CN116230422B - Preparation method of chiffon-shaped graphene/polyaniline supercapacitor electrode material - Google Patents
Preparation method of chiffon-shaped graphene/polyaniline supercapacitor electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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Abstract
The invention belongs to the technical field of electrode materials of energy storage devices, and discloses a preparation method of a chiffon-shaped graphene/polyaniline (rGO/PANI) super capacitor electrode material. According to the invention, a thin layer MnO 2 grows on rGO sheets through the oxidation-reduction reaction of KMnO 4 and C, then MnO 2 is used as a template agent and an oxidant, and along with the oxidation-reduction reaction, mnO 2 initiates aniline oxidation polymerization and simultaneously generates soluble Mn 2+ to be consumed, so that PANI replicates the morphology of a MnO 2 template, and a thin layer is formed on the rGO sheets to form a chiffon rGO/PANI composite material. Compared with PANI, the gauze-like rGO/PANI composite electrode material prepared by the invention has excellent multiplying power performance and cycle stability, and can be applied and popularized in the field of super capacitor electrode materials.
Description
Technical Field
The invention belongs to the technical field of electrode materials of energy storage devices, and particularly relates to a preparation method of a chiffon-shaped graphene/polyaniline (rGO/PANI) super capacitor electrode material.
Background
PANI is a widely studied supercapacitor electrode material, and has the advantages of high doping capacity, good conductivity, high theoretical specific capacity, good environmental stability and the like, but because PANI is a typical pseudo-capacitor electrode material, charge is stored and released through oxidation-reduction reaction of a polymer chain, the capacitance of the PANI is fast in decay under high current density, and in the continuous charge-discharge process, the volume change of PANI is caused by ion intercalation/deintercalation, so that the property of the PANI is continuously degraded. Researchers have employed a number of effective measures to improve the capacitive properties of PANI electrode materials, with compounding PANI with graphene (rGO) being a very effective approach.
At present, most of rGO/PANI composite materials reported in literature and patent are prepared by oxidizing and polymerizing aniline by taking NH 4)2S2O8 as an oxidant, the prepared rGO/PANI composite material is thicker in sheet layer, PANI vertically grows on an rGO matrix in a burr shape or forms a composite material .(ACS Nano,2012,6,1715–1723.Journal of Physical Chemistry C,2012,116,5420-5426.Electrochimica Acta,2017,228,290–298.Journal of Physics and Chemistry of Solids,2022,165,110673–10689. patent CN 105694031A in a fibrous shape and the like with rGO, and although the capacitance property of the composite materials is improved, a certain difference is still obtained from practical application.
In fact, the capacitance property of the electrode material is closely related to the nano structure, so that the design and preparation of the rGO/PANI composite electrode material with reasonable nano structure are very significant for improving the capacitance property.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a preparation method of a chiffon-shaped graphene/polyaniline (rGO/PANI) super capacitor electrode material with excellent rate capability and cycle stability.
In order to achieve the technical aim, the inventor selects a template agent MnO 2 to oxidize an aniline monomer, mnO 2 is environment-friendly, raw materials for preparation are easy to obtain, the template agent is a strong oxidant under an acidic condition, the reduction potential (1.23 Vvs. NHE) of the template agent is higher than the oxidative polymerization potential (0.55V vs. NHE) of the aniline monomer, and the template agent can be used as a solid oxidant for oxidizing the aniline monomer. The invention has the following overall conception: and growing a thin layer MnO 2 on the rGO sheet layer through the oxidation-reduction reaction of KMnO 4 and C, taking MnO 2 as a template agent and an oxidant, and along with the oxidation-reduction reaction, generating soluble Mn 2+ and being consumed when the oxidation polymerization of aniline is initiated by MnO 2, so that the PANI replicates the morphology of the MnO 2 template, and forming a thin layer on the rGO sheet layer to form a chiffon rGO/PANI composite material.
Specifically, the invention aims at realizing the following technical scheme:
The preparation method of the chiffon rGO/PANI supercapacitor electrode material comprises the following steps:
(1) Preparation of chiffon rGO/MnO 2: adding KMnO 4 into rGO nano-layer dispersion liquid, stirring to dissolve KMnO 4, heating, refluxing, stirring and reacting at 70-80 ℃ for 2-3 h, washing with water, and suction filtering to obtain a chiffon-shaped solid intermediate product rGO/MnO 2;
(2) Preparation of chiffon-like rGO/PANI: adding the chiffon-shaped solid intermediate product rGO/MnO 2 into ultrapure water, performing ultrasonic dispersion to form uniform dispersion, adding an aniline monomer, stirring for 25-40 min to enable the aniline monomer to reach saturated adsorption on the rGO/MnO 2 sheet, precooling in an ice bath, adding a precooled 0.2-0.5 mol/L H 2SO4 solution to adjust the pH value of the system to be 0.4-0.8, stirring and reacting for 6-12H under the ice bath condition, washing with water, washing with alcohol, performing suction filtration, and freeze-drying to obtain the chiffon-shaped rGO/PANI.
Further preferably, the method for preparing the chiffon rGO/PANI supercapacitor electrode material comprises the following steps of (1) a mass ratio of rGO to KMnO 4 of 1: (1.17-2.34).
Further preferably, the preparation method of the gauze-like rGO/PANI super capacitor electrode material is as described above, wherein the heating reflux temperature in the step (1) is 70 ℃, and the reaction time is 2 hours.
Further preferably, the preparation method of the chiffon rGO/PANI super capacitor electrode material is characterized in that the temperature of the ice bath in the step (2) is 0-5 ℃ and the reaction time is 6 hours.
Further preferred is a method for preparing a chiffon-shaped rGO/PANI supercapacitor electrode material as described above, wherein in step (2) the ph=0.4 of the system is adjusted by adding a pre-chilled H 2SO4 solution.
Further preferably, the preparation method of the chiffon-shaped rGO/PANI super capacitor electrode material as described above, wherein the preparation method of the rGO nano-layer dispersion liquid in the step (1) comprises the following steps: adding hydrazine hydrate and ammonia water into the graphite oxide nano layer dispersion liquid system, stirring for 20-40 min at room temperature, continuously stirring for 0.8-1.2 h under the oil bath condition of 94-96 ℃, cooling to room temperature, centrifuging, and removing the rGO nano layer which is not completely stripped to obtain stable and uniformly dispersed rGO nano layer dispersion liquid.
Compared with the prior art, the invention has the following advantages and remarkable improvements:
(1) The preparation method has mild preparation conditions and controllable process, does not need to add an additional oxidant, and can enable aniline monomers to grow two-dimensionally along the interface of the MnO 2 nanometer layer, so that the MnO 2 template agent and the aniline monomers which are adsorbed and saturated in advance react rapidly to form a large number of polymerization centers, thereby greatly consuming MnO 2 in a short time, effectively inhibiting the secondary growth process of PANI, enabling PANI to successfully replicate the shape of the template agent, and the prepared chiffon rGO/PANI has excellent capacitance property.
(2) The chiffon-shaped rGO/PANI composite material prepared by the method has the following advantages: the substrate material rGO has a large specific surface area, and the gauze-like rGO/PANI composite material formed after the PANI thin layer is grown has rich electrochemical reaction active sites, so that full play of pseudocapacitance is facilitated; the excellent conductivity of rGO ensures that the composite material has good conductivity when the PANI is in an insulating state, and is beneficial to the rapid transmission of electrons; the unique structural flexibility of rGO plays an effective role in buffering the volume change of PANI in electrochemical reaction. Therefore, compared with PANI, the gauze-like rGO/PANI composite electrode material has excellent multiplying power performance and cycle stability, and can be applied and popularized in the field of super capacitor electrode materials.
Drawings
FIG. 1 shows XRD patterns of rGO (a) prepared in comparative example 1, rGO/MnO 2 -1 (b) and rGO/PANI-1 (c) prepared in example 1;
FIG. 2 is a TEM photograph of rGO (a) prepared in comparative example 1, rGO/MnO 2 -1 (b) prepared in example 1, rGO/MnO 2 -2 (C) prepared in example 2 and rGO/MnO 2 -C1 (d) prepared in comparative example 2 according to the present invention;
FIG. 3 is a TEM photograph of rGO/PANI-1 (a) prepared in example 1, rGO/PANI-2 (b) prepared in example 2 and rGO/PANI-C1 (C) prepared in comparative example 2 according to the present invention;
FIG. 4 is a FESEM photograph of rGO/PANI-1 (a) prepared in example 1, rGO/PANI-2 (b) prepared in example 2 and rGO/PANI-C1 (C) prepared in comparative example 2;
FIG. 5 is a facial photograph of C, O, N elements of rGO/PANI-1 prepared in example 1 of the present invention;
FIG. 6 is a FESEM photograph of rGO/PANI-3 prepared in example 3 of the present invention;
FIG. 7 is a FESEM photograph of rGO/PANI-4 prepared in example 4 of the present invention;
FIG. 8 is a FESEM photograph of rGO/PANI-5 prepared in example 5 of the present invention;
FIG. 9 is a FESEM photograph of rGO/PANI-6 prepared in example 6 of the present invention;
FIG. 10 is a graph showing constant current charge and discharge curves of the rGO/PANI-1, rGO/PANI-2 and rGO/PANI-C1 prepared in example 1, example 2 and comparative example 2 at current densities of 0.25A/g (a) and 10A/g (b) and a capacitance retention ratio of (C) in the range of 0.25 to 10A/g;
FIG. 11 is a constant current charge-discharge curve of rGO prepared in comparative example 1 at a current density of 0.25A/g;
FIG. 12 is a FESEM photograph (a) of rGO/PANI-C2 prepared in comparative example 3 and constant current charge-discharge curves at current densities of 0.25A/g (b) and 10A/g (C);
FIG. 13 is a FESEM photograph (a) of rGO/PANI-C3 prepared in comparative example 4 and constant current charge-discharge curves at current densities of 0.25A/g (b) and 10A/g (C);
FIG. 14 is a FESEM photograph (a) of PANI prepared in comparative example 5 and constant current charge-discharge curves at current densities of 0.25A/g (b) and 10A/g (c);
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the accompanying tables and examples, which are provided for illustrating the present invention only and should not be construed as limiting the scope of the present invention. In addition, the specific technical operation steps or conditions are not noted in the examples, and are carried out according to the techniques or conditions described in the literature in the field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The preparation and electrochemical testing method of the working electrode are as follows:
Working electrodes were prepared from samples obtained in the examples of the present invention: 3mg of active substance is weighed according to the active substance: acetylene black: the mass ratio of the polytetrafluoroethylene adhesive is 90 percent: 5%:5 percent, sequentially adding the materials into an agate mortar, adding a proper amount of ethanol, grinding into paste, uniformly coating on a stainless steel mesh with the thickness of 1cm multiplied by 1cm to prepare a sandwich structure, baking in an oven at 60 ℃ for 10 hours, and tabletting (the pressure is 5 MPa).
The electrochemical test adopts a three-electrode system, an electrode manufactured by the method is used as a working electrode, a platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the mass ratio capacitance of an electrode material is calculated by testing a constant current charge-discharge curve in H 2SO4 electrolyte with the concentration of 1mol/L, and the capacitance retention rate and the cycle stability of the electrode material are calculated based on the capacitance.
Example 1: preparation of chiffon-like rGO/PANI-1
(1) Adding 34 mu L (50%) of hydrazine hydrate and 200 mu L (25%) of ammonia water into 100mL of GO nano layer dispersion liquid system with the concentration of 0.25mg/mL, stirring for 30min at room temperature, raising the temperature of an oil bath to 95 ℃ and continuously stirring for 1h, cooling to room temperature, centrifuging at 3000rpm for 30min, and removing the rGO nano layer which is not completely stripped, thus obtaining the rGO nano layer dispersion liquid with stable and uniform dispersion.
(2) And (3) adding 20mgKMnO 4 to 95mL of the rGO nano-layer dispersion liquid obtained in the step (1), stirring and dissolving, heating, refluxing and stirring at 70 ℃ for 2 hours, washing with water, and filtering to obtain solid rGO/MnO 2 -1.
(3) Adding 30mL of ultrapure water into the rGO/MnO 2 -1 obtained in the step (2), performing ultrasonic dispersion for 30min to form a uniform dispersion, adding 110 mu L of aniline, stirring for 30min, precooling in an ice bath, adding precooled 20mL of H 2SO4 solution with the concentration of 0.2mol/L, stirring in the ice bath, reacting for 6H, washing with water, washing with alcohol, performing suction filtration, and freeze-drying to obtain the rGO/PANI-1.
XRD pattern analysis was carried out on the solid product obtained in the steps (2) and (3), and as shown in FIGS. 1 (b) and (c), it can be explained from the assignment of the crystal planes to which the diffraction peaks belong: the intermediate product obtained in the step (2) is a complex of rGO and lamellar MnO 2, and the final product obtained in the step (3) is a complex of rGO and PANI, so that the MnO 2 is used as a self-sacrifice template oxidant to successfully oxidize and polymerize aniline. In addition, by TEM scanning, a TEM photograph of rGO/MnO 2 -1 is shown in FIG. 2 (b), it can be seen that the surface of the prepared chiffon-shaped rGO/MnO 2 -1 is uniform, which shows that the MnO 2 layer grows uniformly on the rGO sheet, and the layer thickness is increased compared with that of rGO. The TEM and FESEM photographs of rGO/PANI-1 of FIGS. 3 (a) and 4 (a) are identical in character, indicating that PANI successfully replicates the morphology of the oxidant and ultimately produces a tissue-like product rGO/PANI. In addition, the element surface scanning result further shows that the PANI thin layer on the rGO sheet layer grows uniformly. The mass specific capacitance of the rGO/PANI-1 electrode material at 0.25A/g was calculated from the constant current charge-discharge curves of FIGS. 10 (a) and (b) to be 435F/g, the mass specific capacitance of 10A/g was 364F/g, and the capacitance retention was 84% when the current density was increased from 0.25A/g to 10A/g. After continuous charge and discharge for 1000 times at 10A/g, the mass ratio capacitance is 80% of the initial value.
Example 2: preparation of chiffon-like rGO/PANI-2
(1) Adding 34 mu L (50%) of hydrazine hydrate and 200 mu L (25%) of ammonia water into 100mL of GO nano layer dispersion liquid system with the concentration of 0.25mg/mL, stirring for 30min at room temperature, raising the temperature of an oil bath to 95 ℃ and continuously stirring for 1h, cooling to room temperature, centrifuging at 3000rpm for 30min, and removing the rGO nano layer which is not completely stripped, thus obtaining the rGO nano layer dispersion liquid with stable and uniform dispersion.
(2) And (2) adding 40mgKMnO 4 to 95mL of rGO nano-layer dispersion liquid obtained in the step (1), stirring and dissolving, heating, refluxing and stirring at 70 ℃ for 2 hours, washing with water, and filtering to obtain solid rGO/MnO 2 -2.
(3) Adding 30mL of ultrapure water into the rGO/MnO 2 -2 obtained in the step (2) to carry out ultrasonic dispersion for 30min to form a uniform dispersion, adding 110 mu L of aniline, stirring for 30min, precooling in an ice bath, adding precooled 20mL of H 2SO4 solution with the concentration of 0.2mol/L, stirring in the ice bath, reacting for 6H, washing with water, washing with alcohol, filtering, and freeze-drying to obtain rGO/PANI-2.
And (3) carrying out TEM scanning on the solid product obtained in the step (2), wherein a TEM picture of rGO/MnO 2 -2 is shown as a figure 2 (c), a MnO 2 layer uniformly grows on the rGO sheet layer, and the thickness of the layer is increased compared with that of the layer of rGO/MnO 2 -1. The TEM and FESEM photographs of rGO/PANI-2 of FIGS. 3 (b) and 4 (b) are consistent, indicating that PANI successfully replicates the morphology of the oxidant to ultimately produce a tissue-like product rGO/PANI, with an increased rGO/PANI-2 thickness compared to rGO/PANI-1. The mass specific capacitance of the rGO/PANI-2 electrode material at 0.25A/g was 486F/g, the mass specific capacitance at 10A/g was 370F/g, and the capacitance retention was 76% when the current density was increased from 0.25A/g to 10A/g, as calculated from the constant current charge-discharge curves of FIGS. 10 (a) and (b). The mass ratio capacitance was 74% of the initial value after 1000 times of continuous charge and discharge at 10A/g. Although the increase in the PANI layer thickness of the chiffon-rGO/PANI-2 increases its initial capacitance at low current densities, the rate performance and cycling stability are slightly degraded.
Example 3: preparation of chiffon-like rGO/PANI-3
In this example, the mixture was heated to reflux at 80℃for 2 hours, and the other experimental conditions and the procedure were the same as in example 2. FESEM photograph of the prepared sample rGO/PANI-3 is shown in FIG. 6, which shows that the preparation of gauze-like rGO/PANI was successful under the experimental conditions.
Example 4: preparation of chiffon-like rGO/PANI-4
In this example, the mixture was refluxed at 70℃for 3 hours, and the procedure was the same as in example 2. FESEM pictures of the prepared sample rGO/PANI-4 are shown in FIG. 7, indicating that the preparation of chiffon rGO/PANI was successful under the experimental conditions.
Example 5: preparation of chiffon-like rGO/PANI-5
In this example, the ice bath stirring reaction time was changed to 12 hours in step (3), and the procedure was the same as in example 2 except that experimental conditions were used. FESEM pictures of the prepared sample rGO/PANI-5 are shown in FIG. 8, indicating that the preparation of chiffon rGO/PANI was successful under the experimental conditions.
Example 6: preparation of chiffon-like rGO/PANI-6
In this example, the pre-chilled 20mLH 2SO4 solution concentration was changed to 0.5mol L -1 in step (3), and the other experimental conditions were performed in the same manner as in example 2. FESEM pictures of the prepared sample rGO/PANI-6 are shown in FIG. 9, indicating that the preparation of chiffon rGO/PANI was successful under the experimental conditions.
Comparative example 1: preparation of rGO
In the comparative example, the graphene nano-layer dispersion liquid prepared in the step (1) of the example 1 is filtered, washed with water, washed with alcohol, filtered with suction, and freeze-dried to obtain rGO.
XRD patterns and TEM pictures of the prepared product rGO are shown in fig. 1 (a) and 2 (a), diffraction peaks in fig. 1 (a) belong to characteristic diffraction peaks of rGO, and the thin yarn-like morphology of rGO folds is clearly visible in fig. 2 (a). The constant current charge-discharge curve of the rGO electrode material at the current density of 0.25A/g is shown in FIG. 11, and the mass specific capacitance of the rGO electrode material at the current density of 0.25A/g is only 118F/g.
Comparative example 2: preparation of rGO/PANI-C1
In this comparative example, the mass of KMnO 4 added in the step (2) was changed to 70mg, and the procedure for the experimental conditions was the same as in example 2.
FESEM pictures of the prepared intermediate rGO/MnO 2 -C1 are shown in FIG. 2 (d), and TEM and FESEM pictures of the final product rGO/PANI-C1 are shown in FIG. 3 (C) and FIG. 4 (C). When the KMnO 4 dosage is increased to 70mg, the rGO lamellar surface generates a standing-up scale MnO 2 nano-sheet. The tissue-like morphology of the final product rGO/PANI-C1 disappears, the concave-convex PANI is generated on the rGO surface, and the thickness increase is very obvious. The mass specific capacitance of the rGO/PANI-C1 electrode material at 0.25A/g was calculated from the constant current charge-discharge curves of FIGS. 10 (a) and (b) to be 530F/g, the mass specific capacitance of 10A/g was 298F/g, and the capacitance retention was 56% when the current density was increased from 0.25A/g to 10A/g. After 10A/g is continuously charged and discharged 1000 times, the mass ratio capacitance is 62% of the initial value, and compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials, the rGO/MnO 2 -C1 has remarkably reduced rate capability and cycle stability.
Comparative example 3: preparation of rGO/PANI-C2
In this comparative example, the pre-chilled 20mL H 2SO4 solution concentration was changed to 1mol/L in step (3), and the experimental procedure was the same as in example 2.
FESEM pictures and constant current charge-discharge curves of the prepared sample rGO/PANI-C2 are shown in FIG. 12. The gauze-like morphology disappeared, indicating that the proper H 2SO4 solution concentration in the system plays an important role in the PANI replication of the oxidant morphology. The rGO/PANI-C2 electrode material has a mass specific capacitance of 452F/g and a mass specific capacitance of 306F/g at 0.25A/g, and the capacitance retention rate is 68% when the current density is increased from 0.25A/g to 10A/g. After the charge and discharge of 10A/g for 1000 times, the mass ratio capacitance was 63% of the initial value. The rGO/PANI-C2 has significantly reduced rate capability and cycle stability compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials.
Comparative example 4: preparation of rGO/PANI-C3
(1) Filtering the graphene nano-layer dispersion liquid prepared by the method in the step (1) of the embodiment 1, adding 30mL of ultrapure water, performing ultrasonic dispersion for 30min to form a uniform dispersion liquid, adding 110 mu L of aniline, stirring for 30min, and precooling in an ice bath;
(2) 180mg (NH 4)2S2O8 is added to a solution of H 2SO4 with a concentration of 0.2mol/L and dissolved by stirring, and precooled in an ice bath;
(3) And (3) rapidly adding the solution obtained in the step (2) into the system of the step (1), stirring and reacting for 6 hours in an ice bath, and washing with water, washing with alcohol, filtering and drying to obtain rGO/PANI-C3.
The morphology of the obtained solid product is characterized, the FESEM photo and the constant current charge-discharge curve are shown in figure 13, and the surface of the rGO sheet layer grows into a brush-shaped PANI, so that the MnO 2 template oxidant plays a key role in generating the chiffon-shaped rGO/PANI composite material. The rGO/PANI-C3 electrode material has a mass specific capacitance of 391F/g at 0.25A/g and 272F/g at 10A/g. The capacitance retention was 70% when the current density increased from 0.25A/g to 10A/g. After 1000 times of charge and discharge of 10A/g, the mass ratio capacitance is 72% of the initial value. Compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials, the rGO/PANI-C3 has reduced mass specific capacitance, rate capability and cycle stability.
Comparative example 5: PANI preparation
(1) 110 Mu L of aniline is added into 30mL of ultrapure water and stirred for 30min, and precooled in an ice bath;
(2) 180mg (NH 4)2S2O8 is added to a solution of H 2SO4 with a concentration of 0.2mol/L and dissolved by stirring, and precooled in an ice bath;
(3) And (3) rapidly adding the solution obtained in the step (2) into the system of the step (1), stirring and reacting for 6 hours in an ice bath, and washing with water, washing with alcohol, filtering and drying to obtain PANI.
The morphology of the obtained solid product was characterized, the FESEM photograph and the constant current charge-discharge curve are shown in FIG. 14, and PANI is a curved short nanofiber. The PANI electrode material has a mass specific capacitance of 532F/g at 0.25A/g and a mass specific capacitance of 293F/g at 10A/g. The capacitance retention was 55% when the current density increased from 0.25A/g to 10A/g. After the charge and discharge of 10A/g for 1000 times, the mass ratio capacitance is 60% of the initial value. PANI has significantly reduced rate capability and cycling stability compared to the chiffon-shaped rGO/PANI-1 and rGO/PANI-2 electrode materials.
Table 1 shows mass specific capacitances, capacitance retention rates and cycling stabilities of rGO/PANI-1, rGO/PANI-2, rGO/PANI-C1, rGO/PANI-C2, rGO/PANI-C3 and PANI prepared in examples 1, 2, 3, 4 and 5 of the present invention.
TABLE 1
Claims (6)
1. The preparation method of the chiffon rGO/PANI supercapacitor electrode material comprises the following steps:
(1) Preparation of chiffon rGO/MnO 2: adding KMnO 4 into rGO nano-layer dispersion liquid, stirring to dissolve KMnO 4, heating, refluxing, stirring and reacting at 70-80 ℃ for 2-3 h, washing with water, and suction filtering to obtain a chiffon-shaped solid intermediate product rGO/MnO 2;
(2) Preparation of chiffon-like rGO/PANI: adding the chiffon-shaped solid intermediate product rGO/MnO 2 into ultrapure water, performing ultrasonic dispersion to form uniform dispersion, adding an aniline monomer, stirring for 25-40 min to enable the aniline monomer to reach saturated adsorption on the rGO/MnO 2 sheet, precooling in an ice bath, adding a precooled 0.2-0.5 mol/L H 2SO4 solution to adjust the pH value of the system to be 0.4-0.8, stirring and reacting for 6-12H under the ice bath condition, washing with water, washing with alcohol, performing suction filtration, and freeze-drying to obtain the chiffon-shaped rGO/PANI.
2. The preparation method of Bao Shazhuang rGO/PANI supercapacitor electrode material according to claim 1, wherein in step (1), the mass ratio of rGO to KMnO 4 is 1: (1.17-2.34).
3. The method for preparing Bao Shazhuang rGO/PANI supercapacitor electrode material according to claim 1, wherein the heating reflux temperature in step (1) is 70 ℃ and the reaction time is 2 hours.
4. The method for preparing Bao Shazhuang rGO/PANI super capacitor electrode material according to claim 1, wherein the temperature of the ice bath in the step (2) is 0-5 ℃ and the reaction time is 6h.
5. The method for preparing Bao Shazhuang rGO/PANI supercapacitor electrode material according to claim 1, wherein in step (2), ph=0.4 of the system is adjusted by adding a pre-chilled H 2SO4 solution.
6. The preparation method of Bao Shazhuang rGO/PANI supercapacitor electrode material according to claim 1, wherein the preparation method of the rGO nanolayer dispersion liquid in step (1) is as follows: adding hydrazine hydrate and ammonia water into the graphite oxide nano layer dispersion liquid system, stirring for 20-40 min at room temperature, continuously stirring for 0.8-1.2 h under the oil bath condition of 94-96 ℃, cooling to room temperature, centrifuging, and removing the rGO nano layer which is not completely stripped to obtain stable and uniformly dispersed rGO nano layer dispersion liquid.
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