CN114015105A - Preparation method and application of graphene/polyaniline composite membrane electrode material - Google Patents
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Abstract
The invention discloses a preparation method and application of a graphene/polyaniline composite membrane electrode material. A preparation method of a graphene/polyaniline composite membrane electrode material comprises the following steps: step 1) preparing polyaniline with a two-dimensional nano-sheet structure; step 2) carrying out surface treatment on the obtained polyaniline in the sheet layer by using a positive charge treating agent, and then carrying out layer-by-layer self-assembly on the polyaniline in the sheet layer and the graphene oxide dispersion liquid with negative charge by adopting a spin coating mode to obtain a graphene oxide/polyaniline composite film; and 3) carrying out reduction treatment to obtain the graphene/polyaniline composite membrane electrode material. The preparation method takes the electrostatic action between positive charges and negative charges as a driving force, and enables the polyaniline of the sheet layer with positive charges and the graphene oxide with negative charges to carry out layer-by-layer self-assembly by adopting a spin coating mode through electrostatic attraction, so as to establish a multilayer alternating mixed capacitor layer; by utilizing the synergistic effect of the components, the interaction between the graphene and the conductive polymer interface is improved, and the comprehensive electrochemical performance of the composite electrode material is improved.
Description
Technical Field
The invention relates to an electrode material, in particular to a preparation method and application of a graphene/polyaniline composite membrane electrode material.
Background
As a novel electrochemical energy storage device, the super capacitor has the advantages of high power density, high specific capacitance (hundreds to thousands of farads/gram), excellent rate capability, long cycle life and the like, and has huge application prospect in the aspects of new energy automobiles, aerospace, smart grids, electronic industry and the like. For supercapacitor components, the electrode material is critical.
Common carbon material electrodes comprise carbon nanotubes, graphene, carbon fibers and porous carbon, wherein the two-dimensional graphene has high conductivity and specific surface area and is often used as an electric double layer capacitor electrode material. Due to the stacking of graphene sheets, the active surface area of the graphene is reduced, the ion transmission resistance is increased, and the specific capacity is low. The pseudo-capacitance material of conductive macromolecules (polyaniline, polypyrrole and the like) can generate reversible and rapid oxidation-reduction reaction on the surface of an electrode of the pseudo-capacitance material to store energy.
The double-layer capacitor material graphene and the pseudo-capacitor material conductive polymer electrode material are compounded, and the electrochemical performance of the composite electrode material can show the efficiency of 1+1 to 2 by utilizing the synergistic effect of different electrode energy storage mechanisms. However, if graphene and the pseudocapacitance material are physically mixed, it is difficult to effectively prevent stacking of graphene sheets.
The Chinese invention patent (ZL 202010393674.6) discloses a graphene/polyaniline flexible film, polyaniline is generated only on the surface of graphene, and the polyaniline is easy to generate surface agglomeration and has low specific capacitance. Patent L201711294079.3 discloses a flexible composite electrode material of graphene/polyaniline @ polyaniline, in which a polyaniline nanofiber is synthesized on the surface of a graphene film, and then a polyaniline nanowhisker grows on the polyaniline fiber, so as to obtain a hierarchical composite graphene film structure, but this structure still cannot improve the stacking of graphene sheets. Therefore, how to design the structure of the graphene/conductive polymer pseudocapacitance composite material, regulate and control the surface/interface properties, realize the composite synergistic effect and the like still have challenges.
Disclosure of Invention
The invention provides a preparation method of a graphene/polyaniline composite electrode membrane material aiming at the defects of the prior art, which takes the electrostatic action between positive charges and negative charges as a driving force to ensure that the positively charged laminar polyaniline and the negatively charged graphene oxide are subjected to layer-by-layer self-assembly by electrostatic attraction in a spin coating mode to establish a multilayer alternating mixed capacitor layer; finally, reduction treatment is assisted to prepare the graphene/polyaniline composite electrode membrane material.
According to the graphene/polyaniline composite electrode membrane material, the interaction between graphene and a conductive polymer interface is improved by utilizing the synergistic effect among the components, the steady chemical acting force is constructed, and the comprehensive electrochemical performance of the composite electrode material is improved.
The invention also aims to protect the application of the graphene/polyaniline composite membrane electrode material prepared by the method as a supercapacitor electrode material and in a supercapacitor.
The technical scheme adopted by the invention is as follows:
a preparation method of a graphene/polyaniline composite electrode membrane material comprises the following steps:
(1) the method adopts an emulsion polymerization method, takes aniline as a polymerization monomer, utilizes a surfactant as an oriented template, combines a micelle theory, and obtains the nano-sheet layer polyaniline through an oxidant oxidation polymerization reaction.
The surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl sulfate and tween 80. The mass ratio of the surfactant to the aniline is 0.01: 1-0.1: 1, preferably 0.01: 1.
the oxidant is at least one of ammonium persulfate and potassium persulfate. The mass ratio of the oxidant to the aniline is 0.5: 1-5: 1, preferably 2: 1.
the polymerization reaction is carried out at 0-10 ℃ for 10-48 hours, more preferably at 5 DEG C
The reaction was carried out for 24 hours.
(2) And (2) carrying out surface treatment on the polyaniline of the sheet layer obtained in the step (1) by using a positive charge treating agent to obtain polyaniline with positive charges, and carrying out layer-by-layer self-assembly on the polyaniline with negative charges and the graphene oxide dispersion liquid with negative charges by adopting a spin coating mode to obtain graphene oxide/polyaniline.
The positive charge treating agent is at least one of poly diallyl dimethyl ammonium chloride and polyethyleneimine. The mass ratio of the positive charge treating agent to the polyaniline is 10: 1-1: 1, preferably 3: 1.
the mass concentration of the polyaniline with positive charges is 0.1-5 mg/mL.
The spin coating mode is that the rotating speed of a spin coating instrument is 100-3000 r/min, the dropping liquid amount is 0.1-0.5 mL/time, and the spin coating frequency is 5-50.
The preparation method of the graphene oxide comprises the steps of preparing the graphene oxide by a Hummers method, obtaining graphene oxide powder by freeze drying, and then ultrasonically dispersing the graphene oxide powder in water. The mass concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.5-10 mg/mL.
(3) And (3) carrying out reduction treatment on the graphene oxide/polyaniline obtained in the step (2) to obtain the graphene/polyaniline composite membrane electrode material. The reducing agent is at least one of hydriodic acid, hydrazine hydrate and ascorbic acid.
The spin-coating self-assembly graphene/polyaniline composite electrode membrane material prepared by the method is applied as an electrode material.
The invention has the beneficial effects that:
1. according to the preparation method of the graphene/polyaniline composite electrode membrane material, disclosed by the invention, the composite membrane electrode material is constructed by using the components of the polyaniline laminate and the graphene laminate, the polyaniline laminate can be used as a filler of graphene to effectively prevent the graphene from being stacked, the excellent charge transfer capability of the graphene can be exerted, and meanwhile, the graphene provides an excellent conductive carbon framework for the polyaniline.
2. According to the preparation method of the graphene/polyaniline composite electrode membrane material, the array design of the multilayer alternating mixed capacitor layer is constructed by adopting the positive and negative opposite charge self-assembly and spin coating modes, the interaction force between the graphene and the conductive polymer polyaniline is regulated and controlled, and the comprehensive electrochemical performance of the composite membrane electrode material is improved by utilizing the mutual synergistic effect between the graphene and the conductive polymer polyaniline.
3. According to the preparation method of the graphene/polyaniline composite electrode membrane material, the graphene/polyaniline composite electrode membrane material is prepared by adopting a spin-coating method to prepare a mold and finally assisting reduction treatment, the operation is simple and feasible, and the membrane thickness is controllable.
Drawings
FIG. 1 is a schematic diagram of a graphene/polyaniline composite electrode membrane material prepared by electrostatic self-assembly and spin coating;
FIG. 2 is an SEM photograph of a polyaniline film as a sheet layer obtained in Experimental example 3;
FIG. 3 is a cross-sectional SEM image of the graphene/polyaniline film obtained in Experimental example 3;
fig. 4 is a diagram of a graphene/polyaniline composite membrane obtained in experimental example 4.
Detailed Description
In order to make the technical idea and advantages of the invention for realizing the purpose of the invention more clear, the technical solution of the invention is further described in detail with reference to the accompanying drawings. It should be understood that the following examples are only for illustrating and explaining preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention as claimed in the claims.
Example 1
Referring to fig. 1, the preparation method of the graphene/polyaniline composite membrane electrode material of the invention comprises the following steps:
1) preparing polyaniline with a two-dimensional nano-sheet structure;
2) carrying out surface treatment on the polyaniline of the sheet layer obtained in the step 1) by using a positive charge treating agent to obtain polyaniline with positive charge, and then carrying out layer-by-layer self-assembly on the polyaniline with negative charge and a graphene oxide dispersion liquid with the negative charge by adopting a spin coating mode to obtain a graphene oxide/polyaniline composite film;
3) and (3) carrying out reduction treatment on the graphene oxide/polyaniline composite membrane obtained in the step 2) to obtain the graphene/polyaniline composite membrane electrode material.
In the step 1), emulsion polymerization is adopted to synthesize the polyaniline in a sheet layer: aniline is used as a polymerization monomer, a surfactant is used as an oriented template, and a micelle theory is combined, so that the polyaniline with the nano-sheet layer is obtained through an oxidizing agent oxidation polymerization reaction; the polymerization reaction is carried out at 0-10 ℃ for 10-48 hours. The surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl sulfate and tween 80; the oxidant is at least one of ammonium persulfate and potassium persulfate.
As shown in fig. 1, it is a process flow chart of the method for preparing graphene/polyaniline composite membrane electrode material by electrostatic self-assembly and spin coating. The array design of the multilayer alternating mixed capacitor layer is constructed by using the components of the polyaniline layer and the graphene layer and adopting the modes of self-assembly of charges with opposite polarities and spin coating, so that the interaction force of the graphene and the conductive polymer polyaniline is regulated and controlled, the synergistic effect of the graphene and the conductive polymer polyaniline is utilized, and the comprehensive electrochemical performance of the composite electrode material is improved.
Example 2
The difference between the preparation method of the graphene/polyaniline composite membrane electrode material in the embodiment and the embodiment 1 is that: further, in the step 1), the mass ratio of the surfactant to the aniline is 0.01-0.1: 1; the mass ratio of the oxidant to the aniline is 0.5-5: 1.
example 3
The difference between the preparation method of the graphene/polyaniline composite membrane electrode material in the embodiment and the embodiment 1 or 2 is that: in the step 2), the positive charge treating agent is at least one of poly (diallyldimethylammonium chloride) and polyethyleneimine; the mass ratio of the positive charge treating agent to the polyaniline is 10: 1-1: 1; the mass concentration of the polyaniline with positive electricity is 0.1-5 mg/mL; the mass concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.5-10 mg/mL.
In the step 2), the spin coating mode is that the rotating speed of a spin coater is 100-3000 r/min, the dropping liquid amount is 0.1-0.5 mL/time, and the spin coating frequency is 5-50;
in the step 3), the reducing agent used in the reduction treatment is at least one of hydroiodic acid, hydrazine hydrate and ascorbic acid.
Example 4
A preparation method of a graphene/polyaniline composite electrode membrane material comprises the following steps:
(1) adopting an emulsion polymerization method, taking aniline as a polymerization monomer, utilizing a surfactant as an oriented template, combining a micelle theory, and obtaining nano-sheet layer polyaniline through an oxidant oxidation polymerization reaction;
the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl sulfate and tween 80. The mass ratio of the surfactant to the aniline is 0.01: 1;
the oxidant is at least one of ammonium persulfate and potassium persulfate. The mass ratio of the oxidant to the aniline is 2: 1;
the polymerization reaction was carried out at 5 ℃ for 24 hours.
(2) And (2) carrying out surface treatment on the polyaniline of the sheet layer obtained in the step (1) by using a positive charge treating agent to obtain polyaniline with positive charges, and carrying out layer-by-layer self-assembly on the polyaniline with negative charges and the graphene oxide dispersion liquid with negative charges by adopting a spin coating mode to obtain graphene oxide/polyaniline.
The positive charge treating agent adopts at least one of polydiallyl dimethyl ammonium chloride and polyethyleneimine. The mass ratio of the positive charge treating agent to the polyaniline is 3: 1. the mass concentration of the polyaniline with positive charges is 2 mg/mL.
The rotating speed of the spin coater is 2000r/min, the dropping amount is 0.3 mL/time, and the spin coating times are 30.
The preparation method of the graphene oxide comprises the following steps: graphene oxide is prepared by a Hummers method, graphene oxide powder is obtained by freeze drying, and then the graphene oxide powder is ultrasonically dispersed in water. The mass concentration of graphene oxide in the graphene oxide dispersion liquid is 5 mg/mL.
(3) And (3) carrying out reduction treatment on the graphene oxide/polyaniline obtained in the step (2) to obtain the graphene/polyaniline composite membrane electrode material. The reducing agent is at least one of hydriodic acid, hydrazine hydrate and ascorbic acid.
The following are laboratory examples
Experimental example 1
Firstly, preparing a laminar polyaniline: adding 0.0051g of sodium dodecyl sulfonate, 0.5mL of aniline and 0.255g of oxidant ammonium persulfate (the mass ratio of the surfactant to the aniline is 0.01:1, and the mass ratio of the oxidant to the aniline is 0.5: 1) into 100 mL of water, magnetically stirring and polymerizing for 12 hours at 0 ℃, carrying out vacuum filtration, washing for 3 times by using ethanol and deionized water, and carrying out freeze drying to obtain lamellar polyaniline;
secondly, carrying out charge modification treatment on the polyaniline in the sheet layer, carrying out spin coating with graphene oxide dispersion liquid to form a film, and carrying out reduction treatment:
0.5g of lamellar polyaniline is dispersed in deionized water at the concentration of 2mg/mL, 0.5g of polydiallyldimethylammonium chloride (the mass ratio of the charge treating agent to the polyaniline is 1: 1) is added dropwise, magnetic stirring is carried out for 12 hours, vacuum filtration is carried out, ethanol and deionized water are used for washing for 3 times, and freeze drying is carried out to obtain the polyaniline with positive charges. Respectively putting 0.1mg/mL of polyaniline with positive charges and 1mg/mL of graphene oxide dispersion liquid with negative charges into a 10mL injector, setting the rotation speed on a spin coater to be 100r/min, setting the dropping amount to be 0.1 mL/time, alternately dropping a spin-coating surface, and repeating for 5 times to obtain the graphene oxide/polyaniline composite membrane. Further placing the obtained composite membrane into 50mL hydriodic acid solution, and adding 90 percent of the obtained composite membraneoAnd C, reacting for 4 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane electrode material.
The prepared graphene/polyaniline composite membrane electrode material is subjected to electrochemical performance (charge and discharge) test by using a three-electrode constant current source, the specific mass capacitance of the composite membrane electrode material under the current density of 0.5A/g reaches 480F/g, and the capacitance retention rate is 95% after the composite membrane electrode material is cycled for 2000 times under the current density of 10A/g.
Experimental example 2
Firstly, preparing polyaniline in a lamellar layer, adding 0.0102g of sodium dodecyl sulfate, 0.5mL of aniline and 0.51g of oxidant persulfuric acid (the mass ratio of the surfactant to the aniline is 0.02:1, and the mass ratio of the oxidant to the aniline is 1: 1) into 100 mL of water, magnetically stirring and polymerizing for 24 hours at the temperature of 3 ℃, carrying out suction filtration under reduced pressure, washing for 3 times by using ethanol and deionized water, and carrying out freeze drying to obtain the polyaniline in a lamellar layer.
And secondly, carrying out charge modification treatment on the polyaniline layer, carrying out spin coating with the graphene oxide dispersion liquid to form a film, and carrying out reduction treatment.
0.3g of lamellar polyaniline is dispersed in deionized water at the concentration of 2mg/mL, 0.6g of polyethyleneimine (the mass ratio of the charge treating agent to the polyaniline is 2: 1) is added dropwise, magnetic stirring is carried out for 12 hours, reduced pressure suction filtration is carried out, ethanol and deionized water are used for washing for 3 times, and freeze drying is carried out to obtain the polyaniline with positive charges. Respectively putting 0.5mg/mL of polyaniline with positive charges and 3mg/mL of graphene oxide dispersion liquid with negative charges into a 10mL injector, setting the rotation speed on a spin coater to be 500r/min, setting the dropping amount to be 0.2 mL/time, alternately dropping the spin-coated surface, and repeating for 10 times to obtain the graphene oxide/polyaniline composite membrane. Further placing the obtained composite membrane into 50mL hydriodic acid solution, and adding 90 percent of the obtained composite membraneoAnd C, reacting for 4 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane.
The specific mass capacitance of the composite film under the current density of 0.5A/g reaches 535F/g, and the capacitance retention rate is 98 percent after the composite film is cycled 2000 times under the current density of 10A/g by using a three-electrode constant current charge-discharge test.
Experimental example 3
Preparing the laminar polyaniline: 0.0102g of sodium dodecyl sulfate, 0.5mL of aniline and 1.02g of oxidant persulfuric acid (the mass ratio of the surfactant to the aniline is 0.02:1, and the mass ratio of the oxidant to the aniline is 2: 1) are added into 100 mL of water, magnetic stirring is carried out at 5 ℃ for polymerization for 24 hours, reduced pressure suction filtration is carried out, washing is carried out for 3 times by using ethanol and deionized water, and freeze drying is carried out to obtain the lamellar polyaniline. The SEM image of the polyaniline film with the obtained layer is shown in FIG. 2, wherein the size of the polyaniline layer is 100-500 nm.
Carrying out charge modification treatment on the polyaniline layer, carrying out spin coating film formation with graphene oxide dispersion liquid, and carrying out reduction treatment:
using 0.5g tabletsThe dispersion concentration of the laminar polyaniline in deionized water is 2mg/mL, 1.5g of polyethyleneimine (the mass ratio of the charge treating agent to the polyaniline is 3: 1) is dropwise added, magnetic stirring is carried out for 12 hours, reduced pressure suction filtration is carried out, washing is carried out for 3 times by using ethanol and deionized water, and freeze drying is carried out to obtain the polyaniline with positive charges. Respectively putting 2mg/mL of polyaniline with positive charges and 5mg/mL of graphene oxide dispersion liquid with negative charges into a 10mL injector, setting the rotation speed on a spin coater to be 2000r/min and the dropping liquid amount to be 0.2 mL/time, alternately dropping the spin-coated surface, and repeating for 20 times to obtain the graphene oxide/polyaniline composite membrane. Further placing the obtained composite membrane into 50mL hydriodic acid solution, and adding 90 percent of the obtained composite membraneoAnd C, reacting for 4 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane. The cross-sectional SEM image of the graphene/polyaniline film is shown in fig. 3, and after surface charge treatment, the graphene and polyaniline sheets are tightly bonded due to strong electrostatic attraction.
Carrying out electrochemical performance test: the specific mass capacitance of the composite film under the current density of 0.5A/g reaches 650F/g, and the capacitance retention rate is 97 percent after the composite film is cycled 2000 times under the current density of 10A/g by using a three-electrode constant current charge-discharge test.
Experimental example 4
Preparing the laminar polyaniline: adding 0.0153g of Tween 80, 0.5mL of aniline and 1.02g of potassium persulfate serving as an oxidant (the mass ratio of the surfactant to the aniline is 0.003:1, and the mass ratio of the oxidant to the aniline is 2: 1) into 100 mL of water, magnetically stirring and polymerizing for 24 hours at 5 ℃, carrying out suction filtration under reduced pressure, washing for 3 times by using ethanol and deionized water, and carrying out freeze drying to obtain the lamellar polyaniline.
Carrying out charge modification treatment on the polyaniline layer, carrying out spin coating film formation with graphene oxide dispersion liquid, and carrying out reduction treatment:
0.2g of lamellar polyaniline is dispersed in deionized water at the concentration of 2mg/mL, 1g of polydiallyldimethylammonium chloride (the mass ratio of the charge treating agent to the polyaniline is 5: 1) is added dropwise, magnetic stirring is carried out for 12 hours, reduced pressure suction filtration is carried out, ethanol and deionized water are used for washing for 3 times, and freeze drying is carried out to obtain the polyaniline with positive charges. Dispersing 2mg/mL of polyaniline with positive charges and 5mg/mL of graphene oxide with negative chargesAnd respectively putting the graphene oxide/polyaniline composite membrane into a 10mL injector, alternately dripping the graphene oxide/polyaniline composite membrane into a spin coating surface at a speed of 1000r/min and a dripping amount of 0.3 mL/time on a spin coating instrument, and repeating for 30 times to obtain the graphene oxide/polyaniline composite membrane. The obtained composite membrane was further placed in 50mL of hydrazine hydrate, 100%oAnd C, reacting for 2 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane, wherein a physical diagram of the graphene/polyaniline composite membrane is shown in figure 4, and the graphene/polyaniline composite membrane has certain flexibility and a smooth and flat surface.
The electrochemical performance of the composite membrane is tested by using three-electrode constant current charge and discharge, the specific mass capacitance under the current density of 0.5A/g reaches 545F/g, and the capacitance retention rate is 97 percent after the composite membrane is circulated for 2000 times under the current density of 10A/g.
Experimental example 5
Preparing polyaniline of a lamellar layer: 0.0255g of sodium dodecyl sulfate, 0.5mL of aniline and 1.53g of potassium persulfate serving as an oxidant (the mass ratio of the surfactant to the aniline is 0.05:1, and the mass ratio of the oxidant to the aniline is 3: 1) are added into 100 mL of water, and the mixture is magnetically stirred and polymerized for 24 hours at the temperature of 5 ℃, subjected to vacuum filtration, washed for 3 times by using ethanol and deionized water, and subjected to freeze drying to obtain the lamellar polyaniline.
Carrying out charge modification treatment on the polyaniline layer, carrying out spin coating film formation with graphene oxide dispersion liquid, and carrying out reduction treatment:
0.3g of lamellar polyaniline is dispersed in deionized water at the concentration of 2mg/mL, 2.1g of polyethyleneimine (the mass ratio of the charge treating agent to the polyaniline is 7: 1) is added dropwise, magnetic stirring is carried out for 12 hours, reduced pressure suction filtration is carried out, ethanol and deionized water are used for washing for 3 times, and freeze drying is carried out to obtain the polyaniline with positive charges. Respectively putting 3mg/mL of polyaniline with positive charges and 6mg/mL of graphene oxide dispersion liquid with negative charges into a 10mL injector, setting the rotating speed on a spin coating instrument to be 1500r/min, setting the dropping liquid amount to be 0.4 mL/time, alternately dropping the spin coating surface, and repeating for 30 times to obtain the graphene oxide/polyaniline composite membrane. The resulting composite membrane was further placed in 50mL of ascorbic acid solution (60 mL)oAnd C, reacting for 10 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane.
Carrying out electrochemical performance test: the specific mass capacitance of the composite film under the current density of 0.5A/g reaches 620F/g by using a three-electrode constant current charge-discharge test, and the capacitance retention rate is 98 percent after the composite film is circulated for 2000 times under the current density of 10A/g.
Experimental example 6
Preparing the laminar polyaniline: adding 0.0408g of Tween 80, 0.5mL of aniline and 2.04g of oxidant ammonium persulfate (the mass ratio of the surfactant to the aniline is 0.08:1, and the mass ratio of the oxidant to the aniline is 4: 1) into 100 mL of water, magnetically stirring and polymerizing for 12 hours at 8 ℃, decompressing and filtering, washing for 3 times by using ethanol and deionized water, and freeze-drying to obtain the lamellar polyaniline.
Carrying out charge modification treatment on the polyaniline layer, carrying out spin coating film formation with graphene oxide dispersion liquid, and carrying out reduction treatment:
0.3g of lamellar polyaniline is dispersed in deionized water at the concentration of 2mg/mL, 2.4g of polyethyleneimine (the mass ratio of the charge treating agent to the polyaniline is 8: 1) is added dropwise, magnetic stirring is carried out for 12 hours, reduced pressure suction filtration is carried out, ethanol and deionized water are used for washing for 3 times, and freeze drying is carried out to obtain the polyaniline with positive charges. Respectively putting 4mg/mL of polyaniline with positive charges and 8mg/mL of graphene oxide dispersion liquid with negative charges into a 10mL injector, setting the rotation speed on a spin coater to be 2500r/min and the dropping liquid amount to be 0.4 mL/time, alternately dropping the spin-coated surface, and repeating for 25 times to obtain the graphene oxide/polyaniline composite membrane. Further placing the obtained composite membrane into 50mL hydriodic acid solution, and adding 90 percent of the obtained composite membraneoAnd C, reacting for 4 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane.
And (3) electrochemical performance testing, namely testing that the specific mass capacitance of the composite membrane reaches 530F/g under the current density of 0.5A/g by using three-electrode constant current charge and discharge, and the capacitance retention rate is 96% after the composite membrane is circulated for 2000 times under the current density of 10A/g.
Experimental example 7
Firstly, preparing polyaniline with a lamellar structure, adding 0.051g of sodium dodecyl sulfonate, 0.5mL of aniline and 2.55g of oxidant ammonium persulfate (the mass ratio of the surfactant to the aniline is 0.1: 1, and the mass ratio of the oxidant to the aniline is 5: 1) into 100 mL of water, magnetically stirring and polymerizing for 48 hours at 10 ℃, carrying out vacuum filtration, washing for 3 times by using ethanol and deionized water, and carrying out freeze drying to obtain the polyaniline with the lamellar structure.
Secondly, carrying out charge modification treatment on the polyaniline in the sheet layer, carrying out spin coating with graphene oxide dispersion liquid to form a film, and carrying out reduction treatment: 0.2g of lamellar polyaniline is dispersed in deionized water at the concentration of 2mg/mL, 2g of polydiallyldimethylammonium chloride (the mass ratio of the charge treating agent to the polyaniline is 10: 1) is added dropwise, magnetic stirring is carried out for 12 hours, reduced pressure suction filtration is carried out, ethanol and deionized water are used for washing for 3 times, and freeze drying is carried out to obtain the polyaniline with positive charges. Respectively putting 5mg/mL of polyaniline with positive charges and 10mg/mL of graphene oxide dispersion liquid with negative charges into a 10mL injector, setting the rotation speed on a spin coater to be 3000r/min and the dropping amount to be 0.5 mL/time, alternately dropping the spin-coated surface, and repeating for 50 times to obtain the graphene oxide/polyaniline composite membrane. The obtained composite membrane was further put into 50mL of hydrazine hydrate solution, 100%oAnd C, reacting for 2 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline composite membrane.
By performing electrochemical performance test (using three-electrode constant current charge and discharge test) on the prepared graphene/polyaniline composite membrane electrode material, the specific mass capacitance of the composite membrane under the current density of 0.5A/g reaches 420F/g, and the capacitance retention rate is 95% after the composite membrane is cycled for 2000 times under the current density of 10A/g.
Comparative example 1
According to the comparative example, the composite membrane electrode material is prepared by directly mixing the polyaniline without positive charge treatment and graphene oxide dispersion liquid and performing spin coating, and the comparative example is the performance of the composite electrode material without a static self-assembly process.
Firstly, preparing a laminar polyaniline: 0.0051g of sodium dodecyl sulfonate, 0.5mL of aniline, and 1.02g of ammonium persulfate as an oxidant (the mass ratio of the surfactant to the aniline is 0.01:1, and the mass ratio of the oxidant to the aniline is 2: 1) are added into 100 mL of water, and the mixture is magnetically stirred and polymerized at 5 ℃ for 24 hours, subjected to suction filtration under reduced pressure, washed with ethanol and water for 3 times, and then subjected to freeze drying to obtain the lamellar polyaniline.
Secondly, directly mixing, spin-coating and film-forming the polyaniline layer and the graphene oxide dispersion liquid, and reducing:
directly mixing the 2mg/mL laminar polyaniline dispersion liquid and the 1mg/mL graphene oxide dispersion liquid, putting the mixture into a 10mL injector, setting the rotation speed on a spin coater to be 100r/min, setting the dropping amount to be 0.1 mL/time, alternately dropping a spin-coating surface, and repeating for 10 times to obtain the graphene oxide/polyaniline nanosheet composite membrane. Further placing the obtained composite membrane into 50mL hydriodic acid solution, and adding 90 percent of the obtained composite membraneoAnd C, reacting for 4 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline nanosheet composite membrane.
And finally, performing an electrochemical performance test, wherein the specific mass capacitance of the composite film under the current density of 0.5A/g reaches 230F/g by using a three-electrode constant current charge-discharge test, and the capacitance retention rate is 78% after the composite film is cycled 2000 times under the current density of 10A/g.
Comparative example 2
According to the comparative example, the composite membrane electrode material is prepared by respectively carrying out spin coating on the polyaniline without positive charge treatment and the graphene oxide dispersion liquid, and the performance of the composite electrode material without the electrostatic self-assembly process is compared.
Firstly, preparing polyaniline with a lamellar structure: 0.0051g of sodium dodecyl sulfonate, 0.5mL of aniline, and 1.02g of ammonium persulfate as an oxidant (the mass ratio of the surfactant to the aniline is 0.01:1, and the mass ratio of the oxidant to the aniline is 2: 1) are added into 100 mL of water, and the mixture is magnetically stirred and polymerized at 5 ℃ for 24 hours, subjected to suction filtration under reduced pressure, washed with ethanol and water for 3 times, and then subjected to freeze drying to obtain the lamellar polyaniline.
Secondly, spin coating and reducing the polyaniline and graphene oxide dispersion liquid respectively:
respectively placing the 2mg/mL laminar polyaniline dispersion liquid and the 1mg/mL graphene oxide dispersion liquid into a 10mL injector, setting the rotating speed on a spin coater to be 100r/min, setting the dropping liquid amount to be 0.1 mL/time, alternately dropping the spin-coated surface, and repeating for 10 times to obtain the graphene oxide/polyaniline nanosheet composite membrane. Further placing the obtained composite membrane into 50mL hydriodic acid solution, and adding 90 percent of the obtained composite membraneoAnd C, reacting for 4 hours, taking out the composite membrane, and washing with deionized water to obtain the graphene/polyaniline nanosheet composite membrane.
Finally, electrochemical performance testing was performed: the specific mass capacitance of the composite film under the current density of 0.5A/g reaches 320F/g, and the capacitance retention rate is 82% after the composite film is cycled 2000 times under the current density of 10A/g.
Through comparative example comparative analysis and electrochemical performance test, the composite membrane electrode material preparation method disclosed by the invention has the advantages that the graphene sheet layer and the polyaniline sheet layer are subjected to sheet-to-sheet electrostatic self-assembly, and the prepared composite membrane electrode material can effectively prevent disordered stacking of the graphene and the polyaniline sheet layer, fully exerts the synergistic effect and obtains excellent electrochemical performance. The specific mass capacitance of the composite film can reach 650F/g at a current density of 0.5A/g, and the capacitance retention rate is 97% after the composite film is cycled 2000 times at a high current density of 10A/g. Compared with the method that the composite film electrode material is prepared by respectively carrying out positive charge treatment on the polyaniline layer and carrying out spin coating on the graphene oxide dispersion liquid, the method has the advantage that the capacitance retention rate is remarkably improved.
According to the preparation method of the graphene/polyaniline composite electrode membrane material, the interaction between graphene and a conductive polymer interface can be improved, the static action between positive charges and negative charges is used as a driving force by constructing a stable chemical acting force, so that the layer polyaniline with positive charges and the graphene oxide with negative charges are subjected to electrostatic attraction, and a spin coating mode is adopted for layer-by-layer self-assembly, so that a multilayer alternate mixed capacitor layer is established; finally, reduction treatment is assisted to prepare the graphene/polyaniline composite electrode membrane material.
The comprehensive electrochemical performance of the composite electrode material is improved by the interaction of the conductive polymer polyaniline of the lamellar layer and the graphene of the lamellar layer and the synergistic effect among the components.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be construed as limiting the invention. Other modifications of the invention will occur to those skilled in the art without the benefit of this disclosure and it is intended to cover within the scope of the invention any modifications that fall within the spirit and scope of the invention or the equivalents thereof which may be substituted by one of ordinary skill in the art without departing from the scope of the invention.
Claims (10)
1. A preparation method of a graphene/polyaniline composite membrane electrode material is characterized by comprising the following steps: the method comprises the following steps:
1) preparing polyaniline with a two-dimensional nano-sheet structure;
2) carrying out surface treatment on the polyaniline of the sheet layer obtained in the step 1) by using a positive charge treating agent to obtain polyaniline with positive charge, and then carrying out layer-by-layer self-assembly on the polyaniline with negative charge and a graphene oxide dispersion liquid with the negative charge by adopting a spin coating mode to obtain a graphene oxide/polyaniline composite film;
3) and (3) carrying out reduction treatment on the graphene oxide/polyaniline composite membrane obtained in the step 2) to obtain the graphene/polyaniline composite membrane electrode material.
2. The method for preparing the graphene/polyaniline composite membrane electrode material according to claim 1, which is characterized in that: in the step 1), emulsion polymerization is adopted to synthesize the polyaniline in a sheet layer: aniline is used as a polymerization monomer, a surfactant is used as an oriented template, and a micelle theory is combined, so that the polyaniline with the nano-sheet layer is obtained through an oxidizing agent oxidation polymerization reaction; the polymerization reaction is carried out at 0-10 ℃ for 10-48 hours.
3. The method for preparing the graphene/polyaniline composite membrane electrode material according to claim 2, which is characterized in that: the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl sulfate and tween 80; the oxidant is at least one of ammonium persulfate and potassium persulfate.
4. The method for preparing a graphene/polyaniline composite membrane electrode material according to claim 2 or 3, which is characterized in that: the mass ratio of the surfactant to the aniline is 0.01: 1-0.1: 1.
5. the method for preparing a graphene/polyaniline composite membrane electrode material according to claim 2 or 3, which is characterized in that: the mass ratio of the oxidant to the aniline is 0.5: 1-5: 1.
6. the method for preparing the graphene/polyaniline composite membrane electrode material according to claim 4, which is characterized in that: the mass ratio of the oxidant to the aniline is 0.5: 1-5: 1.
7. the method for preparing a graphene/polyaniline composite membrane electrode material according to claim 1, 2, 3 or 6, which is characterized in that: in the step 2), the positive charge treating agent is at least one of poly (diallyldimethylammonium chloride) and polyethyleneimine; the mass ratio of the positive charge treating agent to the polyaniline is 10: 1-1: 1.
8. the preparation method of the graphene/polyaniline nanosheet composite electrode material as claimed in claim 7, wherein: in the step 2), the mass concentration of the polyaniline with positive charges is 0.1-5 mg/mL; the mass concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.5-10 mg/mL.
9. The method for preparing a graphene/polyaniline composite membrane electrode material according to claim 1, 2, 3, 6 or 8, which is characterized in that: in the step 2), the spin coating mode is that the rotating speed of a spin coater is 100-3000 r/min, the dropping liquid amount is 0.1-0.5 mL/time, and the spin coating frequency is 5-50; in the step 3), the reducing agent used in the reduction treatment is at least one of hydroiodic acid, hydrazine hydrate and ascorbic acid.
10. The graphene/polyaniline composite membrane electrode material obtained by the preparation method of claim 1 is applied to a super capacitor.
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