CN103903879B - 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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- CN103903879B CN103903879B CN201410055555.6A CN201410055555A CN103903879B CN 103903879 B CN103903879 B CN 103903879B CN 201410055555 A CN201410055555 A CN 201410055555A CN 103903879 B CN103903879 B CN 103903879B
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 239000003990 capacitor Substances 0.000 claims abstract description 21
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 52
- 239000011324 bead Substances 0.000 claims description 26
- 239000007772 electrode material Substances 0.000 claims description 23
- 239000004793 Polystyrene Substances 0.000 claims description 19
- 229920002223 polystyrene Polymers 0.000 claims description 18
- 239000013047 polymeric layer Substances 0.000 claims description 16
- 229920001690 polydopamine Polymers 0.000 claims description 14
- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 229920000767 polyaniline Polymers 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 11
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 239000001259 polydextrose Substances 0.000 claims description 7
- 229920001100 Polydextrose Polymers 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940035035 polydextrose Drugs 0.000 claims description 6
- 235000013856 polydextrose Nutrition 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 shitosan Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 abstract description 6
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- 239000007864 aqueous solution Substances 0.000 description 7
- 229920001940 conductive polymer Polymers 0.000 description 7
- 239000002121 nanofiber Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052756 noble gas Inorganic materials 0.000 description 3
- 150000002835 noble gases Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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Classifications
-
- 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
A kind of the present invention relates to grapheme material application and preparation field, more particularly, it relates to porous graphene/MnO2Multiple
Close thin film and preparation method thereof, and using this material as need not any binding agent, conductive agent self-supporting electrode material be used for surpassing
In level capacitor.
Background technology
Graphene be a kind of by carbon atom with sp2 hybrid orbital form hexangle type be in honeycomb lattice flat film, be one
The two-dimensional material of individual carbon atom thickness, Graphene is not only the thinnest one kind in known materials, also unusual rigid；As list
Matter, the speed that it transmits electronics at room temperature is all faster than known conductor, and Graphene has unusual electric conductivity, exceeds steel
The intensity of ferrum decades of times and fabulous light transmission.
Ultracapacitor, i.e. electrochemical capacitor, be one kind can provide high-power output, have long service life and
The cleaning electric energy storing device of stability, meets " low-carbon (LC) " expanding economy and requires, Graphene super capacitor even more receives people
Great attention, compound electric motor-car, portable electric appts and signal control etc. field there is extensive potential application.Press
According to Mechanism of electrochemical behaviors of anhydrous, ultracapacitor can be divided into double layer capacitor and pseudocapacitors.Double layer capacitor is mainly using carbon
Sill, the electrode material of pseudocapacitors mainly has transition metal oxide and conducting polymer.
With the requirements at the higher level to power-supply device for the electronic product, the self-supporting without any binding agent and conductive agent is super
Capacitor material is more and more widely paid close attention to and is studied.Two-dimensional graphene paper is because of its good electric conductivity and higher ratio table
Area, is a kind of ideal globality, self-supporting super capacitor electrode material, but in actual applications, Graphene
Piling up of lamella makes the effective area forming electric double layer reduce.Therefore, whether research can overcome this defect to its modification.
Chemical modification grapheme material is applied in Graphene-Based Ultracapacitors mono- literary composition by Ruoff et al. first
In electrode material for super capacitor, it has however been found that the ratio capacitance of water system and organic system electrolyte is all relatively low, it is thought and makes
The quality main cause more undesirable than electric capacity is become to be：The chemical modification Graphene electrodes material of reduction preparation is reunited again and is caused
Its effective ratio area substantially reduces it is impossible to adsorb substantial amounts of electrolyte ion.
In order to improve the energy density of graphene-based electrode material, Graphene/polymer and graphene/oxide further
Composite occurs in succession.Because abundant oxygen-containing functional group on graphene oxide can be metal-oxide, conducting polymer
Deng growth avtive spot is provided, form graphene nanocomposite material, thus can be by grapheme material high circulation life-span and steady
Qualitatively feature is combined with the Dominant Facies of transition metal oxide/conductive polymer electrodes material high specific capacitance, prepares performance
More excellent hybrid supercapacitor electrode material.As CN102558857A discloses a kind of graphene/polyaniline nanofiber
The preparation method of composite, the method comprises the following steps：A kind of graphene oxide powder is provided, dissolves this Graphene oxygen
Compound powder is to obtain a graphene oxide solution, and carries out functionalization to activate this to this graphene oxide solution
Graphene oxide, provides a polyaniline nano fiber, dissolves this conducting polymer to obtain a conductive polymer solution, mixing
Described conductive polymer solution and the described graphene oxide solution through functionalization, make described conducting polymer and warp
The graphene oxide of overactivation occurs chemical reaction pre- to obtain one graphene oxide/polyaniline nano fiber composite
Thing solution processed, the solvent in removal described graphene oxide/polyaniline nano fiber composite precast thing solution is to obtain
Graphene oxide/polyaniline nano fiber composite precast thing powder, reduces this graphene oxide/Nano fiber polyaniline
Dimension composite, separates dried and obtains a grapheme/polyaniline nanometer fibrous composite material.The graphite that the method is obtained
Alkene/polyaniline nano fiber composite is bonded upper polyaniline by chemical method, thus improve the capacitive property of material and steady
Qualitative, but the pi-pi accumulation due to Graphene and van der Waals interaction, its effective ratio area is not still high.And prepared being combined
Material be pulverulence, need additive during preparing ultracapacitor, this considerably increases ultracapacitor quality and
Cost.
Content of the invention
An object of the present invention is to provide a kind of porous graphene/MnO2The preparation method of laminated film.The present invention
Preparation method low cost, environmental friendliness, simply easy to carry out, prepared laminated film is greatly improved for ultracapacitor
The performance of ultracapacitor.
One of in order to achieve the above object, the present invention adopts following preparation method：
A kind of porous graphene/MnO2The preparation method of laminated film, comprises the steps：
1) provide a kind of spherical template, in spherical template Surface coating one layer of polymeric layer, the method for coating of this step is existing
There is technology, for example, one layer of polymeric can be obtained in template surface polyreaction by mix and blend method；In template bead surface bag
Covering very thin one layer of polymeric is to be unlikely to subside going removing template metapore structure can preserve complete as far as possible, simultaneously
N contained by polymeric layer can increase the fake capacitance of ultracapacitor again；
2) providing a kind of graphene oxide solution, by step 1) gained is coated with the template bead of polymeric layer and oxidation stone
Black alkene solution mix homogeneously, vacuum filtration, after drying, composite membrane is stripped down from filter membrane；The preferred vacuum filtration of sucking filtration, its
In composite membrane be by the functional group on the oxygen-containing functional group and polymeric layer on Graphene between interaction, through vacuum
The uniform thin film of sucking filtration self assembly；
3) by step 2) gained composite membrane high annealing, obtain porous structural film；
4) by step 3) gained thin film hydro-thermal reaction in potassium permanganate solution obtains porous graphene/MnO2THIN COMPOSITE
Film.
It is active material that the present invention chooses Graphene and manganese dioxide, carries out pore-creating with template to Graphene, in template
Surface coating polymeric layer, thus effectively keeping the pore structure of porous graphene, effectively prevents Graphene from reuniting；In hydro-thermal bar
By the surface of manganese dioxide load to pore structure and edge under part；Using the good filming of graphene oxide, preparation is not required to add
Enter the self-supporting electrode material of any binding agent and conductive agent.
Ultracapacitor charge and discharge process is with the dual embedded/deintercalation of electronics and ion, thus electrode material is carried out
Porous designs, and prepares three-dimensional porous structure thin film, its crossings on different level three-dimensional porous structure is not only provided that bigger reaction
Active area, and excellent diffusion admittance can be provided for electrolyte ion.The preparation method of the present invention is simple, economical, easy to be grasped
Make.
According to the present invention, step 1) described in spherical template in bead easily remove, described easy removal is passed through simple
Chemicals logos can be so that bead to be removed, the removal of bead is the general knowledge of this area；Be preferably polystyrene (PS) bead,
Silicon oxide pellets or polymethyl methacrylate (PMMA) bead, PS can be gone using the method such as calcining or toluene dissolving
Remove, what silicon dioxide was commonly used is HF etching, what PMMA commonly used is that calcining removes.
Preferably, a diameter of 200nm～2 μm of described bead, for example, 250-500nm, 400-900nm, 800nm-1 μ
M, 1.5-2 μm etc..
According to the present invention, step 1) described in polymeric layer be polydextrose, shitosan, poly-dopamine, polyaniline or poly-
Azole polymer layer it is preferred that described polymeric layer thickness be 10～100nm, for example, 15nm, 30nm, 50nm, 70nm,
85nm, 95nm etc..
According to the present invention, step 2) described in graphene oxide prepared by chemical method；The chemical preparation of graphene oxide
Method can be using methods such as Hummers method, Brodie method or Staudenmaier.
Brodie method is first with HNO of being fuming3Process natural micro powder graphite, when graphite is oxidized, nitrate ion invades people's stone
Ink sheet interlayer, then puts into KClO again4Aoxidize further, subsequently throw reactant in a large amount of water of people, filtered, be washed to filter
Liquid, after neutrality, is dried, obtains graphite oxide.
Staudemaier method is with concentrated sulphuric acid and fuming nitric aicd mixed acid, graphite powder to be processed, also with
KClO4For oxidant.
Hummers method is by graphite powder and anhydrous nitric acid sodium（NaNO3）It is added in the concentrated sulphuric acid being placed in ice bath, strongly
Stirring is lower to add KMnO4, and use volume fraction 3%H2O2Reduce remaining potassium permanganate and MnO2So as to it is solvable to become colorless
MnSO4.Under the process of hydrogen peroxide, suspension becomes glassy yellow.Filter, wash 3 times, then vacuum dehydration obtains.Obtained
Oxidized graphite flake layer there is 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 prepares graphene oxide using improving Hummers method：When 25mL concentrated sulphuric acid is heated to 90 DEG C
Add 5g K2S2O8With 5g P2O5, it is stirred continuously until mixture stops heating after being completely dissolved, be subsequently adding 6g native graphite
Powder, by mixture under 80 DEG C of water-baths agitating heating 5h.Mixture is cooled to after room temperature, uses a large amount of deionized water rinsings, take out
Filter products therefrom.Add concentrated sulphuric acid and potassium permanganate in this product, react 2h under 35 DEG C of water-baths, be then slowly added into 1.5mL
Deionized water, after stirring reaction 2h, adds the H of 25mL30% in mixture2O2, now mixed liquor be changed into bright khaki.
Supernatant is removed, successively with a large amount of 5%HCl and deionized water rinsing to neutrality after standing overnight.Finally separated with centrifuge, obtain
Graphite oxide to high concentration.By gained graphite oxide dilute, supersound process obtains final product the homogeneous scattered oxidation stone of yellowish-brown
Black alkene solution.
Preferably, the mass ratio of graphene oxide and the spherical template being coated with polymeric layer is 2～10:1.With cladding
There is the increase of the template bead of polymeric layer, the three-D pore structure of composite membrane can increase, thus laminated film and electrolyte has
Effect contact area can increase, but film property and electric conductivity can decrease, so will ensure complex while increasing pore structure
Film property and electric conductivity, rather than unconfined increase pore structure, increase specific surface area.
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,
For example, 480 DEG C, 550 DEG C, 600 DEG C, 750 DEG C etc. and be incubated, it is incubated 3-5h, then natural cooling room temperature, described protectiveness gas
Atmosphere is realized by being passed through noble gases；Described noble gases are not with graphene oxide and the template bead that is coated with polymeric layer
The gas of reaction it is preferred that described protective gas be nitrogen, helium, neon, argon, Krypton, xenon, a kind in radon gas or extremely
Few 2 kinds of combination, more preferably nitrogen and/or argon.
Described protective atmosphere be embodied as technology well-known to those skilled in the art, for example can be under first high flow rate
Logical noble gases 10min excludes oxidizing gas, then reduces flow velocity.The residual of oxidizing gas in described protective atmosphere
Amount can make N in polymeric layer slough and can not form carbon-coating containing N, thus under the influence of in single step reaction potassium permanganate reduction, and
The fake capacitance of N offer is provided.
Preferably, the speed of described intensification be 5～20 DEG C/min, for example, 7 DEG C/min, 10 DEG C/min, 15 DEG C/min, 18
DEG C/min etc., the time of described insulation is 4～8h, for example, 4.5h, 5h, 6h, 7.5h etc..
According to the present invention, step 4) concentration of described potassium permanganate solution is 3-10mmol/L, for example, 3.5mmol/L,
5mmol/L, 6mmol/L, 7.5mmol/L, 8mmol/L, 9.5mmol/L etc..The concentration of potassium permanganate decides load MnO2's
Thickness, it is 3-10mmol/L that the present invention selects the concentration of potassium permanganate solution, can make the MnO of load2Thickness suitable.Hydro-thermal
The temperature of reaction is 150-200 DEG C, preferably 180 DEG C.
Hydro-thermal reaction is to load upper manganese dioxide, keeps toughness of thin film etc. simultaneously.
The second object of the present invention is to provide the porous graphene/MnO of methods described preparation2Laminated film, described
Laminated film is poroid sandwich structure, and bore dia is 200nm～2 μm, and the aperture that laminated film is finally obtained is little with used
The aperture of ball masterplate is consistent, and lamellar distribution of manganese dioxide is in vestibule and on bore edges.
The third object of the present invention is to provide the purposes of described laminated film, uses it for the preparation of ultracapacitor,
Described porous graphene/MnO2Laminated film is self-supporting electrode material, need not any bond when assembling ultracapacitor
Agent and conductive agent.When assembling ultracapacitor, except electrode material uses the porous composite film of present invention offer, others are such as
Electrolyte, collector, spacer are all not particularly limited, in the case of miscellaneous part identical, using the composite membrane of the present invention
Capacitor as electrode material has more excellent cyclical stability, ratio electricity compared with other materials as the capacitor of electrode material
Appearance and high rate performance etc..
According to the present invention, using the step that described laminated film assembles super capacitor it is：Described laminated film is cut intoDisk, as electrode material, be assembled into the ultracapacitor of sandwich structure.
Porous graphene/the MnO of present invention preparation2Laminated film, as self-supporting super capacitor electrode material, is not required to
Add any binding agent, conductive agent, mechanical performance and super capacitor performance are good, show high-rate charge-discharge capability and height
The advantages of cycle life；Its crossings on different level three-dimensional porous structure is conducive to increasing the contact area of electrode material and electrolyte, and
It is provided that bigger reactivity area, and excellent diffusion admittance can be provided for electrolyte ion, thus improving capacitive character
Energy.
Good cycling stability, higher than electric capacity, forthright again is shown with the ultracapacitor of the electrode material of present invention assembling
Can be excellent, it is adaptable to flexible electronic device etc. the features such as material conductivity is good, compound electric motor-car, portable electric appts and
The fields such as signal control have broad application prospects.
Brief description
Fig. 1 prepares porous graphene/MnO for the present invention2The schematic flow sheet of laminated film method.
Fig. 2 is the porous graphene/MnO of clad preparation for the embodiment of the present invention 1 dopamine2The scanning of laminated film
Electron microscope；
Fig. 3 is that the embodiment of the present invention 3 makees the hole Graphene/MnO of clad preparation with polydextrose2The scanning of laminated film
Electron microscope；
Fig. 4 is that the difference of two electrode tests of ultracapacitor of the embodiment of the present invention 1 assembling sweeps the cyclic voltammetric under speed
Figure；
Fig. 5 is the change curve with scanning speed for the ratio electric capacity of the ultracapacitor of the embodiment of the present invention 1 assembling；
Fig. 6 is the crossing current charging and discharging curve under the different electric current densities of ultracapacitor of the embodiment of the present invention 1 assembling；
Fig. 7 is the stable circulation test curve under 0.1A/g for the ultracapacitor of the embodiment of the present invention 1 assembling.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
The concrete technology flow process of embodiment refers to Fig. 1.
Embodiment 1
With reference to Fig. 1, the PS bead that 100mg average diameter is about 300nm is scattered in the Tris-HCl of the DA of 2mg/mL（pH
=8.5）In solution, reaction 15h is stirred at room temperature, is then centrifuged for, washs, drying and to obtain PS@PDA powder.PS@PDA powder is separated into
The aqueous solution of 10mg/mL, takes 0.25mL and 10mL graphite weak solution (1.25mg/mL) ultrasonic disperse 40min, then mixes this
Laminated film is stripped down after naturally drying from filter membrane by liquid vacuum filtration, obtains PS@PDA@GO composite membrane.In an ar atmosphere
At 500 DEG C, this composite membrane is made annealing treatment 5h, remove removing template PS bead, obtain hollow-core construction graphene composite film.This film is put in
In 10mM potassium permanganate solution, hydro-thermal reaction 25min at 180 DEG C, porous graphene/MnO as shown in Figure 22Laminated film.
This composite membrane is cut into the disk of a diameter of 1cm, choose two tablet qualities close as electrode material, glass fibre membrane as every
Film, 1M Na2SO4Aqueous solution is electrolyte, assembles two electrode super capacitors with Swagelok type battery.
Fig. 2 is after removing template is removed in annealed process, is about the cross-section morphology figure of the thick thin film of 5um it can be seen that composite membrane
Assume uniform porous honeycomb structure, the cavernous structure that these connect not only increases the structural area with electrolyte, simultaneously
It is effectively prevented the easy reunion of Graphene.
Fig. 4 is that the difference of two electrode tests sweeps under speed to obtain cyclic voltammogram, in 1～300mV/s scope inner curve can be in all
Now preferable rectangle, shows that this ultracapacitor has preferable capacitive property.
Fig. 5 sweeps for difference and obtains ratio electric capacity under speed, when sweeping speed for 1mV/s, reaches 136F/g than electric capacity（Quality used by calculating
For whole membrane electrode quality）.
Fig. 6 is to obtain charging and discharging curve figure under different electric current densities, and in 0.1～20A/g, charging and discharging curve all can present approximately
Isosceles triangle, shows that this ultracapacitor has good reversibility and excellent high rate performance.
Fig. 7 is stable circulation test curve under 0.1A/g for this assembling ultracapacitor, is as can be seen from the figure following
After ring 500 times, the ratio electric capacity of material remains at more than 90%, illustrate that this material has preferable cyclical stability.
Embodiment 2
With reference to Fig. 1, the PS bead that 100mg average diameter is about 300nm is scattered in the Tris-HCl of the DA of 2mg/mL（pH
=8.5）In solution, reaction 10h is stirred at room temperature, is then centrifuged for, washs, drying and to obtain PS@PDA powder.PS@PDA powder is separated into
The aqueous solution of 10mg/mL, takes 0.25mL and 10mL graphite weak solution (1.25mg/mL) ultrasonic disperse 40min, then mixes this
Laminated film is stripped down after naturally drying from filter membrane by liquid vacuum filtration, obtains PS@PDA@GO composite membrane.In an ar atmosphere
At 500 DEG C, this composite membrane is made annealing treatment 5h, remove removing template PS bead, obtain hollow-core construction graphene composite film.This film is put in
In 10mM potassium permanganate solution, hydro-thermal reaction 25min under the conditions of 180 DEG C.
Calculating this material than electric capacity by constant current charge-discharge is 75.2F/g（Electric current is 0.1A/g, and electrochemical window is 0-
0.8V）, the polymerization reaction time due to coating PDA is 10h, shorter than 15h in embodiment 1, and polymeric layer is just thinner, thus multiple
The contribution closing PDA contrast electric capacity in membrane electrode material just reduces, thus less compared with the material in embodiment 1 than electric capacity.
Embodiment 3
The PS bead that 100mg average diameter is about 300nm is scattered in the glucose solution of 0.5M, and reaction is stirred at room temperature
24h, be then centrifuged for, wash, drying polydextrose cladding PS powder.Above-mentioned powder is separated into the aqueous solution of 10mg/ml,
Take this solution 1mL and 10mL graphite weak solution (1.25mg/mL) ultrasonic disperse 40min, then by this mixed liquor vacuum filtration, from
After so drying, laminated film is stripped down from filter membrane, obtain PS@PGL@GO composite membrane.This is multiple at 500 DEG C in an ar atmosphere
Close film annealing 5h, remove removing template PS bead, obtain hollow-core construction graphene composite film.This film is put in 5mM potassium permanganate water
Hydro-thermal reaction 20min in solution.This composite membrane is cut into the disk of a diameter of 1cm, choose two tablet qualities close as electrode
Material, glass fibre membrane is as barrier film, 1M Na2SO4Aqueous solution is electrolyte, assembles two electrode supers with Swagelok type battery
Capacitor, calculating it than electric capacity by constant current charge-discharge test is 78.2F/g.Due to adding 1mL polydextrose cladding
PS, then Graphene proportion accordingly reduces, thus the electric conductivity of material can be reduced, so than electric capacity compared with embodiment 1
Reduce.
Fig. 3 be the present embodiment be obtained composite membrane scanning electron microscope (SEM) photograph, it can be seen that this thin film present uniformly many
Hole alveolate texture, due to Polydextrose, under 500 DEG C of high temperature, carbonization forms amorphous carbon, sees in the hole portion and edge to see
See the manganese dioxide of many.
Embodiment 4
The PMMA bead of 100mg is scattered in the Tris-HCl of the DA of 2mg/mL（pH=8.5）In solution, it is stirred at room temperature anti-
Answer 15h, be then centrifuged for, wash, drying and to obtain PMMA@PDA powder.PMMA@PDA powder is separated into the aqueous solution of 10mg/mL, takes
0.25mL and 10mL graphite weak solution (1.25mg/mL) ultrasonic disperse 40min, then by this mixed liquor vacuum filtration, dries in the air naturally
After dry, laminated film is stripped down from filter membrane, obtain PMMA@PDA@GO composite membrane.This is combined at 800 DEG C in an ar atmosphere
Film makes annealing treatment 3h, removes removing template PMMA bead, obtains hollow-core construction graphene composite film.This film is put in 10mM potassium permanganate water
In solution, hydro-thermal reaction 25min under the conditions of 180 DEG C.
This composite membrane is cut into the disk of a diameter of 1cm, choose two tablet qualities close as electrode material, glass fibre
Film is as barrier film, 1M Na2SO4Aqueous solution is electrolyte, assembles two electrode super capacitors with Swagelok type battery, by perseverance
It is 122.7F/g that stream charge-discharge test calculates it than electric capacity.
Embodiment according to the present invention can also be diversified, and template can also be that silicon dioxide is little in addition to PS bead
Ball, polymethyl methacrylate (PMMA) bead etc. easily remove bead.Coated polymer layer except polydextrose and poly-dopamine,
Can also be shitosan, polyaniline, polypyrrole etc..A kind of porous graphene/MnO proposed by the present invention2Laminated film self-supporting
Electrode material for super capacitor good cycling stability, high rate performance higher than electric capacity are excellent, the features such as material conductivity is good, are suitable for
In flexible electronic device etc..
It should be noted that and understanding, without departing from the spirit and scope of the present invention required by appended claims
In the case of, various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to the technical scheme of protection
Scope is not limited by given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (14)
1. a kind of porous graphene/MnO2The preparation method of laminated film, comprises the steps：
1) provide a kind of spherical template, in spherical template Surface coating one layer of polymeric layer；
2) providing a kind of graphene oxide solution, by step 1) gained is coated with template bead and the graphene oxide of polymeric layer
Solution mix homogeneously, vacuum filtration, after drying, composite membrane is stripped down from filter membrane；
3) by step 2) gained composite membrane high annealing, obtain porous structural film；
4) by step 3) gained thin film hydro-thermal reaction in potassium permanganate solution obtains porous graphene/MnO2Laminated film；
Step 1) described in polymeric layer be polydextrose, shitosan, poly-dopamine, polyaniline or polypyrrole polymers layer, institute
The thickness stating polymeric layer is 10～100nm.
2. preparation method as claimed in claim 1 is it is characterised in that step 1) described in spherical template in bead easily go
Remove.
3. preparation method as claimed in claim 2 is it is characterised in that the bead in described spherical template is that polystyrene is little
Ball, silicon oxide pellets or polymethyl methacrylate bead.
4. the preparation method as described in any one of claim 1-3 is it is characterised in that a diameter of 200nm～2 μ of described bead
m.
5. the preparation method as described in any one of claim 1-3 is it is characterised in that step 2) as described in graphene oxide pass through
Prepared by chemical method.
6. the preparation method as described in any one of claim 1-3 is it is characterised in that step 2) graphene oxide and be coated with poly-
The mass ratio of the spherical template of compound layer is 2～10:1.
7. the preparation method as described in any one of claim 1-3 is it is characterised in that step 3) condition of described annealing is to protect
Under shield atmosphere, it is warmed up to 450 DEG C～800 DEG C and is incubated, then natural cooling room temperature.
8. preparation method as claimed in claim 7 it is characterised in that described protective gas be nitrogen, helium, neon, argon,
1 kind in Krypton, xenon, radon gas or at least 2 kinds of combination.
9. preparation method as claimed in claim 8 is it is characterised in that described protective gas is nitrogen and/or argon.
10. preparation method as claimed in claim 7 is it is characterised in that the speed of described intensification is 5～20 DEG C/min, described
The time of insulation is 4～8h.
11. preparation methoies as described in any one of claim 1-3 are it is characterised in that step 4) described potassium permanganate solution
Concentration is 3-10mmol/L.
A kind of 12. porous graphene/MnO by the preparation of claim 1-11 any one methods described2Laminated film, its feature exists
In described laminated film is poroid sandwich structure, and bore dia is 200nm～2 μm, and lamellar distribution of manganese dioxide is in vestibule
And on bore edges.
The purposes of the laminated film described in 13. claim 12 is it is characterised in that by described porous graphene/MnO2Laminated film
For the preparation of ultracapacitor, described porous graphene/MnO2Laminated film is electrode material.
14. purposes as claimed in claim 13 are it is characterised in that utilize the step that described laminated film assembles super capacitor
For：Described laminated film is cut intoDisk, as electrode material, be assembled into the super capacitor of sandwich structure
Device.
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