CN103903879A - Porous grapheme/ MnO2 composite film and preparation method and application thereof - Google Patents
Porous grapheme/ MnO2 composite film and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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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
Abstract
The invention relates to a porous grapheme/ MnO2 composite film and a preparation method and application thereof. The preparation method comprises the following steps of (1), providing a ball-shaped formwork and coating the surface of the ball-shaped formwork with a polymer layer; (2) providing graphene oxide solution, evenly mixing a small formwork ball coated with the polymer layer obtained in the step (1) with the graphene oxide solution, performing vacuum filtration, and stripping the composite film from a filter membrane after drying; (3) performing high temperature annealing on the composite film obtained in the step (2) to obtain a film of a porous structure; (4) putting the film obtained in the step (3) into potassium permanganate solution to perform hydrothermal reaction to obtain the porous grapheme/ MnO2 composite film. No any binder or conductive agent is needed to be added to the porous composite film prepared by the method, and the porous composite film is good mechanical property and super capacitive performance, has the advantages of being good in high-rate charge and discharge performance, long in circle life and the like, and can be applied to preparing super-capacitors and improve performance of super-capacitors greatly.
Description
Technical field
The present invention relates to grapheme material Application and preparation field, more particularly, relate to a kind of porous graphene/MnO
2laminated film and preparation method thereof, and using this material as being used for ultracapacitor without any binding agent, conductive agent self-supporting electrode material.
Background technology
Graphene is a kind ofly to form with sp2 hybridized orbit the flat film that hexangle type is honeycomb lattice by carbon atom, is the two-dimensional material of a carbon atom thickness, and Graphene is not only one the thinnest in known materials, also very firmly hard; As simple substance, it is all faster than known conductor that it at room temperature transmits the speed of electronics, and Graphene has unusual electric conductivity, exceeds the intensity of iron and steel decades of times and fabulous light transmission.
Ultracapacitor, it is electrochemical capacitor, it is a kind of clean electric energy storing device that high-power output can be provided, there is long service life and stability, meet " low-carbon (LC) " expanding economy requirement, Graphene super capacitor has been subject to people's great attention especially, has potential application widely in fields such as compound electric motor-car, portable electric appts and signal controlling.According to Mechanism of electrochemical behaviors of anhydrous, ultracapacitor can be divided into double electric layer capacitor and fake capacitance device.Double electric layer capacitor mainly uses carbon-based material, and the electrode material of fake capacitance device mainly contains transition metal oxide and conducting polymer.
Follow the requirements at the higher level of electronic product to power-supply device, do not add the self-supporting super capacitor material of any binding agent and conductive agent and paid close attention to more and more widely and study.Two dimension Graphene paper, because of its good conductivity and higher specific area, be a kind of comparatively desirable globality, self-supporting super capacitor electrode material, but in actual applications, the accumulation of graphene sheet layer reduces the effective area that forms electric double layer.Therefore, whether research can overcome this defect to its modification.The people such as Ruoff are applied to chemical modification grapheme material in electrode material for super capacitor first in Graphene-Based Ultracapacitors mono-literary composition, but, the ratio capacitance of finding water system and organic system electrolyte is all lower, it is thought and causes the quality main cause more undesirable than electric capacity to be: the chemical modification Graphene electrodes material of reduction preparation is again reunited and causes its effective ratio area greatly to reduce, and cannot adsorb a large amount of electrolyte ions.
In order further to improve the energy density of graphene-based electrode material, Graphene/polymer and Graphene/oxide composite occur in succession.Because oxygen-containing functional group abundant on graphene oxide can provide avtive spot for the growth of metal oxide, conducting polymer etc., form graphene nanocomposite material, thereby the feature of high grapheme material cycle life and stability can be combined with the advantage of transition metal oxide/conductive polymer electrodes material high specific capacitance, prepare the hybrid supercapacitor electrode material that performance is more excellent.As CN102558857A discloses a kind of preparation method of grapheme/polyaniline nanometer fibrous composite material, the method comprises the following steps: a kind of graphene oxide powder is provided, dissolve this graphene oxide powder to obtain a graphene oxide solution, and this graphene oxide solution is carried out to functionalization to activate this graphene oxide, one polyaniline nano fiber is provided, dissolve this conducting polymer to obtain a conductive polymer solution, mix described conductive polymer solution and the described graphene oxide solution through functionalization, make described conducting polymer and through the graphene oxide generation chemical reaction of overactivation to obtain one graphene oxide/polyaniline nano fiber composite precast thing solution, remove solvent in described graphene oxide/polyaniline nano fiber composite precast thing solution to obtain graphene oxide/polyaniline nano fiber composite precast thing powder, reduce this graphene oxide/polyaniline nano fiber composite material, separate dry processing and obtain a grapheme/polyaniline nanometer fibrous composite material.The grapheme/polyaniline nanometer fibrous composite material that the method makes connects polyaniline by chemical method key, thereby has improved capacitive property and the stability of material, but due to pi-pi accumulation and the van der Waals interaction of Graphene, its effective ratio area is still not high.And the composite material making is pulverulence, to prepare in ultracapacitor process and need additive, this has increased quality and the cost of ultracapacitor greatly.
Summary of the invention
One of object of the present invention is to provide a kind of porous graphene/MnO
2the preparation method of laminated film.Preparation method's cost of the present invention is low, environmental friendliness, be simply easy to carry out, the laminated film making can improve the performance of ultracapacitor greatly for ultracapacitor.
One of in order to achieve the above object, the present invention adopts the method that is prepared as follows:
A kind of porous graphene/MnO
2the preparation method of laminated film, comprises the steps:
1) provide a kind of spherical template, at the coated one layer of polymeric layer in spherical template surface, the method for coating of this step is prior art, for example, can obtain one layer of polymeric in template surface polymerization reaction by mix and blend method; Be can preserve as much as possible complete and be unlikely to subside for pore structure after removing template at the coated very thin one layer of polymeric in template bead surface, the contained N of polymeric layer can increase again the fake capacitance of ultracapacitor simultaneously;
2) providing a kind of graphene oxide solution, by step 1) the gained template bead that is coated with polymeric layer mixes with graphene oxide solution, and vacuum filtration, strips down composite membrane after drying from filter membrane; The preferred vacuum filtration of suction filtration, composite membrane is wherein by the interaction between the functional group on oxygen-containing functional group and polymeric layer on Graphene, the uniform film forming through vacuum filtration self assembly;
3) by step 2) gained composite membrane high annealing, obtain porous structural film;
4) by step 3) gained film hydro-thermal reaction in liquor potassic permanganate obtains porous graphene/MnO
2laminated film.
The present invention chooses Graphene and manganese dioxide is active material, Graphene is carried out to pore-creating by template, thereby effectively keeps the pore structure of porous graphene at template surface coated polymer layer, effectively prevents that Graphene from reuniting; Manganese dioxide load is arrived to surface and the edge of pore structure under hydrothermal condition; Utilize the good filming of graphene oxide, preparation does not need to add the self-supporting electrode material of any binding agent and conductive agent.
Ultracapacitor charge and discharge process is followed the dual embedding/deintercalation of electronics and ion, thereby electrode material is carried out to porous design, prepare three-dimensional porous structure film, its crossings on different level three-dimensional porous structure can not only provide larger reactivity area, and can provide good diffusion admittance for electrolyte ion.Preparation method of the present invention is simple, economical, easy to operate.
According to the present invention, step 1) bead in described spherical template easily removes, and described easy removal just can remove bead by simple chemicals logos, the general knowledge that the removal of bead is this area; Be preferably polystyrene (PS) bead, silicon dioxide bead or polymethyl methacrylate (PMMA) bead, PS can use the methods such as calcining or toluene dissolving to remove, what silicon dioxide was conventional is HF etching, and what PMMA was conventional is that calcining is removed.
Preferably, the diameter of described bead is 200nm～2 μ m, for example, be 250-500nm, 400-900nm, 800nm-1 μ m, 1.5-2 μ m etc.
According to the present invention, step 1) described polymeric layer is polydextrose, shitosan, poly-dopamine, polyaniline or polypyrrole polymers layer, preferably, the thickness of described polymeric layer is 10～100nm, for example, be 15nm, 30nm, 50nm, 70nm, 85nm, 95nm etc.
According to the present invention, step 2) described graphene oxide prepared by chemical method; The chemical preparation process of graphene oxide can adopt the methods such as Hummers method, Brodie method or Staudenmaier.
Brodie method is first with the HNO of being fuming
3process natural micro powder graphite, when graphite is oxidized, nitrate ion is invaded between people's graphite flake layer, and then drops into KClO
4further oxidation, throws reactant in National People's Congress's water gaging subsequently, filters, and is washed to filtrate and approaches after neutrality, dry, obtains graphite oxide.
Staudemaier method is with the concentrated sulfuric acid and fuming nitric aicd mixed acid, graphite powder to be processed, and is equally also with KClO
4for oxidant.
Hummers method is by graphite powder and anhydrous nitric acid sodium (NaNO
3) join the concentrated sulfuric acid being placed in ice bath, under strong stirring, add KMnO
4, and use volume fraction 3%H
2o
2reduce remaining potassium permanganate and MnO
2, make its soluble MnSO that becomes colorless
4.Under the processing of hydrogen peroxide, suspension becomes glassy yellow.Filter, wash 3 times, then vacuum dehydration obtains.The oxidized graphite flake layer obtaining has pleat beryllium type structure, and oxygen content is larger, and functional group, can fine dispersion in pure water compared with horn of plenty.
Preferably, the present invention adopts and improves Hummers legal system for graphene oxide: when the 25mL concentrated sulfuric acid is heated to 90 DEG C, add 5g K
2s
2o
8with 5g P
2o
5, constantly stir until mixture stops heating after dissolving completely, then add 6g natural graphite powder, by mixture agitating heating 5h under 80 DEG C of water-baths.Mixture is cooled to after room temperature, uses a large amount of deionized water rinsings, suction filtration products therefrom.In this product, add the concentrated sulfuric acid and potassium permanganate, under 35 DEG C of water-baths, react 2h, then slowly add 1.5mL deionized water, after stirring reaction 2h, to the H that adds 25mL30% in mixture
2o
2, now mixed liquor becomes bright khaki.After hold over night, remove supernatant, successively use a large amount of 5%HCl and deionized water rinsing to neutral.Finally separate with centrifuge, obtain the graphite oxide of high concentration.Gained graphite oxide is diluted with water, and ultrasonic processing obtains the graphene oxide solution that yellowish-brown homogeneous disperses.
Preferably, graphene oxide is 2～10:1 with the mass ratio of the spherical template that is coated with polymeric layer.Along with being coated with the increase of template bead of polymeric layer, the three-D pore structure of composite membrane can increase, thereby effective contact area of laminated film and electrolyte can increase, but film forming and conductivity can decrease, so will ensure film forming and the conductivity of compound when increasing pore structure, instead of unconfined pore structure, increase specific area of increasing.
According to the present invention, step 3) condition of described annealing is under protective gas atmosphere, is warmed up to 450 DEG C～800 DEG C, be for example 480 DEG C, 550 DEG C, 600 DEG C, 750 DEG C etc. and insulation, insulation 3-5h, then naturally cooling room temperature, described protective atmosphere is realized by passing into inert gas; Described inert gas is the gas not reacting with graphene oxide and the template bead that is coated with polymeric layer; preferably; described protective gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas, more preferably nitrogen and/or argon gas.
Described protective atmosphere be embodied as technology well-known to those skilled in the art, for example can first high flow rate under logical inert gas 10min get rid of oxidizing gas, then reduce flow velocity.In described protective atmosphere, the residual quantity of oxidizing gas can make N in polymeric layer slough and can not form containing N carbon-coating, thereby affects the reduction of potassium permanganate in next step reaction, and loses the fake capacitance that N provides.
Preferably, the speed of described intensification is 5～20 DEG C/min, for example, be 7 DEG C/min, 10 DEG C/min, 15 DEG C/min, 18 DEG C/min etc., and the time of described insulation is 4～8h, for example, be 4.5h, 5h, 6h, 7.5h etc.
According to the present invention, step 4) concentration of described liquor potassic permanganate is 3-10mmol/L, for example, be 3.5mmol/L, 5mmol/L, 6mmol/L, 7.5mmol/L, 8mmol/L, 9.5mmol/L etc.The concentration of potassium permanganate is determining load MnO
2thickness, it is 3-10mmol/L that the present invention selects the concentration of liquor potassic permanganate, can make the MnO of load
2thickness suitable.The temperature of hydro-thermal reaction is 150-200 DEG C, is preferably 180 DEG C.
Hydro-thermal reaction is for manganese dioxide in load, keeps the toughness of film etc. simultaneously.
Porous graphene/the MnO that provides described method to prepare is provided two of object of the present invention
2laminated film, described laminated film is poroid sandwich structure, and bore dia is 200nm～2 μ m, and the aperture that finally makes laminated film is consistent with the aperture of bead masterplate used, and sheet distribution of manganese dioxide is in vestibule and on bore edges.
Three of object of the present invention is to provide the purposes of described laminated film, uses it for the preparation of ultracapacitor, described porous graphene/MnO
2laminated film is self-supporting electrode material, assembling when ultracapacitor without any binding agent and conductive agent.In the time of assembling ultracapacitor, except electrode material uses porous composite film provided by the invention, all limiting less than concrete as electrolyte, collector, spacer of other, in the situation that miscellaneous part is identical, use composite membrane of the present invention as the capacitor of electrode material compared with other materials as the capacitor of electrode material there is more excellent cyclical stability, than electric capacity and high rate performance etc.
According to the present invention, utilize the step of described laminated film assembling super capacitor to be: described laminated film is cut into
disk, as electrode material, be assembled into the ultracapacitor of sandwich structure.
Porous graphene/MnO prepared by the present invention
2laminated film, as self-supporting super capacitor electrode material, does not need to add any binding agent, conductive agent, and mechanical performance and super capacitor are functional, show the advantage such as high-rate charge-discharge capability and high cycle life; Its crossings on different level three-dimensional porous structure is conducive to increase the contact area of electrode material and electrolyte, and larger reactivity area can be provided, and can provide good diffusion admittance for electrolyte ion, thereby improves capacitive property.
Ultracapacitor with electrode material assembling of the present invention shows good cycling stability, higher than electric capacity, high rate performance is excellent, the features such as material good conductivity, be applicable to flexible electronic device etc., have broad application prospects in fields such as compound electric motor-car, portable electric appts and signal controlling.
Brief description of the drawings
Fig. 1 is that the present invention prepares porous graphene/MnO
2the schematic flow sheet of laminated film method.
Fig. 2 is that the embodiment of the present invention 1 use dopamine is porous graphene/MnO prepared by coating layer
2the scanning electron microscope (SEM) photograph of laminated film;
Fig. 3 is hole Graphene/MnO that the embodiment of the present invention 3 is prepared as coating layer with polydextrose
2the scanning electron microscope (SEM) photograph of laminated film;
Fig. 4 is that the difference of two electrode tests of the ultracapacitor assembled of the embodiment of the present invention 1 is swept the cyclic voltammogram under speed;
Fig. 5 is that the ratio electric capacity of the ultracapacitor assembled of the embodiment of the present invention 1 is with the change curve of sweep speed;
Fig. 6 is the crossing current charging and discharging curve under the different current densities of the ultracapacitor assembled of the embodiment of the present invention 1;
Fig. 7 is the stable circulation test curve of the ultracapacitor assembled of the embodiment of the present invention 1 under 0.1A/g.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
The concrete technology flow process of embodiment refers to Fig. 1.
With reference to figure 1, the PS bead that 100mg average diameter is about to 300nm is scattered in the Tris-HCl(pH=8.5 of the DA of 2mg/mL) in solution, stirring at room temperature reaction 15h, then centrifugal, wash, dry and to obtain PS PDA powder.PS@PDA powder is separated into the aqueous solution of 10mg/mL, get 0.25mL and the ultrasonic dispersion 40min of 10mL graphite weak solution (1.25mg/mL), then by this mixed liquor vacuum filtration, after naturally drying, laminated film is stripped down from filter membrane, obtain PS@PDA@GO composite membrane.In Ar atmosphere at 500 DEG C by this composite membrane annealing in process 5h, remove template PS bead, obtain hollow-core construction graphene composite film.This film is put in 10mM potassium permanganate solution, hydro-thermal reaction 25min at 180 DEG C, as shown in Figure 2 porous graphene/MnO
2laminated film.This composite membrane is cut into the disk that diameter is 1cm, choose two tablet qualities close as electrode material, glass fibre membrane is as barrier film, 1M Na
2sO
4the aqueous solution is electrolyte, assembles two electrode super capacitors with Swagelok type battery.
Fig. 2 removes after template, is about the cross-section morphology figure of the film that 5um is thick through annealing in process, can find out that composite membrane presents uniform porous honeycomb structure, the cavernous structure of these connections has not only increased the structural area with electrolyte, has effectively prevented the easy reunion of Graphene simultaneously.
Fig. 4 is that the difference of two electrode tests is swept the lower cyclic voltammogram that to obtain of speed, all can present good rectangle at 1～300mV/s scope inner curve, shows that this ultracapacitor has good capacitive property.
It is lower than electric capacity that Fig. 5 is that difference is swept speed, and in the time sweeping speed for 1mV/s, reaching 136F/g(than electric capacity, to calculate quality used be whole membrane electrode quality).
Fig. 6 obtains charging and discharging curve figure under different current densities, at 0.1～20A/g, charging and discharging curve all can present approximate isosceles triangle, shows that this ultracapacitor has good invertibity and excellent high rate performance.
Fig. 7 is the stable circulation test curve of this assembling ultracapacitor under 0.1A/g, is as can be seen from the figure circulating after 500 times, and the ratio electric capacity of material still remains on more than 90%, illustrates that this material has good cyclical stability.
Embodiment 2
With reference to figure 1, the PS bead that 100mg average diameter is about to 300nm is scattered in the Tris-HCl(pH=8.5 of the DA of 2mg/mL) in solution, stirring at room temperature reaction 10h, then centrifugal, wash, dry and to obtain PS PDA powder.PS@PDA powder is separated into the aqueous solution of 10mg/mL, get 0.25mL and the ultrasonic dispersion 40min of 10mL graphite weak solution (1.25mg/mL), then by this mixed liquor vacuum filtration, after naturally drying, laminated film is stripped down from filter membrane, obtain PS@PDA@GO composite membrane.In Ar atmosphere at 500 DEG C by this composite membrane annealing in process 5h, remove template PS bead, obtain hollow-core construction graphene composite film.This film is put in 10mM potassium permanganate solution, at 180 DEG C of Water Under thermal response 25min.
Calculating this material by constant current charge-discharge is that 75.2F/g(electric current is 0.1A/g than electric capacity, electrochemical window is 0-0.8V), because the polymerization reaction time of coated PDA is 10h, shorter than 15h in embodiment 1, polymeric layer is just thinner, thereby in compound film electrode material, the contribution of PDA contrast electric capacity has just weakened, so less compared with the material in embodiment 1 than electric capacity.
Embodiment 3
The PS bead that 100mg average diameter is about to 300nm is scattered in the glucose solution of 0.5M, stirring at room temperature reaction 24h, then centrifugal, wash, dry and to obtain the coated PS powder of polydextrose.Above-mentioned powder is separated into the aqueous solution of 10mg/ml, get this solution 1mL and the ultrasonic dispersion 40min of 10mL graphite weak solution (1.25mg/mL), then by this mixed liquor vacuum filtration, after naturally drying, laminated film is stripped down from filter membrane, obtain PS@PGL@GO composite membrane.In Ar atmosphere at 500 DEG C by this composite membrane annealing in process 5h, remove template PS bead, obtain hollow-core construction graphene composite film.This film is put in to hydro-thermal reaction 20min in 5mM potassium permanganate solution.This composite membrane is cut into the disk that diameter is 1cm, choose two tablet qualities close as electrode material, glass fibre membrane is as barrier film, 1M Na
2sO
4the aqueous solution is electrolyte, assembles two electrode super capacitors with Swagelok type battery, and testing and calculating it by constant current charge-discharge is 78.2F/g than electric capacity.Owing to having added the coated PS of 1mL polydextrose, the corresponding reduction of Graphene proportion so, thus can reduce the conductivity of material, so reduce to some extent compared with embodiment 1 than electric capacity.
Fig. 3 is the scanning electron microscope (SEM) photograph that the present embodiment makes composite membrane, as can be seen from the figure, this film presents uniform porous honeycomb structure, due to Polydextrose under 500 DEG C of high temperature carbonization form amorphous carbon, in inside, hole and edge see many manganese dioxide.
The PMMA bead of 100mg is scattered in to the Tris-HCl(pH=8.5 of the DA of 2mg/mL) in solution, stirring at room temperature reaction 15h, then centrifugal, wash, dry and to obtain PMMA@PDA powder.PMMA@PDA powder is separated into the aqueous solution of 10mg/mL, get 0.25mL and the ultrasonic dispersion 40min of 10mL graphite weak solution (1.25mg/mL), then by this mixed liquor vacuum filtration, naturally after drying, laminated film is stripped down from filter membrane, obtain PMMA@PDA@GO composite membrane.In Ar atmosphere at 800 DEG C by this composite membrane annealing in process 3h, remove template PMMA bead, obtain hollow-core construction graphene composite film.This film is put in 10mM potassium permanganate solution, at 180 DEG C of Water Under thermal response 25min.
This composite membrane is cut into the disk that diameter is 1cm, choose two tablet qualities close as electrode material, glass fibre membrane is as barrier film, 1M Na
2sO
4the aqueous solution is electrolyte, assembles two electrode super capacitors with Swagelok type battery, and testing and calculating it by constant current charge-discharge is 122.7F/g than electric capacity.
The execution mode the present invention relates to can also be diversified, and template can also be that silicon dioxide bead, polymethyl methacrylate (PMMA) bead etc. are easily removed bead except PS bead.Coated polymer layer, except polydextrose and poly-dopamine, can also be shitosan, polyaniline, polypyrrole etc.A kind of porous graphene/MnO that the present invention proposes
2the features such as laminated film self-supporting super capacitor electrode material good cycling stability, higher than electric capacity, high rate performance is excellent, material good conductivity, are applicable to flexible electronic device etc.
Should be noted that and understand, in the situation that not departing from the desired the spirit and scope of the present invention of accompanying claim, can make various amendments and improvement to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subject to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a porous graphene/MnO
2the preparation method of laminated film, comprises the steps:
1) provide a kind of spherical template, at the coated one layer of polymeric layer in spherical template surface;
2) providing a kind of graphene oxide solution, by step 1) the gained template bead that is coated with polymeric layer mixes with graphene oxide solution, and vacuum filtration, strips down composite membrane after drying from filter membrane;
3) by step 2) gained composite membrane high annealing, obtain porous structural film;
4) by step 3) gained film hydro-thermal reaction in liquor potassic permanganate obtains porous graphene/MnO
2laminated film.
2. preparation method as claimed in claim 1, is characterized in that step 1) bead in described spherical template easily removes; Be preferably polystyrene sphere, silicon dioxide bead or polymethyl methacrylate bead.
3. preparation method as claimed in claim 1 or 2, is characterized in that, the diameter of described bead is 200nm～2 μ m.
4. the preparation method as described in claim 1-3 any one, it is characterized in that, step 1) described polymeric layer is polydextrose, shitosan, poly-dopamine, polyaniline or polypyrrole polymers layer, preferred, the thickness of described polymeric layer is 10～100nm.
5. the preparation method as described in claim 1-4 any one, is characterized in that step 2) described graphene oxide prepared by chemical method;
Preferably, graphene oxide is 2～10:1 with the mass ratio of the spherical template that is coated with polymeric layer.
6. the preparation method as described in claim 1-5 any one, it is characterized in that, step 3) condition of described annealing is under protective gas atmosphere, be warmed up to 450 DEG C～800 DEG C and insulation, then naturally cooling room temperature, preferably, described protective gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas, more preferably nitrogen and/or argon gas;
Preferably, the speed of described intensification is 5～20 DEG C/min, and the time of described insulation is 4～8h.
7. the preparation method as described in claim 1-6 any one, is characterized in that step 4) concentration of described liquor potassic permanganate is 3-10mmol/L.
8. a porous graphene/MnO who prepares by method described in claim 1-7 any one
2laminated film, is characterized in that, described laminated film is poroid sandwich structure, and bore dia is 200nm～2 μ m, and sheet distribution of manganese dioxide is in vestibule and on bore edges.
9. the purposes of laminated film claimed in claim 8, is characterized in that, by described porous graphene/MnO
2laminated film is for the preparation of ultracapacitor, described porous graphene/MnO
2laminated film is electrode material.
10. purposes as claimed in claim 9, is characterized in that, utilizes the step of described laminated film assembling super capacitor to be: described laminated film is cut into
disk, as electrode material, be assembled into the ultracapacitor of sandwich structure.
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