CN103421188B - A kind of preparation method of sheet polypyrrole with high conductivity - Google Patents
A kind of preparation method of sheet polypyrrole with high conductivity Download PDFInfo
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- CN103421188B CN103421188B CN201310331976.2A CN201310331976A CN103421188B CN 103421188 B CN103421188 B CN 103421188B CN 201310331976 A CN201310331976 A CN 201310331976A CN 103421188 B CN103421188 B CN 103421188B
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Abstract
A kind of preparation method of high conductivity sheets of conductive polypyrrole: utilize ultrasonic wave to be uniformly dispersed in deionized water for stirring the sulfonic acid funtionalized graphene dispersion of trace, pyrrole monomer is injected sulfonic acid funtionalized graphene solution, continue to stir and add oxygenant after ultrasonic disperse, can obtain the electric polypyrrole with sheet structure at 0-30 DEG C of reaction 6-24h under agitation condition, oxygenant is any one in ammonium persulphate, Potassium Persulphate, FERRIC CHLORIDE ANHYDROUS, nine water iron nitrates, anhydrous ironic sulfate.The present invention utilizes the chemical action between the functional group on functionalization graphene nanometer sheet surface and pyrrole monomer, induction pyrroles is polymerized to the polypyrrole with sheet structure, functionalization graphene plays the effect of seed pattern and doping agent simultaneously, the polypyrrole prepared can obtain higher specific conductivity and ratio capacitance, can be used as anti-corrosion of metal corrosion material and electrode material for super capacitor.
Description
Technical field
The present invention relates to conducting polymer materials, specifically, be utilize sulfonic acid funtionalized graphene nanometer sheet to induce preparation to have the electric polypyrrole of sheet structure by the method for in-situ polymerization, this sheet polypyrrole with high conductivity can be applicable to anti-corrosion of metal or electrode material for super capacitor.
Background technology
The advantage that conductive polymers nano/micron structure has low-dimensional materials and organic conductor because of it simultaneously causes concern.Polypyrrole is as the typical conductive polymers of one, and have the advantages such as environmental stability is good, specific conductivity is high, easy synthesis, the synthesis of nano/micron structure polypyrrole causes the great interest of people.In recent years, have in order and the polypyrrole of specific morphology, such as pipe, line, rod, band, fiber enjoy the favor of people because of its special performance and the application in electricity, optics and other instruments.
At present, the preparation method of nano/micron structural conductive polymer mainly contains hard template method, soft template method and electrochemical polymerization method.Wherein, hard template method is comparatively conventional, but aftertreatment is loaded down with trivial details.Soft template method due to building-up process simple, condition is easy to control, is easy to the advantages such as mass-producing operation and is widely used.Have in the process of special micromorphology polypyrrole so that the synthesis of self-assembly soft template method is various, usually need in reaction system, add some auxiliary reagents (doping agent), as inorganic or organic acid, tensio-active agent, dyestuff and cyclodextrin etc., to obtain that there is the homogeneous special appearance polypyrrole of structure.
Utilize a small amount of conductive polymer nanometer fiber or electric spinning polymer fiber [Zhang XY, Manohar SK, Bulk synthesis polypyrrole nanofibers by seeding approach.J.AM.Chen.Soc., 2004, 126:12714-12715.Wang FC, Xu XP, Gong J, Luo YQ, Hou YL, Zheng XF, Qu LY.Polyaniline microrods synthesized by a polyoxometalates/poly (vinyl alcohol) microfibers template.Mater.Lett., 2005, 59:3982-3985.] electric polymer can be induced to be polymerized to the nanofibrous structures of one dimension as seed, but the standby electrically conductive polyaniline of this kind of seed pattern legal system is only limitted to the nano/micron fiber/rod/line of one dimension.On the one hand, the specific conductivity of this type of conductive polymers is also unsatisfactory, cannot obtain high ratio capacitance when being applied to electrode material for super capacitor; On the other hand, one dimension conductive polymers alloy and metal anticorrosion in apply and be restricted.
Summary of the invention
For above technical problem, the object of the invention is to a kind of preparation method of sheet polypyrrole with high conductivity, technique is simple, and the sheet polypyrrole of acquisition has higher specific conductivity and higher ratio capacitance.
In order to realize foregoing invention object, provide technical scheme as follows:
A preparation method for sheet polypyrrole with high conductivity, step is as follows:
(1) by sulfonic acid funtionalized graphene dispersion in water, stir and utilize ultrasonic wave disperse make graphene dispersing solution, for subsequent use;
The concentration of sulfonic acid funtionalized graphene dispersing solution is 0.05-0.5mg/mL, and preferably scope is 0.1-0.3mg/mL;
(2) pyrrole monomer is injected to the graphene dispersing solution of step (1), stirs and utilize ultrasonic wave to disperse forming reactions system, for subsequent use;
The mass ratio of sulfonate functional functionalized graphene and pyrrole monomer is 1:300-1:10; Pyrroles is before use through heavily steaming;
(3) oxygenant is dissolved in the water makes solution, the reaction system that (2) formed slowly is dropped to according to the rate of addition of 0.02-0.5mL/min, mix, reaction 6-24h is carried out in 0-30 DEG C at agitation condition, the product deionized water obtained is cleaned repeatedly, and in vacuum drying oven 60 DEG C of dry 24h, obtain the electric polypyrrole with sheet structure.
Oxygenant is any one in ammonium persulphate, Potassium Persulphate, FERRIC CHLORIDE ANHYDROUS, nine water iron nitrates or anhydrous ironic sulfate; The mol ratio of pyrroles and oxygenant is 1:1-1:4.
The invention has the advantages that:
1, the sulfonate ion of sulfonic acid funtionalized graphenic surface, hydroxyl can induce pyrroles's nucleation in its vicinity, and copy the sheet structure (shown in structural formula 1) of graphene nanometer sheet.
The sheet structure prepared by this method (reaches 10 because effect that sulfonated graphene nanometer sheet plays seed and doping agent has higher specific conductivity simultaneously
1s/cm), there is not been reported both at home and abroad for this kind of method, and have higher ratio capacitance, applied range, can be used as such as anti-corrosion of metal and electrode material for super capacitor.
2, employing single stage method carries out home position polymerization reaction, and equipment is simple, processing ease, easily expands scale production.
Accompanying drawing explanation
Fig. 1 is the SEM photo that the embodiment of the present invention 1 prepares sulfonate functional functionalized graphene and sheet polypyrrole, left figure is the sulfonate functional functionalized graphene SEM photo of amplification 5000 times, right figure is the SEM photo of the sheet polypyrrole of amplification 25000 times, adopt JSM-5610 type scanning electron microscope (Japanese JEOL company) to test, sample is gold,platinized before testing.From SEM image, sulfonated graphene presents the microstructure that nanoscale twins connects.Polypyrrole is typical sheet structure, lamella size 200-600nm, and lamellar spacing is 10-20nm.
Fig. 2 is the cyclic voltammetry curve (electrolytic solution: 1M H of sheet polypyrrole prepared by the embodiment of the present invention 1
2sO
4, sweep speed=10mV/s).As seen from Figure 2, the CV curve shape of sheet polypyrrole prepared by embodiment 1, close to rectangle, shows desirable electrochemical capacitance characteristic.
Fig. 3 is the charging and discharging curve (electrolytic solution: 1MH of sheet polypyrrole prepared by the embodiment of the present invention 1
2sO
4, current density=1A/g).As can be seen from Figure 3, the ratio capacitance of sheet polypyrrole that prepared by embodiment 1 can basis:
calculate, wherein C
mfor ratio capacitance, I is discharging current, and △ t is discharge time, and m is the quality of active substance, and △ V is the volts lost in discharge process, and the ratio capacitance calculating sheet polypyrrole prepared by embodiment 1 then can reach 306F/g.
Embodiment
Below by way of specific embodiment, foregoing of the present invention is described in further detail.But this should be interpreted as content of the present invention is only limitted to following example.
Through heavily steaming before the pyrroles that following examples adopt uses.
Embodiment 1
A preparation method for sheet polypyrrole with high conductivity, comprises the following steps:
(1) by 1mg sulfonate functional functionalized graphene, (preparation method is see Ding B, Lu XJ, Yuan CZ, Yang SD, Han YQ, Zhang XG, Che Q.One-step electrochemical composite polymerization of polypyrrole integrated with functionalized graphene/carbon nanotubes nanostructured composite film for electrochemical capacitors.Electrochim.Acta, 2012, 62:132-139.) be scattered in 20mL water, stir and utilize ultrasonic wave to disperse to make graphene dispersing solution, for subsequent use.
(2) by 300mg(4.4776mmol) pyrroles (purchased from German Aldrich) monomer is injected to the graphene dispersing solution of step (1), stirs and utilizes ultrasonic wave to disperse forming reactions system, for subsequent use.
(3) by 1.022g(4.4776mmol) ammonium persulphate (purchased from Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in 20mL water and makes solution, and drop to the rate of addition of 0.02mL/min the reaction system that (2) formed, mix.
(4) carry out reaction 12h at agitation condition in 30 DEG C, the product deionized water obtained cleaned repeatedly, and in vacuum drying oven 60 DEG C of dry 24h, obtain the electric polypyrrole with sheet structure.
Embodiment 2
Embodiment 2 difference from Example 1 is that the 1mg sulfonate functional functionalized graphene in step (1) becomes 2mg sulfonate functional functionalized graphene, 300mg(4.4776mmol in step (2)) pyrrole monomer becomes 400mg(5.9701mmol) pyrrole monomer, the 1.022g(4.4776mmol in step (3)) ammonium persulphate becomes 3.2276g(11.9402mmol) Potassium Persulphate.The rate of addition of 0.02mL/min becomes the rate of addition of 0.05mL/min.30 DEG C in step (4) become 25 DEG C.
Embodiment 3
Embodiment 3 difference from Example 1 is that the 1mg sulfonate functional functionalized graphene in step (1) becomes 4mg sulfonate functional functionalized graphene, 300mg(4.4776mmol in step (2)) pyrrole monomer becomes 400mg(5.9701mmol) pyrrole monomer, the 1.022g(4.4776mmol in step (3)) ammonium persulphate becomes 1.4525g(8.9552mmol) FERRIC CHLORIDE ANHYDROUS.The rate of addition of 0.02mL/min becomes the rate of addition of 0.1mL/min.30 DEG C in step (4) become 15 DEG C, and reaction 12h becomes 24h.
Embodiment 4
Embodiment 4 difference from Example 1 is that the 1mg sulfonate functional functionalized graphene in step (1) becomes 6mg sulfonate functional functionalized graphene, the 1.022g(4.4776mmol in step (3)) ammonium persulphate becomes 7.2358g(17.9104mmol) nine water iron nitrates.The rate of addition of 0.02mL/min becomes the rate of addition of 0.2mL/min.30 DEG C in step (4) become 5 DEG C, and reaction 12h becomes 6h.
Embodiment 5
Embodiment 5 difference from Example 1 is that the 1mg sulfonate functional functionalized graphene in step (1) becomes 10mg sulfonate functional functionalized graphene, 300mg(4.4776mmol in step (2)) pyrrole monomer becomes 100mg pyrrole monomer (1.4925mmol), the 1.022g(4.4776mmol in step (3)) ammonium persulphate becomes 1.194g(2.985mmol) anhydrous ironic sulfate.The rate of addition of 0.02mL/min becomes the rate of addition of 0.5mL/min.30 DEG C in step (4) become 0 DEG C, and reaction 12h becomes 18h.
Embodiment 1-5 prepares shown in the performance perameter chart 1 of sheet polypyrrole:
Table 1
Claims (6)
1. a preparation method for sheet polypyrrole with high conductivity, is characterized in that step is as follows:
(1) by sulfonic acid funtionalized graphene dispersion in water, stir and utilize ultrasonic wave disperse make graphene dispersing solution, for subsequent use; The concentration of sulfonic acid funtionalized graphene dispersing solution is 0.05-0.5mg/mL;
(2) pyrrole monomer is injected to the graphene dispersing solution of step (1), stirs and utilize ultrasonic wave to disperse forming reactions system, for subsequent use;
(3) oxygenant is dissolved in the water makes solution, slowly drop to the reaction system that step (2) is formed, mix, at agitation condition in 0-30 DEG C of reaction 6-24h, product deionized water cleans repeatedly, and in vacuum drying oven inner drying, obtains the electric polypyrrole with sheet structure, the mol ratio of pyrroles and oxygenant is 1:1-1:4, and oxygenant rate of addition is 0.02-0.5mL/min.
2. the preparation method of sheet polypyrrole with high conductivity according to claim 1, is characterized in that the concentration of sulfonic acid funtionalized graphene dispersing solution in step (1) is 0.1-0.3mg/mL.
3. the preparation method of sheet polypyrrole with high conductivity according to claim 1, is characterized in that the pyrroles of step (2) is before use through heavily steaming.
4. the preparation method of sheet polypyrrole with high conductivity according to claim 1, is characterized in that: the mass ratio of sulfonate functional functionalized graphene and pyrrole monomer is 1:300-1:10.
5. the preparation method of sheet polypyrrole with high conductivity according to claim 1, is characterized in that: the oxygenant in step (3) is the one in ammonium persulphate, Potassium Persulphate, FERRIC CHLORIDE ANHYDROUS, nine water iron nitrates or anhydrous ironic sulfate.
6. the preparation method of sheet polypyrrole with high conductivity according to claim 1, it is characterized in that, the bake out temperature of step (3) is 60 DEG C, and drying time is 24h.
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| CN104934236A (en) * | 2015-04-30 | 2015-09-23 | 河海大学 | Method of preparing electroactive molecule grafted graphene doped conductive polymer electrode materials |
| CN105086377B (en) * | 2015-09-22 | 2017-10-24 | 苏州高通新材料科技有限公司 | Sulfonated graphene conductive high molecular dispersion liquid, its preparation method and application |
| CN107290418A (en) * | 2017-05-05 | 2017-10-24 | 华南理工大学 | It is a kind of based on nitrogen-doped graphene without enzyme sensor and its preparation method and application |
| CN108675284A (en) * | 2018-05-14 | 2018-10-19 | 江苏大学 | Polypyrrole/Ni (OH)2The preparation method and application of/sulfonated graphene ternary composite electrode material |
| CN112331792B (en) * | 2020-10-19 | 2021-12-10 | 浙江大学 | Light-emitting device based on polypyrrole conductive layer for flexible display screen |
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| CN102051048A (en) * | 2010-11-10 | 2011-05-11 | 西北师范大学 | Polypyrrole/graphene nano composite and preparation method thereof |
| CN102702520A (en) * | 2012-06-08 | 2012-10-03 | 武汉工程大学 | Preparation method for composite material of sulfonated graphene/polypyrrole |
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| CN102051048A (en) * | 2010-11-10 | 2011-05-11 | 西北师范大学 | Polypyrrole/graphene nano composite and preparation method thereof |
| CN102702520A (en) * | 2012-06-08 | 2012-10-03 | 武汉工程大学 | Preparation method for composite material of sulfonated graphene/polypyrrole |
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