene oxide deionized water dispersion liquid is volatilized completely, i.e., in a reservoir
Substrate surface forms one layer of graphene oxide film；The concentration of graphene oxide in the graphene oxide deionized water dispersion liquid
For 2g/L；
(2) substrate of the surface covered with graphene oxide film that step (1) obtains is taken, substrate is put into a reaction under high pressure
In kettle, it is identical with reaction kettle liner bottom size and containing 1ml mass concentrations that a piece of size is added in this autoclave liner
Filter paper for 80% hydrazine hydrate aqueous solution.This autoclave is put into the baking oven that temperature is 95 DEG C again and heats 12h, it can be complete
It is put into the electronation of graphene oxide film therein in pairs.
It opens reaction kettle to take out the graphene film material restored, respectively with deionized water and alcohol solvent to it
It is washed, dries, graphene film material can be obtained.
(3) it is clipped on one side as working electrode, Ag/AgCl conducts with electrode holder using above-mentioned prepared graphene film
Reference electrode, Pt are used as to electrode, and immersion concentration of aniline is 0.05mol/L, the aqueous electrolysis that sulfuric acid concentration is 0.5mol/L
In liquid, and electrode is respectively connected to electrochemical workstation.It is 0.75V in voltage, electrochemical polymerization is carried out under conditions of constant voltage
60s polymerize polyaniline in graphene film surface electrochemistry.Finally working electrode is taken out, is cleaned with deionized water, to prepare
The graphene film composite material of Polyaniline-modified will prepare electrode and be named as c-RGO/PANI.
Embodiment 3
(1) graphite oxide being added in deionized water, ultrasound stripping 2h obtains graphene oxide deionized water dispersion liquid,
Gained graphene oxide deionized water dispersion liquid addition bottom is covered in the container at glass chip bottom, and the container is placed in 60
In DEG C baking oven for 24 hours, until the solvent deionized water in graphene oxide deionized water dispersion liquid is volatilized completely, i.e., in a reservoir
Substrate surface forms one layer of graphene oxide film；The concentration of graphene oxide in the graphene oxide deionized water dispersion liquid
For 2g/L；
(2) substrate of the surface covered with graphene oxide film that step (1) obtains is taken, substrate is put into a reaction under high pressure
In kettle, it is a concentration of for and immersion 1ml identical with reaction kettle liner bottom size that a piece of size is added in this autoclave liner
The filter paper of 80% hydrazine hydrate solution.It is to heat 12h in 95 DEG C of baking oven that this autoclave is put into temperature again, can be completed pair
It is put into the electronation of graphene oxide film therein.
It opens reaction kettle to take out the graphene film material restored, respectively with deionized water and alcohol solvent to it
It is washed, dries, graphene film material can be obtained.
(3) it is clipped on one side as working electrode, Ag/AgCl conducts with electrode holder using above-mentioned prepared graphene film
Reference electrode, Pt are used as to electrode, and immersion concentration of aniline is 0.05mol/L, the aqueous electrolysis that sulfuric acid concentration is 0.5mol/L
In liquid, and electrode is respectively connected to electrochemical workstation.It is 0.75V in voltage, electrochemical polymerization is carried out under conditions of constant voltage
900s polymerize polyaniline in graphene film surface electrochemistry.Finally working electrode is taken out, is cleaned with deionized water, with system
The graphene film composite material of standby Polyaniline-modified, will prepare electrode and is named as c-RGO/PANI.
Comparative example 1
(1) graphite oxide is added in solvent deionization, ultrasound stripping 2h obtains the dispersion of graphene oxide deionized water
Gained graphene oxide deionized water dispersion liquid addition bottom is covered in the container at glass chip bottom, and the container is put by liquid
In 60 DEG C of baking ovens for 24 hours, until the solvent deionized water in graphene oxide deionized water dispersion liquid is volatilized completely, i.e., in container
In substrate surface formed one layer of graphene oxide film；Graphene oxide in the graphene oxide deionized water dispersion liquid
A concentration of 2g/L；
(2) substrate of the surface covered with graphene oxide film that step (1) obtains is taken, substrate is put into a reaction under high pressure
In kettle, a piece of size is added in this autoclave liner as and immersion 1ml mass concentration identical with reaction kettle liner bottom size
Filter paper for 80% hydrazine hydrate solution.This autoclave is put into the baking oven that temperature is 95 DEG C again and heats 12h, can be completed
To being put into the electronation of graphene oxide film therein.
It opens reaction kettle to take out the graphene film material restored, respectively with deionized water and alcohol solvent to it
It is washed, dries, graphene film material can be obtained.It is named as c-RGO.
Comparative example 2
Merely using Pt pieces as working electrode, Ag/AgCl, as to electrode, immerses aniline as reference electrode, Pt
In a concentration of 0.05mol/L, the aqueous electrolyte that sulfuric acid concentration is 0.5mol/L, and electrode is respectively connected to electrochemical operation
It stands.It is 0.75V in voltage, electrochemical polymerization 900s is carried out under conditions of constant voltage, in graphene film surface aggregate polyaniline.
Finally working electrode is taken out, cleaning is cleaned with deionized water, to prepare polyaniline/graphene composite material.Electrode is named
For PANI.
Wherein the quality of electrode surface polyaniline active material can be calculated by quality difference value.I.e. in Pt piece electrochemistry
Quality is weighed before polymerization polyaniline, by weighing electrode tablet quality again after 900s electrochemical polymerizations, calculates the difference of the two, i.e. electricity
The quality of pole surface polyaniline active material.
Test experiments：
Take electrode c-RGO and c-RGO/PANI respectively in the sulfuric acid electrolyte of 1mol/L, voltage range for -0.2~
Under conditions of 0.8, sweep speed carries out cyclic voltammetry scan in the range of being 0.002-0.02V/s.It can be found that simple stone
Black alkene electrode (c-RGO) shows the cyclic voltammetric figure of similar rectangle, and multipair oxygen is presented in the figure of combination electrode
Change reduction peak shape, the electrochemical reaction activity shown by polyaniline, (as shown in Figure 2).
Meanwhile take electrode c-RGO, PANI and c-RGO/PANI respectively in the sulfuric acid electrolyte of 1mol/L respectively, in electricity
For under conditions of -0.2-0.8, sweep speed carries out cyclic voltammetry scan under conditions of being 0.002V/s between pressure area.Pass through Fig. 3
(a) in, it can be seen that the area of Polyaniline-modified graphene film combination electrode c-RGO/PANI is maximum in these three electrodes, says
Its bright capacitance is maximum.Take electrode c-RGO, PANI and c-RGO/PANI respectively in the sulfuric acid electrolyte of 1mol/L again, in electricity
Under conditions of current density is 0.1A/g, constant current charge-discharge test is carried out to it, as shown in Fig. 3 (b).It is learnt by calculating, this
The specific capacity of three kinds of electrode materials be respectively 160.75F/g, 365F/g, 465F/g, the wherein capacity of c-RGO/PANI electrodes most
Greatly, illustrate that polyaniline produces the synergistic effect of storeroom with graphene.C-RGO/PANI electrode materials can be used as it is good from
The flexible electrode material for super capacitor of support.
The explanation of above example is only intended to help to understand the method for the present invention 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 domain.
Claims (10)
1. a kind of preparation method of the graphene film of Polyaniline-modified, which is characterized in that include the following steps：
(a) preparation of graphene oxide film：Graphene oxide film is prepared using the method for solvent volatilization self assembly；
(b) reduction of graphene oxide film：The oxygen that step (a) is prepared using hydrazine hydrate steam in autoclave
Graphite alkene film is reduced into graphene film；
(c) preparation of the graphene film of Polyaniline-modified：Polyaniline is polymerize in step (b) graphite using the method for electrochemistry
Alkene thin-film material surface obtains the graphene film of Polyaniline-modified.
2. preparation method as described in claim 1, which is characterized in that the preparation of step (a) graphene oxide film
It is as follows：
Graphite oxide is added in deionization, ultrasound stripping 2-3h obtains graphene oxide deionized water dispersion liquid, by gained oxygen
Graphite alkene deionized water dispersion liquid adds in bottom and is covered in the container of substrate, and the container is placed in temperature range for 30-120
DEG C baking oven in 12-48h, until graphene oxide deionized water dispersion liquid in deionized water volatilize completely, i.e., in a reservoir
Substrate surface formed one layer of graphene oxide film；Graphene oxide is dense in the graphene oxide deionized water dispersion liquid
It spends for 1-5g/L.
3. preparation method as claimed in claim 2, which is characterized in that the substrate is in sheet glass, Pt pieces, PET sheet
It is one or more.
4. preparation method as claimed in claim 3, which is characterized in that the substrate is sheet glass, and the sheet glass is through clear
The sheet glass washed, wherein, the method for the cleaning is：Sheet glass is cleaned by ultrasonic successively with deionized water, ethyl alcohol, acetone respectively
10min, and dried up with nitrogen.
5. preparation method as described in claim 1, which is characterized in that the reduction of step (b) graphene oxide film
It is as follows：Substrate of the surface that step (a) obtains covered with graphene oxide film is taken, it is anti-that substrate is put into a high pressure
Answer in kettle, add in the filter paper of a piece of certain density hydrazine hydrate aqueous solution containing 0.5-5ml in autoclave, then by this
Autoclave is put into the baking oven that temperature is 50-150 DEG C and heats, and to form hydrazine hydrate steam, reacts 4-48h, be washed out,
Drying obtains graphene film.
6. preparation method as claimed in claim 5, which is characterized in that in the step (b), deionized water and second is respectively adopted
Alcoholic solvent washs the graphene film after reduction reaction.
7. preparation method as claimed in claim 5, which is characterized in that the size of the filter paper and autoclave liner bottom surface
Product size is adapted.
8. preparation method as claimed in claim 5, which is characterized in that the mass concentration of the hydrazine hydrate aqueous solution is 80%.
9. preparation method as described in claim 1, which is characterized in that the graphene film of step (c) Polyaniline-modified
Preparation be as follows：By the use of the graphene film prepared by step (b) as working electrode, Ag/AgCl is as reference
Electrode, Pt are used as to electrode, and immersion concentration of aniline is 0.01-0.1mol/L, the aqueous electricity that sulfuric acid concentration is 0.1-1mol/L
It solves in liquid, and electrode is respectively connected to electrochemical workstation, be 0-1V in voltage, electrochemical polymerization is carried out under conditions of constant voltage
Then 60-900s takes out working electrode, cleaned with deionized water to get to the graphene film of Polyaniline-modified.
10. the preparation method such as a kind of graphene film of Polyaniline-modified of claim 1-9 any one of them is prepared poly-
Application of the graphene film of aniline modification in electrode material.
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| CN111146461A (en) * | 2019-12-31 | 2020-05-12 | 中北大学 | Preparation method of paper-graphite-PANI-Pt electrode and application of paper-graphite-PANI-Pt electrode in H catalysis2O2Application in electroreduction reaction |
| CN114740062A (en) * | 2022-02-16 | 2022-07-12 | 陕西化工研究院有限公司 | Method for detecting hydrazine by electrochemistry |
| CN114778616A (en) * | 2022-04-29 | 2022-07-22 | 集美大学 | Graphene sensor and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110211809A (en) * | 2019-04-28 | 2019-09-06 | 中科广化（重庆）新材料研究院有限公司 | A kind of porous graphene/polyaniline composite film and the preparation method and application thereof |
| CN111146461A (en) * | 2019-12-31 | 2020-05-12 | 中北大学 | Preparation method of paper-graphite-PANI-Pt electrode and application of paper-graphite-PANI-Pt electrode in H catalysis2O2Application in electroreduction reaction |
| CN111146461B (en) * | 2019-12-31 | 2021-06-04 | 中北大学 | Preparation method of paper-graphite-PANI-Pt electrode and application of paper-graphite-PANI-Pt electrode in H catalysis2O2Application in electroreduction reaction |
| CN114740062A (en) * | 2022-02-16 | 2022-07-12 | 陕西化工研究院有限公司 | Method for detecting hydrazine by electrochemistry |
| CN114740062B (en) * | 2022-02-16 | 2024-05-14 | 陕西化工研究院有限公司 | Method for detecting hydrazine by adopting electrochemistry |
| CN114778616A (en) * | 2022-04-29 | 2022-07-22 | 集美大学 | Graphene sensor and preparation method and application thereof |
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Denomination of invention: Preparation method and application of polyaniline modified graphene thin film Effective date of registration: 20231128 Granted publication date: 20190924 Pledgee: Agricultural Bank of China Limited Hangzhou Yuhang Branch Pledgor: ZHEJIANG HUAZHENG NEW MATERIAL GROUP Co.,Ltd. Registration number: Y2023980067733 |