CN103971942A - Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof - Google Patents
Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof Download PDFInfo
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- CN103971942A CN103971942A CN201410221388.8A CN201410221388A CN103971942A CN 103971942 A CN103971942 A CN 103971942A CN 201410221388 A CN201410221388 A CN 201410221388A CN 103971942 A CN103971942 A CN 103971942A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 112
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 62
- 239000010439 graphite Substances 0.000 claims description 62
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 27
- -1 iron ion Chemical class 0.000 claims description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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 graphene/polyaniline/ferric oxide composite material applied to a supercapacitor. The graphene/polyaniline/ferric oxide composite material applied to the supercapacitor is formed by compounding graphene, polyaniline and ferric oxide, wherein the polyaniline is wrapped around the graphene, and the ferric oxide is grown on the graphene wrapped with the polyaniline. The obtained graphene/polyaniline/ferric oxide composite material takes full advantages of the functions of all the components, and not only makes use of the double-electrode-layer capacitive property of the graphene, but also makes use of the oxidoreduction electrochemical property of the polyaniline and the graphene, the specific capacitance of graphene-based electrode materials is increased, the cycle life reaches 5000 times, the electrochemical performance of graphene-based capacitors is improved greatly, and the graphene/polyaniline/ferric oxide composite material has the wider application prospects in the fields such as supercapacitors and solar cells.
Description
Technical field
The present invention relates to a kind of graphene/polyaniline/ferric oxide composite material that can be used as electrode of super capacitor and preparation method thereof.
Background technology
Ultracapacitor, a kind of energy storage device of the fast charge/discharge between ordinary capacitor and secondary cell, it has the features such as short, long service life of charging interval, good temp characteristic, energy savings and environmental protection, military and civilian on have huge application prospect.Electrode material for super capacitor is divided into two classes, one class is the super capacitor material with electric double layer energy storage character, this class material comprises the material with carbon elements such as active carbon, carbon fiber, carbon nano-tube and graphene film, this class material has 10 to 200F/g specific capacitance, charge and discharge circulation life is long, can reach more than 10000 times, but all in all specific capacitance is not high, another kind of is the fake capacitance equipment material with redox characteristic, both organic/inorganic substance, as ruthenium-oxide, manganese oxide, tin oxide, the materials such as iron oxide, there is again conducting polymer composite, as polyaniline, polythiophene, polypyrrole etc., this class material is owing to having redox characteristic, capacitance is very large, can reach specific capacitance more than 500F/g, but the shortcoming of this class material is because redox reaction occurs in material bodies, cause volume generation acute variation in material charge and discharge process, there is defect in structure, affect the cycle life of electrode material, cycle-index can only be 3000 left and right.Therefore, a lot of research and development work concentrates on the electrode material of the electrode material of electric double layer mechanism and redox mechanism is combined with each other, be prepared into hybrid material for ultracapacitor, as by inorganic nano manganese oxide, on tin oxide even load carbon nano-tube or graphene film surface, or conducting polymer is coated on carbon nano-tube or graphene film, the capacitor material of preparation had both had electric double layer capacitance characteristic, there is fake capacitance characteristic simultaneously, more than specific capacitance reaches 800F/g, conduct electricity very well simultaneously, the material with carbon element of mechanical property excellence can play good supporting role to redox materials.
Recently, have researcher at the first load ferric oxide nanometer particle in Graphene surface, then on Graphene/iron oxide hybrid surface polymerization one deck polyaniline, the ratio electric capacity obtaining is 638F/g, and cycle-index is (J.Mater.Chem., 2012 on 5000 electric capacity, 22,16844-16850).But, owing to loading on the ferric oxide nano particles on Graphene surface, by polyaniline-coated layer, covered, can not give full play of the electrochemical action of each component, cause not higher as expected than electric capacity.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of graphene/polyaniline/ferric oxide composite material that is applied to ultracapacitor and preparation method thereof for the deficiency of above-mentioned prior art existence, has improved the chemical property of graphene-based capacitor.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
Be applied to graphene/polyaniline/ferric oxide composite material of ultracapacitor, it is to be compounded to form by Graphene, polyaniline, iron oxide, and described polyaniline-coated is on Graphene, and described iron oxide is grown on the Graphene that is coated with polyaniline.
A preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor, comprises the steps:
(1) by the mol ratio of graphite oxide and aniline, be 1:(1～10), aniline monomer and hydrochloric acid are joined to the aqueous solution of graphite oxide, under 0～5 ℃ of condition, drip while stirring initiator solution, being added dropwise to complete rear continuation stirs 2～5 hours, gained solid is separated, obtained the compound of polyaniline/graphite oxide;
(2) compound of polyaniline/graphite oxide is reduced with reducing agent, then isolate the compound of polyaniline/Graphene;
(3) according to the mol ratio of graphite oxide and iron ion, be 1:(1～20), the compound of soluble ferric iron salt and polyaniline/Graphene is mixed in water, disperse and stir after 1～3 hour, drip while stirring wherein concentrated ammonia liquor, in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is (1～8): 1, after being added dropwise to complete, continue to stir 1～3 hour, still aging 8～24 hours again, obtain suspension; Again by resulting suspension under nitrogen or inert gas shielding, in temperature, be to react 1～6 hour under 120～180 ℃ of conditions, then solid is wherein separated, obtain graphene/polyaniline/ferric oxide composite material.
Press such scheme, the concentration of aqueous solution of described graphite oxide is 0.1mol/L.After described graphite oxide is mixed with water, ultrasonic dispersion 30-60 minute, can obtain the aqueous solution of graphite oxide.
Press such scheme, described initator can be selected (NH
4)
2s
2o
8, K
2cr
2o
7, KIO
3, FeCl
3, FeCl
4, H
2o
2, Ce (SO
4)
2, MnO
2, BPO (benzoyl peroxide), wherein (NH
4)
2sO
8due to metal ion not, oxidability is strong, and convenient post-treatment is the most frequently used oxidant.In the present invention, adopting initiator solution is the ammonium persulfate solution of concentration 0.04mol/L, and the mol ratio of ammonium persulfate and aniline is 1:(1～2).
Press such scheme, the concentration of hydrochloric acid in the aqueous solution of graphite oxide in described step (1)
mol/L; In step (1), rate of addition is 0.15mL/s～0.3mL/s.
Press such scheme, described reducing agent is hydrazine hydrate or sodium borohydride, and reducing agent and graphite oxide mol ratio are (10～100): 1.Hydrazine hydrate is as reducing agent, concentration preferably 85%, and sodium borohydride is as reducing agent, the aqueous solution of the preferred 0.1mol/L of concentration.
Press such scheme, in described step (2), reduction adopts hydrazine hydrate, and reducing condition is to reflux more than 12 hours at 90 ℃～100 ℃.
Press such scheme, it is 0.05mol/L～0.2mol/L that the addition of the middle water of step (3) makes the molar concentration of molysite; Describedly be separated into ultrasonic dispersion, the time is 30-60 minute; The time of described stirring is 4～8 hours; The concentration of concentrated ammonia liquor is 28%, and rate of addition is 0.15mL/s～0.3mL/s.
Press such scheme, the preparation method of described graphite oxide is: according to (1～5g): (0.2～2g): the ratio of (30～150ml), graphite, sodium nitrate and 98% concentrated sulfuric acid are mixed, at blender, add while stirring potassium permanganate, the mass ratio of potassium permanganate and graphite is (0.2-8): 1, more than treating that potassium permanganate adds the 12h of continuation stirring afterwards; Add wherein again deionized water, the volume ratio of deionized water and the concentrated sulfuric acid is 1:(0.05-1.5), adding concentration is 30% hydrogen peroxide again, the volume ratio of hydrogen peroxide and the concentrated sulfuric acid is 1:(0.5-15), obtain yellow suspension-turbid liquid, adopt and filter or centrifugal method, solid is separated, dry, be graphite oxide.
Principle of the present invention is: the carboxyl on graphite oxide surface acts on mutually with the amido on aniline, first aniline is adsorbed on to the surface of graphite oxide, then under the effect of initator, causes aniline monomer, and polyaniline-coated is surperficial at graphite oxide; And then under the effect of reducing agent, be converted into the Graphene of coated polyaniline; Then utilize the complexing of the amido of polyaniline to metal ion, iron ion is adsorbed on to the Graphene surface that is coated with polyaniline, by adding alkaline reagent (ammoniacal liquor), make iron ion be converted into iron hydroxide, and the Graphene that loads on coated polyaniline is surperficial, finally by crossing hydro-thermal reaction, make iron hydroxide resolve into alpha-ferric oxide, thereby obtain the Graphene of area load iron oxide, coated polyaniline, i.e. graphene/polyaniline/ferric oxide composite material.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention utilizes the effect of graphite oxide and aniline monomer that polyaniline-coated is surperficial to Graphene, amido absorption iron ion on recycling polyaniline chain, the surface that alpha-ferric oxide is embedded in to graphene/polyaniline obtains graphene/polyaniline/ferric oxide composite material, is skillfully constructed.Simultaneously, resulting graphene/polyaniline/the ferric oxide composite material of the present invention, this structure takes full advantage of the effect of each component, both utilized the electric double layer capacitance character of Graphene, also utilized the redox electrochemical properties of polyaniline and Graphene, increased the specific capacitance of graphene-based electrode material, cycle life reaches 5000 times, greatly improved the chemical property of graphene-based capacitor, made it in fields such as ultracapacitor, solar cells, there is more wide application prospect.
Accompanying drawing explanation
Fig. 1 is the preparation method's of graphene/polyaniline/ferric oxide composite material schematic flow sheet.
Fig. 2 is the XRD collection of illustrative plates of embodiment 1 graphene/polyaniline/ferric oxide composite material, and wherein PANI is polyaniline abbreviation.
Fig. 3 a is the transmission electron microscope picture of Graphene, the transmission electron microscope picture of the compound of b embodiment 1 intermediate product polyaniline/Graphene, (c) transmission electron microscope picture of graphene/polyaniline/ferric oxide composite material.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but the present invention is not only confined to the following examples.
Embodiment 1
1, prepare graphite oxide: get crystalline flake graphite (1g), sodium nitrate (0.2g) and the concentrated sulfuric acid (30ml) are put into 1000ml beaker, at blender, add while stirring potassium permanganate (1g), after adding, continue to stir 14h; Add wherein deionized water (100ml), then to add concentration be 30% hydrogen peroxide (10ml), now suspension-turbid liquid is yellow, adopts and filters or centrifugal method, and solid is separated, and dries, and is graphite oxide, stand-by again.
2, be applied to graphene/polyaniline/ferric oxide composite material of ultracapacitor, it is to be compounded to form by Graphene, polyaniline, iron oxide, and described polyaniline-coated is on Graphene, and described iron oxide is grown on the Graphene that is coated with polyaniline.
3, the above-mentioned preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor, comprises the steps:
(1) 0.005mol graphite oxide is disperseed 30 minutes in 50ml deionized water for ultrasonic, the concentrated hydrochloric acid 4ml that adds wherein aniline monomer (mol ratio of aniline monomer and graphite oxide is 1:1) and 36%, then under ice bath, magnetic agitation limit, limit drips the ammonium persulfate solution (mol ratio of ammonium persulfate and aniline monomer is 1:1) of 0.04mol/mL, and rate of addition is 0.15mL/s, being added dropwise to complete rear continuation stirs 2 hours, by solid centrifugation wherein out, obtain the compound of polyaniline/graphite oxide again;
(2) above-mentioned resulting polyaniline/graphite oxide composite is all mixed with 0.05mol hydrazine hydrate (hydrazine hydrate concentration 85%), at 90 ℃, reflux 12 hours, solid filtering is wherein separated, obtain the compound of polyaniline/Graphene;
(3) by iron ion and graphite oxide mol ratio, be 1:1, the compound of polyaniline/Graphene and ferric nitrate powder (wherein iron ion 0.005mol) are joined in 100ml deionized water and ultrasonic dispersion 1 hour, stir again 4 hours, then (in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is 1:1 to drip while stirring wherein concentrated ammonia liquor, concentrated ammonia liquor concentration is 26%), and rate of addition is 0.15mL/s; After being added dropwise to complete, continue to stir 1 hour, more static ageing 8 hours; then by the suspension obtaining under nitrogen protection, temperature is to react 1 hour under 120 ℃ of conditions; after having reacted, solid is separated, obtained graphene/polyaniline/ferric oxide composite material.
From Fig. 2, Fig. 3, the end product of embodiment 1 preparation is confirmed as graphene/polyaniline/ferric oxide composite material, a process for preparing graphene/polyaniline/iron oxide three-component compound system, polyaniline grafted being coated on Graphene, iron oxide is long on graphene sheet layer as strawberry.This structure will be given full play to the effect of each component, and the ratio electric capacity of composite material is improved greatly, and cycle life is also very long.
Embodiment 2
1, prepare graphite oxide: get crystalline flake graphite (1g), sodium nitrate (0.2g) and the concentrated sulfuric acid (30ml) are put into 1000ml beaker, at blender, add while stirring potassium permanganate (1g), after adding, continue to stir 14h; Add wherein deionized water (100ml), then to add concentration be 30% hydrogen peroxide (10ml), now suspension-turbid liquid is yellow, adopts and filters or centrifugal method, and solid is separated, and dries, and is graphite oxide, stand-by again.
2, be applied to graphene/polyaniline/ferric oxide composite material of ultracapacitor, it is to be compounded to form by Graphene, polyaniline, iron oxide, and described polyaniline-coated is on Graphene, and described iron oxide is grown on the Graphene that is coated with polyaniline.
3, the above-mentioned preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor, comprises the steps:
(1) 0.005mol graphite oxide is disperseed 30 minutes in 50ml deionized water for ultrasonic, the concentrated hydrochloric acid 16ml that adds wherein aniline monomer (mol ratio of aniline monomer and graphite oxide is 10:1) and 36%, then under ice bath, magnetic agitation limit, limit drips the ammonium persulfate solution (mol ratio of ammonium persulfate and aniline monomer is 1:2) of 0.04mol/mL, and rate of addition is 0.3mL/s, being added dropwise to complete rear continuation stirs 5 hours, by solid centrifugation wherein out, obtain the compound of polyaniline/graphite oxide again;
(2) above-mentioned resulting polyaniline/graphite oxide composite is all mixed with 0.05mol hydrazine hydrate (hydrazine hydrate concentration 85%), at 100 ℃, reflux 14 hours, solid filtering is wherein separated, obtain the compound of polyaniline/Graphene;
(3) by iron ion and graphite oxide mol ratio, be 20:1, the compound of polyaniline/Graphene and ferric nitrate powder (wherein iron ion 0.1mol) are joined in 100ml deionized water and ultrasonic dispersion 3 hours, stir again 3 hours, then drip while stirring wherein concentrated ammonia liquor (in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is 4:1), and rate of addition is 0.15mL/s; After being added dropwise to complete, continue to stir 3 hours, more static ageing 16 hours; then by the suspension obtaining under nitrogen protection, temperature is to react 6 hours under 180 ℃ of conditions; after having reacted, solid is separated, obtained graphene/polyaniline/ferric oxide composite material.
Embodiment 3
1. crystalline flake graphite (3g), sodium nitrate (1.1g) and the concentrated sulfuric acid (90ml) are put into 1000ml beaker, at blender, add while stirring potassium permanganate (4.5g), continue to stir 16h after adding; Add wherein deionized water (350ml), then to add concentration be 30% hydrogen peroxide (35ml), now suspension-turbid liquid is yellow, adopts and filters or centrifugal method, and solid is separated, and dries stand-by again.
2, be applied to graphene/polyaniline/ferric oxide composite material of ultracapacitor, it is to be compounded to form by Graphene, polyaniline, iron oxide, and described polyaniline-coated is on Graphene, and described iron oxide is grown on the Graphene that is coated with polyaniline.
3, the above-mentioned preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor, comprises the steps:
(1) 0.005mol graphite oxide is disperseed 30 minutes in 50ml deionized water for ultrasonic, the concentrated hydrochloric acid 8ml that adds wherein aniline monomer (mol ratio of aniline monomer and graphite oxide is 5:1) and 36%, then under ice bath, magnetic agitation limit, limit drips the ammonium persulfate solution (mol ratio of ammonium persulfate and aniline monomer is 1:1) of 0.04mol/mL, and rate of addition is 0.2mL/s, being added dropwise to complete rear continuation stirs 3 hours, by solid centrifugation wherein out, obtain the compound of polyaniline/graphite oxide again;
(2) above-mentioned resulting polyaniline/graphite oxide composite is all mixed with 0.025mol hydrazine hydrate (hydrazine hydrate concentration 85%), at 100 ℃, reflux 16 hours, solid filtering is wherein separated, obtain the compound of polyaniline/Graphene;
(3) by iron ion and graphite oxide mol ratio, be 20:1, the compound of polyaniline/Graphene and ferric nitrate powder (wherein iron ion 0.1mol) are joined in 100ml deionized water and ultrasonic dispersion 3 hours, stir again 3 hours, then drip while stirring wherein concentrated ammonia liquor (in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is 4:1), and rate of addition is 0.15mL/s; After being added dropwise to complete, continue to stir 3 hours, more static ageing 16 hours; then by the suspension obtaining under nitrogen protection, temperature is to react 6 hours under 180 ℃ of conditions; after having reacted, solid is separated, obtained graphene/polyaniline/ferric oxide composite material.
(3) by iron ion and graphite oxide mol ratio, be 10:1, the compound of polyaniline/Graphene and ferric nitrate powder (wherein iron ion 0.05mol) are joined in 100ml deionized water and ultrasonic dispersion 3 hours, stir again 3 hours, then drip while stirring wherein concentrated ammonia liquor (in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is 2:1), and rate of addition is 0.2mL/s; After being added dropwise to complete, continue to stir 2 hours, more static ageing 10 hours; then by the suspension obtaining under nitrogen protection, temperature is to react 3 hours under 160 ℃ of conditions; after having reacted, solid is separated, obtained graphene/polyaniline/ferric oxide composite material.
Embodiment 4
1. crystalline flake graphite (5g), sodium nitrate (2g) and the concentrated sulfuric acid (150ml) are put into 1000ml beaker, at blender, add while stirring potassium permanganate (8g), continue to stir 12h after adding; Add wherein deionized water (600ml), then to add concentration be 30% hydrogen peroxide (60ml), now suspension-turbid liquid is yellow, adopts and filters or centrifugal method, and solid is separated, and dries stand-by again.
2, be applied to graphene/polyaniline/ferric oxide composite material of ultracapacitor, it is to be compounded to form by Graphene, polyaniline, iron oxide, and described polyaniline-coated is on Graphene, and described iron oxide is grown on the Graphene that is coated with polyaniline.
3, the above-mentioned preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor, comprises the steps:
(1) 0.005mol graphite oxide is disperseed 30 minutes in 50ml deionized water for ultrasonic, the concentrated hydrochloric acid 10ml that adds wherein aniline monomer (mol ratio of aniline monomer and graphite oxide is 8:1) and 36%, then under ice bath, magnetic agitation limit, limit drips the ammonium persulfate solution (mol ratio of ammonium persulfate and aniline monomer is 1:1.5) of 0.04mol/mL, and rate of addition is 0.3mL/s, being added dropwise to complete rear continuation stirs 2 hours, by solid centrifugation wherein out, obtain the compound of polyaniline/graphite oxide again;
(2) above-mentioned resulting polyaniline/graphite oxide composite is all mixed with 0.05mol hydrazine hydrate (hydrazine hydrate concentration 85%), at 100 ℃, reflux 18 hours, solid filtering is wherein separated, obtain the compound of polyaniline/Graphene;
(3) by iron ion and graphite oxide mol ratio, be 8:1, the compound of polyaniline/Graphene and iron chloride powder (wherein iron ion 0.04mol) are joined in 100ml deionized water and ultrasonic dispersion 3 hours, stir again 3 hours, then drip while stirring wherein concentrated ammonia liquor (in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is 2:1), and rate of addition is 0.2mL/s; After being added dropwise to complete, continue to stir 2 hours, more static ageing 8 hours; then by the suspension obtaining under nitrogen protection, temperature is to react 3 hours under 180 ℃ of conditions; after having reacted, solid is separated, obtained graphene/polyaniline/ferric oxide composite material.
Application testing
Graphene/polyaniline/ferric oxide composite material prepared by the present invention carries out performance test as electrode material.Concrete method of testing is: graphene/polyaniline/iron oxide compound, acetylene black and ptfe emulsion (80:15:5 proportioning in mass ratio) are mixed into glue and stick in nickel foam; the sodium sulphate of 1mol/L of take is electrolyte; on Shanghai China occasion electrochemical workstation, carry out cyclic voltammetric and charge-discharge test, test data is referring to table 1.As shown in Table 1, graphene/polyaniline/ferric oxide composite material, as electrode of super capacitor, can reach 890F/g than electric capacity, and cycle-index can reach 5000 times.
Table 1
Comparative example: with Graphene, graphene/polyaniline compound, Graphene/iron oxide compound as a comparison, result is as shown in table 1.
Wherein, the preparation method of Graphene is that conventional preparation method is: the graphite oxide using in the present invention is reduced with hydrazine hydrate.The preparation method of graphene/polyaniline is the preparation method's step 2 (2) in embodiment 2 referring to the present invention; The preparation method of Graphene/iron oxide compound is: directly graphite oxide and molysite are disperseed to blend in deionized water; under agitation drip concentrated ammonia liquor; then by the suspension obtaining under nitrogen protection, temperature is to react 6 hours under 180 ℃ of conditions; after having reacted; again solid taking-up is placed in to hydrazine hydrate and reduces, obtain Graphene/ferric oxide composite material.
Claims (10)
1. a graphene/polyaniline/ferric oxide composite material that is applied to ultracapacitor, it is characterized in that it is to be compounded to form by Graphene, polyaniline, iron oxide, described polyaniline-coated is on Graphene, and described iron oxide is grown on the Graphene that is coated with polyaniline.
2. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 1, is characterized in that it comprises the steps:
(1) mol ratio of pressing aniline and graphite oxide is (1～10): 1, aniline monomer and hydrochloric acid are joined to the aqueous solution of graphite oxide, under 0～5 ℃ of condition, drip while stirring initiator solution, being added dropwise to complete rear continuation stirs 2～5 hours, gained solid is separated, obtained the compound of polyaniline/graphite oxide;
(2) compound of polyaniline/graphite oxide is reduced with reducing agent, then isolate the compound of polyaniline/Graphene;
(3) according to the mol ratio of graphite oxide and iron ion, be 1:(1～20), the compound of soluble ferric iron salt and polyaniline/Graphene is mixed in water, disperse and stir after 1～3 hour, drip while stirring wherein concentrated ammonia liquor, in concentrated ammonia liquor, the mol ratio of ammonia and iron ion is (1～8): 1, after being added dropwise to complete, continue to stir 1～3 hour, still aging 8～24 hours again, obtain suspension; Again by resulting suspension under nitrogen or inert gas shielding, in temperature, be to react 1～6 hour under 120～180 ℃ of conditions, then solid is wherein separated, obtain graphene/polyaniline/ferric oxide composite material.
3. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, the concentration of aqueous solution that it is characterized in that graphite oxide is 0.1mol/L, after described graphite oxide is mixed with water, ultrasonic dispersion 30-60 minute, can obtain the aqueous solution of graphite oxide.
4. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, is characterized in that described initator is (NH
4)
2s
2o
8, K
2cr
2o
7, KIO
3, FeCl
3, FeCl
4, H
2o
2, Ce (SO
4)
2, MnO
2, a kind of in benzoyl peroxide.
5. according to the preparation method of the graphene/polyaniline/ferric oxide composite material that is applied to ultracapacitor described in claim 1 or 4, it is characterized in that described initator is the ammonium persulfate solution of concentration 0.04mol/L, the mol ratio of ammonium persulfate and aniline is 1:(1～2).
6. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, is characterized in that the concentration 0.8～4mol/L of hydrochloric acid in the aqueous solution in described step (1); In step (1), rate of addition is 0.15mL/s～0.3mL/s.
7. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, is characterized in that described reducing agent is hydrazine hydrate or sodium borohydride, and reducing agent and graphite oxide mol ratio are (10～100): 1.
8. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, it is characterized in that in described step (2), reduction adopts hydrazine hydrate, reducing condition is to reflux more than 12 hours at 90 ℃～100 ℃.
9. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, is characterized in that in step (3) that it is 0.05mol/L～0.2mol/L that the addition of water makes the molar concentration of molysite; Describedly be separated into ultrasonic dispersion, the time is 30-60 minute; The time of described stirring is 4～8 hours; The concentration of concentrated ammonia liquor is 28%, and rate of addition is 0.15mL/s～0.3mL/s.
10. the preparation method who is applied to the graphene/polyaniline/ferric oxide composite material of ultracapacitor according to claim 2, the preparation method who it is characterized in that described graphite oxide is: according to (1～5g): (0.2～2g): the ratio of (30～150ml), graphite, sodium nitrate and 98% concentrated sulfuric acid are mixed, at blender, add while stirring potassium permanganate, the mass ratio of potassium permanganate and graphite is (0.2-8): 1, more than treating that potassium permanganate adds the 12h of continuation stirring afterwards; Add wherein again deionized water, the volume ratio of deionized water and the concentrated sulfuric acid is 1:(0.05-1.5), adding concentration is 30% hydrogen peroxide again, the volume ratio of hydrogen peroxide and the concentrated sulfuric acid is 1:(0.5-15), obtain yellow suspension-turbid liquid, adopt and filter or centrifugal method, solid is separated, dry, be graphite oxide.
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