CN110010362B - Preparation method of polyaniline/graphene composite nano-film electrode - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 241
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 150
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 122
- 239000000243 solution Substances 0.000 claims description 116
- 239000002904 solvent Substances 0.000 claims description 54
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
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- 229910052802 copper Inorganic materials 0.000 claims description 10
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- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
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- 238000001878 scanning electron micrograph Methods 0.000 description 7
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention discloses a preparation method of a polyaniline/graphene composite nano-film electrode, which comprises the following steps: preparing graphene dispersion liquid, preparing aniline solution, and polymerizing aniline: dropwise adding an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; standing the graphene dispersion liquid to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid; preparing a polyaniline/graphene composite nano-film electrode: and (3) depositing the polyaniline/graphene in the polyaniline/graphene dispersion solution on the surface of the negative electrode by an electrophoresis method to obtain a layer of uniform polyaniline/graphene composite nanosheets, nanospheres or compact nano-films. The graphene/polyaniline composite nano-film electrode prepared by the method has the advantages of good compatibility with a substrate, uniform appearance and excellent electrical property.
Description
Technical Field
The invention relates to a preparation method of a polyaniline/graphene composite nano film electrode, belonging to the technical field of super capacitors, film batteries and organic solar batteries.
Background
Graphene (Graphene Oxide) is a hexagonal periodic close-packed two-dimensional carbon nanomaterial consisting of carbon atoms in a SP2 hybridized manner. Compared with the conventional carbon material, the graphene material has a larger specific surface area, higher electrical conductivity and superior stability, and is considered to be one of the most promising electrode materials, particularly in the application fields of supercapacitors, thin film batteries and the like. Meanwhile, since the specific capacitance of graphene is relatively low, the application of graphene in the field of commercial electrode materials is also limited.
Polyaniline (Poly Aniline) is a common conductive polymer electrode material and has the characteristics of easily obtained raw materials, environmental friendliness and simple preparation process. Polyaniline has multiple redox states, and has higher specific capacitance (-200F/g) compared with other conductive polymers. Currently, polyaniline has become one of the popular research materials for thin film batteries and supercapacitors. However, the cyclic stability of polyaniline is relatively low, which also limits its application in the field of thin film electrode materials. One feasible method is to say that polyaniline and graphene are compounded, so that the advantages of polyaniline and graphene are complementary, and the polyaniline and graphene have high specific capacitance and good cycle stability. Up to now, methods for preparing polyaniline/graphene composite materials include hydrothermal method, in-situ chemical oxidative polymerization method, electrochemical polymerization method, interfacial polymerization method, and the like. Although polyaniline/graphene synthesized by the methods has high specific capacitance, the process is relatively complex and is not beneficial to large-scale preparation, and meanwhile, the synthesized material is adhered to a substrate electrode by using an adhesive, the resistance of the electrode is increased by the presence of the adhesive, so that the application of the polyaniline/graphene on a thin-film electrode is greatly limited. Therefore, the method for preparing the polyaniline/graphene film electrode has low cost, simple process and no need of an adhesive and has important practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a polyaniline/graphene composite nano-film electrode, wherein the polyaniline/graphene composite material which is uniformly dispersed is directly deposited on a working electrode by an electrophoresis method, and the prepared film is uniform, good in stability, simple in method, low in cost and beneficial to large-scale application.
In order to achieve the above purpose, the invention provides a preparation method of a polyaniline/graphene composite nano-film electrode, which comprises the following steps:
preparing a graphene dispersion liquid: uniformly mixing graphene, a first solvent and a surfactant to prepare a graphene dispersion liquid;
preparing an aniline solution: adding aniline into a solvent II, and stirring the solvent II to completely dissolve aniline into the solvent II to form a uniform aniline solution;
polymerization of aniline: dropwise adding an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; standing the graphene dispersion liquid to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid;
preparing a polyaniline/graphene composite nano-film electrode: and (3) depositing the polyaniline/graphene in the polyaniline/graphene dispersion solution on the surface of the negative electrode by an electrophoresis method to obtain a layer of uniform polyaniline/graphene composite nanosheets, nanospheres or compact nano-films.
Further, the preparation of the graphene dispersion liquid in the invention comprises the following steps: dissolving graphene in a first solvent, wherein the first solvent is ethanol or isopropanol, carrying out ultrasonic treatment on the first solvent by using an ultrasonic instrument, then dropwise adding a surfactant into the first solvent, and carrying out ultrasonic treatment on the first solvent again by using the ultrasonic instrument to uniformly disperse the graphene in the first solvent to form a graphene dispersion solution.
Further, the preparation of the aniline solution in the invention comprises the following steps: slowly dripping aniline into a second solvent, and stirring the second solvent to completely dissolve the aniline into the second solvent to form a uniform and transparent aniline solution;
further, the polymerization of aniline in the present invention comprises the following steps: slowly dripping an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; standing the graphene dispersion liquid for 3 days to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid;
further, the preparation of the polyaniline/graphene composite nano-film electrode in the invention: carrying out ultrasonic treatment on the polyaniline/graphene dispersion liquid for 10min, then preparing a polyaniline/graphene composite film by using an electrophoresis method by taking a conductive substrate as a negative electrode in a working electrode and a copper sheet as a positive electrode in the working electrode; taking out the prepared polyaniline/graphene composite film electrode and naturally drying;
the conductive substrate is one of a copper sheet, a nickel sheet, gold-plated polyterephthalic acid plastic and a nickel-plated polyterephthalic acid plastic film;
the voltage applied by the electrophoresis method is 10-60V, the distance between the anode and the cathode is 2-5 cm, the electrophoresis is carried out at room temperature, and the deposition time is 10-100 min.
Further, in the invention, the single-layer graphene powder is dissolved in the first solvent, the first solvent is subjected to ultrasonic treatment for 10min by an ultrasonic instrument, then the magnesium nitrate solution surfactant is dropwise added into the first solvent, and the first solvent is subjected to ultrasonic treatment for 10min by the ultrasonic instrument again, so that the single-layer graphene powder is uniformly dispersed in the first isopropanol solution to form the graphene dispersion liquid.
Further, the second solvent is an isopropanol solution, the solubility of the prepared aniline solution is 0.05-1.0M/L, and the content of graphene in the prepared graphene dispersion liquid is 1-20 mg/L.
Furthermore, the surfactant is prepared by dissolving one or more of magnesium nitrate, sodium dodecyl sulfate and sodium dodecyl sulfate in isopropanol solution, and the concentration of the surfactant is 0.01-1 mM/L.
Further, in the step of polymerizing aniline, adding an acid solution into the graphene dispersion liquid, wherein the acid solution is one or more of a mixed solution of nitric acid and an isopropanol solution, a mixed solution of hydrochloric acid and an isopropanol solution, and a mixed solution of sulfuric acid and isopropanol; the concentration of the acid solution is 0.001-0.01 mM/L; the graphene dispersion may be allowed to stand for 8 hours to 30 days.
Further, the polyaniline/graphene composite nano-film electrode is formed by compounding graphene and a polyaniline nano-material, and the polyaniline nano-material is directly attached to the graphene nanosheet.
The invention achieves the following beneficial effects:
the polyaniline/graphene composite nano-film prepared by the method has uniform appearance and good compatibility with a substrate, and is more favorable for the polyaniline/graphene composite nano-film to construct a thin-film battery or a super capacitor through a subsequent means; the preparation method provided by the invention has the advantages of simple process, low cost, no need of an adhesive, compatibility with most of thin film electrodes and large-scale preparation; according to the preparation method, the thickness, the morphology and the components of the polyaniline/graphene composite film electrode can be changed by regulating and controlling the graphene concentration, the aniline concentration, the electrophoresis voltage, the positive and negative electrode spacing, the electrophoresis time and other conditions.
Drawings
Fig. 1 is an SEM image of a polyaniline/graphene composite nano-film electrode according to a first embodiment of the present invention;
fig. 2 is a schematic view of a cyclic voltammetry curve of a polyaniline/graphene composite nano-film electrode prepared in the first embodiment of the present invention measured in a 1M LiCl solution;
fig. 3 is a schematic view of a constant current charge-discharge curve of a polyaniline/graphene composite nano-film electrode prepared in the first embodiment of the present invention measured in a 1M LiCl solution;
fig. 4 is an SEM image of a polyaniline/graphene composite nano-film electrode prepared in example two of the present invention;
fig. 5 is an SEM image of a polyaniline/graphene composite nano-film electrode prepared in the third embodiment of the present invention;
fig. 6 is an SEM image of a polyaniline/graphene composite nano-film electrode prepared in example four of the present invention;
fig. 7 is an SEM image of a polyaniline/graphene composite nano-film electrode prepared in example five of the present invention;
fig. 8 is an SEM image of a polyaniline/graphene composite nano-film electrode prepared in example six of the present invention.
Detailed Description
The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example one
A preparation method of a polyaniline/graphene composite nano-film electrode comprises the following steps:
preparing a graphene dispersion liquid: uniformly mixing graphene, a first solvent and a surfactant to prepare a graphene dispersion liquid;
preparing an aniline solution: adding aniline into a solvent II, and stirring the solvent II to completely dissolve aniline into the solvent II to form a uniform aniline solution;
polymerization of aniline: dropwise adding an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; standing the graphene dispersion liquid to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid;
preparing a polyaniline/graphene composite nano-film electrode: and (3) depositing the polyaniline/graphene in the polyaniline/graphene dispersion solution on the surface of the negative electrode by an electrophoresis method to obtain a layer of uniform polyaniline/graphene composite nanosheets, nanospheres or compact nano-films.
Further, the preparation of the graphene dispersion liquid in the invention comprises the following steps: dissolving graphene in a first solvent, wherein the first solvent is ethanol or isopropanol, the isopropanol has a better dispersion effect, performing ultrasonic treatment on the first solvent by using an ultrasonic instrument, dropwise adding a surfactant into the first solvent, and performing ultrasonic treatment on the first solvent by using the ultrasonic instrument again to uniformly disperse the graphene in the first solvent to form a graphene dispersion solution.
Further, the preparation of the aniline solution in the invention comprises the following steps: slowly dripping aniline into a second solvent, and stirring the second solvent to completely dissolve the aniline into the second solvent to form a uniform and transparent aniline solution;
further, the polymerization of aniline in the present invention comprises the following steps: slowly dripping an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; standing the graphene dispersion liquid for 3 days to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid;
further, the preparation of the polyaniline/graphene composite nano-film electrode in the invention: carrying out ultrasonic treatment on the polyaniline/graphene dispersion liquid for 10min, then preparing a polyaniline/graphene composite film by using an electrophoresis method by taking a conductive substrate as a negative electrode in a working electrode and a copper sheet as a positive electrode in the working electrode; taking out the prepared polyaniline/graphene composite film electrode and naturally drying;
the conductive substrate is one of a copper sheet, a nickel sheet, a gold-plated plastic film and a nickel-plated plastic film, the gold-plated plastic film can be a gold-plated poly-terephthalic acid plastic film, and the nickel-plated plastic film can be a nickel-plated poly-terephthalic acid plastic film;
the voltage applied by the electrophoresis method is 10-60V, the distance between the anode and the cathode is 2-5 cm, the electrophoresis is carried out at room temperature, and the deposition time is 10-100 min.
Further, in the invention, the single-layer graphene powder is dissolved in the first solvent, the first solvent is subjected to ultrasonic treatment for 10min by an ultrasonic instrument, then the magnesium nitrate solution surfactant is dropwise added into the first solvent, the first solvent is subjected to ultrasonic treatment for 10min by the ultrasonic instrument again, so that the single-layer graphene powder is uniformly dispersed in the first isopropanol solution to form the graphene dispersion liquid, and the magnesium nitrate can charge the graphene, so that the graphene is easier to disperse.
Further, the second solvent is an isopropanol solution, the solubility of the prepared aniline solution is 0.05-1.0M/L, and the content of graphene in the prepared graphene dispersion liquid is 1-20 mg/L.
Furthermore, the surfactant is prepared by dissolving one or more of magnesium nitrate, sodium dodecyl sulfate and sodium dodecyl sulfate in isopropanol solution, and the concentration of the surfactant is 0.01-1 mM/L.
Further, in the step of polymerizing aniline, adding an acid solution into the graphene dispersion liquid, wherein the acid solution is one or more of a mixed solution of nitric acid and an isopropanol solution, a mixed solution of hydrochloric acid and an isopropanol solution, and a mixed solution of sulfuric acid and isopropanol; the concentration of the acid solution is 0.001-0.01 mM/L; the graphene dispersion may be allowed to stand for 8 hours to 30 days.
Further, the polyaniline/graphene composite nano-film electrode is formed by compounding graphene and a polyaniline nano-material, and the polyaniline nano-material is directly attached to the graphene nanosheet.
1 mg of single-layer graphene powder is weighed and dispersed in 100 mL of isopropanol solution, and the solution is fully dispersed by ultrasonic treatment for 10min by an ultrasonic instrument. Preparing 0.01M/L magnesium nitrate/isopropanol solution by using isopropanol, dropwise adding 2mL of magnesium nitrate/isopropanol solution into the graphene/isopropanol solution, stirring the graphene/isopropanol solution uniformly by using a glass rod, and then carrying out ultrasonic treatment on the graphene/isopropanol solution for 20 min by using an ultrasonic instrument to uniformly disperse graphene powder to obtain the graphene dispersion liquid. Preparing 1M/L aniline/isopropanol solution to obtain aniline solution, dropwise adding 10 mL aniline solution into the dispersed graphene dispersion liquid, uniformly stirring by using a glass rod, then carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument, and standing the graphene dispersion liquid for 1 day to ensure that aniline is fully polymerized on the surface of graphene to form the polyaniline/graphene dispersion liquid. And (3) carrying out ultrasonic treatment on the standing polyaniline/graphene dispersion liquid for 10min to uniformly disperse the polyaniline/graphene dispersion liquid. And then pouring the graphite electrode into an electrophoresis tank, taking gold-plated PET as a working electrode and a copper sheet as a working negative electrode, keeping the distance between the positive electrode and the negative electrode at 2 cm, adding 40V voltage for electrophoresis for 10min, taking out, and naturally drying to obtain the black graphene polyaniline composite film electrode. Fig. 1-1 is an SEM image of a polyaniline/graphene composite nano-film electrode prepared in example 1 of the present invention; fig. 1-2 is a schematic view of a cyclic voltammetry curve of a polyaniline/graphene composite nano-film electrode prepared in example 1 of the present invention measured in a 1M LiCl solution; fig. 1 to 3 are schematic diagrams of constant current charging and discharging curves of the polyaniline/graphene composite nano-film electrode prepared in example 1 of the present invention measured in a 1M LiCl solution.
Example two
Weighing 1 mg of single-layer graphene powder, dispersing the single-layer graphene powder in 100 mL of isopropanol solution, and performing ultrasonic treatment by using an ultrasonic instrument for 10min to fully disperse the single-layer graphene powder to obtain a graphene dispersion solution. Preparing 0.01M/L sodium dodecyl sulfate/isopropanol solution by using isopropanol, dropwise adding 2mL sodium dodecyl sulfate/isopropanol solution into the graphene dispersion liquid, stirring the graphene dispersion liquid uniformly by using a glass rod, and then ultrasonically treating the graphene dispersion liquid for 20 min by using an ultrasonic instrument to uniformly disperse the graphene. Preparing 1M/L aniline/isopropanol solution to obtain aniline solution, dropwise adding 10 mL aniline solution into the well-dispersed graphene dispersion liquid, stirring the graphene dispersion liquid uniformly by using a glass rod, then carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument, and standing the graphene dispersion liquid for 20 days to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid. And (3) carrying out ultrasonic treatment on the standing polyaniline/graphene dispersion liquid for 10min to uniformly disperse the graphene and the polyaniline. And then pouring the polyaniline/graphene dispersion liquid into an electrophoresis tank, taking a copper sheet as a positive electrode in a working electrode and a copper sheet as a working negative electrode, keeping the distance between the positive electrode and the negative electrode at 2 cm, adding 40V voltage for electrophoresis for 10min, taking out, and naturally drying to obtain the black polyaniline/graphene composite film electrode. Fig. 2 is an SEM picture of the polyaniline/graphene composite nano-film electrode prepared in example 2 of the present invention.
EXAMPLE III
1 mg of single-layer graphene powder is weighed and dispersed in 100 mL of isopropanol solution, and the solution is fully dispersed by ultrasonic treatment for 10min by an ultrasonic instrument. Preparing 0.01M/L sodium dodecyl sulfate/isopropanol solution by using isopropanol, dropwise adding 2mL sodium dodecyl sulfate/isopropanol solution into the graphene/isopropanol solution, uniformly stirring by using a glass rod, and then performing ultrasonic treatment for 20 min by using an ultrasonic instrument to uniformly disperse the solution. Preparing 1M/L aniline/isopropanol solution, dripping 10 mL of aniline/isopropanol solution into the dispersed graphene/isopropanol solution, stirring uniformly by using a glass rod, then carrying out ultrasonic treatment for 20 min by using an ultrasonic instrument, and standing for 20 days. And (4) carrying out ultrasonic treatment on the solution after standing for 10min to uniformly disperse the solution. And then pouring the polyaniline/graphene composite thin film electrode into an electrophoresis tank, taking gold-plated PET as a working electrode and a nickel sheet as a working negative electrode, keeping the distance between the positive electrode and the negative electrode at 2 cm, carrying out electrophoresis at 10V for 10min, taking out, and naturally drying to obtain the black polyaniline/graphene composite thin film electrode. Fig. 3 is an SEM picture of the polyaniline/graphene composite nano-film electrode prepared in example 3 of the present invention.
Example four
Weighing 1 mg of single-layer graphene powder, dispersing the single-layer graphene powder in 100 mL of isopropanol solution, and performing ultrasonic treatment by using an ultrasonic instrument for 10min to fully disperse the single-layer graphene powder. Preparing 0.01M/L magnesium nitrate/isopropanol solution by using isopropanol, dropwise adding 2mL of magnesium nitrate/isopropanol solution into the graphene/isopropanol solution, uniformly stirring by using a glass rod, and then carrying out ultrasonic treatment for 20 min by using an ultrasonic instrument to uniformly disperse single-layer graphene powder to form graphene dispersion liquid. Preparing 1M/L aniline/isopropanol solution to obtain aniline solution, dropwise adding 10 mL aniline solution into the well-dispersed graphene dispersion liquid, stirring the graphene dispersion liquid uniformly by using a glass rod, then carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument, and standing the graphene dispersion liquid for 20 days to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid. And (3) carrying out ultrasonic treatment on the standing polyaniline/graphene dispersion liquid for 10min to uniformly disperse the polyaniline/graphene dispersion liquid. And then pouring the polyaniline/graphene dispersion liquid into an electrophoresis tank, taking gold-plated PET as a working electrode and gold-plated poly-terephthalic acid plastic film as a working negative electrode, keeping the distance between the positive electrode and the negative electrode at 2 cm, carrying out electrophoresis at 40V for 30 min, taking out, and naturally drying to obtain the black polyaniline/graphene composite film electrode. Fig. 4 is an SEM picture of the polyaniline/graphene composite nano-film electrode prepared in example 4 of the present invention.
EXAMPLE five
1 mg of single-layer graphene powder is weighed and dispersed in 100 mL of isopropanol solution, and the solution is fully dispersed by ultrasonic treatment for 10min by an ultrasonic instrument. Preparing 0.01M/L magnesium nitrate/isopropanol solution by using isopropanol, dropwise adding 2mL of magnesium nitrate/isopropanol solution into the graphene/isopropanol solution, uniformly stirring by using a glass rod, and then performing ultrasonic treatment for 20 min by using an ultrasonic instrument to uniformly disperse the solution to obtain the graphene dispersion liquid. Preparing 1M/L aniline/isopropanol solution to obtain aniline solution, dropwise adding 10 mL aniline solution into the dispersed graphene dispersion liquid, stirring the graphene dispersion liquid uniformly by using a glass rod, then carrying out ultrasonic treatment for 20 min by using an ultrasonic instrument, and standing the graphene dispersion liquid for 3 days to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid. And (3) carrying out ultrasonic treatment on the standing polyaniline/graphene dispersion liquid for 10min to uniformly disperse the polyaniline/graphene dispersion liquid. And then pouring the polyaniline/graphene dispersion liquid into an electrophoresis tank, taking gold-plated PET as a working electrode and a copper sheet as a working negative electrode, keeping the distance between the positive electrode and the negative electrode at 2 cm, carrying out electrophoresis at 40V for 10min, taking out, and naturally drying to obtain the black polyaniline/graphene composite film electrode. Fig. 5 is an SEM picture of the polyaniline/graphene composite nano-film electrode prepared in example 5 of the present invention.
EXAMPLE six
1 mg of single-layer graphene powder is weighed and dispersed in 100 mL of isopropanol solution, and the solution is fully dispersed by ultrasonic treatment for 10min by an ultrasonic instrument. Preparing 0.01M/L magnesium nitrate/isopropanol solution by using isopropanol, dropwise adding 2mL of magnesium nitrate/isopropanol solution into the graphene/isopropanol solution, uniformly stirring by using a glass rod, and then performing ultrasonic treatment for 20 min by using an ultrasonic instrument to uniformly disperse the solution to obtain the graphene dispersion liquid. Preparing 1M/L aniline/isopropanol solution to obtain aniline solution, dropwise adding 10 mL aniline solution into the well-dispersed graphene dispersion liquid, stirring the graphene dispersion liquid uniformly by using a glass rod, then carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument, and standing the graphene dispersion liquid for 3 days to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid. And (3) carrying out ultrasonic treatment on the standing polyaniline/graphene dispersion liquid for 10min to uniformly disperse the polyaniline/graphene dispersion liquid. And then pouring the polyaniline/graphene dispersion liquid into an electrophoresis tank, taking nickel-plated PET as a working electrode and a nickel-plated poly-p-phthalic acid plastic film as a working negative electrode, keeping the distance between the positive electrode and the negative electrode at 2 cm, carrying out electrophoresis at 40V for 10min, taking out, and naturally drying to obtain the black polyaniline/graphene composite film electrode. Fig. 6 is an SEM picture of the polyaniline/graphene composite nano-film electrode prepared in example 6 of the present invention.
In the method, the concentration of the dispersion liquid, the standing time, the electrophoresis voltage, the electrophoresis time, the substrate and the like have certain influence on the thickness and the appearance of the polyaniline/graphene composite film, and for example, as the standing days increase, polyaniline attached to the surface of the graphene has fine nano-sheets which are gradually converted into a compact film. The above examples describe in detail preferred embodiments of the invention. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several modifications and modifications (such as dispersion type, solution concentration, ultrasonic time, solution standing time, electrophoresis voltage, electrophoresis time, two-electrode distance, substrate type, etc.) can be made to the method of the present invention, and these modifications and modifications also fall into the protection scope of the present invention.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a polyaniline/graphene composite nano-film electrode is characterized by comprising the following steps:
preparing a graphene dispersion liquid: uniformly mixing graphene, a first solvent and a surfactant to prepare a graphene dispersion liquid;
preparing an aniline solution: adding aniline into a solvent II, and stirring the solvent II to completely dissolve aniline into the solvent II to form a uniform aniline solution;
polymerization of aniline: dropwise adding an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; standing the graphene dispersion liquid to ensure that aniline is fully polymerized on the surface of graphene to form polyaniline/graphene dispersion liquid;
preparing a polyaniline/graphene composite nano-film electrode: depositing polyaniline/graphene in the polyaniline/graphene dispersion solution on the surface of the negative electrode by an electrophoresis method to obtain a layer of uniform polyaniline/graphene composite nanosheets, nanospheres or compact nano films;
the preparation of the graphene dispersion liquid comprises the following steps: dissolving graphene in a first solvent, wherein the first solvent is ethanol or isopropanol, performing ultrasonic treatment on the first solvent by using an ultrasonic instrument, dropwise adding a surfactant into the first solvent, and performing ultrasonic treatment on the first solvent again by using the ultrasonic instrument to uniformly disperse the graphene in the first solvent to form a graphene dispersion solution;
the second solvent is an isopropanol solution, the solubility of the prepared aniline solution is 0.05-1.0M/L, and the content of graphene in the prepared graphene dispersion liquid is 1-20 mg/L;
the surfactant is prepared by dissolving one or more of magnesium nitrate, sodium dodecyl sulfate and sodium dodecyl sulfate in isopropanol solution, and the concentration of the surfactant is 0.01-1 mM/L.
2. The preparation method of the polyaniline/graphene composite nano-film electrode according to claim 1, wherein the single-layer graphene powder is dissolved in the first solvent, the first solvent is subjected to ultrasonic treatment by an ultrasonic instrument for 10min, then a magnesium nitrate solution surfactant is added into the first solvent, the first solvent is subjected to ultrasonic treatment by the ultrasonic instrument for 10min again, and the single-layer graphene powder is uniformly dispersed in the first isopropanol solution to form a graphene dispersion solution;
the preparation of the aniline solution comprises the following steps: slowly dripping aniline into the solvent II, and stirring the solvent II to completely dissolve aniline into the solvent II to form a uniform and transparent aniline solution.
3. The method for preparing the polyaniline/graphene composite nano-film electrode according to claim 1, wherein the polymerization of aniline comprises the following steps: slowly dripping an aniline solution into the graphene dispersion liquid, uniformly stirring the graphene dispersion liquid, and carrying out ultrasonic treatment on the graphene dispersion liquid for 20 min by using an ultrasonic instrument to fully disperse the graphene dispersion liquid; and standing the graphene dispersion liquid for 3 days to ensure that aniline is fully polymerized on the surface of the graphene to form the polyaniline/graphene dispersion liquid.
4. The method for preparing the polyaniline/graphene composite nano-film electrode according to claim 1, wherein the steps of preparing the polyaniline/graphene composite nano-film electrode are as follows: carrying out ultrasonic treatment on the polyaniline/graphene dispersion liquid for 10min, then preparing a polyaniline/graphene composite film by using an electrophoresis method by taking a conductive substrate as a negative electrode in a working electrode and a copper sheet as a positive electrode in the working electrode; taking out the prepared polyaniline/graphene composite film electrode and naturally drying;
the conductive substrate is one of a copper sheet, a nickel sheet, a gold-plated plastic film and a nickel-plated plastic film;
the voltage applied by the electrophoresis method is 10-60V, the distance between the anode and the cathode is 2-5 cm, the electrophoresis is carried out at room temperature, and the deposition time is 10-100 min.
5. The method for preparing a polyaniline/graphene composite nano-film electrode as claimed in claim 1, wherein in the step of polymerizing aniline, one or more of an acid solution is added to the graphene dispersion, wherein the acid solution is a mixed solution of nitric acid and isopropanol solution, a mixed solution of hydrochloric acid and isopropanol solution, and a mixed solution of sulfuric acid and isopropanol solution; the concentration of the acid solution is 0.001-0.01 mM/L; and standing the graphene dispersion liquid for 8 hours to 30 days.
6. The polyaniline/graphene composite nano-film electrode prepared by the method of claim 1, wherein the polyaniline/graphene composite nano-film electrode is formed by compounding graphene and polyaniline nano-materials, and the polyaniline nano-materials are directly attached to graphene nano-sheets.
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