CN104119529A - Preparation method of polyaniline/graphene composite material with nano tubular structure - Google Patents
Preparation method of polyaniline/graphene composite material with nano tubular structure Download PDFInfo
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- CN104119529A CN104119529A CN201410376084.9A CN201410376084A CN104119529A CN 104119529 A CN104119529 A CN 104119529A CN 201410376084 A CN201410376084 A CN 201410376084A CN 104119529 A CN104119529 A CN 104119529A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 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 47
- 239000000463 material Substances 0.000 claims abstract description 27
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 24
- 239000011718 vitamin C Substances 0.000 claims abstract description 24
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 52
- 229910002804 graphite Inorganic materials 0.000 claims description 42
- 239000010439 graphite Substances 0.000 claims description 42
- 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
- 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
- 239000000243 solution Substances 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000013067 intermediate product 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
- 239000012153 distilled water Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000004160 Ammonium persulphate Substances 0.000 claims description 9
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001914 filtration 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
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- -1 stir 20 minutes Substances 0.000 claims description 8
- 230000017105 transposition Effects 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 abstract description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 abstract description 2
- 229930003268 Vitamin C Natural products 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 description 8
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 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
- 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
- 239000002121 nanofiber Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention discloses a preparation method of a polyaniline/graphene composite material with a nano tubular structure, which comprises the following steps: dispersing aniline into an aqueous solution of vitamin C, and adding prepared graphene oxide; after uniform dispersion, adding ammonium persulfate to initiate polymerization; and reacting for 12 hours at room temperature to obtain the polyaniline/graphene composite material with a nano tubular structure. The method disclosed by the invention is simple in preparation process and green and environment-friendly; and the prepared polyaniline/graphene nano composite material has uniform morphology and relatively high electrochemical performance.
Description
Technical field
The invention belongs to matrix material preparing technical field, 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 being made up of carbon atom, is the flat film that a kind of hexangle type being made up of with sp2 hybridized orbital carbon atom is honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.It has the peculiar properties such as very large specific surface area, excellent electroconductibility and thermal conductivity, very high mechanical strength, can be widely used in the electrode materials of battery and ultracapacitor, has caused scientist's huge interest and concern.But Graphene, as electrode materials, has low ratio electric capacity, simultaneously, Graphene and graphene oxide thereof easily occur stacking in the process of preparation, have affected its dispersiveness and surface wettability in ionogen, have reduced reference area and the specific conductivity of material.Therefore the interlamellar spacing of controlling Graphene is the current major subjects that needs solution.
Polyaniline is a kind of common conductive polymers, have synthetic simple, specific surface area with low cost, large, good environmental stability and very high theory, than electric capacity, have great application prospect as electrode material for super capacitor.But unique energy storage mechanism---doping and dedoping process, thus make it in charge and discharge process, can generation volume change cause special capacity fade comparatively fast and degradation shortcoming under cyclical stability.
Therefore, by Graphene and polyaniline are carried out compound, polyaniline is in the interlayer polymerization of Graphene, effectively hinder the stacking of Graphene, simultaneously Graphene provides skeleton for polyaniline, strengthen the mechanical property of self, so the matrix material of preparation both can have been taken into account high specific conductivity, high-specific surface area and the good mechanical property of Graphene, can take into account again the high ratio electric capacity of polyaniline.
With the Graphene of chemical preparation; main hydrazine hydrate and the sodium borohydride of using is as reductive agent (M.M. Sk; et al; Synthesis of graphene/vitamin C template-controlled polyaniline nanotubes composite for high performance supercapacitor electrode. Polymer 2014; 55,798-805; K. Zhang, et al, Graphene/Polyaniline Nanofiber Composites as Supercapacitor Electrodes. Chem. Mater. 2010,22,1392-1401; H.J. Shin, et al, Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance, Adv. Funct. Mater. 2009,19,1987-1992.), but these reductive agents are not only poisonous, harmful, and need at relatively high temperature, (90 DEG C of left and right) just can give full play to reductive action, preparation technology is loaded down with trivial details simultaneously.Therefore, adopt reductive agent a kind of environmental protection and reaction conditions gentleness, graphene oxide is reduced very necessary.The present invention is using vitamins C as template, aniline is by hydrogen bond self-assembly, after in-situ polymerization, the redox graphene that (utilizes the reductibility that vitamins C is stronger) using vitamins C as reductive agent, 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 carries out hydrogen bond self-assembly taking vitamins C as template, forms subsequently the matrix material of tubular structure 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 there is 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 that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues more than 20 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is the one in 4:1,2:1,1:1,0.5:1,0.25:1 and 0.1:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
The inventive method preparation technology is simple, environmental protection, and prepared polyaniline/graphene nanocomposite material pattern homogeneous, has higher chemical property.
Brief description of the drawings
Fig. 1 is that the SEM figure of polyaniline/graphene nanocomposite material and the SEM of polyaniline material prepared by the embodiment of the present invention 7 of the nano tubular structure prepared of the embodiment of the present invention 1 schemes, the SEM figure of the polyaniline material that wherein (a) prepared for embodiment 7, the SEM figure of the polyaniline/graphene nanocomposite material of the nano tubular structure of (b) preparing for embodiment 1.
Fig. 2 is the polyaniline/graphene composite material of the nano tubular structure prepared of the embodiment of the present invention 1 constant current charge-discharge curve under different current densities, and result shows: polyaniline/graphene nanocomposite material under constant current charge-discharge condition, the ratio electric capacity of current density while being 1 A/g can reach 662 F/g.
Embodiment
embodiment 1:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues 25 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is 4:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
embodiment 2:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues 25 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is 2:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
embodiment 3:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues 25 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is 1:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
embodiment 4:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues 25 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is 0.5:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
embodiment 5:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues 25 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is 0.25:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
embodiment 6:
(1) preparation of graphite oxide
3 grams of Graphite Powder 99s are joined in the round-bottomed flask that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues 25 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide.
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color.
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is 0.1:1 with the mol ratio of the aniline adding.
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution.
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1.
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
embodiment 7:
(1) hydrochloric acid soln of 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, makes mixed solution.
(2) ammonium persulfate solution is dropwise joined in the mixed solution that step (1) makes, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (1) in the ammonium persulfate solution dripping is 1:1.
(3) carry out filtering and washing with the intermediate product that deionized water makes step (2), until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make 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 that fills 270 milliliters of sulfuric acid and 30 milliliters of phosphoric acid mixed solutions, stir 20 minutes, graphite is carried out to preoxidation; Then gradation is the potassium permanganate of 18 grams to adding total amount in flask, continues more than 20 minutes, is no more than 35 DEG C by ice-water bath control temperature of reaction, and graphite is reoxidized; After 1 hour, treat that system temperature is stable, it is 50 DEG C that temperature of reaction is set, 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 below 40 DEG C, is transferred in the beaker of 1 liter, again slowly add 100 ml distilled waters, be cooled to room temperature, contain to 300 milliliters of impourings in beaker the superoxol that 15 milliliters of mass concentrations are 30%, treat that system temperature is down to room temperature, finish reaction, system is glassy yellow; With deionized water, hydrochloric acid, ethanol, product is carried out to eccentric cleaning successively, centrifugal rotational speed is 4000 revs/min, until system is neutral; Finally the product obtaining is carried out to vacuum filtration, in the vacuum drying oven of 50 DEG C, be dried 24 hours, make graphite oxide;
(2) preparation of nano tubular structure polyaniline/graphene nanocomposite material
A. get graphite oxide prepared by 0.02 gram of step (1) and join in the beaker that fills 50 ml deionized water, ultrasonic dispersion 1 hour, makes the graphene oxide dispersion liquid of brown color;
B. taking vitamins C joins in the flask that fills 30 ml deionized water, after stirring at room temperature 0.5 hour, by flask transposition in ice-water bath, then to the hydrochloric acid soln that adds 0.5 milliliter of aniline of having purified and 2 milliliter of 1 mol/L in flask, under the condition of ice-water bath, stir 0.5 hour, make mixed solution; The vitamins C taking is the one in 4:1,2:1,1:1,0.5:1,0.25:1 and 0.1:1 with the mol ratio of the aniline adding;
C. step (2) a are walked to the graphene oxide dispersion liquid making and join step (2) b and walk in the mixed solution making, in ice-water bath, stir 1 hour, make uniform brown color mixed solution;
D. ammonium persulfate solution dropwise being joined to step (2) c walks in the mixed solution making, under the condition of ice-water bath, stir 12 hours, make intermediate product, the mol ratio of the aniline adding in ammonium persulphate and step (2) b steps in the ammonium persulfate solution dripping is 1:1;
E. with deionized water, step (2) d are walked to the intermediate product making and carry out filtering and washing, until filtrate is neutral, again to the hydrochloric acid soln that adds 2 milliliter of 1 mol/L in filter cake, polyaniline is fully adulterated, finally filter cake is inserted in the vacuum drying oven of 50 DEG C dry 24 hours, grind and collect, make the polyaniline/graphene nanocomposite material of nano tubular structure.
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Application publication date: 20141029 Assignee: Sales and Operation Department of Qiyue Paper Products in Xixiangtang District, Nanning Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044309 Denomination of invention: Preparation Method of Polyaniline/Graphene Composite Materials with Nanotube Structure Granted publication date: 20160406 License type: Common License Record date: 20231027 |