CN104119529B - The preparation method of the polyaniline/graphene composite material of nano tubular structure - Google Patents
The preparation method of the polyaniline/graphene composite material of nano tubular structure Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 239000004160 Ammonium persulphate Substances 0.000 claims abstract description 10
- 235000019395 ammonium persulphate Nutrition 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 52
- 239000005457 ice water Substances 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 42
- 229910002804 graphite Inorganic materials 0.000 claims description 41
- 239000010439 graphite Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000011049 filling Methods 0.000 claims description 24
- 235000019154 vitamin C Nutrition 0.000 claims description 22
- 239000011718 vitamin C Substances 0.000 claims description 22
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- 239000012153 distilled water Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 230000017105 transposition Effects 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a kind of preparation method of polyaniline/graphene composite material of nano tubular structure.Aniline is distributed in the ascorbic aqueous solution, then adds the graphene oxide prepared, after being uniformly dispersed, add ammonium persulphate initiated polymerization, react 12 hours under room temperature, obtain the polyaniline/graphene composite material of nano tubular structure.The inventive method preparation technology is simple, environmental protection, and prepared polyaniline/graphene nanocomposite material pattern homogeneous, there is higher chemical property.
Description
Technical field
The invention belongs to technical field of composite preparation, particularly a kind of preparation method of polyaniline/graphene composite material of nano tubular structure.
Background technology
Graphene (graphene) is a kind of novel material of the individual layer sheet structure be made up of carbon atom, and the flat film of to be a kind of by carbon atom with the hexangle type that sp2 hybridized orbital forms be honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.It has very large specific surface area, excellent electroconductibility and the peculiar property such as thermal conductivity, very high mechanical strength, can be widely used in the electrode materials of battery and ultracapacitor, cause huge interest and the concern of scientist.But Graphene, as electrode materials, has low ratio capacitance, simultaneously, Graphene and graphene oxide thereof easily occur stacking in the process of preparation, have impact on its dispersiveness in the electrolyte and surface wettability, reduce reference area and the specific conductivity of material.Therefore the interlamellar spacing controlling Graphene is the current major subjects needing to solve.
Polyaniline is a kind of common conductive polymers, and have synthesis simple, with low cost, large specific surface area, good environmental stability and very high theoretical ratio capacitance, have great application prospect as electrode material for super capacitor.But the energy storage mechnism of uniqueness---doping and dedoping process, makes it volume change can occur in charge and discharge process thus causes special capacity fade degradation shortcoming comparatively fast and under cyclical stability.
Therefore, by Graphene and polyaniline are carried out compound, polyaniline is polymerized at the interlayer of Graphene, effectively hinder the stacking of Graphene, Graphene is that polyaniline provides skeleton simultaneously, enhance the mechanical property of self, so the matrix material of preparation both can take into account high specific conductivity, high-specific surface area and the good mechanical property of Graphene, the high ratio capacitance of polyaniline can be taken into account again.
With the Graphene of chemical preparation; main use hydrazine hydrate and sodium borohydride are as reductive agent (M.M.Sk; etal; Synthesisofgraphene/vitaminCtemplate-controlledpolyanili nenanotubescompositeforhighperformancesupercapacitorelec trode.Polymer2014; 55,798-805; K.Zhang, etal, Graphene/PolyanilineNanofiberCompositesasSupercapacitorE lectrodes.Chem.Mater.2010,22,1392-1401; H.J.Shin, etal, Efficientreductionofgraphiteoxidebysodiumborohydrideandi tseffectonelectricalconductance, Adv.Funct.Mater.2009,19,1987-1992.), but these reductive agents are not only poisonous, harmful, and need (about 90 DEG C) at a relatively high temperature just can give full play to reductive action, preparation technology is loaded down with trivial details simultaneously.Therefore, adopt a kind of environmental protection and reaction conditions gentleness reductive agent, reduces very necessary to graphene oxide.The present invention is using vitamins C as template, aniline passes through H-bonding self-assembly, after in-situ polymerization, using vitamins C as reductive agent (utilizing the reductibility that vitamins C is stronger) redox graphene, a step preparation has the polyaniline/graphene composite material of nano tubular structure.In the present invention, vitamins C has two effects in reaction process: (1) aniline is that template carries out H-bonding self-assembly with vitamins C, is formed the matrix material of tubular structure subsequently by oxypolymerization and graphite oxide; (2) green reducing agent vitamins C can reduce to graphene oxide.This thinking has no bibliographical information at present.
Summary of the invention
The object of the invention is to utilize ascorbic template action and reductive action, provide an a kind of step preparation to have the method for the polyaniline/graphene composite material of nano tube structure and good electrical chemical property.
Concrete steps are:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues more than 20 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken and the mol ratio of the aniline added are the one in 4:1,2:1,1:1,0.5:1,0.25:1 and 0.1:1.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
The inventive method preparation technology is simple, environmental protection, and prepared polyaniline/graphene nanocomposite material pattern homogeneous, there is higher chemical property.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the SEM figure of the polyaniline/graphene nanocomposite material of nano tubular structure prepared by the embodiment of the present invention 1 and the polyaniline material of the embodiment of the present invention 7 preparation, the wherein SEM figure of (a) polyaniline material of preparing for embodiment 7, the SEM of the polyaniline/graphene nanocomposite material of the nano tubular structure that (b) prepare for embodiment 1 schemes.
Fig. 2 is the constant current charge-discharge curve of polyaniline/graphene composite material under different current densities of nano tubular structure prepared by the embodiment of the present invention 1, and result shows: polyaniline/graphene nanocomposite material under constant current charge-discharge condition, the ratio capacitance of current density when being 1A/g can reach 662F/g.
Embodiment
embodiment 1:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues 25 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken is 4:1 with the mol ratio of the aniline added.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
embodiment 2:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues 25 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken is 2:1 with the mol ratio of the aniline added.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
embodiment 3:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues 25 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken is 1:1 with the mol ratio of the aniline added.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
embodiment 4:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues 25 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken is 0.5:1 with the mol ratio of the aniline added.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
embodiment 5:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues 25 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken is 0.25:1 with the mol ratio of the aniline added.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
embodiment 6:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues 25 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color.
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken is 0.1:1 with the mol ratio of the aniline added.
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1.
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
embodiment 7:
(1) hydrochloric acid soln getting 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L adds in flask, stirs 1 hour under the condition of ice-water bath, obtained mixed solution.
(2) ammonium persulfate solution is dropwise joined in the obtained mixed solution of step (1), stir 12 hours under the condition of ice-water bath, obtained intermediate product, the mol ratio of the aniline added in ammonium persulphate and step (1) in the ammonium persulfate solution dripped is 1:1.
(3) filtering and washing is carried out with the intermediate product that deionized water is obtained to step (2), until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. obtained polyaniline material.
Claims (1)
1. a preparation method for the polyaniline/graphene composite material of nano tubular structure, is characterized in that concrete steps are:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask filling 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, preoxidation is carried out to graphite; Then gradation adds the potassium permanganate that total amount is 18 grams in flask, continues more than 20 minutes, controls temperature of reaction and is no more than 35 DEG C, reoxidize graphite with ice-water bath; After 1 hour, treat that system temperature is stablized, arranging temperature of reaction is 50 DEG C, react 12 hours, stop heating, treat that system temperature is down to room temperature, dropwise add 100 ml distilled waters, control temperature of reaction and be no more than 80 DEG C, then, the system for the treatment of is cooled to less than 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, in beaker, an impouring 300 milliliters is the superoxol of 30% containing 15 milliliters of mass concentrations, treats that system temperature is down to room temperature, terminate reaction, system is glassy yellow; Carry out eccentric cleaning with deionized water, hydrochloric acid, ethanol to product successively, centrifugal rotational speed is 4000 revs/min, until system is in neutral; Finally the product obtained is carried out vacuum filtration, drying 24 hours in the vacuum drying oven of 50 DEG C, i.e. obtained graphite oxide;
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. getting graphite oxide prepared by 0.02 gram of step (1) joins in the beaker filling 50 ml deionized water, ultrasonic disperse 1 hour, the graphene oxide dispersion of obtained brown color;
B. taking vitamins C joins in the flask filling 30 ml deionized water, stirring at room temperature is after 0.5 hour, by flask transposition in ice-water bath, then in flask, add the hydrochloric acid soln of 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L, stir 0.5 hour under the condition of ice-water bath, obtained mixed solution; The vitamins C taken and the mol ratio of the aniline added are the one in 4:1,2:1,1:1,0.5:1,0.25:1 and 0.1:1;
C. step (2) a is walked obtained graphene oxide dispersion to join in the obtained mixed solution of step (2) b step, stir 1 hour in ice-water bath, obtained uniform brown color mixed solution;
D. ammonium persulfate solution dropwise being joined step (2) c walks in obtained mixed solution, stir 12 hours under the condition of ice-water bath, obtained intermediate product, in the ammonium persulfate solution dripped, the mol ratio of the aniline that ammonium persulphate and step (2) b add in walking is 1:1;
E. with deionized water, obtained intermediate product is walked to step (2) d and carry out filtering and washing, until filtrate is in neutral, the hydrochloric acid soln of 2 milliliter of 1 mol/L is added again in filter cake, polyaniline is fully adulterated, finally filter cake to be inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grinding is collected, i.e. polyaniline/the graphene nanocomposite material of obtained nano tubular structure.
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