CN102532894B - Preparation method of graphite oxide/polypyrrole composite material - Google Patents
Preparation method of graphite oxide/polypyrrole composite material Download PDFInfo
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- CN102532894B CN102532894B CN 201210003652 CN201210003652A CN102532894B CN 102532894 B CN102532894 B CN 102532894B CN 201210003652 CN201210003652 CN 201210003652 CN 201210003652 A CN201210003652 A CN 201210003652A CN 102532894 B CN102532894 B CN 102532894B
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Abstract
The invention relates to a preparation method of a graphite oxide/polypyrrole composite material, which belongs to the technology of graphite oxide and conductive macromolecule composite materials and solves the problems of conductivity, heat stability, manufacturing process and cost of the composite material. The preparation method of the graphite oxide/polypyrrole composite material comprises the following steps: step 1, adding graphite oxide into acid-doped solution of a surfactant for ultrasonic dispersion to form graphite oxide solution with uniform dispersion; step 2, adding a pyrrole monomer in the solution obtained in the step 1 and then continuously forming mixed solution through ultrasonic dispersion; step 3, gradually and slowly dripping the acid-doped solution formed after an oxidant is added into the solution formed in the step 2, and agitating and polymerizing for a period of time; step 4, finally adding alcoholic solution to terminate the reaction; and step 5, filtering, washing and vacuum-drying mixed solution obtained in the step 4 to obtain the graphite oxide/polypyrrole composite material. The preparation method has stronger application prospect and economic benefit in the fields such as super capacitor electrode materials, chemical power supplies, sensors, environment, life science and the like.
Description
Technical field
The invention belongs to the composite technology of graphite oxide and conducting polymer.Graphite oxide/polypyrrole composite material and preparation method thereof particularly.
Background technology
Conductive polymers claims again conducting polymer, and referring to can be by doping or the means such as compound, makes specific conductivity can reach polymkeric substance in semi-conductor and conductor scope.Polypyrrole (PPy) powder that the black title of pyrroles arranged just was synthesized as far back as 1916, but people did not recognize the conductivity of this polymkeric substance at that time.Diaz etc. had reported in the solution that contains 1% acetonitrile that the preparation specific conductivity was better, heat-staple PPy afterwards.Until 20 century 70s, Hideki Shirakawa finds that the polyacetylene after doping has the electroconductibility near metal, and the conductive polymers field just arouses widespread concern.PPy has obtained more deep research due to its excellent electroconductibility and simple synthesis technique.But eigenstate conductive polymers electroconductibility is very poor, and is insoluble in organic solvent, is difficult to processing, and these factors have restricted it and used widely.In order further to improve these performances of PPy, the researchist finds, add various additives and carried out doping or compound with nanoparticle in building-up process, not only effectively improved the specific conductivity of PPy, but also its thermostability and mechanical ductility have been improved, the PPy matrix material has shown good photoelectric properties, thereby becomes the focus of domestic and international research.
Because the conduction of graphite oxide and conductive polymers conjugated structure synergy can strengthen matrix electroconductibility, but the enhancing of implementation structure again simultaneously, and the interaction of polypyrrole and graphite oxide can significantly improve the resistance toheat of material, is suitable for doing high-temperature electrode material.
In the preparation of present graphite oxide/polypyrrole, cost of manufacture is higher, as high in the tensio-active agent cost that uses or difficult acquisition; Prepare by electrochemical method, productive rate is lower; The synthetic not high deficiency of polypyrrole conductivity.
Summary of the invention
The object of the present invention is to provide that a kind of electroconductibility is good, Heat stability is good, manufacture craft is simple and cost is relatively low graphite oxide/polypyrrole composite material and preparation method thereof.
Technical scheme of the present invention:
A kind of preparation method of graphite oxide/polypyrrole composite material, this preparation method's step comprises:
Step 2 joins the graphite oxide of step 1 weighing in the surfactant soln of step 1 preparation, ultra-sonic dispersion, and ultrasonic time is 20min～60min, forms finely dispersed graphite oxide solution;
Step 3 in the gained graphite oxide solution, adds the pyrrole monomer of step 1 weighing in step 2, then continue by ultra-sonic dispersion, and ultrasonic time is 10min～30min, makes it form mixed solution;
In the mixed solution of step 4 to the step 3 gained, dropwise adding slowly with mixed solution with the oxidizing agent solution in the step 1 of volume, is under 15 ℃～-5 ℃ in temperature, stirs 3h～6h, after adding the methyl alcohol or ethanol with its equal volume, and stopped reaction;
The mixed solution that step 5 obtains step 4 carries out obtaining graphite oxide/polypyrrole composite material after suction filtration, washing, vacuum drying.
Tensio-active agent in described step 1 comprises: Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide.
Oxygenant in described step 1 comprises: ammonium persulphate or iron trichloride.
The present invention compared with prior art, its advantage is remarkable: (1) utilizes the large specific surface area of graphite oxide, form binding site with Surface Oxygen base group, by hydroxy-acid group and tensio-active agent to the pyrrole monomer coating function, make the pyrroles be coated on equably on graphite oxide, improve its specific surface area, form graphite oxide/polypyrrole mixture; (2) prepare the operating process of this material simple, with short production cycle, productive rate is high, and not high to equipment requirements, cost is lower; (3) interaction of polypyrrole and graphite oxide can significantly improve the resistance toheat of material, be suitable for doing high-temperature electrode material, and adding of polypyrrole made up the low shortcoming of graphite oxide electric conductivity, can comparatively strong application prospect and economic benefit be arranged in fields such as electrode material for super capacitor, chemical power source, sensor, environment, life sciences.
Description of drawings
Fig. 1 .1 is the hot weightless picture of polypyrrole.
Fig. 1 .2 is the hot weightless picture of graphite oxide/polypyrrole composite material.
The SEM figure of Fig. 2 graphite oxide/polypyrrole composite material.
Embodiment
Embodiment one
The preparation method of graphite oxide/polypyrrole composite material comprises:
Step 2 joins graphite oxide in surfactant soln in step 1, ultrasonic 60min;
Step 3 is added drop-wise to pyrrole monomer in the step 2 product, and ultrasonic 30min disperses to form pyrroles's mixed solution;
Step 4 dropwise adds the oxidizing agent solution in step 1 in the solution that obtains in the step 3 under-5 ℃, stir the methyl alcohol termination reaction that adds 66.75ml after 6h;
Step 5 after deionized water, ethanol repetitive scrubbing, obtains graphite oxide/polypyrrole composite material with above-mentioned mixed solution suction filtration after vacuum-drying.
The scanning electron microscope of gained matrix material is seen Fig. 2, and as shown in the figure, the polypyrrole in matrix material is long in the oxidized graphite flake layer equably, has formed and has adhered to good graphite oxide/polypyrrole mixture.
Embodiment two
The preparation method of graphite oxide/polypyrrole composite material comprises:
Step 2 joins graphite oxide in surfactant soln in step 1, ultrasonic 20min;
Step 3 is added drop-wise to pyrrole monomer in the step 2 product, and ultrasonic 10min disperses to form pyrroles's mixed solution;
Step 4 dropwise adds the oxidizing agent solution in step 1 in the solution that obtains in the step 3 under 15 ℃, stir the ethanol termination reaction that adds 66.75ml after 3h;
Step 5 after deionized water, ethanol repetitive scrubbing, obtains graphite oxide/polypyrrole composite material with above-mentioned mixed solution suction filtration after vacuum-drying.
Embodiment three
The preparation method of graphite oxide/polypyrrole composite material comprises:
Step 2 joins graphite oxide in surfactant soln in step 1, ultrasonic 40min;
Step 3 is added drop-wise to pyrrole monomer in the step 2 product, and ultrasonic 20min disperses to form pyrroles's mixed solution;
Step 4 under 5 ℃, dropwise adds the oxidizing agent solution in step 1 in the solution that obtains in the step 3, stir the methyl alcohol termination reaction that adds 66.75ml after 5h;
Step 5 after deionized water, ethanol repetitive scrubbing, obtains graphite oxide/polypyrrole composite material with above-mentioned mixed solution suction filtration after vacuum-drying.
Embodiment four
The preparation method of graphite oxide/polypyrrole composite material comprises:
Step 2 joins graphite oxide in surfactant soln in step 1, ultrasonic 60min;
Step 3 is added drop-wise to pyrrole monomer in the step 2 product, and ultrasonic 30min disperses to form pyrroles's mixed solution;
Step 4 dropwise adds the oxidizing agent solution in step 1 in the solution that obtains in the step 3 under 0 ℃, stir the methyl alcohol termination reaction that adds 66.75ml after 6h;
Step 5 after deionized water, ethanol repetitive scrubbing, obtains graphite oxide/polypyrrole composite material with above-mentioned mixed solution suction filtration after vacuum-drying.
Fig. 1 .2 is the hot weightless picture of graphite oxide/polypyrrole composite material, wherein the DTA curve is differential thermal curve, the stable material (reference substance) that any chemical reaction and physical change do not occur under certain experimental temperature with certain in expression with the unknown material of equivalent in the situation that in equivalent environment the constant speed alternating temperature compare, reduction showing as thermo-negative reaction, increases to show as thermopositive reaction; The TG curve is the abbreviation of thermogravimetric analysis (Thermogravimetric Analysis, TG or TGA), is quality-time curve; The Time curve is time temperature curve, and the expression temperature can be found out over time, after having added graphite oxide, the thermostability of matrix material is improved a lot.
The SEM figure of Fig. 2 graphite oxide/polypyrrole composite material, BACPCS4800 represents field emission scanning electron microscope, and 15.0kV is acceleration voltage, and 14.3mm is operating distance, and 40.0k is magnification, 1.00 microns is scale.
Claims (3)
1. the preparation method of a graphite oxide/polypyrrole composite material, is characterized in that, this preparation method's step comprises:
Step 1 is to get tensio-active agent in 1: 1～2: 1 by the ratio of tensio-active agent and the amount of substance of pyrrole monomer, and the solution of putting into 1mol/L camphorsulfonic acid or hydrochloric acid or sulfuric acid is made the surfactant soln of 0.13mol/L～0.26mol/L; Be to get oxygenant in 0.2: 1～2: 1 by the ratio of the amount of substance of oxygenant and pyrrole monomer, putting into 1mol/L camphorsulfonic acid or hydrochloric acid or sulphuric acid soln and make the oxidizing agent solution of 0.026mol/L～0.26mol/L, is weighing in 0.1: 1～0.6: 1 by the mass ratio of graphite oxide and pyrrole monomer;
Step 2 joins the graphite oxide of step 1 weighing in the surfactant soln of step 1 preparation, ultra-sonic dispersion, and ultrasonic time is 20min～60min, forms finely dispersed graphite oxide solution;
Step 3 in the gained graphite oxide solution, adds the pyrrole monomer of step 1 weighing in step 2, then continue by ultra-sonic dispersion, and ultrasonic time is 10min～30min, makes it form mixed solution;
In the mixed solution of step 4 to the step 3 gained, dropwise adding slowly with mixed solution with the oxidizing agent solution in the step 1 of volume, is under 15 ℃～-5 ℃ in temperature, stirs 3h～6h, after adding the methyl alcohol or ethanol with its equal volume, and stopped reaction;
The mixed solution that step 5 obtains step 4 carries out obtaining graphite oxide/polypyrrole composite material after suction filtration, washing, vacuum drying.
2. the preparation method of a kind of graphite oxide/polypyrrole composite material according to claim 1 is characterized in that:
Tensio-active agent in described step 1 comprises: Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide.
3. the preparation method of a kind of graphite oxide/polypyrrole composite material according to claim 1 is characterized in that:
Oxygenant in described step 1 comprises: ammonium persulphate or iron trichloride.
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| CN104292458B (en) * | 2014-11-06 | 2016-09-21 | 黑龙江科技大学 | The preparation method of polypyrrole/exfoliated-graphite composite |
| CN105336928B (en) * | 2015-09-30 | 2017-12-22 | 湘潭大学 | Preparation method and application of polypyrrole-coated carbon fluoride cathode material |
| CN108666535B (en) * | 2017-03-31 | 2021-09-03 | 比亚迪股份有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
| CN107519846A (en) * | 2017-07-31 | 2017-12-29 | 华南理工大学 | A kind of graphene/silicon dioxide Pt/Polypyrrole composite material and preparation method and application |
| CN107501932A (en) * | 2017-09-04 | 2017-12-22 | 苏州宇希新材料科技有限公司 | A kind of preparation method of lightweight polypyrrole material |
| CN109762328B (en) * | 2019-01-25 | 2021-05-25 | 广州大学 | Polypyrrole in-situ intercalation graphite antistatic plastic and preparation method thereof |
| CN110813376B (en) * | 2019-11-13 | 2020-10-13 | 许昌学院 | Polypyrrole-modified nano bismuth oxybromide photocatalytic material and preparation method and application thereof |
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| CN101544823A (en) | 2009-04-17 | 2009-09-30 | 华东理工大学 | Composite material with high conductivity intercalation structure and preparation method thereof |
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| CN101544823A (en) | 2009-04-17 | 2009-09-30 | 华东理工大学 | Composite material with high conductivity intercalation structure and preparation method thereof |
Non-Patent Citations (2)
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| 傅玲."氧化石墨和聚吡咯/氧化石墨纳米复合材料的制备、表征及应用研究".《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》.2005,(第7期),第18页2.3.3节，第43页4.3.2节，第44页表4.5. |
| 傅玲."氧化石墨和聚吡咯/氧化石墨纳米复合材料的制备、表征及应用研究".《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》.2005,(第7期),第18页2.3.3节,第43页4.3.2节,第44页表4.5. * |
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