CN103346024B - The preparation method of high-conductivity flexible graphene membrane electrode - Google Patents
The preparation method of high-conductivity flexible graphene membrane electrode Download PDFInfo
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Abstract
The present invention overcomes in prior art and is easily broken in graphene film film forming procedure, and fold the imperfect deficiency of degree, the preparation method of a kind of high-conductivity flexible graphene membrane electrode is provided, step is as follows: use graphite oxide dispersion prepared by Hummers method, conductive carbon material and high polymer it is simultaneously introduced in dispersion liquid, ultrasonic vibration is uniformly dispersed, then graphite oxide film forming is made, again the reduction of graphite oxide film is i.e. prepared high-conductivity flexible graphene film, the shape that prepared graphene film can be cut into needs is needed i.e. to obtain high-conductivity flexible graphene membrane electrode according to reality application.The invention has the beneficial effects as follows: the conductivity of graphene film prepared by the present invention is 200～1000S/cm, electrochemistry capacitance is up to 190F/g, and thickness is 120～300 μm, has high conductivity and flexibility concurrently, can be cut into difformity and thickness.
Description
Technical field
The invention belongs to graphene film preparing technical field, particularly relate to the preparation method of graphene film electrode.
Background technology
A kind of novel between secondary cell and traditional capacitor that ultracapacitor is 20th century 70～grows up the eighties
Energy storage device, it has the characteristic of physical capacitor and battery concurrently, is provided that more higher energy density than physical capacitor, compares battery
Higher power density and longer cycle life.Exploitation function admirable, life-span length, cheap, the electricity that has wide range of applications
Pole is the core topic of ultracapacitor research, but in order to enable dusty material to glue in the preparation process of existing most of electrode
Knot prevents from coming off together, needs to add nonconducting binding agent, thus reduces the electrochemistry capacitance of ultracapacitor.Meanwhile,
Different applied environments needs the ultracapacitor of difformity and specification, so preparation has the electrode material tool of collapsible performance
There is highly important Research Significance.
Graphene is the Two-dimensional Carbon atomic crystal in recent years found, is by the former molecular six side's honeycombs of monolayer carbon, is so far
The thinnest material found.Graphene has the most peculiar character and boundless application prospect, is applied especially to super electricity
Container and new electronic component.High-conductivity flexible graphene film disclosure satisfy that modern society's needs to new electrode materials,
Through becoming the focus of current researcher research.Modern production needs special shape ultracapacitor, so needing preparation to cut out
Subtract into the electrode of difformity and thickness, but be easily broken in film forming procedure at graphene film, and it is the best to fold degree.
Summary of the invention
The present invention overcomes in prior art and is easily broken in graphene film film forming procedure, and folds the imperfect deficiency of degree, it is provided that
The preparation method of a kind of high-conductivity flexible graphene membrane electrode, by adulterating conductive carbon and high polymer improves graphene film simultaneously
Electric conductivity and the method for flexility.The method is the most controlled, and the graphene film prepared have pliability good, conduction
Excellent performance, can the advantage prepared of large area.These characteristics are allowed to have potential actual application value in ultracapacitor field.
The technical solution used in the present invention is as follows: the preparation method of a kind of high-conductivity flexible graphene membrane electrode, and step is as follows:
The graphite oxide dispersion using Hummers method to prepare, is then simultaneously introduced conductive carbon material and high polymer in dispersion liquid,
Ultrasonic vibration is uniformly dispersed, and then makes graphite oxide film forming, then the reduction of graphite oxide film is i.e. prepared high-conductivity flexible graphene
Film, needs the shape that prepared graphene film can be cut into needs i.e. to obtain high-conductivity flexible graphene film electricity according to reality application
Pole.
As preferably, described conduction Carbon Materials is that activated carbon, carbon black BP-2000, acetylene black, carbon fiber, graphite or carbon are received
In mitron any one, conductive carbon material mass ratio in graphene film is 0.2～20wt.%.
As preferably, described high polymer is epoxy resin, polyethylene terephthalate or polyimides, high polymer be
In graphene film, mass ratio is 0.1～10wt.%.
As preferably, the method for described graphite oxide film forming is vacuum filtration method or spraying process, when using vacuum filtration method, and oxygen
The size of functionalized graphene film can regulate according to the size of the size of filter membrane used and Suction filtration device.
As preferably, the reduction of described graphite oxide uses hydrogen heat reducing process or HI solution reduction.Both reducing process efficiency is high,
Can produce in enormous quantities, and the Repeatability of material is high.
Further, above-mentioned hydrogen heat reducing process reduction process is: by graphite oxide film under hydrogen and nitrogen mixture are protected
It is warming up to 1050 DEG C with the speed of 1～10 DEG C/min, is incubated 0.1～2h, is naturally cooling to room temperature.Wherein hydrogen mixes with nitrogen
In gas, hydrogen and nitrogen mass are than for 5:95～15:85, and the speed that is passed through of hydrogen is 100ml/min.
Further, above-mentioned HI solution reduction reduction process is: it is 10～80wt.% that graphene oxide membrane is put into concentration
HI solution in, under the conditions of 30～200 DEG C, react 0.5～5h, the mass ratio of HI and graphite oxide film is 5:1～30:1.
Present invention optimizes the conditions such as thermal reduction temperature, hydrogen ratio, response time and HI solution concentration so that the graphite of preparation
Alkene film reaches optimum performance.
The invention has the beneficial effects as follows: it is simple that the inventive method has technique, synthesis is convenient, technique is the highest and easy to equipment requirements
In remarkable advantages such as realizations.The conductivity of graphene film prepared by the present invention is 200～1000S/cm, and electrochemistry capacitance is up to 190
F/g, the thickness of graphene film can according to graphite oxide used and doping material with carbon element number regulate, thickness is 120～300
μm, by conduction Carbon Materials and the control of high polymer doping so that product flexibility will not be affected because of the doping of conductive material,
Also will not affect the electric conductivity of product because of the doping of high polymer, make product have high conductivity and flexibility concurrently, can be cut into not
Similar shape and thickness, it is possible to meet the electrode of various special shape.
Accompanying drawing explanation
The SEM figure of the graphene film of Fig. 1 embodiment 1 preparation；
The XRD figure of the graphene film of Fig. 2 embodiment 1 preparation；
The circulation volt of graphene film after the pure graphene film (a) of Fig. 3, doping 0.2wt.% conductive carbon black (b) and 20wt.% (c) acetylene black
Antu；
The cyclic voltammogram of graphene film after the pure graphene film (a) of Fig. 4, doping 5wt.% (b) and 10wt.% (c) acetylene black；
Fig. 5 adulterates the graphene film of 5wt.% carbon fiber and the 10wt.% polyimides cyclic voltammogram under difference sweeps speed；
Fig. 6 adulterates the graphene film of 10wt.% acetylene black and the 10wt.% epoxy resin cyclic voltammogram under difference sweeps speed.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail:
Embodiment 1 is adulterated the preparation of graphene film of 0.2wt.% conductive carbon black and 0.1wt.% epoxy resin
(1) preparation of graphite oxide
The Hummers method improved is used to prepare graphite oxide (GO).0.5g graphite powder is mixed under the conditions of ice bath and strong stirring
With 0.25g potassium nitrate, it is subsequently adding 12ml concentrated sulphuric acid, is slow added into 1.5g KMnO4.After oxidation reaction 96h, slow
The slow 150ml deionized water that adds dilutes, and the solution after oil bath is inverted in beaker, is cooled to room temperature by oil bath 24h at 98 DEG C,
The most dropwise instill 5ml H2O2(35wt%) reaction 30min, is continued.Soak with the HCl of 250ml5%, then wash,
Centrifugal.First with 12000rpm, solution is centrifuged 10min to take and precipitate below, until upper solution pH is about 7.Then
It is centrifuged 10min with 3000rpm again, takes solution above it, i.e. prepare GO dispersion liquid standby.
(2) doping 0.2wt.% conductive carbon black BP-2000 and 0.1wt.% epoxy resin
Taking the graphite oxide solution of 100ml0.23mg/ml, 0.2% and 0.1wt.% according to graphene film mass ratio are mixed respectively
Miscellaneous conductive carbon black and B44 epoxy resin (bisphenol A type epoxy resin).
(3) preparation of graphite oxide film
Take above-mentioned graphite oxide solution to be placed in beaker, ultrasonic vibration about 0.5h, solution is placed on alumina formwork, vacuum
Sucking filtration, sucking filtration terminates to be placed in baking oven and to be dried 0.5h at 60 DEG C, takes out the film that nature comes off, is graphite oxide film.
(4) HI reducing process prepares graphite oxide film
Graphite oxide film is taken a part be placed in beaker, beaker adds 80wt.%HI solution, HI and graphite oxide film quality
Amount ratio is 5:1,30 DEG C of reaction 5h under the conditions of oil bath, and question response is down to during room temperature take out film, is positioned in deionized water and cleans
The HI solution on surface, is doping 0.2wt.% conductive carbon black and the graphene film of 0.1wt.% epoxy resin.
Measure the voltage-to-current change of the thin film obtained with comprehensive physical property measuring instrument (PPMS, Quantum Design), and calculate
The conductivity of this graphene film.In the present embodiment, the conductivity of the graphene film of preparation is 200S/cm.Prepared by the method
Graphene film is flexible very well, non-friable, collapsible reduction.Fig. 1 is the SEM of Flexible graphene film prepared by embodiment 1 method
Figure, as can be seen from the figure the thickness of film is relatively average, about in 120～169 μm.
Fig. 2 is the graphite oxide film prepared of embodiment 1 method and the XRD figure of graphene film.From curve (b) it can be seen that
Graphite oxide film has a diffraction maximum the strongest in 2 θ=10.49 °, can calculate oxidation according to bragg's formula (2dsin θ=n λ)
Graphite layers is away from for 0.84nm, and the interlamellar spacing of native graphite is only 0.33nm, illustrates that the introducing of oxygenated functional group enhances stone
Layer of ink expanded, and add the hydrophilic of graphite oxide.It can be seen that graphene film is in 2 θ=22.80 ° from curve (a)
There is the diffraction maximum of left and right, and the diffraction maximum in 2 θ=10.49 ° has disappeared, and illustrates that oxygenated functional group is reduced, due to stone
Ink is not acted on by Van der Waals force, and the final graphite flake layer peeled off becomes Graphene, and the interlamellar spacing of Graphene
It is computed as 0.36nm.
Embodiment 2 is adulterated the preparation of graphene film of 20wt.% acetylene black and 10wt.% polyethylene terephthalate
(1) preparation method of graphite oxide is with embodiment 1.
(2) doping 20wt.% acetylene black and 10wt.% polyethylene terephthalate.
Take the graphite oxide solution of 100ml0.23mg/ml, respectively according to mass ratio 20wt.% and 10wt.% doping conductive acetylene
Black and polyethylene terephthalate.
(3) preparation method of graphite oxide film uses spraying process, graphite oxide dispersion is loaded in spray gun reservoir, is uniformly sprayed onto glass
On sheet, drying and forming-film.
(4) HI reducing process prepares graphite oxide film: graphite oxide film is taken a part and is placed in beaker, adds 10 in beaker
Wt.%HI solution, HI and graphite oxide film quality ratio is for 30:1,200 DEG C of reaction 0.5h under the conditions of oil bath, and question response is down to
Take out film during room temperature, be positioned in deionized water the HI solution cleaning surface, be doping 20wt.% conductive acetylene black and 10
The graphene film of wt.% polyethylene terephthalate.
In the present embodiment, the conductivity of the graphene film of preparation is 830S/cm.
(5) graphene film electrochemical property test
With graphene film as working electrode, platinum electrode is to electrode, and Hg/HgO electrode is that reference electrode is circulated volt-ampere survey
Examination.Potential window is-0.5～0.3V, and electrolyte is 6M KOH.
Embodiment 3 is adulterated the preparation of graphene film of 5wt.% carbon fiber and 10wt.% polyimides
(1) preparation method of graphite oxide is with embodiment 1
(2) method of doping mass ratio 5wt.% carbon fiber and 10wt.% polyimides is with embodiment 2.
(3) preparation method of graphite oxide film is with embodiment 1
(4) thermal reduction prepares graphene film
Under hydrogen and nitrogen mixture are protected, above-mentioned graphite oxide film is warming up to 1050 DEG C with the speed of 1 DEG C/min, insulation
0.1h, is naturally cooling to room temperature, and wherein hydrogen and hydrogen in nitrogen mixed gas and nitrogen mass are than for 5:95, being passed through of hydrogen
Speed is 100ml/min.
In the present embodiment, the conductivity of the graphene film of preparation is 560S/cm.
(5) graphene film electrochemical property test method is with embodiment 2.
Embodiment 4 is adulterated the preparation of graphene film of 10wt.% acetylene black and 10wt.% epoxy resin
(1) preparation method of graphite oxide is with embodiment 1
(2) method of doping mass ratio 10wt.% acetylene black and 10wt.% epoxy resin is with embodiment 2
(3) preparation method of graphite oxide film is with embodiment 1
(4) thermal reduction prepares the process of graphene film:
Under hydrogen and nitrogen mixture are protected, above-mentioned graphite oxide film is warming up to 1050 DEG C with the speed of 5 DEG C/min, is incubated 2
H, is naturally cooling to room temperature, and wherein hydrogen and hydrogen in nitrogen mixed gas and nitrogen mass are than for 15:85, hydrogen be passed through speed
Degree is 100ml/min.
In the present embodiment, the conductivity of the graphene film of preparation is 1000S/cm.
(5) graphene film electrochemical property test method is with embodiment 2
Use the above-mentioned several method can unrestricted choice conduction Carbon Materials and high polymer and the amount of doping.
The preparation of comparative example undoped p graphene film
(1) preparation method of graphite oxide is with embodiment 1
(2) preparation method of graphite oxide film is with embodiment 1
(3) HI reducing process prepares the process of graphene film with embodiment 1
(4) graphene film electrochemical property test method is with embodiment 2
The flexible graphene film substantially prepared not as the inventive method of the graphene film that comparative example prepares is flexible, be not suitable for folding,
Cutting.
Fig. 3 is the doping 0.2wt.% conductive carbon black graphene film electrode that the pure graphene film for preparing of comparative example, embodiment 1 prepare
Cyclic voltammogram with the doping 20wt.% acetylene black graphene film electrode that embodiment 2 prepares.According to the cyclic voltammetric area of pictural surface and public affairs
FormulaCalculate the electrochemistry capacitance of electrode material.Wherein, CmElectrochemistry specific volume for electrode material
Amount (unit is F/g), υ be cyclic voltammetry scan speed (V/s), m be the quality (g) of electrode active material, Δ V is potential window
Interval (V), V0For initial potential, I is sweep current (A).Understand, sweeping speed under the conditions of 5mV/s, pure graphene film
It is 35.2F/g than electric capacity, and the ratio electric capacity being doped with the graphene film of 0.2wt.% conductive carbon black has reached 90F/g, be doped with
The ratio electric capacity of the graphene film of 20wt.% acetylene black increases to 104F/g.This result is it should be apparent that add conductive carbon black
After acetylene black, the chemical property of graphene film is substantially improved.
Fig. 4 is pure graphene film, the doping 5wt.% prepared as described in Example 2 and the 10wt.% acetylene that comparative example prepares
The cyclic voltammogram of black rear graphene film.It can be seen that under the conditions of sweeping speed 5mV/s, 5wt.% and 10wt.% second of adulterating
The ratio electric capacity of the graphene film of acetylene black respectively reaches 130 and 190F/g, and the property of the graphene film of doping 10wt.% acetylene black is described
The graphene film of doping 5wt.% acetylene black can be better than.
Fig. 5 is that the graphene film of the prepared doping 5wt.% carbon fiber of embodiment 3 and 10wt.% polyimides sweeps speed in difference
Under cyclic voltammogram.Obtained the area of its electro-chemical activity by Origin software analysis, recycling formula is obtained it and is compared electric capacity.
The graphene film of doping 5wt.% carbon fiber and 10wt.% polyimides ratio under speed is swept in 2,5,10,20 and 50mV/s
Electric capacity is respectively 170,141,99,92 and 56F/g.
Fig. 6 is that embodiment 4 is adulterated graphene film the following under difference sweeps speed of 10wt.% acetylene black and 10wt.% epoxy resin
Ring voltammogram.This graphene film ratio electric capacity under speed is swept in 2,5,10,20 and 50mV/s is respectively 181,149,119,
69 and 24F/g.
Claims (6)
1. the preparation method of a high-conductivity flexible graphene membrane electrode, it is characterised in that: step is as follows,
Use Hummers method to prepare graphite oxide dispersion, dispersion liquid is simultaneously introduced conductive carbon material and high polymer, ultrasonic
Concussion is uniformly dispersed, and then makes graphite oxide film forming, then the reduction of graphite oxide film is i.e. prepared high-conductivity flexible graphene film,
The shape that prepared graphene film is cut into needs is needed i.e. to obtain high-conductivity flexible graphene membrane electrode according to reality application,
Described high polymer is polyethylene terephthalate or polyimides,
The method of described graphite oxide film forming is vacuum filtration method or spraying process, and described spraying process is, is disperseed by graphite oxide
Liquid loads in spray gun reservoir, is uniformly sprayed onto on sheet glass, drying and forming-film.
The preparation method of high-conductivity flexible graphene membrane electrode the most according to claim 1, it is characterised in that: described
Conductive carbon material be in activated carbon, carbon black BP-2000, acetylene black, carbon fiber, graphite or CNT any one, conduction
Material with carbon element mass ratio in graphene film is 0.2～20wt.%.
The preparation method of high-conductivity flexible graphene membrane electrode the most according to claim 1, it is characterised in that: described
High polymer mass ratio in graphene film is 0.1～10wt.%.
The preparation method of high-conductivity flexible graphene membrane electrode the most according to claim 1, it is characterised in that: described oxygen
The reduction of fossil ink film uses hydrogen heat reducing process or HI solution reduction.
The preparation method of high-conductivity flexible graphene membrane electrode the most according to claim 4, it is characterised in that: described
Hydrogen heat reducing process reduction process is, by graphite oxide film with the speed of 1～10 DEG C/min under hydrogen and nitrogen mixture are protected
It is warming up to 1050 DEG C, is incubated 0.1～2h, is naturally cooling to room temperature；
Wherein hydrogen and hydrogen in nitrogen mixed gas and nitrogen mass are than for 5:95～15:85, and the speed that is passed through of hydrogen is
100ml/min。
The preparation method of high-conductivity flexible graphene membrane electrode the most according to claim 4, it is characterised in that: described
HI solution reduction reduction process is, is put into by graphite oxide film in the HI solution that concentration is 10～80wt.%, at 30～200 DEG C
Under the conditions of, reacting 0.5～5h, HI is 5:1～30:1 with the mass ratio of graphite oxide film.
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| CN106698407B (en) * | 2017-03-16 | 2019-11-05 | 北京化工大学 | A kind of Flexible graphene film, preparation method and flexible device including it that can be folding |
| CN107381544A (en) * | 2017-06-16 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of graphene film and its preparation method and application |
| WO2019033360A1 (en) * | 2017-08-17 | 2019-02-21 | Sabic Global Technologies, B.V. | Carbon microtube composite film electrode |
| CN107500271A (en) * | 2017-08-31 | 2017-12-22 | 北京化工大学 | Flexible graphene film and Flexible graphene based composites film and preparation method thereof |
| CN108376615A (en) * | 2018-03-03 | 2018-08-07 | 济宁利特纳米技术有限责任公司 | A kind of button ultracapacitor graphene-based electrode slice and preparation method thereof |
| CN108795393B (en) * | 2018-06-08 | 2021-01-29 | 东莞市鸿亿导热材料有限公司 | Method for manufacturing carbon fiber flexible graphite sheet |
| CN112697853A (en) * | 2020-12-03 | 2021-04-23 | 盐城工学院 | Reduced graphene oxide modified electrode and preparation method and application thereof |
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