CN103346024A - Method for preparing high-conductivity flexible graphene membrane electrode - Google Patents
Method for preparing high-conductivity flexible graphene membrane electrode Download PDFInfo
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Abstract
The invention provides a method for preparing a high-conductivity flexible graphene membrane electrode. The defects that in the prior art, in the process of membrane formation, a graphene membrane is prone to cracking and not good enough in folding degree are overcome. The method includes the following steps that a Hummers method is adopted for preparing graphite oxide dispersing liquid, electric conduction carbon material and high polymers are simultaneously added into the dispersing liquid, the dispersing liquid is evenly dispersed through ultrasonic vibration, graphite oxide is made to be a film, then the graphite oxide film is reduced and a high-conductivity flexible graphene film is prepared. According to actual needs, the prepared graphene film is tailored to be in a needed shape, and therefore the high-conductivity flexible graphene film electrode is obtained. The method for preparing the high-conductivity flexible graphene membrane electrode has the advantages that the electric conductivity of the graphene film is 200-1000S/cm, the electrochemistry capacity can reach 190F/g, the thickness is 120-300 microns, and the graphene film has high conductivity and flexibility and can be tailored to be in different shapes with different thicknesses.
Description
Technical field
The invention belongs to the graphene film preparing technical field, relate in particular to the Graphene membrane electrode preparation method.
Background technology
Ultracapacitor is a kind of novel energy-storing device between secondary cell and traditional capacitor that grows up 70～eighties of 20th century, it has the characteristic of physical capacitor and battery concurrently, can provide the energy density higher than physical capacitor, than the higher power density of battery and longer cycle life.Exploitation function admirable, life-span electrode long, cheap, that have wide range of applications are the core topic of ultracapacitor research, but for can being bonded together, dusty material prevents from coming off in the preparation process of existing most of electrodes, need to add nonconducting binding agent, thereby reduced the electrochemistry capacitance of ultracapacitor.Simultaneously, different applied environments needs the ultracapacitor of difformity and specification, has very important Research Significance so preparation has the electrode material of collapsible performance.
Graphene is the two-dimentional carbon atom crystal of finding in recent years, by six side's honeycombs that the monolayer carbon atom is formed, is the thinnest material of finding so far.Graphene has a lot of peculiar character and boundless application prospect, especially is applied to ultracapacitor and new electronic component.High conductivity flexible graphite alkene film can satisfy modern society to the needs of novel electrode material, has become the focus of current researcher research.Modern production needs the special shape ultracapacitor, thus need preparation can be cut into the electrode of difformity and thickness, but break easily in film forming procedure at graphene film, and folding degree is good inadequately.
Summary of the invention
The present invention overcomes in the prior art breaks in the graphene film film forming procedure easily, and the imperfect deficiency of folding degree, a kind of high conductivity flexible graphite alkene membrane electrode preparation method is provided, improves the method for graphene film electric conductivity and flexility by conductive doped carbon of while and high polymer.This method simple controllable, but and the graphene film of preparation have that pliability is good, the advantage of the excellent large-area preparation of electric conductivity.These characteristics make it to have potential actual application value in the ultracapacitor field.
The technical solution used in the present invention is as follows: a kind of high conductivity flexible graphite alkene membrane electrode preparation method, and step is as follows:
Adopt the graphite oxide dispersion liquid of Hummers method preparation, in dispersion liquid, add conductive carbon material and high polymer then simultaneously, ultrasonic concussion is uniformly dispersed, make the graphite oxide film forming then, again graphite oxide film reduction is namely made high conductivity flexible graphite alkene film, can namely obtain high conductivity flexible graphite alkene membrane electrode with making the shape that graphene film is cut into needs according to the practical application needs.
As preferably, described conduction raw material of wood-charcoal material be in activated carbon, carbon black BP-2000, acetylene black, carbon fiber, graphite or the carbon nano-tube any one, conductive carbon material mass ratio in graphene film is 0.2～20wt.%.
As preferably, described high polymer is epoxy resin, PETG or polyimides, and high polymer is 0.1～10wt.% for mass ratio in graphene film.
As preferably, the method for described graphite oxide film forming is vacuum filtration method or spraying process, and when adopting the vacuum filtration method, the size of graphene oxide film can be regulated according to the size of used filter membrane and the size of suction filtration device.
As preferably, hydrogen heat reducing process or HI solution reduction method are adopted in described graphite oxide reduction.These two kinds of reducing process efficient height can be produced in enormous quantities, and the repetition performance height of material.
Further, above-mentioned hydrogen heat reducing process reduction process is: under the protection of hydrogen and nitrogen mixture the graphite oxide film is warming up to 1050 ℃ with the speed of 1～10 ℃/min, insulation 0.1～2h is cooled to room temperature naturally.Wherein hydrogen and nitrogen mass ratio are 5:95～15:85 in hydrogen and the nitrogen mixture body, and the feeding speed of hydrogen is 100ml/min.
Further, above-mentioned HI solution reduction method reduction process is: the graphene oxide film is put into the HI solution that concentration is 10～80wt.%, and under 30～200 ℃ of conditions, reaction 0.5～5h, the mass ratio of HI and graphite oxide film is 5:1～30:1.
The present invention has optimized conditions such as thermal reduction temperature, hydrogen ratio, reaction time and HI solution concentration, makes the graphene film of preparation reach optimum performance.
The invention has the beneficial effects as follows: it is simple that the inventive method has technology, and synthetic convenient, technology is less demanding and be easy to remarkable advantage such as realization to equipment.The conductance of the graphene film of the present invention's preparation is 200～1000S/cm, electrochemistry capacitance can reach 190F/g, how much thickness of graphene film can regulating according to used graphite oxide and doping carbon material, thickness is 120～300 μ m, control by conduction raw material of wood-charcoal material and high polymer doping, make and can not influence product flexibility because of the doping of electric conducting material, also can not influence the electric conductivity of product because of the doping of high polymer, make product have high conductivity and flexibility concurrently, difformity and thickness can be cut into, the electrode of various special shapes can be satisfied.
Description of drawings
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 cyclic voltammogram of graphene film after the pure graphene film of Fig. 3 (a), doping 0.2wt.% conductive carbon black (b) and 20wt.% (c) acetylene black;
The cyclic voltammogram of graphene film after the pure graphene film of Fig. 4 (a), doping 5wt.% (b) and 10wt.% (c) acetylene black;
Fig. 5 mixes the graphene film of 5wt.% carbon fiber and 10wt.% polyimides at the different cyclic voltammograms of sweeping under the speed;
Fig. 6 mixes the graphene film of 10wt.% acetylene black and 10wt.% epoxy resin at the different cyclic voltammograms of sweeping under the speed.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
The preparation of the graphene film of embodiment 1 doping 0.2wt.% conductive carbon black and 0.1wt.% epoxy resin
(1) preparation of graphite oxide
Adopt improved Hummers legal system to be equipped with graphite oxide (GO).Under ice bath and powerful stirring condition, mix 0.5g graphite powder and 0.25g potassium nitrate, add the 12ml concentrated sulfuric acid then, slowly add 1.5g KMnO again
4Behind the oxidation reaction 96h, slowly add the dilution of 150ml deionized water, 98 ℃ of following oil bath 24h are inverted in the solution after the oil bath in the beaker, and cool to room temperature dropwise splashes into 5ml H then
2O
2(35wt%), continue reaction 30min.HCl with 250ml5% soaks, and washing is centrifugal then.Earlier solution being got with the centrifugal 10min of 12000rpm and precipitated below it, is about 7 up to upper solution pH.And then with the centrifugal 10min of 3000rpm, get solution above it, it is standby namely to make the GO dispersion liquid.
(2) doping 0.2wt.% conductive carbon black BP-2000 and 0.1wt.% epoxy resin
Get the graphite oxide solution of 100ml0.23mg/ml, respectively according to the conductive doped carbon black of 0.2% and 0.1wt.% and the B44 epoxy resin (bisphenol A type epoxy resin) of graphene film mass ratio.
(3) preparation of graphite oxide film
Get above-mentioned graphite oxide solution and place beaker, the about 0.5h of ultrasonic concussion places solution on the alumina formwork, and vacuum filtration, suction filtration finish to be placed in the baking oven in 60 ℃ of dry 0.5h down, take out the film that nature comes off, and are the graphite oxide film.
(4) the HI reducing process prepares the graphite oxide film
The graphite oxide film is got a part place beaker, in beaker, add 80wt.%HI solution, HI is 5:1 with graphite oxide film quality ratio, 30 ℃ of reaction 5h under the oil bath condition, when being down to room temperature, takes out question response film, be positioned over the HI solution of cleaning the surface in the deionized water, be the graphene film of doping 0.2wt.% conductive carbon black and 0.1wt.% epoxy resin.
The voltage-to-current of the film that measures with comprehensive rerum natura measuring instrument (PPMS, Quantum Design) changes, and calculates the conductance of this graphene film.The conductance of the graphene film for preparing in the present embodiment is 200S/cm.Graphene film flexibility by the method preparation is fine, non-friable, collapsible reduction.Fig. 1 is the SEM figure of the flexible graphite alkene film of embodiment 1 method preparation, and as can be seen from the figure the thickness of film is average, greatly about 120～169 μ m.
Fig. 2 is the graphite oxide film of embodiment 1 method preparation and the XRD figure of graphene film.From curve (b) as can be seen, the graphite oxide film ° has a very strong diffraction maximum in 2 θ=10.49, can calculate the graphite oxide interlamellar spacing according to bragg's formula (2dsin θ=n λ) is 0.84nm, and the interlamellar spacing of native graphite only is 0.33nm, the introducing that oxygenated functional group is described has strengthened the expanded of graphite linings, and has increased the hydrophily of graphite oxide.From curve (a) as can be seen, graphene film has one diffraction maximum about 2 θ=22.80 °, and the diffraction maximum in 2 θ=10.49 ° has disappeared, illustrate that oxygenated functional group is reduced, owing to be not subjected to the effect of Van der Waals force between graphite linings and the layer, the graphite flake layer of finally peeling off becomes Graphene, and the interlamellar spacing of Graphene must be 0.36nm as calculated.
The preparation of the graphene film of embodiment 2 doping 20wt.% acetylene blacks and 10wt.% PETG
(1) preparation method of graphite oxide is with embodiment 1.
(2) doping 20wt.% acetylene black and 10wt.% PETG.
Get the graphite oxide solution of 100ml0.23mg/ml, respectively according to mass ratio 20wt.% and the conductive doped acetylene black of 10wt.% and PETG.
(3) preparation method of graphite oxide film adopts spraying process, and the graphite oxide dispersion liquid is packed in the spray gun container, evenly is sprayed onto on the sheet glass drying and forming-film.
(4) the HI reducing process prepares the graphite oxide film: the graphite oxide film is got a part place beaker, in beaker, add 10wt.%HI solution, HI is 30:1 with graphite oxide film quality ratio, 200 ℃ of reaction 0.5h under the oil bath condition, when being down to room temperature, takes out question response film, be positioned in the deionized water HI solution of cleaning the surface, be the graphene film of the black and 10wt.% PETG of doping 20wt.% conductive acetylene.
The conductance of the graphene film for preparing in the present embodiment is 830S/cm.
(5) graphene film electrochemical property test
Be work electrode with the graphene film, platinum electrode is to electrode, and the Hg/HgO electrode is that reference electrode carries out the cyclic voltammetric test.Potential window is-0.5～0.3V, and electrolyte is 6M KOH.
The preparation of the graphene film of embodiment 3 doping 5wt.% carbon fibers 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 the protection of hydrogen and nitrogen mixture, above-mentioned graphite oxide film is warming up to 1050 ℃ with the speed of 1 ℃/min; insulation 0.1h; naturally be cooled to room temperature, wherein hydrogen and nitrogen mass ratio are 5:95 in hydrogen and the nitrogen mixture body, and the feeding speed of hydrogen is 100ml/min.
The conductance of the graphene film for preparing in the present embodiment is 560S/cm.
(5) graphene film electrochemical property test method is with embodiment 2.
The preparation of the graphene film of embodiment 4 doping 10wt.% acetylene blacks 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 the protection of hydrogen and nitrogen mixture, above-mentioned graphite oxide film is warming up to 1050 ℃ with the speed of 5 ℃/min; insulation 2h; naturally be cooled to room temperature, wherein hydrogen and nitrogen mass ratio are 15:85 in hydrogen and the nitrogen mixture body, and the feeding speed of hydrogen is 100ml/min.
The conductance of the graphene film for preparing in the present embodiment is 1000S/cm.
(5) graphene film electrochemical property test method is with embodiment 2
Adopt above-mentioned several method can freely select the amount of conduction raw material of wood-charcoal material and high polymer and doping.
Comparative example is the preparation of doped graphene film not
(1) preparation method of graphite oxide is with embodiment 1
(2) preparation method of graphite oxide film is with embodiment 1
(3) the 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 obviously graphene film flexibility not as the inventive method preparation of the graphene film that comparative example makes is good, is not suitable for folding, cutting.
The cyclic voltammogram of the doping 20wt.% acetylene black graphene film electrode that the doping 0.2wt.% conductive carbon black graphene film electrode that the pure graphene film that Fig. 3 makes for comparative example, embodiment 1 make and embodiment 2 make.According to the cyclic voltammetric area of pictural surface and formula
Calculate the electrochemistry capacitance of electrode material.Wherein, C
mBe the electrochemical specific capacity (unit is F/g) of electrode material, υ is cyclic voltammetry scan speed (V/s), and m is the quality (g) of electrode active material, and Δ V is potential window interval (V), V
0Be initial potential, I is sweep current (A).As can be known, be that the ratio electric capacity of pure graphene film is 35.2F/g under the 5mV/s condition sweeping speed, and the ratio electric capacity of the graphene film of the 0.2wt.% conductive carbon black that mixed has reached 90F/g, the ratio electric capacity of the graphene film of the 20wt.% acetylene black of having mixed is increased to 104F/g.This result can find out clearly and added after conductive carbon black and the acetylene black that the chemical property of graphene film significantly promotes.
The pure graphene film that Fig. 4 makes for comparative example, by the cyclic voltammogram of graphene film after the doping 5wt.% of the method for embodiment 2 preparation and the 10wt.% acetylene black.As we know from the figure, sweeping under the fast 5mV/s condition, the ratio electric capacity of the graphene film of doping 5wt.% and 10wt.% acetylene black reaches 130 and 190F/g respectively, illustrates that the performance of the graphene film of doping 10wt.% acetylene black is better than the graphene film of doping 5wt.% acetylene black.
The doping 5wt.% carbon fiber that Fig. 5 makes for embodiment 3 and the graphene film of 10wt.% polyimides are at the different cyclic voltammograms of sweeping under the speed.Obtain the area of its electro-chemical activity by the Origin software analysis, the recycling formula is obtained it and is compared electric capacity.The graphene film of doping 5wt.% carbon fiber and 10wt.% polyimides 2,5,10,20 and 50mV/s sweep ratio electric capacity under the speed and be respectively 170,141,99,92 and 56F/g.
Fig. 6 for the graphene film of embodiment 4 doping 10wt.% acetylene blacks and 10wt.% epoxy resin at the different cyclic voltammograms of sweeping under the speed.This graphene film 2,5,10,20 and 50mV/s sweep ratio electric capacity under the speed and be respectively 181,149,119,69 and 24F/g.
Claims (7)
1. high conductivity flexible graphite alkene membrane electrode preparation method, it is characterized in that: step is as follows:
Adopt the Hummers legal system to be equipped with the graphite oxide dispersion liquid, in dispersion liquid, add conductive carbon material and high polymer simultaneously, ultrasonic concussion is uniformly dispersed, make the graphite oxide film forming then, again graphite oxide film reduction is namely made high conductivity flexible graphite alkene film, can namely obtain high conductivity flexible graphite alkene membrane electrode with making the shape that graphene film is cut into needs according to the practical application needs.
2. high conductivity flexible graphite alkene membrane electrode according to claim 1 prepares, it is characterized in that: described conduction raw material of wood-charcoal material be in activated carbon, carbon black BP-2000, acetylene black, carbon fiber, graphite or the carbon nano-tube any one, conductive carbon material mass ratio in graphene film is 0.2～20wt.%.
3. high conductivity flexible graphite alkene membrane electrode according to claim 1 prepares, it is characterized in that: described high polymer is epoxy resin, PETG or polyimides, and high polymer is 0.1～10wt.% for mass ratio in graphene film.
4. preparing of high conductivity flexible graphite alkene membrane electrode according to claim 1, it is characterized in that: the method for described graphite oxide film forming is vacuum filtration method or spraying process.
5. preparing of high conductivity flexible graphite alkene membrane electrode according to claim 1 is characterized in that: described graphite oxide reduction employing hydrogen heat reducing process or HI solution reduction method.
6. high conductivity flexible graphite alkene membrane electrode according to claim 5 prepares, it is characterized in that: described hydrogen heat reducing process reduction process is: at hydrogen and nitrogen mixture, protection down is warming up to 1050 ℃ with the graphite oxide film with the speed of 1～10 ℃/min, insulation 0.1～2h is cooled to room temperature naturally;
Wherein hydrogen and nitrogen mass ratio are 5:95～15:85 in hydrogen and the nitrogen mixture body, and the feeding speed of hydrogen is 100ml/min.
7. high conductivity flexible graphite alkene membrane electrode according to claim 5 prepares, it is characterized in that: described HI solution reduction method reduction process is: the graphene oxide film is put into the HI solution that concentration is 10～80wt.%, under 30～200 ℃ of conditions, reaction 0.5～5h, the mass ratio of HI and graphite oxide film is 5:1～30:1.
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| CN105671689A (en) * | 2016-01-13 | 2016-06-15 | 郑州大学 | Straight-wire graphene fiber and application of straight-wire graphene fiber used as electric suction device |
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| CN106698407A (en) * | 2017-03-16 | 2017-05-24 | 北京化工大学 | Flexible graphene film capable of being repeatedly folded, preparation method of flexible graphene film and flexible device comprising flexible graphene film |
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| 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 |
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| 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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