CN112625440B - High-conductivity polyaniline-graphene composite material and preparation method and application thereof - Google Patents
High-conductivity polyaniline-graphene composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-conductivity polyaniline-graphene composite material and a preparation method and application thereof, wherein methyl methacrylate and an auxiliary comonomer methacryloyloxyethyl trimethyl ammonium chloride are copolymerized in a suspension polymerization manner, and simultaneously graphene oxide and a copolymerization product are added in situ to realize compounding; adding the prepared polymethyl methacrylate/methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide composite material into an aniline polymerization reaction system, and etching and reducing the product to obtain the polyaniline-graphene composite material. According to the invention, the graphene filler is added into the polyaniline for compounding, so that the electrical property is greatly improved compared with pure polyaniline, the method successfully improves the dispersibility of the graphene in the matrix, and the problem of the polyaniline material in the aspect of electrical property is solved.
Description
Technical Field
The invention relates to the technical field of composite conductive materials, in particular to a high-conductivity polyaniline-graphene composite material and a preparation method and application thereof.
Background
Polyaniline (PANI) is a semi-flexible conductive polymer with unique electrical and optical properties. Compared with the traditional polymer, the conjugated structure on the PANI molecular chain endows the PANI with unique electrical properties, the conductivity and electrochemical properties of the PANI can be obviously improved after the PANI molecular chain is subjected to treatment such as doping and the like, the PANI has good application prospect for preparing the conductive polymer, and the PANI molecular chain draws strong attention of the scientific community once being discovered, and is one of the most researched conductive polymers in recent decades. PANI is now widely used in applications such as electromagnetic interference shielding, rechargeable batteries, photovoltaic cells, chemical sensors, gas separation membranes, etc. In addition, compared with other conductive polymers, PANI has wide applications in the fields of secondary batteries, supercapacitors, biological/chemical sensors, organic light emitting diodes and the like due to its low cost, readily available raw materials, easy synthesis, good environmental stability and high conductivity.
PANI, however, has low electrical conductivity compared to metals and poor mechanical properties and processability, and thus it is often necessary to modify it. Graphene has great potential as a filler of a composite material, and can improve the mechanical, electrical and thermal properties of a polymer matrix. The graphene is added into the PANI matrix as a conductive nano filler, so that the conductivity of the PANI can be obviously improved. However, due to the characteristic of easy agglomeration of the nanofiller, the nanofiller usually needs to be organically modified before being used, so that the preparation process of the composite material is more complicated and the preparation process is more tedious, and meanwhile, the performance of the composite material can be influenced by the addition of the modifier. These side effects can add to a large extent economic costs for industrial production.
Disclosure of Invention
The invention aims to provide a high-conductivity polyaniline-graphene composite material aiming at the problems of complex process and poor product performance of a PANI composite material prepared by modifying a nano filler in the prior art, and the composite material has good conductivity. On the premise of not carrying out organic modification on the nano filler, the composite material with excellent performance is obtained.
According to the preparation method of the high-conductivity polyaniline-graphene composite material, based on the fact that the surface charge of GO is electronegative, methacryloyloxyethyl trimethyl ammonium chloride (MTC) with positive charges is used as an auxiliary monomer to be copolymerized with Methyl Methacrylate (MMA), the control of the charge environment of a matrix is achieved, GO nano fillers are added to conduct polymerization, composite microspheres obtained through polymerization are used as templates, an aniline polymerization system is introduced to prepare the PANI-graphene composite material, and the influence of the addition amount of graphene and different preparation methods on the performance of the composite material is researched
In another aspect of the present invention, an application of the highly conductive polyaniline-graphene composite material is provided.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the preparation method of the high-conductivity polyaniline-graphene composite material comprises the following steps:
and 2, uniformly mixing a dispersing agent, a surfactant, methyl methacrylate and the ultrasonic dispersion liquid obtained in the step 1 to obtain a reaction system, placing the reaction system in an inert gas atmosphere, heating to a temperature higher than the temperature of an initiator, adding the initiator to initiate polymerization, carrying out polymerization reaction, filtering, washing and drying to obtain methyl methacrylate-methacryloyloxyethyl trimethylammonium chloride-graphene oxide copolymer powder P (MMA-co-MTC)/GO, which is marked as P (M-M)/GO. As shown in fig. 4, P (M-M)/GO is in a smooth composite microsphere shape in the microstructure, the microspheres are gathered together, and GO is coated in the composite microsphere.
And 3, dissolving an aniline monomer in a hydrochloric acid solution, adding the methyl methacrylate-methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide copolymer powder obtained in the step 2, uniformly mixing, continuously stirring, adding an initiator to initiate polymerization, filtering, washing and drying to obtain a polyaniline-polymethyl methacrylate/methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide composite product PANI-P (MMA-co-MTC)/GO. As shown in fig. 5, PANI generated after polymerization of aniline monomer is wrapped on the surface of P (M-M)/GO microsphere.
And 4, dissolving the composite product obtained in the step 3 in an organic solvent, continuously stirring, filtering, washing and drying after the composite product is dissolved, and obtaining a dried product: polyaniline-graphene oxide composite PANI-GO. In the process, P (M-M) in the center is dissolved in an organic solvent to obtain GO wrapped by PANI, and when PMMA is etched away, the GO is built on the inner side of the PANI structure.
And 5, adding the dried product and a reducing agent into water, heating and continuously stirring, and filtering, washing and drying the product after the reaction is finished to obtain the polyaniline-graphene composite material PANI-rGO, wherein the PANI-rGO is in a petal-shaped appearance, and petal-shaped structures are mutually overlapped.
In the above technical scheme, the addition amount of the graphene oxide is 1 wt% -5 wt%, preferably 2 wt% of the addition amount of the aniline monomer.
In the above technical scheme, in the reaction system in step 2, two monomers, namely methacryloyloxyethyl trimethyl ammonium chloride and methyl methacrylate, form an oil phase, the amount of the methyl methacrylate monomer is 90-97 wt% of the mass of the oil phase, the amount of the methacryloyloxyethyl trimethyl ammonium chloride is 3-10 wt% of the mass of the oil phase, water, graphene oxide, a dispersant and a surfactant form a water phase, and the volume ratio of the water phase to the oil phase is 2.5-4.5.
In the technical scheme, the mass of the dispersing agent in the step 2 is 2.5-3 wt% of the mass of the oil phase, the dosage of the surfactant is 0.1-0.15 wt% of the mass of the oil phase, the mass of the graphene oxide in the step 1 is 0.0l-2.0 wt% of the mass of the oil phase, and the mass of the graphene oxide in the copolymer powder added in the step 3 is 1.0-5.0 wt% of the mass of the aniline monomer in the step 3.
In the above technical solution, the dispersant in step 2 is basic magnesium carbonate, calcium hydroxy phosphate (HAP), hydroxyethyl cellulose (HEC) or tricalcium phosphate, preferably hydroxyethyl cellulose (HEC).
In the above technical solution, the surfactant in step 2 is Sodium Dodecyl Benzene Sulfonate (SDBS), Sodium Dodecyl Sulfate (SDS), or sodium glycocholate, and is preferably Sodium Dodecyl Benzene Sulfonate (SDBS).
In the above technical scheme, the initiator in step 2 is Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), Benzoyl Peroxide (BPO) or bis (2-Ethyl) Hexyl Peroxydicarbonate (EHP), preferably Benzoyl Peroxide (BPO).
In the above technical solution, the inert gas in step 2 is nitrogen, helium or argon, preferably nitrogen.
In the technical scheme, the temperature of the initiator in the step 2 is 70-80 ℃, and the polymerization reaction time is 5-8 hours. The polymerization time is determined according to the amount of reactants, and the polymerization reaction is long enough to ensure that the two monomers realize higher conversion rate during copolymerization.
In the above technical scheme, the polymerization reaction time in step 3 is preferably 24 hours, and the initiator is potassium persulfate (KPS) or Ammonium Persulfate (APS), preferably Ammonium Persulfate (APS).
In the above technical solution, the organic solvent in step 4 is acetone, ethyl acetate, dichloromethane or chloroform, preferably dichloromethane.
In the above technical scheme, the reducing agent in step 5 is vitamin C, the temperature is increased to 80-95 ℃, preferably 90 ℃, and the stirring is continued for 1-2 hours, preferably 1.5 hours.
On the other hand, the high-conductivity polyaniline-graphene composite material prepared by the preparation method is provided.
In the above technical scheme, the high-conductivity polyaniline-graphene composite material is a network structure formed by overlapping petal-shaped structures.
In the technical scheme, the resistivity of the high-conductivity polyaniline-graphene composite material is 0.008-3.02k omega-cm, and the conductivity is 3.310-1250 multiplied by 10 -4 S/cm, when the addition amount of the graphene oxide is 2 wt% of that of the aniline monomer, the resistivity of the high-conductivity polyaniline-graphene composite material is 0.008 kOmega-cm, and the conductivity is 1250 multiplied by 10 -4 S/cm。
In another aspect of the present invention, the application of the highly conductive polyaniline-graphene composite material in electromagnetic interference shielding, rechargeable batteries, photovoltaic cells, chemical sensors or gas separation membranes is also included.
In another aspect of the present invention, the application of methyl methacrylate and methacryloyloxyethyl trimethyl ammonium chloride in the preparation of the high-conductivity polyaniline-graphene composite material is further included, wherein the mass ratio of the methyl methacrylate to the methacryloyloxyethyl trimethyl ammonium chloride is (90-97): (3-10).
Compared with the prior art, the invention has the beneficial effects that:
1. according to the technical scheme, an auxiliary monomer methacryloyloxyethyl trimethyl ammonium chloride with positive charges is copolymerized with methyl methacrylate to realize regulation and control of a matrix charge environment, graphene oxide with negative charges is introduced into a matrix, dispersion of the graphene oxide in a copolymer matrix is promoted through electrostatic interaction, the prepared polymethyl methacrylate/methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide is introduced into an aniline polymerization system as a template, and the prepared composite material is etched and reduced to finally obtain the polyaniline-graphene composite material.
2. The reaction process of the invention does not involve the modification of the nano-filler, and the obtained polyaniline-graphene composite material has excellent performance and simple and easy preparation process.
3. The polyaniline-graphene composite material prepared by the technical scheme successfully improves the dispersion condition of graphene in a polymer matrix, and greatly improves the conductivity.
Drawings
FIG. 1 is an XPS spectrum of the product before and after GO reduction.
FIG. 2 is a Raman spectrum of the product before and after GO reduction.
FIG. 3 is an XRD spectrum of the product before and after GO reduction.
FIG. 4 is a scanning morphology of the PMMA/TMAC-graphene oxide composite microspheres prepared in the examples.
FIG. 5 is a scanning morphology of the polyaniline-poly (methyl methacrylate)/poly (methacryloyloxyethyl trimethyl ammonium chloride) -graphene oxide composite prepared in example 2.
FIG. 6 is a scanning topography of the PANI/rGO composite prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
According to the invention, based on the fact that the surface charge of GO is electronegative, methacryloyloxyethyl trimethyl ammonium chloride (MTC) with positive charges is used as an auxiliary monomer to be copolymerized with Methyl Methacrylate (MMA), the control of the charge environment of a substrate is realized, GO nano fillers are added to carry out polymerization, composite microspheres obtained by polymerization are used as templates, an aniline polymerization system is introduced to prepare the PANI-graphene composite material, and the influence of the addition amount of graphene and different preparation methods on the performance of the composite material is researched.
Example 1 (graphene oxide added in an amount of 1 wt% based on the amount of aniline added)
(1) 3.7736g of GO dispersion (1.59 wt%) and 3.0g of MTC were added to 50mL of deionized water and ultrasonically dispersed; 0.9g of hydroxyethyl cellulose (HEC) and 0.036g of Sodium Dodecylbenzenesulfonate (SDBS) were added to 100mL of deionized water, mixed, and then added to a three-necked flask, and stirred at a low speed of 400 r/min. Sequentially adding 27.0g of MMA monomer, GO subjected to ultrasonic dispersion and MTC suspension into a three-neck bottle, heating to 75 ℃, continuously maintaining inert atmosphere, adding 0.3g of Benzoyl Peroxide (BPO) to initiate polymerization, and adjusting the rotating speed to 700 r/min; after reacting for 6 hours, stopping heating, and continuing stirring; after 30min, reducing the rotating speed to 400 r/min; the reaction was complete after 15 min. Cooling and filtering the reaction system, repeatedly washing and filtering the product by deionized water, and drying the product at 50 ℃ in vacuum to constant weight to obtain a P (MMA-co-MTC)/GO nano composite, which is recorded as P (M-M)/GO, wherein the mass percent of graphene oxide in the prepared P (M-M)/GO is 0.2 wt%;
(2) 0.3g of aniline monomer was added to 80mL of hydrochloric acid solution. Adding 1.5g P (M-M)/GO composite microspheres into the solution, adding 0.45g of Ammonium Persulfate (APS) to initiate polymerization, continuously stirring for 24h at room temperature, finishing the reaction, filtering and drying to obtain a PANI-P (MMA-co-MTC)/GO nano composite; dissolving the dried product in 100mL of dichloromethane, continuously stirring for 3h, repeatedly washing the filtered product with dichloromethane, and vacuum drying at 50 ℃ to constant weight; 0.02g of vitamin C is dissolved in 60mL of deionized water, the dried product is added, and the reaction is finished after stirring for 1.5h at 90 ℃. And cooling and filtering the reaction system, and drying the reaction system at 50 ℃ in vacuum to constant weight to obtain the PANI-rGO nano composite, which is marked as PANI-rGO-1.
Example 2 (graphene oxide added in an amount of 2 wt% based on the amount of aniline added)
(1) 3.7736g of GO dispersion (1.59 wt%) and 3.0g of MTC were added to 50mL of deionized water and ultrasonically dispersed; 0.9g HEC and 0.036g SDBS were added to 100mL deionized water, mixed and added to a three-necked flask and stirred at a low speed of 400 r/min. Sequentially adding 27.0g of MMA monomer, GO subjected to ultrasonic dispersion and MTC suspension into a three-neck bottle, heating to 75 ℃, continuously maintaining inert atmosphere, adding 0.3g of BPO to initiate polymerization, and adjusting the rotating speed to 700 r/min; after reacting for 6 hours, stopping heating, and continuing stirring; after 30min, reducing the rotating speed to 400 r/min; the reaction was complete after 15 min. Cooling and filtering the reaction system, repeatedly washing and filtering the product by deionized water, and drying the product at 50 ℃ in vacuum to constant weight to obtain a P (MMA-co-MTC)/GO nano composite, which is recorded as P (M-M)/GO, wherein the mass percent of graphene oxide in the prepared P (M-M)/GO is 0.2 wt%;
(2) 0.3g of aniline monomer was added to 80mL of hydrochloric acid solution. Adding 3.0g P (M-M)/GO composite microspheres into the solution, adding 0.45g APS to initiate polymerization, continuously stirring for 24h at room temperature, ending the reaction, filtering and drying to obtain PANI-P (MMA-co-MTC)/GO nano composite; dissolving the dried product in 100mL of dichloromethane, continuously stirring for 3h, repeatedly washing the filtered product with dichloromethane, and vacuum drying at 50 ℃ to a constant weight; 0.04g of vitamin C is dissolved in 60mL of deionized water, and the dried product is added and stirred at 90 ℃ for 1.5h, thus completing the reaction. And cooling and filtering the reaction system, and drying the reaction system at 50 ℃ in vacuum to constant weight to obtain the PANI-rGO nano composite, which is marked as PANI-rGO-2. .
Example 3 (graphene oxide added in an amount of 3 wt% based on the amount of aniline added)
(1) 3.7736g of GO dispersion (1.59 wt%) and 3.0g of MTC were added to 50mL of deionized water and ultrasonically dispersed; 0.9g HEC and 0.036g SDBS were added to 100mL deionized water, mixed and added to a three-necked flask and stirred at a low speed of 400 r/min. Sequentially adding 27.0g of MMA monomer, GO subjected to ultrasonic dispersion and MTC suspension into a three-neck bottle, heating to 75 ℃, continuously maintaining inert atmosphere, adding 0.3g of BPO to initiate polymerization, and adjusting the rotating speed to 700 r/min; after reacting for 6 hours, stopping heating, and continuing stirring; after 30min, reducing the rotating speed to 400 r/min; the reaction was complete after 15 min. Cooling and filtering the reaction system, repeatedly washing and filtering the product by deionized water, and drying the product at 50 ℃ in vacuum to constant weight to obtain a P (MMA-co-MTC)/GO nano composite, which is recorded as P (M-M)/GO, wherein the mass percent of graphene oxide in the prepared P (M-M)/GO is 0.2 wt%; (2) 0.3g of aniline monomer is added to 80mL of hydrochloric acid solution. Adding 4.5g P (M-M)/GO composite microspheres into the solution, adding 0.45g of APS to initiate polymerization, continuously stirring at room temperature for 24h, ending the reaction, filtering and drying to obtain a PANI-P (MMA-co-MTC)/GO nano composite; dissolving the dried product in 100mL of dichloromethane, continuously stirring for 3h, repeatedly washing the filtered product with dichloromethane, and vacuum drying at 50 ℃ to a constant weight; 0.06g of vitamin C is dissolved in 60mL of deionized water, the dried product is added, and the reaction is finished after stirring for 1.5h at 90 ℃. And cooling and filtering the reaction system, and drying the reaction system at 50 ℃ in vacuum to constant weight to obtain the PANI-rGO nano composite, which is marked as PANI-rGO-3.
Example 4 (graphene oxide added in an amount of 4 wt% based on the amount of aniline added)
(1) 3.7736g of GO dispersion (1.59 wt%) and 3.0g of MTC were added to 50mL of deionized water and ultrasonically dispersed; 0.9g HEC and 0.036g SDBS were added to 100mL deionized water, mixed and added to a three-necked flask and stirred at a low speed of 400 r/min. Sequentially adding 27.0g of MMA monomer, GO subjected to ultrasonic dispersion and MTC suspension into a three-neck bottle, heating to 75 ℃, continuously maintaining inert atmosphere, adding 0.3g of BPO to initiate polymerization, and adjusting the rotating speed to 700 r/min; after reacting for 6 hours, stopping heating, and continuing stirring; after 30min, reducing the rotating speed to 400 r/min; the reaction was complete after 15 min. Cooling and filtering the reaction system, repeatedly washing and filtering the product by deionized water, and drying the product at 50 ℃ in vacuum to constant weight to obtain a P (MMA-co-MTC)/GO nano composite, which is recorded as P (M-M)/GO, wherein the mass percent of graphene oxide in the prepared P (M-M)/GO is 0.2 wt%;
(2) 0.3g of aniline monomer was added to 80mL of hydrochloric acid solution. Adding 6.0g P (M-M)/GO composite microspheres into the solution, adding 0.45g of APS to initiate polymerization, continuously stirring at room temperature for 24h, ending the reaction, filtering and drying to obtain a PANI-P (MMA-co-MTC)/GO nano composite; dissolving the dried product in 100mL of dichloromethane, stirring for 3h, repeatedly washing the filtered product with dichloromethane, and vacuum drying at 50 ℃ to constant weight; 0.08g of vitamin C is dissolved in 60mL of deionized water, the dried product is added, and the reaction is finished after stirring for 1.5h at 90 ℃. And cooling and filtering the reaction system, and drying the reaction system at 50 ℃ in vacuum to constant weight to obtain the PANI-rGO nano composite, which is marked as PANI-rGO-4.
Example 5 (graphene oxide added 5 wt% of aniline)
(1) 3.7736g of GO dispersion (1.59 wt%) and 3.0g of MTC were added to 50mL of deionized water and ultrasonically dispersed; 0.9g HEC and 0.036g SDBS were added to 100mL deionized water, mixed and added to a three-necked flask and stirred at a low speed of 400 r/min. Sequentially adding 27.0g of MMA monomer, GO subjected to ultrasonic dispersion and MTC suspension into a three-neck bottle, heating to 75 ℃, continuously maintaining inert atmosphere, adding 0.3g of BPO to initiate polymerization, and adjusting the rotating speed to 700 r/min; after reacting for 6 hours, stopping heating, and continuing stirring; after 30min, reducing the rotating speed to 400 r/min; the reaction was complete after 15 min. Cooling and filtering the reaction system, repeatedly washing and filtering the product by deionized water, and drying the product at 50 ℃ in vacuum to constant weight to obtain a P (MMA-co-MTC)/GO nano composite, which is recorded as P (M-M)/GO, wherein the mass percent of graphene oxide in the prepared P (M-M)/GO is 0.2 wt%;
(2) 0.3g of aniline monomer is added to 80mL of hydrochloric acid solution. Adding 7.5g P (M-M)/GO composite microspheres into the solution, adding 0.45g of APS to initiate polymerization, continuously stirring at room temperature for 24h, ending the reaction, filtering and drying to obtain a PANI-P (MMA-co-MTC)/GO nano composite; dissolving the dried product in 100mL of dichloromethane, continuously stirring for 3h, repeatedly washing the filtered product with dichloromethane, and vacuum drying at 50 ℃ to a constant weight; 0.10g of vitamin C is dissolved in 60mL of deionized water, the dried product is added, and the reaction is finished after stirring for 1.5h at 90 ℃. And cooling and filtering the reaction system, and drying the reaction system at 50 ℃ in vacuum to constant weight to obtain the PANI-rGO nano composite, which is marked as PANI-rGO-5.
Comparative example 1 (addition amount of reduced graphene oxide was 1 wt% of that of aniline)
(1) Adding 6.289g of GO and 0.2g of vitamin C into 50mL of deionized water, performing ultrasonic dispersion, stirring at 90 ℃ for 1.5h, then finishing the reaction, cooling and filtering the reaction system, repeatedly washing the filtered product with deionized water, and performing vacuum drying at 50 ℃ to constant weight to obtain rGO;
(2) adding 0.003g of rGO into 76mL of deionized water, carrying out ultrasonic dispersion, adding 0.3g of aniline monomer and 4mL of hydrochloric acid into the dispersion, adding 0.45g of initiator APS to initiate polymerization, continuously stirring for 24h at room temperature, ending the reaction, filtering and drying to obtain the PANI-rGO nano composite, and marking as PANI/rGO-pair 1.
Comparative example 2 (addition amount of reduced graphene oxide was 2 wt% of that of aniline)
(1) Adding 6.289g of GO and 0.2g of vitamin C into 50mL of deionized water, performing ultrasonic dispersion, stirring at 90 ℃ for 1.5h, then finishing the reaction, cooling and filtering the reaction system, repeatedly washing the filtered product with deionized water, and performing vacuum drying at 50 ℃ to constant weight to obtain rGO;
(2) adding 0.006g of rGO into 76mL of deionized water, performing ultrasonic dispersion, adding 0.3g of aniline monomer and 4mL of hydrochloric acid into the dispersion, adding 0.45g of initiator APS to initiate polymerization, continuously stirring at room temperature for 24h, ending the reaction, filtering and drying to obtain the PANI-rGO nano composite, which is marked as PANI/rGO-p 2.
Comparative example 3 (reduced graphene oxide added in an amount of 3 wt% of the amount of aniline added)
(1) Adding 6.289g of GO and 0.2g of vitamin C into 50mL of deionized water, performing ultrasonic dispersion, stirring at 90 ℃ for 1.5h, then finishing the reaction, cooling and filtering the reaction system, repeatedly washing the filtered product with deionized water, and performing vacuum drying at 50 ℃ to constant weight to obtain rGO;
(2) adding 0.009g rGO into 76mL of deionized water, performing ultrasonic dispersion, adding 0.3g of aniline monomer and 4mL of hydrochloric acid into the dispersion, adding 0.45g of initiator APS to initiate polymerization, continuously stirring for 24h at room temperature, ending the reaction, filtering and drying to obtain the PANI-rGO nano composite, which is marked as PANI/rGO-pair 3.
Comparative example 4 (reduced graphene oxide was added in an amount of 4 wt% based on the amount of aniline)
(1) Adding 6.289g of GO and 0.2g of vitamin C into 50mL of deionized water, performing ultrasonic dispersion, stirring at 90 ℃ for 1.5h, then finishing the reaction, cooling and filtering the reaction system, repeatedly washing the filtered product with deionized water, and performing vacuum drying at 50 ℃ to constant weight to obtain rGO;
(2) adding 0.012g of rGO into 76mL of deionized water, performing ultrasonic dispersion, adding 0.3g of aniline monomer and 4mL of hydrochloric acid into the dispersion, adding 0.45g of initiator APS to initiate polymerization, continuously stirring at room temperature for 24h, ending the reaction, filtering and drying to obtain the PANI-rGO nano composite, which is marked as PANI/rGO-p-4.
Comparative example 5 (addition amount of reduced graphene oxide is 5 wt% of that of aniline)
(1) Adding 6.289g of GO and 0.2g of vitamin C into 50mL of deionized water, performing ultrasonic dispersion, stirring at 90 ℃ for 1.5h, then finishing the reaction, cooling and filtering the reaction system, repeatedly washing the filtered product with deionized water, and performing vacuum drying at 50 ℃ to constant weight to obtain rGO;
(2) adding 0.015g of rGO into 76mL of deionized water, performing ultrasonic dispersion, adding 0.3g of aniline monomer and 4mL of hydrochloric acid into the dispersion, adding 0.45g of initiator APS to initiate polymerization, continuously stirring for 24h at room temperature, finishing the reaction, filtering and drying to obtain the PANI-rGO nano composite, and marking as PANI/rGO-pair 5.
FIG. 1 is an X-ray photoelectron spectrum of the product before and after GO reduction in the comparative example, with the carbon and oxygen contents listed in Table 1. The oxygen content of the reduced product is greatly reduced, the carbon-oxygen ratio is obviously improved, the successful reduction of GO by vitamin C is demonstrated, most of oxygen-containing functional groups are removed, and the element contents of GO and rGO in figure 1 are shown in the following table 1.
TABLE 1 elemental contents of GO and rGO
FIG. 2 is the Raman spectrogram of GO product before and after reduction in comparative example, and the Raman ratio I of relative peak intensity is calculated from 2 spectral lines in the figure D /I G Is marked in figure 2. I of the product before and after reduction D /I G The change shows that in the process of reducing GO, oxygen-containing functional groups on the surface of GO are removed, defects are left on graphene, and the reduced graphene oxide (rGO) I obtained after reduction is used as a product D /I G The value increased, demonstrating that vitamin C successfully reduced GO.
FIG. 3 is an X-ray diffraction pattern of the product before and after GO reduction in the comparative example. GO appears an obvious characteristic peak about 11.8 degrees before the reduction, GO does not appear obvious characteristic peak after the reduction, indicate that lamella orderly arrangement's structure is destroyed, in the process of vitamin C reduction GO, oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy group on GO surface have been removed, prepare single-layer or few number of layers's rGO, it piles up the orderly structure and disappears, therefore the XRD atlas is a relatively smooth curve, prove GO is reduced to rGO by vitamin C success.
Successful GO reduction by vitamin C is demonstrated in FIGS. 1-3, and it is also demonstrated that PANI/GO in examples 1-5 can be reduced to PANI/rGO by vitamin C.
FIG. 4 is a scanned topography of the P (M-M)/GO composite microspheres prepared in the examples, which shows that the composite microspheres have a smoother surface. In the figure, the microsphere structure is P (M-M)/GO, and the background is a metal substrate for an electron microscope scanning experiment.
Fig. 5 is a scanning topography diagram of the polyaniline-polymethyl methacrylate/methacryloyloxyethyl trimethylammonium chloride-graphene oxide composite material prepared in example 2, and it can be seen that PANI generated after the monomers are polymerized wraps the surface of the polymethyl methacrylate/methacryloyloxyethyl trimethylammonium chloride-graphene oxide composite microsphere, a wrinkled morphology is generated, and the surface smoothness is obviously reduced.
Fig. 6 is a PANI/rGO scanning morphology diagram prepared in example 2, which shows that after organic solvent etching and reducing agent reduction, a petal-shaped morphology composite material is finally obtained, and petal-shaped structures are overlapped with each other to form a certain network structure.
The resistivity and conductivity of the products obtained in examples 1 to 5 and those obtained in comparative examples 1 to 5 were measured by a four-probe method using a RTS-9 type four-probe tester, and the results are shown in Table 2 below.
TABLE 2 resistivity and conductivity of the examples and comparative examples
As can be seen from table 2, the conductivity of the sample of examples 1 to 5 tended to increase and then decrease as the graphene addition ratio increased, and the maximum value was reached when the graphene addition amount was 2 wt% of the aniline mass in example 2. Compared with a comparative sample with the same addition amount of graphene, the conductivity is improved by about 1000 times. This is because the graphene is well dispersed in the sample obtained in the example, and the dispersion is optimal at this ratio.
The polyaniline-graphene composite material can be prepared by adjusting the process parameters according to the content of the invention, and shows the performance basically consistent with the embodiment.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (11)
1. A preparation method of a high-conductivity polyaniline-graphene composite material is characterized by comprising the following steps:
step 1, adding graphene oxide and methacryloyloxyethyl trimethyl ammonium chloride into water, and performing ultrasonic dispersion uniformly to obtain an ultrasonic dispersion liquid;
step 2, uniformly mixing a dispersing agent, a surfactant, methyl methacrylate and the ultrasonic dispersion liquid obtained in the step 1 to obtain a reaction system, wherein the dispersing agent is basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl cellulose or tricalcium phosphate, two monomers of methacryloyloxyethyl trimethyl ammonium chloride and methyl methacrylate form an oil phase, the amount of methyl methacrylate monomer is 90-97 wt% of the mass of the oil phase, the amount of methacryloyloxyethyl trimethyl ammonium chloride is 3-10 wt% of the mass of the oil phase, water, graphene oxide, the dispersing agent and the surfactant form a water phase, the volume ratio of the water phase to the oil phase is 2.5-4.5, placing the reaction system in an inert gas atmosphere, heating to above the temperature of the initiator, adding the initiator to initiate polymerization, carrying out polymerization reaction, filtering and washing, drying to obtain methyl methacrylate-methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide copolymer powder;
step 3, dissolving an aniline monomer in a hydrochloric acid solution, adding the methyl methacrylate-methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide copolymer powder obtained in the step 2, uniformly mixing, continuously stirring, adding an initiator to initiate polymerization, filtering, washing and drying to obtain a polyaniline-polymethyl methacrylate/methacryloyloxyethyl trimethyl ammonium chloride-graphene oxide composite product PANI-P (MMA-co-MTC)/GO;
and 4, dissolving the composite product obtained in the step 3 in an organic solvent, continuously stirring, filtering, washing and drying after the composite product is dissolved, and obtaining a dried product: the polyaniline-graphene oxide composite material PANI-GO is prepared by mixing an organic solvent, namely acetone, ethyl acetate, dichloromethane or trichloromethane;
step 5, adding the dried product and a reducing agent into water, heating and continuously stirring, and filtering, washing and drying the product after the reaction is finished to obtain the polyaniline-graphene composite material;
the addition amount of the graphene oxide is 1-4 wt% of that of the aniline monomer.
2. The method for preparing the highly conductive polyaniline-graphene composite material according to claim 1, wherein the addition amount of the graphene oxide is 2 wt% of the addition amount of the aniline monomer.
3. The method for preparing the highly conductive polyaniline-graphene composite material as described in claim 1, wherein the mass of the dispersant in step 2 is 2.5 to 3 wt% of the mass of the oil phase, the amount of the surfactant is 0.1 to 0.15 wt% of the mass of the oil phase, and the mass of the graphene oxide in step 1 is 0.0l to 2.0 wt% of the mass of the oil phase.
4. The method for preparing the highly conductive polyaniline-graphene composite material as described in claim 1, wherein the dispersant in step 2 is hydroxyethyl cellulose, and the surfactant in step 2 is sodium dodecylbenzenesulfonate, sodium dodecylsulfate, or sodium glycocholate;
the initiator in the step 2 is azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide or di (2-ethyl) hexyl peroxydicarbonate;
the inert gas in the step 2 is nitrogen, helium or argon;
the temperature of the initiator in the step 2 is 70-80 ℃, and the polymerization reaction time is 5-8 hours.
5. The method for preparing the highly conductive polyaniline-graphene composite material according to claim 4, wherein the surfactant in step 2 is sodium dodecylbenzenesulfonate, the initiator in step 2 is benzoyl peroxide, and the inert gas in step 2 is nitrogen.
6. The method for preparing the highly conductive polyaniline-graphene composite material as described in claim 1, wherein the polymerization reaction time in step 3 is 24 hours, and the initiator is potassium persulfate or ammonium persulfate;
the reducing agent in the step 5 is vitamin C, the temperature is increased to 80-95 ℃, and the stirring is continued for 1-2 hours.
7. The method for preparing the highly conductive polyaniline-graphene composite material according to claim 6, wherein the initiator in step 3 is ammonium persulfate, the organic solvent in step 4 is dichloromethane, and the temperature rise in step 5 is 90 ℃ and the continuous stirring time is 1.5 hours.
8. The high-conductivity polyaniline-graphene composite material prepared by the preparation method according to any one of claims 1 to 7, wherein the microstructure of the high-conductivity polyaniline-graphene composite material is a network formed by overlapping petal-shaped structures.
9. The highly conductive polyaniline-graphene composite according to claim 8, wherein the highly conductive polyaniline-graphene composite has a resistivity of 0.008-3.02k Ω cm and a conductivity of 3.310-1250 x 10 -4 S/cm。
10. The highly conductive polyaniline-graphene composite material according to claim 9, wherein the addition amount of graphene oxide is 2 wt% of the addition amount of aniline monomer, the resistivity of the highly conductive polyaniline-graphene composite material is 0.008 kq cm, and the conductivity is 1250 × 10 -4 S/cm。
11. Use of the highly conductive polyaniline-graphene composite as claimed in claim 8 in electromagnetic interference shielding, rechargeable batteries, photovoltaic cells, chemical sensors, or gas separation membranes.
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