CN111554521A - Preparation method of graphene/polyaniline flexible thin film electrode material - Google Patents
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 18
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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
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Abstract
The invention discloses a preparation method of a graphene/polyaniline flexible thin film electrode material, and belongs to the field of super capacitor energy storage device materials. The method comprises the following steps: (1) dispersing an oxidant and Graphene Oxide (GO) in deionized water to obtain a mixed solution; (2) carrying out reduced pressure suction filtration operation on the mixed solution to prepare a GO film adsorbing an oxidant; (3) immersing the GO thin film into a mixed solution of doping acid and aniline to obtain a GO/PANI thin film with Polyaniline (PANI) polymerized in situ on the surface; (4) and immersing the GO/PANI film into a reducing agent solution, and heating and reducing to obtain the graphene/polyaniline flexible film electrode material. The invention solves the problem that the cycle stability of a composite film is poor due to the fact that GO surface oxidation groups cannot be effectively utilized in the traditional construction scheme of a graphene/polyaniline flexible electrode material. The preparation method is simple to operate and good in repeatability, and the product can be directly used as a flexible electrode material.
Description
Technical Field
The invention relates to a material for a super capacitor energy storage device and a preparation method thereof, in particular to a graphene/polyaniline flexible thin film electrode material and a preparation process thereof.
Background
Polyaniline (PANI) is a typical conductive polymer material, has the advantages of low cost, easy synthesis, good flexibility and high capacitance, and is often applied to electrode materials of super capacitors. Graphene Oxide (GO) is a high-performance two-dimensional nano material, the surface of which contains hydroxyl, epoxy and other oxidizing groups, and can complete a self-assembly process through hydrogen bonds and an acidic medium oxidant, so that active sites are provided for the polymerization reaction of aniline, and reliable support is provided for the construction of a graphene/polyaniline composite material. At present, the flexible electronic industry is on the rise, higher requirements are put on the performance of the flexible super capacitor, and a chance is brought to the research of the preparation method of the high-performance graphene/polyaniline flexible thin-film electrode material.
However, in Amin Goljanian Talbrizi et al (Amin Goljanian Tabrizi, NasserArsani. A new route for the synthesis of polyaniline nanoarrays on graphene oxides for high-performance supercapacitors).Electrochimica Acta2018, 265, 379-. The method skillfully utilizes the oxidizing groups contained on the surface of GO to enable APS to be adsorbed on the surface of GO so as to initiate the in-situ polymerization reaction of aniline. However, in this scheme, there is a relatively excessive amount of oxidant, which is not self-assembled with GO but in a free state, and the free oxidant can induce aniline monomer to undergo polymerization to generate free PANI, but the interaction between the free PANI and graphene only depends on pi-pi stacking to perform interaction or even does not generate interaction, thereby severely limiting the improvement of the cycling stability of PANI. Furthermore, free PANI, which does not interact with graphene, is prone to disordered network packing, which is detrimental to better contact of the redox sites with the electrolyte and faster diffusion of protons and electrons inside the active materialThereby reducing the cycling stability of the electrode material.
In addition, Huai-Ping Cong et al (Huai-Ping Cong, Xiao-Chen ren. Flexiblegraphene-polyanaline composite paper for high-performance supercapacitors).Energy Environ.Sci2013, 6, 1185-1191) is that the conventional preparation method of the graphene/polyaniline flexible supercapacitor electrode is that GO is firstly subjected to heat treatment and reduced into a graphene flexible film, and then PANI is polymerized on the film. In this scheme, after GO is reduced, the oxidized groups on GO are eliminated, so that aniline loses the active sites where polymerization occurs, and as in the above case, free PANI interacting with graphene only by pi-pi stacking is generated, and the cycle stability of the electrode material is also reduced.
Disclosure of Invention
Aiming at the problems that GO surface oxidation groups cannot be effectively utilized, the interaction between free polyaniline and graphene is weak, and finally the circulation stability of the flexible thin film electrode material is poor in the traditional construction scheme of the graphene/polyaniline flexible electrode material, the invention aims to provide a preparation method of the graphene/polyaniline flexible thin film electrode material with greatly improved circulation stability, covalent bond links between polyaniline and the surfaces of all layers of graphene are established, the regular accumulation of polyaniline is realized, and the specific capacity and the circulation stability of the composite material are improved.
The invention adopts a preparation method of decompression suction filtration and in-situ polymerization, which comprises the following steps: firstly, preparing a GO dispersion liquid absorbing an oxidant into a flexible film through a reduced pressure suction filtration operation, wherein in the step, the free oxidant which does not complete a self-assembly process with GO is removed while the oxidized groups on GO are completely reserved, so that the generation of free PANI is reduced, and the defect that the free PANI is easy to generate disordered network accumulation is avoided; and then placing the GO thin film in an aniline monomer solution for PANI in-situ chemical polymerization, wherein the step makes full use of the oxidation groups contained on the surface of GO, provides active sites for the polymerization reaction of aniline, and avoids the defect that the interaction between free PANI and graphene is only dependent on pi-pi accumulation for interaction and even does not generate interaction. In a word, the method establishes covalent bond linkage between PANI and the surface of each graphene layer sheet, and simultaneously realizes the regular accumulation of polyaniline so as to achieve the purpose of improving the specific capacity and the cycling stability of the composite material.
The purpose of the invention is realized by the following process method:
a preparation method of a graphene/polyaniline flexible thin film electrode material comprises the following steps:
(1) dissolving an oxidant in deionized water to obtain a clear solution, and uniformly dispersing GO in the oxidant solution by adopting ultrasonic waves to obtain a mixed solution of the oxidant and GO;
(2) carrying out reduced pressure suction filtration operation on the mixed solution obtained in the step (1) to prepare a GO film adsorbing an oxidant;
(3) sequentially dissolving doping acid and aniline monomers in deionized water to obtain an acid monomer mixed solution; then immersing the GO film obtained in the step (2) into the acidic aniline monomer mixed solution, placing a reaction system in a low-temperature environment, and stirring at a low speed to obtain a GO/PANI film with in-situ polymerized PANI on the surface;
(4) dissolving a reducing agent in deionized water to obtain a reducing agent solution, then immersing the GO/PANI thin film obtained in the step (3) in the reducing agent solution, and heating and reducing to obtain the graphene/polyaniline flexible thin film electrode material.
The oxidant in the step (1) is an acidic medium oxidant, and includes but is not limited to ammonium persulfate, potassium dichromate, hydrogen peroxide and the like; the concentration range of the oxidant is 19.0-76.0mg/mL, and the optimal concentration range of the oxidant is 19.0-38.0 mg/mL; the concentration range of GO in the finally obtained mixed solution is 0.5-1.0mg/mL, the ultrasonic power is 250-300W, and the ultrasonic time is 15-20 min.
The aperture of the filter membrane used in the decompression suction filtration operation in the step (2) is 0.2-0.45 μm, the material is polytetrafluoroethylene or nylon-66, and the vacuum pressure of a vacuum pump is 0.2 Pa.
The doping acid in the step (3) includes, but is not limited to, water-soluble polyaniline doping acids such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like, the molar concentration range of the doping acid is 0.5-1 mol/L, the molar concentration range of the aniline monomer is 0.005-0.04mol/L, and the optimal aniline monomer concentration range is 0.005-0.01 mol/L; the low temperature environment is 0-5 ℃, the stirring speed is 60-100 rap/min, and the reaction time is 12-24 h.
The reducing agent types in the step (4) include but are not limited to hydrazine hydrate and derivatives thereof, ascorbic acid, hydroiodic acid and other GO reducing agents; the heating temperature is 90-95 ℃, and the reaction time is 1-1.5 h.
The molecular weight, conductivity and other properties of the PANI are greatly influenced by the using amount of the oxidant and the concentration of the monomer. The concentration of the oxidizing agent (in the range from 19.0 to 76.0 mg/mL) and the aniline monomer concentration (in the range from 0.005 to 0.04 mol/L) in the above-mentioned process parameters therefore have a decisive influence on the properties of the end product. When the concentration of the oxidant and the concentration of the aniline monomer are too high, the agglomeration condition of PANI on the GO outer layer sheet becomes serious, and the total polymerization PANI amount on the surface of each GO layer sheet is gradually reduced, so that the performances of the product, such as electrochemical capacity, cycling stability and the like, are affected, therefore, in the preparation process of the graphene/polyaniline flexible thin-film electrode material, the optimal concentration range of the oxidant is 19.0-38.0 mg/mL, and the optimal concentration range of the aniline monomer is 0.005-0.01 mol/L.
Compared with the prior art, the preparation process of the graphene/polyaniline film electrode material adopted by the invention has the advantages of simple operation and good repeatability, and the product can be directly used as a flexible electrode material. Meanwhile, covalent bond linkage between PANI and the surface of each graphene layer sheet is established, and the regular accumulation of polyaniline is realized, so that the aims of improving the specific capacity and the cycling stability of the composite material are fulfilled. The thin film electrode material is widely applied in the field of flexible super capacitor energy storage devices, and has very important practical significance and value.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
Fig. 2 is a cross-sectional scanning electron micrograph of the graphene/polyaniline flexible thin film electrode materials prepared in examples 1 and 3.
Fig. 3 is a surface scanning electron microscope photograph of the graphene/polyaniline flexible thin film electrode materials prepared in examples 1 and 3.
Fig. 4 is a full-spectrum of the surface analysis of the graphene/polyaniline flexible thin-film electrode material prepared in examples 1 and 2 by the X-ray photoelectron spectroscopy.
Fig. 5 is a diffraction pattern of a slightly incident X-ray of the graphene/polyaniline flexible thin-film electrode material prepared in example 3.
Fig. 6 is a graph showing the cycle stability of the graphene/polyaniline flexible thin-film electrode material prepared in example 3.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Example 1:
(1) 380 mg Ammonium Persulfate (APS) was dissolved in 10 mL deionized water to give a clear solution; adding 5 mg of GO into an APS solution, and ultrasonically dispersing for 20 min by adopting ultrasonic waves with the power of 250W to obtain a mixed solution;
(2) carrying out reduced pressure suction filtration operation on the mixed solution obtained in the step (1) to prepare an APS-adsorbed GO film;
(3) dissolving 92 mu L of aniline and 1339 mu L of concentrated sulfuric acid in 50 mL of deionized water to obtain a mixed solution, and placing the mixed solution in a low-temperature environment at 0 ℃ for pre-cooling; immersing the GO film obtained in the step (2) into the mixed solution, and continuously placing the GO film in a low-temperature environment at 0 ℃ for sufficient 24 hours under slow stirring to react to obtain a GO/PANI film with PANI polymerized on the surface;
(4) dissolving 100 mu L of hydrazine hydrate in 50 mL of deionized water to obtain a hydrazine hydrate solution; and (3) washing the film obtained in the step (3) for multiple times by using ethanol and deionized water to remove unreacted substances, immersing the film into the hydrazine hydrate solution, heating the film at 95 ℃ for 1 h to obtain a graphene/polyaniline flexible film, washing the flexible film for multiple times by using deionized water to remove redundant hydrazine hydrate, and drying the flexible film at 60 ℃ to obtain a final product.
The cross-sectional microscopic morphology of the prepared sample is shown as a in fig. 2, the whole thin film presents lamellar morphology, and the PANI is uniformly distributed on each layer of the GO. The surface microscopic morphology of the prepared sample is shown as a in fig. 3, PANI is in an agglomerated state at a specific position of the GO surface, and the rest positions are in a uniformly spread state. The full spectrum of the X-ray photoelectron spectroscopy surface analysis of the prepared sample is shown as a in FIG. 4, and the flexible film mainly contains C, N, O three elements.
Example 2:
(1) dissolving 190 mg of APS in 10 mL of deionized water to obtain a clear solution; adding 5 mg of GO into an APS solution, and ultrasonically dispersing for 20 min by adopting ultrasonic waves with the power of 250W to obtain a mixed solution;
(2) carrying out reduced pressure suction filtration operation on the mixed solution obtained in the step (1) to prepare an APS-adsorbed GO film;
(3) dissolving 92 mu L of aniline and 1339 mu L of concentrated sulfuric acid in 50 mL of deionized water to obtain a mixed solution, and placing the mixed solution in a low-temperature environment at 0 ℃ for pre-cooling; immersing the GO film obtained in the step (2) into the mixed solution, and continuously placing the GO film in a low-temperature environment at 0 ℃ for sufficient 24 hours under slow stirring to react to obtain a GO/PANI film with PANI polymerized on the surface;
(4) dissolving 100 mu L of hydrazine hydrate in 50 mL of deionized water to obtain a hydrazine hydrate solution; and (3) washing the film obtained in the step (3) for multiple times by using ethanol and deionized water to remove unreacted substances, immersing the film into the hydrazine hydrate solution, heating the film at 95 ℃ for 1 h to obtain a graphene/polyaniline flexible film, washing the flexible film for multiple times by using deionized water to remove redundant hydrazine hydrate, and drying the flexible film at 60 ℃ to obtain a final product.
The full spectrum of the X-ray photoelectron spectroscopy surface analysis of the prepared sample is shown as b in FIG. 4, and the flexible film mainly contains C, N, O three elements.
Example 3:
(1) 380 mg APS was dissolved in 10 mL deionized water to give a clear solution; adding 5 mg of GO into an APS solution, and ultrasonically dispersing for 20 min by adopting ultrasonic waves with the power of 250W to obtain a mixed solution;
(2) carrying out reduced pressure suction filtration operation on the mixed solution obtained in the step (1) to prepare an APS-adsorbed GO film;
(3) dissolving 23 mu L of aniline and 1339 mu L of concentrated sulfuric acid in 50 mL of deionized water to obtain a mixed solution, and placing the mixed solution in a low-temperature environment at 0 ℃ for pre-cooling; immersing the GO film obtained in the step (2) into the mixed solution, and continuously placing the GO film in a low-temperature environment at 0 ℃ for sufficient 24 hours under slow stirring to react to obtain a GO/PANI film with PANI polymerized on the surface;
(4) dissolving 100 mu L of hydrazine hydrate in 50 mL of deionized water to obtain a hydrazine hydrate solution; and (3) washing the film obtained in the step (3) for multiple times by using ethanol and deionized water to remove unreacted substances, immersing the film into the hydrazine hydrate solution, heating the film at 95 ℃ for 1 h to obtain a graphene/polyaniline flexible film, washing the flexible film for multiple times by using deionized water to remove redundant hydrazine hydrate, and drying the flexible film at 60 ℃ to obtain a final product.
The cross-sectional microscopic morphology of the prepared sample is shown as b in fig. 2, the whole thin film presents lamellar morphology, and the PANI is uniformly distributed on each layer of GO. The surface microscopic morphology of the prepared sample is shown as b in fig. 3, PANI presents a uniform spinous process-like morphology, and two aggregation states of chain entanglement and aggregation of PANI alone do not occur. A slightly incident X-ray diffraction (GIXRD) analysis of the prepared samples is shown in FIG. 5, where comparative rGO film samples are at 2θTypical diffraction peaks occur around = 25 °, and the prepared flexible film sample was 2 ° except that this diffraction peak was maintained thereθThe increase in intensity of diffraction peaks around = 17 ° and 30 ° occurs, which are related to the presence of PANI. In addition, the diffraction peak of the GIXRD spectrogram of the flexible film sample is shifted to the left as a whole, and the reason is that PANI positioned between graphene layers and each graphene layer generate covalent bond interaction, so that the interplanar spacing of graphene is enlarged. The cycle stability curve for the prepared sample is shown in FIG. 6, with the flexible film sample at 0.5A g-1Specific capacity at current density of 462F g-1And the capacity retention rate is 97.3 percent after 1000 cycles of charge and discharge. The specific capacity of the graphene/polyaniline film electrode sample related by the invention is higher than that of the graphene/polyaniline film electrode sample adopting reduced pressureAbout 250F g of rGO flexible thin film electrode prepared by suction filtration method-1The specific capacity of the graphene/polyaniline flexible electrode material is far higher than the capacity retention rate of 52% of a pure PANI electrode material after 1000 cycles, and is also higher than the capacity retention rate of 82% of the graphene/polyaniline flexible electrode material prepared by the Huai-Ping Cong in the technical background in the traditional preparation method of the graphene/polyaniline flexible electrode material.
Example 4:
(1) 380 mg APS was dissolved in 10 mL deionized water to give a clear solution; adding 5 mg of GO into an APS solution, and ultrasonically dispersing for 20 min by adopting ultrasonic waves with the power of 250W to obtain a mixed solution;
(2) carrying out reduced pressure suction filtration operation on the mixed solution obtained in the step (1) to prepare an APS-adsorbed GO film;
(3) dissolving 46 mu L of aniline and 1339 mu L of concentrated sulfuric acid in 50 mL of deionized water to obtain a mixed solution, and placing the mixed solution in a low-temperature environment at 0 ℃ for pre-cooling; immersing the GO film obtained in the step (2) into the mixed solution, and continuously placing the GO film in a low-temperature environment at 0 ℃ for sufficient 24 hours under slow stirring to react to obtain a GO/PANI film with PANI polymerized on the surface;
(4) dissolving 100 mu L of hydrazine hydrate in 50 mL of deionized water to obtain a hydrazine hydrate solution; and (3) washing the film obtained in the step (3) for multiple times by using ethanol and deionized water to remove unreacted substances, immersing the film into the hydrazine hydrate solution, heating the film at 95 ℃ for 1 h to obtain a graphene/polyaniline flexible film, washing the flexible film for multiple times by using deionized water to remove redundant hydrazine hydrate, and drying the flexible film at 60 ℃ to obtain a final product.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. A preparation method of a graphene/polyaniline flexible thin film electrode material is characterized by comprising the following steps:
(1) dissolving an oxidant in deionized water to obtain a clear solution, and uniformly dispersing graphene oxide in the oxidant solution by adopting ultrasonic waves to obtain a mixed solution of the oxidant and the graphene oxide;
(2) carrying out reduced pressure suction filtration operation on the mixed solution obtained in the step (1) to prepare a graphene oxide film for adsorbing an oxidant;
(3) sequentially dissolving doping acid and aniline monomers in deionized water to obtain an acid monomer mixed solution; then immersing the graphene oxide film obtained in the step (2) into the acidic aniline monomer mixed solution, placing the reaction system in a low-temperature environment, and stirring at a low speed to obtain a graphene oxide/polyaniline film with polyaniline polymerized in situ on the surface;
(4) dissolving a reducing agent in deionized water to obtain a reducing agent solution, then immersing the graphene oxide/polyaniline film obtained in the step (3) in the reducing agent solution, and heating and reducing to obtain the graphene/polyaniline flexible film electrode material.
2. The preparation method of the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1, wherein the oxidant in step (1) is an acidic medium oxidant, including but not limited to ammonium persulfate, potassium dichromate or hydrogen peroxide; the concentration range of the oxidant is 19.0-76.0mg/mL, and the concentration range of the graphene oxide in the mixed solution is 0.5-1.0 mg/mL.
3. The preparation method of the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1 or 2, wherein the concentration range of the oxidant is 19.0-38.0 mg/mL.
4. The method for preparing the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1, wherein the ultrasonic power is 250- & lt300W, and the ultrasonic time is 15-20 min.
5. The method for preparing a graphene/polyaniline flexible thin-film electrode material as claimed in claim 1, wherein the aperture of the filter membrane used in the reduced-pressure suction filtration operation in step (2) is 0.2-0.45 μm, and the material is polytetrafluoroethylene or nylon-66.
6. The preparation method of the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1 or 5, wherein the vacuum pressure of a vacuum pump in the decompression suction filtration operation is 0.2 Pa.
7. The method for preparing the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1, wherein the doping acid in step (3) includes but is not limited to sulfuric acid, hydrochloric acid or p-toluenesulfonic acid, the molar concentration of the doping acid is in the range of 0.5-1 mol/L, the molar concentration of aniline monomer is in the range of 0.005-0.04mol/L, the low-temperature environment is in the range of 0-5 ℃, the stirring speed is 60-100 rap/min, and the reaction time is 12-24 h.
8. The preparation method of the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1 or 7, wherein the concentration of the aniline monomer is in the range of 0.005-0.01 mol/L.
9. The method for preparing the graphene/polyaniline flexible thin-film electrode material as claimed in claim 1, wherein the reducing agent species in step (4) include, but are not limited to, hydrazine hydrate and its derivatives, ascorbic acid or hydroiodic acid; the heating temperature is 90-95 ℃, and the reaction time is 1-1.5 h.
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