CN111128472B - Method for preparing conductive polymer film on graphene surface through electrodeposition - Google Patents
Method for preparing conductive polymer film on graphene surface through electrodeposition Download PDFInfo
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- CN111128472B CN111128472B CN201911305221.9A CN201911305221A CN111128472B CN 111128472 B CN111128472 B CN 111128472B CN 201911305221 A CN201911305221 A CN 201911305221A CN 111128472 B CN111128472 B CN 111128472B
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Abstract
The invention discloses a method for preparing a conductive polymer film on the surface of graphene by electrodeposition. The preparation method comprises the steps of directly depositing a conductive polymer film with submicron-order thickness on the surface of powder by an electrodeposition method, directly dispersing graphene into corresponding monomer solution of the conductive polymer, carrying out electrodeposition preparation by a three-electrode system under uniform stirring, taking a platinum sheet as a working electrode and a platinum net as an auxiliary electrode, applying an anode potential on the working electrode to generate corresponding free radicals of the monomer, enabling the graphene powder to collide and contact with the platinum electrode, and depositing the conductive polymer on the surface of the graphene by a free radical polymerization reaction. The conductive polymer film prepared by the method has good binding force with graphene, and the defect that the conductive polymer is difficult to directly deposit on the surface of the common graphene in the traditional technology is overcome. The graphene modified by the conductive polymer film is expected to be applied to the fields of metal corrosion and protection, supercapacitors, industrial analysis and separation and the like.
Description
Technical Field
The invention relates to surface modification of graphene, in particular to a method for preparing a conductive polymer film on the surface of graphene by direct electrodeposition, which has good binding force and adjustable thickness.
Background
Graphene is a novel and popular two-dimensional carbon nanomaterial in recent years, and is widely applied to various fields such as supercapacitors, electrochemical sensors, photocatalysis, nano drug loading, metal corrosion and protection and the like due to excellent mechanical properties, good conductivity, super large theoretical specific surface area, excellent shielding performance and the like. However, due to the defects of smooth surface, lack of active sites, high chemical inertness, poor dispersibility in water and the like, the common graphene can only break through the application limit by adopting a surface chemical modification method. At present, most of graphene surface modification is realized by taking graphene oxide or reduced graphene oxide as a raw material and realizing load modification through rich oxygen-containing functional groups on the graphene oxide or reduced graphene oxide. The direct surface modification of graphene through approaches such as thin film deposition and molecular modification is very little.
The conductive polymer integrates the characteristics of metal and polymer, has excellent conductive capability, good photoelectric property, simple and convenient synthesis, controllable appearance, low cost, environment friendliness and unique redox characteristics, and is widely applied to the fields of supercapacitors, metal corrosion and protection, electrocatalysis, electrochemical analysis sensing and the like. However, the conductive polymer is too weak in mechanical toughness in a neutral state to be useful for applications, and thus, the conductive polymer forms a complex with other functional materials to be useful for extending the functions of the conductive polymer and improving its performance in applications. In the electrochemical or in-situ chemical polymerization process of the conductive polymer, pi-pi interaction exists between the conductive polymer and the carbon material, so that the conductive polymer can easily realize uniform coating of the nano carbon material. However, no matter chemical polymerization or electropolymerization, most of the current composite materials of the conductive polymer and the graphene are compounded with graphene oxide or reduced graphene oxide, and a large amount of powder-grade conductive polymer-graphene composite materials prepared directly on common graphene are not reported.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a method for preparing a conductive polymer film on the surface of graphene by electrodeposition, namely a preparation method for directly growing a conductive polymer film with good bonding force and controllable morphology and thickness on the surface of graphene.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a conductive polymer film on the surface of graphene by electrodeposition comprises the following steps:
1) preparing a deposition precursor solution: adding an organic solvent with the volume ratio of 0.3-1.3 to deionized water, 0.05-3M of conductive polymer monomer solution and 0.5-2M of inorganic acid, and uniformly stirring for later use;
2) adding the prepared deposition precursor solution into a three-electrode electrolytic tank, adding 1-100 mg/mL of graphene, and ultrasonically stirring uniformly, wherein Ag/AgCl is used as a reference electrode, a platinum sheet is used as a working electrode, and a platinum net is used as a counter electrode;
3) carrying out electrodeposition under the condition of keeping stirring, wherein the deposition temperature is 20-60 ℃;
4) washing the deposition product with deionized water and ethanol, and centrifugally drying, wherein the centrifugal separation speed of the deposition product is 1000-10000 rpm, the centrifugal time is 1-10 min, and the drying temperature of the deposition product is 50-100 ℃.
The organic solvent is one or more of ethanol, methanol, N-dimethylformamide, tetrahydrofuran, acetonitrile and 1, 4-dioxane.
The conductive polymer monomer solution is one or more of aniline, pyrrole, thiophene and pyridine.
The inorganic acid is one or more of hydrochloric acid, sulfuric acid, phosphoric acid and perchloric acid.
The electrodeposition is anodic electrodeposition, and the deposition potential is 0.5-1.5V.
The deposition time of the electrodeposition is 5-60 min.
The invention has the beneficial effects that: compared with the existing method for depositing the conductive polymer on the surface of the graphene oxide or the reduced graphene oxide by adopting a chemical polymerization method, the method realizes that the conductive polymer film with controllable thickness and appearance and good binding force is electrodeposited on the common graphene in one step, and is expected to be applied to industrial batch production.
Drawings
FIG. 1 is SEM photographs of graphene before (a) and after (b) polypyrrole electrodeposition;
fig. 2 is a fourier infrared spectrum of graphene (bottom) and polypyrrole-loaded graphene (top) after electrodeposition.
Detailed Description
The invention discloses a method for preparing a conductive polymer/graphene powder composite nano material by direct electrodeposition on the surface of graphene. The preparation method comprises the steps of directly depositing a conductive polymer film with submicron-order thickness on the surface of powder by an electrodeposition method, directly dispersing graphene into corresponding monomer solution of the conductive polymer, carrying out electrodeposition preparation by a three-electrode system under uniform stirring, taking a platinum sheet as a working electrode and a platinum net as an auxiliary electrode, applying an anode potential on the working electrode to generate corresponding free radicals of the monomer, enabling the graphene powder to collide and contact with the platinum electrode, and depositing the conductive polymer on the surface of the graphene by a free radical polymerization reaction. The possible working principle of the method is that the graphene nanosheet in the solution collides with the working electrode (Pt sheet) to realize electric contact, so that electrochemical polymerization reaction can occur on the surface of graphene.
Compared with the conventional chemical polymerization and electrochemical polymerization conductive polymers, the conductive polymer film prepared by the method has good binding force with graphene, and solves the problem that the conventional technology can only deposit the conductive polymer on the surface of graphene oxide or reduced graphene oxide and is difficult to directly deposit the conductive polymer on the surface of the common graphene, and the method is simple, controllable, environment-friendly, safe and low in cost, and is expected to realize large-scale industrial application.
Example 1
Electropolymerization of pyrroles on graphene powder
1) Preparing a precursor solution: adding 50 mL of deionized water and 50 mL of ethanol into a 50 mL small beaker, preparing 1M concentration by using a proper amount of concentrated phosphoric acid, preparing 0.2M concentration by using a proper amount of pyrrole monomer, and uniformly stirring for later use;
2) adding graphene into the precursor solution to enable the concentration of the graphene to be 0.1 mg/mL, carrying out ultrasonic treatment for 10 min to uniformly disperse the graphene, wherein the ultrasonic power is 150W, Ag/AgCl is used as a reference electrode, a platinum sheet is used as a working electrode, a platinum net is used as a counter electrode, the electrodeposition potential is 1V, the deposition time is 30 min, and the deposition temperature is 25 ℃;
3) cleaning with ethanol for three times after deposition, centrifuging at 9000 rpm for 10 min, and oven drying at 80 deg.C
Scanning Electron Microscope (SEM) observation and Fourier infrared spectrum test are carried out on the obtained sample, and as is obvious from the attached figure 1, the surface of the polypyrrole on the electrodeposition in the figure 1b is rougher than that of the original graphene, and the thickness of the polypyrrole is near 300 nm, which shows that the polypyrrole is successfully coated on the graphene with the method. The relevant vibration peaks of phosphate anions and pyrrole can be seen from the Fourier infrared spectrum of FIG. 2, which indicates that the polypyrrole-graphene composite material doped with phosphate anions is prepared by electrodeposition on the surface of graphene.
Example 2
Changing the concentration of pyrrole monomer in example 1, replacing phosphoric acid with sulfuric acid, replacing ethanol in the solvent with N, N-dimethylformamide of the same volume, removing water from the obtained sample powder at a high temperature of 120 ℃ for 2 days, weighing the sample mass, calculating the loading amount of polypyrrole, and counting the thickness of the nano oxide film on the graphene under a scanning electron microscope, wherein the test results are shown in table 1.
TABLE 1 graphene-polypyrrole composite nanomaterial monomer concentration impact test results
| Pyrrole monomer concentration (M) | Graphene quality (g) | Product quality (g) | Conductive Polymer Loading (g) | Average thickness (nm) |
| 0.05 | 0.0020 | 0.0304 | 0.0284 | 289 |
| 0.10 | 0.0020 | 0.0322 | 0.0302 | 306 |
| 0.15 | 0.0021 | 0.0361 | 0.0340 | 322 |
| 0.20 | 0.0019 | 0.0363 | 0.0344 | 330 |
Changing the deposition potential of the electrodeposition in the example 1, wherein the deposition time is still 30 min, replacing the inorganic acid with hydrochloric acid, replacing ethanol in the solvent with methanol, removing water from the obtained sample powder in an oven at 120 ℃ for 2 days at a high temperature, weighing the sample mass, calculating the loading amount of polypyrrole, and counting the thickness of the nano oxide film on the graphene under a scanning electron microscope, wherein the test results are shown in table 2.
TABLE 2 graphene-polypyrrole composite nanomaterial deposition potential impact test results
| Potential for deposition | Graphene quality (g) | Product quality (g) | Conductive Polymer Loading (g) | Average thickness (nm) |
| 0.8 | 0.0021 | 0.0315 | 0.0294 | 302 |
| 1.0 | 0.0022 | 0.0342 | 0.0320 | 325 |
| 1.2 | 0.0020 | 0.0363 | 0.0343 | 313 |
| 1.4 | 0.0019 | 0.0362 | 0.0343 | 306 |
Example 4
Changing the electrodeposition time in example 1, the deposition potential is still 1.0V, replacing the inorganic acid with perchloric acid, replacing ethanol in the solvent with tetrahydrofuran of the same volume, removing water in the obtained sample powder in an oven at 120 ℃ for 2 days at high temperature, weighing the sample mass, calculating the loading amount of polypyrrole, and counting the thickness of the nano oxide film on the graphene under a scanning electron microscope, wherein the test results are shown in table 3.
TABLE 3 graphene-polypyrrole composite nanomaterial deposition time impact test results
| Deposition time (min) | Graphene quality (g) | Product quality (g) | Conductive Polymer Loading (g) | Average thickness (nm) |
| 10 | 0.0020 | 0.0256 | 0.0236 | 196 |
| 20 | 0.0023 | 0.0289 | 0.0266 | 210 |
| 30 | 0.0019 | 0.0322 | 0.0303 | 306 |
| 40 | 0.0021 | 0.0350 | 0.0329 | 325 |
Example 5
Changing 0.2M pyrrole monomer in example 1 into 0.2M aniline monomer and 0.2M thiophene monomer, preparing graphene-polyaniline and graphene-polythiophene composite materials, removing water from the obtained sample powder in an oven at 120 ℃ for 2 days at high temperature, weighing sample mass, respectively calculating the load of two conductive polymers, and counting the thickness of the nano oxide film on the graphene under a scanning electron microscope, wherein the test results are shown in Table 4.
TABLE 4 graphene-conducting polymer composite nanomaterial test results
| Species of conductive polymers | Graphene quality (g) | Product quality (g) | Conductive Polymer Loading (g) | Average thickness (nm) |
| Polyaniline (PANI) | 0.0021 | 0.0240 | 0.0219 | 95 |
| Polythiophenes | 0.0022 | 0.0320 | 0.0298 | 269 |
The above-described embodiments are intended to be illustrative, rather than restrictive, of the present invention, and any modifications and variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.
Claims (6)
1. A method for preparing a conductive polymer/graphene powder composite nano material by direct electrodeposition on the surface of graphene is characterized by comprising the following steps:
1) preparing a deposition precursor solution: adding an organic solvent with the volume ratio of 0.3-1.3 to deionized water, 0.05-3M of conductive polymer monomer solution and 0.5-2M of inorganic acid, and uniformly stirring for later use;
2) adding the prepared deposition precursor solution into a three-electrode electrolytic tank, adding 1-100 mg/mL of graphene, and ultrasonically stirring uniformly, wherein Ag/AgCl is used as a reference electrode, a platinum sheet is used as a working electrode, and a platinum net is used as a counter electrode;
3) carrying out electrodeposition under the condition of keeping stirring, wherein the deposition temperature is 20-60 ℃;
4) washing the deposition product with deionized water and ethanol, and centrifugally drying, wherein the centrifugal separation speed of the deposition product is 1000-10000 rpm, the centrifugal time is 1-10 min, and the drying temperature of the deposition product is 50-100 ℃.
2. The method according to claim 1, wherein the organic solvent is one or more of ethanol, methanol, N-dimethylformamide, tetrahydrofuran, acetonitrile, 1, 4-dioxane.
3. The method according to claim 1, wherein the conductive polymer monomer solution is one or more of aniline, pyrrole, thiophene and pyridine.
4. The method according to claim 1, wherein the inorganic acid used is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid.
5. The method according to claim 1, wherein the electrodeposition is anodic electrodeposition and the deposition potential is 0.5 to 1.5V.
6. The method according to claim 1, wherein the electrodeposition time is 5 to 60 min.
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