CN106024427A - Polyaniline nanotube modified ultrathin graphene membrane electrode and preparation method thereof - Google Patents
Polyaniline nanotube modified ultrathin graphene membrane electrode and preparation method thereof Download PDFInfo
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- CN106024427A CN106024427A CN201610617152.5A CN201610617152A CN106024427A CN 106024427 A CN106024427 A CN 106024427A CN 201610617152 A CN201610617152 A CN 201610617152A CN 106024427 A CN106024427 A CN 106024427A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 44
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 239000002071 nanotube Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000002121 nanofiber Substances 0.000 claims abstract description 44
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention provides a polyaniline nanotube modified ultrathin graphene membrane electrode. The polyaniline nanotube modified ultrathin graphene membrane electrode is formed by compositing a graphene composite membrane and a polyaniline nanotube. Firstly, graphene and manganese dioxide nanofiber are composited to form the graphene/manganese dioxide nanofiber composite membrane, and then an aniline monomer is formed on the surface of the graphene/manganese dioxide nanofiber composite membrane so as to adopt manganese dioxide nanofiber as a template to form a polyaniline nanotube through polymerization. The preparation method of the polyaniline nanotube modified ultrathin graphene membrane electrode is simple, the thickness of the membrane and the content of polyaniline is controllable, the high volume ratio capacitance and the good mass ratio capacitance are achieved, and the polyaniline nanotube modified ultrathin graphene membrane electrode can be applied to an electrode material of a portable energy storage device.
Description
Technical field
The present invention relates to electrochemical energy storage field, be specifically related to the ultra-thin Graphene that a kind of polyaniline nanotube is modified
Membrane electrode and preparation method thereof.
Background technology
Portable energy storage device needs electrode material to be provided simultaneously with high-quality specific capacity and high-volume and capacity ratio, from
And can fully reduce quality and the volume of device.At present, people are mainly rational by changing electrode structure
Regulation and control quality capacitive property and volumetric capacitance performance, make both performances reach optimal.
The electrode material of fake capacitance ultracapacitor is mainly metal-oxide or conducting polymer, and energy storage mechnism is not
Being same as common double layer capacitor, it relies on electrode surface and internal Reversible redox reaction, provides
Higher specific discharge capacity and energy density.But, compared with material with carbon element, the circulation of fake capacitance electrode material is steady
Qualitative poor, power density is relatively low.It has been found that can significantly improve fake capacitance by compound with material with carbon element
The cycle life of ultracapacitor.Graphene, as a kind of Two-dimensional Carbon material, has electric-conductivity heat-conductivity high, quickly
Electron mobility, high-specific surface area, excellent chemical stability and mechanical property, be widely used in lithium electricity
Pond and ultracapacitor.Based on electric double layer principle, graphene sheet layer can quickly discharge and recharge, have good
Capacitive property, especially has a high power density, therefore its compound with fake capacitance electrode material can obtain excellent
Different chemical property.People generally utilize self-assembling technique, situ aggregation method, inkjet technology, electrification
Learn deposition technique and can obtain the combination electrode of Graphene and polyaniline.Additionally, except simple mechanical compress,
The bulk density of electrode can be greatly enhanced by compress techniques such as vacuum filtration, capillary tube compression, heat treatments,
Thus improve the volumetric capacitance performance of electrode of super capacitor.
Obtain high volumetric capacitance performance electrode it is critical only that the bulk density improving electrode, but the densification of electrode
Structure is unfavorable for electrolyte ion diffusion and charge migration, causes quality to be deteriorated than reduction and the high rate performance of electric capacity.
Therefore, electrode structure prepares high volume, the electrode of high-quality capacitive property becomes a great challenge in optimization
A difficult problem.
Summary of the invention
Because the drawbacks described above of prior art, in order to preferably improve the capacitive property of Graphene electrodes, the present invention
Utilize manganese dioxide nano fiber matrix polymerization method, by regulating and controlling the microcosmic of graphene/polyaniline nano-fiber film
Structure, carrys out balance mass than electric capacity and volumetric capacitance performance, it is thus achieved that high volumetric performance and relative high quality
The ultra-thin graphene membrane electrode that the polyaniline nanotube of energy is modified.
The ultra-thin graphene membrane electrode that the polyaniline nanotube of the present invention is modified is by graphene composite film and to gather
Aniline nano pipe is compounded to form.Specifically, first it is compounded to form graphite by Graphene and manganese dioxide nano fiber
Alkene/manganese dioxide nano fiber laminated film, wherein manganese dioxide nano fiber accounts for Graphene/manganese dioxide nano fibre
The percentage by weight of dimension laminated film is 20%～80%, and then aniline monomer is fine at Graphene/manganese dioxide nano
The surface of dimension laminated film forms polyaniline nanotube with manganese dioxide nano fiber for matrix polymerization, thus obtains
The graphene composite film that polyaniline nanotube is modified, it can be applied to super as ultra-thin graphene membrane electrode
In capacitor.
The preparation method of the ultra-thin graphene membrane electrode that the polyaniline nanotube of the present invention is modified includes following step
Rapid:
A, the preparation of manganese dioxide nano fiber: by the most soluble in water to potassium sulfate, potassium peroxydisulfate, manganese sulfate,
Mix homogeneously forms solution；Solution is proceeded in reactor, be heated to 180～220 DEG C, after reaction 12～24h,
Product is centrifuged, washes, is dried, obtain the powder of manganese dioxide nano fiber.
In above-mentioned steps A, in described solution, the concentration of potassium sulfate is 5～10mg/mL, described potassium sulfate,
Potassium peroxydisulfate, the mol ratio of manganese sulfate are 1:2:1, and described manganese sulfate is preferably Manganous sulfate monohydrate.Described dry
Dry being preferably is vacuum dried 12～24h at 60～80 DEG C.
B, the reduction of graphene oxide: be dispersed in water by graphene oxide, add surfactant, ultrasonic place
Reason 0.5～2h, obtains graphene oxide dispersion, adds reducing agent, is heated to 90～120 DEG C, reaction 6～
24h, obtains redox graphene dispersion liquid.
In above-mentioned steps B, described graphene oxide can be by Hummers method, Brodie method or
Prepared by Staudenmaier method, the concentration of described graphene oxide dispersion is 0.1～5mg/mL.Described table
Face activating agent is cationic surfactant or anion surfactant, such as polyacrylamide, dodecyl
Sodium sulfonate, triton x-100, dodecylbenzene sodium sulfonate etc..Described reducing agent is preferably the hydrazine hydrate of 85%,
Addition is 1～3mL.
The preparation of C, Graphene/manganese dioxide nano fiber laminated film: disperse at above-mentioned redox graphene
Liquid adds manganese dioxide nano fiber, carries out ultrasonic disperse, decompression sucking filtration successively, naturally dry, finally filter
Film comes off, and obtains Graphene/manganese dioxide nano fiber laminated film.
In above-mentioned steps C, the concentration of described redox graphene dispersion liquid is 0.1～2mg/mL, described
The mass ratio of manganese dioxide nano fiber and redox graphene is 0.25～4:1.Described ultrasonic disperse uses super
The ultrasonication of acoustical power 100～200W, ultrasonic time is 0.5～2h.The filter membrane that described decompression sucking filtration uses
Any one in Kynoar filter membrane, cellulose acetate sheets, cellulose filter membrane or anodised aluminium filter membrane
Kind.Described naturally drying refers under natural environment, air drying 12～24h.
The preparation of the ultra-thin graphene membrane electrode that D, polyaniline nanotube are modified: by above-mentioned Graphene/titanium dioxide
Manganese nanofiber laminated film joins dissolved with in the sulfuric acid solution of aniline monomer, forms reactant liquor, stands 6～24
After h, respectively with water and ethanol alternately washing, after drying, obtain the ultra-thin graphene film that polyaniline nanotube is modified
Electrode.
In above-mentioned steps D, in described sulfuric acid solution, the concentration of aniline is 0.01～0.1mol/L, sulphuric acid dense
Degree is 1mol/L, and in described reactant liquor, the mol ratio of manganese dioxide and aniline is 1:10～20.Described drying
Temperature is preferably 40～60 DEG C.
The thickness of the ultra-thin graphene membrane electrode that the polyaniline nanotube that the present invention obtains is modified is only 4～20
μm, area density is 0.36～1.2mg/cm2, bulk density is 0.18～1.99g/cm3。
Compared with other membrane electrodes, the ultra-thin graphene membrane electrode system that the polyaniline nanotube of the present invention is modified
Preparation Method is simple, and film thickness and polyaniline content are controlled.The more important thing is, the polyaniline that the present invention obtains is received
The ultra-thin graphene membrane electrode that mitron is modified has higher volumetric capacitance value and excellent quality compares electric capacity
Value, can be applicable to the electrode material of portable energy-storing device.
Accompanying drawing explanation
Fig. 1 is the ultra-thin graphene membrane electrode of the polyaniline nanotube modification of a preferred embodiment of the invention
Stereoscan photograph；
Fig. 2 is the ultra-thin graphene membrane electrode of the polyaniline nanotube modification of a preferred embodiment of the invention
Quality is than capacitive property figure；
Fig. 3 is the ultra-thin graphene membrane electrode of the polyaniline nanotube modification of a preferred embodiment of the invention
Volumetric capacitance performance map.
Detailed description of the invention
Below by specific embodiment and combine the mode of accompanying drawing the present invention is further elaborated.
The ultra-thin graphene membrane electrode that the polyaniline nanotube of the present invention is modified can be simply by aforementioned four step
A, B, C, D prepare, and below each step will be provided one or more preferred embodiment respectively.
Embodiment is A.1
In one preferred embodiment of the present invention, preparing manganese dioxide nano fiber in step A can be by following
Step realizes: 0.266g potassium sulfate, 0.826g potassium peroxydisulfate and 0.258g manganese sulfate monohydrate are dissolved in 40 successively
In mL deionized water, mix homogeneously molten clear after, proceed to reactor and carry out hydro-thermal reaction, react 12h at 190 DEG C,
Centrifugal washing, 80 DEG C of dry 24h obtain manganese dioxide nano fiber powder.
Embodiment is B.1
In one preferred embodiment of the present invention, preparing redox graphene solution in step B can be by following step
Rapid realize: weigh graphene oxide 600mg prepared by Hummers method and be scattered in 600mL deionized water, add
Entering 1.5g dodecylbenzene sodium sulfonate as surfactant, ultrasonic 1h obtains graphene oxide dispersion；Add 3mL
The hydrazine hydrate of 85%, oil bath is heated to 100 DEG C, obtains redox graphene dispersion liquid after reaction 12h.This enforcement
Concentration can be adjusted to 0.87 by adding deionized water further by the redox graphene dispersion liquid that example obtains
mg/mL。
Embodiment is C.1
In a preferred embodiment of the invention, step C is prepared Graphene/manganese dioxide nano fiber THIN COMPOSITE
Film can be realized by following steps: takes above-mentioned 6mg manganese dioxide nano fiber and joins 27.6mL reduction-oxidation graphite
In alkene dispersion liquid, carry out the sucking filtration that reduces pressure after ultrasonic 0.5h, naturally dry, slough filter membrane, obtain Graphene/titanium dioxide
Manganese nanofiber (20%) laminated film.
Embodiment is C.2
In another preferred embodiment of the present invention, step C is prepared Graphene/manganese dioxide nano fiber and is combined
Thin film can be realized by following steps: takes above-mentioned 15mg manganese dioxide nano fiber and joins 17.2mL reduction-oxidation
In graphene dispersing solution, carry out after ultrasonic 0.5h reduce pressure sucking filtration, naturally dry, slough filter membrane, obtain Graphene/
Manganese dioxide nano fiber (50%) laminated film.
Embodiment is C.3
In a preferred embodiment of the invention, step C is prepared Graphene/manganese dioxide nano fiber THIN COMPOSITE
Film can be realized by following steps: takes above-mentioned redox graphene dispersion liquid 6.9mL, adds the above-mentioned dioxy of 24mg
Changing manganese nanofiber, ultrasonic 0.5h, reduce pressure sucking filtration, naturally dries, sloughs filter membrane, obtains Graphene/manganese dioxide and receive
Rice fiber (80%) laminated film.
Embodiment is D.1
In a preferred embodiment of the invention, step D is prepared the ultra-thin Graphene that polyaniline nanotube is modified
Thin film can be realized by following steps: by above-mentioned Graphene/manganese dioxide nano fiber (20%) laminated film 1.62mg
Join in the sulfuric acid solution (1M) of the 2mL dissolved with 7.1 μ L aniline monomers, stand after 6h, respectively with water and
Ethanol alternately washing, 60 DEG C of drying, obtain the ultra-thin graphene film that polyaniline nanotube is modified.
The ultra-thin graphene film that the polyaniline nanotube that the present embodiment obtains is modified, thickness is 7.07 μm, area density
For 1.2mg/cm2, bulk density is 1.70g/cm3.It is assembled into two electrode devices and carries out electro-chemical test, obtain it
Big quality is 211F/g than electric capacity, and maximum volume is 359F/cm than electric capacity3。
Embodiment is D.2
In another preferred embodiment of the present invention, step D is prepared the ultra-thin graphite that polyaniline nanotube is modified
Alkene thin film can be realized by following steps: by above-mentioned Graphene/manganese dioxide nano fiber (50%) laminated film 1.47mg
Join in the sulfuric acid solution (1M) of the 3.4mL dissolved with 12 μ L aniline monomers, after standing 6h, use water respectively
Wash and ethanol alternately washing, 60 DEG C of drying, obtain the ultra-thin graphene film that polyaniline nanotube is modified.
The ultra-thin graphene film that the polyaniline nanotube that the present embodiment obtains is modified, thickness is 4.02 μm, area
Density is 0.80mg/cm2, bulk density is 1.99g/cm3.The scanning electron microscope (SEM) photograph of Fig. 1 shows the present embodiment
The cross-section morphology of ultra-thin graphene film modified of polyaniline nanotube, can intuitively arrive graphene sheet layer
Layer is piled into compact texture, and upper and lower surface has modified polyaniline nanotube.Fig. 2 shows the polyphenyl of the present embodiment
The quality capacitive property of the ultra-thin graphene membrane electrode that amine is nanometer tube modified, is assembled into two electrode devices and carries out electricity
Test chemical, obtaining its biggest quality than electric capacity is 363F/g.Fig. 3 shows the polyaniline nano of the present embodiment
The volumetric capacitance performance of the ultra-thin graphene membrane electrode that pipe is modified, is assembled into two electrode devices and carries out electrochemistry survey
Examination, obtaining its maximum volume than electric capacity is 722F/cm3。
Embodiment is D.3
In another preferred embodiment of the present invention, step D is prepared the ultra-thin graphite that polyaniline nanotube is modified
Alkene thin film can be realized by following steps: by above-mentioned Graphene/manganese dioxide nano fiber (80%) laminated film 2.03mg
Join in the sulfuric acid solution (1M) of the 6.5mL dissolved with 23 μ L aniline monomers, after standing 6h, use water respectively
With ethanol alternately washing, 60 DEG C of drying, obtain the ultra-thin graphene film that polyaniline nanotube is modified.
The ultra-thin graphene film that the polyaniline nanotube that the present embodiment obtains is modified, thickness is 20.0 μm, area density
For 0.36mg/cm2, bulk density is 0.18g/cm3.It is assembled into two electrode devices and carries out electro-chemical test, obtain it
The biggest quality is 956F/g than electric capacity, and maximum volume is 172F/cm than electric capacity3。
The preferred embodiment of the present invention described in detail above.Should be appreciated that the ordinary skill of this area without
Creative work just can make many modifications and variations according to the design of the present invention.Therefore, all the art
Middle technical staff is the most on the basis of existing technology by logical analysis, reasoning or limited
Test available technical scheme, all should be in the protection domain being defined in the patent claims.
Claims (10)
1. the ultra-thin graphene membrane electrode that a polyaniline nanotube is modified, it is characterised in that described thin-film electro
Pole is compounded to form by Graphene/manganese dioxide nano fiber laminated film and polyaniline nanotube, wherein Graphene and
Manganese dioxide nano fiber is compounded to form described Graphene/manganese dioxide nano fiber laminated film, and aniline monomer exists
The surface of described Graphene/manganese dioxide nano fiber laminated film is gathered with described manganese dioxide nano fiber for template
Close and form described polyaniline nanotube.
2. membrane electrode as claimed in claim 1, it is characterised in that described manganese dioxide nano fiber accounts for institute
The percentage by weight stating Graphene/manganese dioxide nano fiber laminated film is 20%～80%.
3. membrane electrode as claimed in claim 1, it is characterised in that the thickness of described membrane electrode be 4～
20 μm, area density is 0.36～1.2mg/cm2, bulk density is 0.18～1.99g/cm3。
4. the preparation method of membrane electrode as claimed in claim 1, it is characterised in that described method include with
Lower step:
A, the preparation of manganese dioxide nano fiber: by the most soluble in water to potassium sulfate, potassium peroxydisulfate, manganese sulfate,
Mix homogeneously forms solution；Described solution is proceeded in reactor, is heated to 180～220 DEG C, react 12～24
After h, product is centrifuged, washes, is dried, obtain described manganese dioxide nano fiber；
B, the reduction of graphene oxide: be dispersed in water by graphene oxide, add surfactant, ultrasonic place
Reason 0.5～2h, obtains graphene oxide dispersion, adds reducing agent, is heated to 90～120 DEG C, reaction 6～
24h, obtains redox graphene dispersion liquid；
The preparation of C, Graphene/manganese dioxide nano fiber laminated film: the described oxygen reduction obtained in step B
Functionalized graphene dispersion liquid adds the described manganese dioxide nano fiber that obtains of step A, carry out successively ultrasonic disperse,
Decompression sucking filtration, naturally dry, finally slough filter membrane, obtain described Graphene/manganese dioxide nano fiber THIN COMPOSITE
Film；
The preparation of the ultra-thin graphene membrane electrode that D, polyaniline nanotube are modified: the described stone that step C is obtained
Ink alkene/manganese dioxide nano fiber laminated film joins dissolved with in the sulfuric acid solution of aniline monomer, forms reactant liquor,
After standing 6～24h, respectively with water and ethanol alternately washing, after drying, obtain what described polyaniline nanotube was modified
Ultra-thin graphene membrane electrode.
5. preparation method as claimed in claim 4, it is characterised in that potassium sulfate in solution described in step A
Concentration be 5～10mg/mL, described potassium sulfate, potassium peroxydisulfate, the mol ratio of manganese sulfate are 1:2:1.
6. preparation method as claimed in claim 4, it is characterised in that described in step B, graphene oxide is
Prepared by Hummers method, Brodie method or Staudenmaier method, described graphene oxide dispersion
Concentration is 0.1～5mg/mL.
7. preparation method as claimed in claim 4, it is characterised in that surfactant described in step B is
Polyacrylamide, dodecyl sodium sulfate, triton x-100 or dodecylbenzene sodium sulfonate.
8. preparation method as claimed in claim 4, it is characterised in that reducing agent described in step B is 85%
Hydrazine hydrate, addition is 1～3mL.
9. preparation method as claimed in claim 4, it is characterised in that reduction-oxidation graphite described in step C
The concentration of alkene dispersion liquid is 0.1～2mg/mL.
10. preparation method as claimed in claim 4, it is characterised in that described in step D in sulfuric acid solution
The concentration of aniline is 0.01～0.1mol/L, and the concentration of sulphuric acid is 1mol/L；In described reactant liquor manganese dioxide and
The mol ratio of aniline is 1:10～20.
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