A PPy-Cu2O-C 60 Ternary composites, methods of making and using the same

Abstract

The application relates to a PPy-Cu2O-C 60 A ternary composite material, a preparation method and application thereof, comprising the following steps: (1) mixing water and dichloromethane, and ultrasonic treatment to form a uniform oil-water mixed solution; pyrrole monomers, aniline monomers, Cu2O powder and C 60 Powder are added into the oil-water mixed solution, and after ultrasonic and stirring treatment, an oil-in-water emulsion system containing polymer monomers, Cu2O and C 60 Powder is formed; (2) an oxidant solution is added into the emulsion system obtained in the step (1), and an oxidation polymerization reaction is carried out to obtain a composite product containing a polymer; (3) the composite product obtained in the step (2) is filtered and cleaned, and then is subjected to centrifugal separation, cleaning and drying to obtain the PPy-Cu2O-C 60 Ternary composite material.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials technology, specifically relating to a PPy-Cu2O-C 60 Ternary composite materials, their preparation methods, and applications. Background Technology

[0002] Conductive polymers are a class of polymeric materials with a conjugated π-electron backbone structure. They combine the processability of traditional polymers with the conductivity of metallic materials, showing broad application prospects in fields such as antistatic coatings, electromagnetic shielding, energy storage, and sensing.

[0003] In recent years, conductive polymers such as polyaniline (PANI), polypyrrole (PPy), and polythiophene have occupied an important position in the research of supercapacitor electrode materials due to their excellent pseudocapacitive effect, good processability, and cost-effectiveness. PPy, as a typical conductive polymer, has shown great application potential due to its high conductivity and excellent electrochemical reactivity. However, the cycling stability and capacity decay of PPy still limit its application. Therefore, improving its electrochemical performance and enhancing the stability of the material has become a current research challenge. Polymer modification and compounding with other materials can effectively improve the polymer's capacitance performance, stability, and cycle life.

[0004] Fullerene (C 60 As a carbon-based material with a unique spherical structure, carbon has gradually become an important material for enhancing the performance of supercapacitor electrodes due to its high specific surface area and excellent electron transport capability. 60 The overall performance of a capacitor can be improved by enhancing the conductivity of the electrode material and improving charge storage efficiency. However, C 60 However, there are some limitations in practical applications, mainly its poor dispersibility in solution, which affects its uniform distribution and efficient energy storage capacity in electrode materials. To solve this problem, researchers have used C... 60 It can be combined with materials such as conductive polymers or metal oxides to improve its dispersibility and stability in the electrode, thereby enhancing its electrochemical performance.

[0005] To overcome the performance limitations of single materials, composite materials have become a key strategy for improving the performance of supercapacitor electrodes in recent years. By rationally combining different materials, synergistic effects can be achieved, fully leveraging the advantages of each material. However, despite the significant application potential of these composite materials, several challenges remain in practical applications, particularly regarding material uniformity, stability, and performance degradation during high-frequency charge-discharge processes. Therefore, optimizing the material preparation process, improving cycle stability, and reducing production costs are crucial for their practical application. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention provides a PPy-Cu2O-C 60 Ternary composite materials, their preparation methods, and applications.

[0007] To achieve the above technical objectives, the present invention adopts the following technical solution: This invention provides a PPy-Cu2O-C 60 The preparation method of ternary composite materials includes the following steps: (1) Water and dichloromethane are mixed and ultrasonically treated to form a homogeneous oil-water mixture; pyrrole monomer, aniline monomer, Cu2O powder and C are added to the oil-water mixture. 60 The powder, after being subjected to ultrasonication and stirring, forms a mixture containing polymer monomers, Cu2O, and C. 60 Oil-in-water emulsion system; (2) Add an oxidant solution to the emulsion system obtained in step (1) to carry out an oxidative polymerization reaction to obtain a composite product containing polymer; (3) The composite product obtained in step (2) is filtered and washed, then centrifuged, washed and dried to obtain the PPy-Cu2O-C 60 Ternary composite materials; Among them, the Cu2O powder and C 60 The powders work together to act as emulsion stabilizers, thereby controlling the size of the oil-in-water droplets and thus regulating the size of the composite material particles.

[0008] In some embodiments, in step (1), the water, dichloromethane, pyrrole monomer, aniline monomer, Cu2O powder, and C 60 The powder addition ratio is 40-60 mL: 8-12 mL: 180-220 μL: 40-60 μL: 40-60 mg: 40-60 mg. In some embodiments, in step (1), the ultrasonic treatment time is 10 to 20 minutes and the stirring time is 20 to 40 minutes.

[0009] In some embodiments, in step (2), the oxidant is ammonium persulfate ((NH4)2S2O8); the ammonium persulfate is dissolved in pure water to form a solution and then slowly added dropwise to the emulsion system; the time for the oxidative polymerization reaction is 0.5 to 2 h; the ammonium persulfate is dissolved in the aqueous phase and reaches the surface of the dissolved polymer monomer droplets through diffusion, and the polymerization reaction is completed at the droplet interface.

[0010] In some embodiments, in step (3), the cleaning step uses water and ethanol alternately to remove residual dichloromethane solvent from the surface of the product.

[0011] In some embodiments, the preparation method of Cu2O powder includes the following steps: mixing ethylene glycol with water, adding copper sulfate pentahydrate, glucose and sodium hydroxide, dissolving by ultrasonication, transferring to a hydrothermal reactor, heating at 100-140°C for 15-30 h, cooling and filtering, washing with water and ethanol, and drying to obtain Cu2O nanoparticles with a diameter of 8-12 nm.

[0012] In some embodiments, the addition ratio of ethylene glycol, water, copper sulfate pentahydrate, glucose, and sodium hydroxide is 20–40 mL: 4–6 mL: 0.1–0.2 g: 2–4 g: 0.05–0.2 g.

[0013] This invention provides a PPy-Cu2O-C 60 The ternary composite material is prepared by the method described above; the composite material uses polypyrrole (PPy) copolymerized with polyaniline as the matrix, Cu2O nanoparticles and C 60 Fullerene composites are loaded onto the PPy matrix with particle diameters of 15–30 nm; at a scan rate of 50 mV / s, the specific capacitance of the composite material is not less than 500 F / g; at a current density of 2 A / g, the energy density of the composite material is not less than 210 Wh / kg.

[0014] In some embodiments, the volume ratio of pyrrole monomer to aniline monomer in the polyaniline copolymerized polypyrrole is 4:1; the polyaniline component is used to promote the reaction of PPy with Cu2O and C. 60 The effective combination between the components enhances the interfacial interaction between the ternary components; in the composite material, PPy provides energy storage through the pseudocapacitive effect, Cu2O enhances the charge and discharge efficiency, and C... 60 The three components exhibit a synergistic enhancement effect, improving electron transport performance.

[0015] This invention provides the above-mentioned PPy-Cu2O-C 60 The application of ternary composite materials in the preparation of supercapacitor electrodes, using the aforementioned PPy-Cu2O-C 60 The ternary composite material, used as the active electrode material and with Nafion as the binder, is loaded onto the surface of the current collector. The electrode exhibits stable electrochemical performance in a 1 mol / L Na₂SO₄ electrolyte within a voltage range of -0.5 V to 0.5 V (vs. SCE), with a specific capacitance that is at least 80% higher than that of a single PPy electrode.

[0016] The beneficial effects of this invention are: This invention proposes a method using polypyrrole (PPy), cuprous oxide (Cu2O), and fullerene (C) 60A ternary composite material with PPy as the main component. This composite material, through the design of its material composition and synthesis route, combines the pseudocapacitive effect of PPy, the electrochemical energy storage characteristics of Cu2O, and the properties of C. 60 The high-efficiency electron transport capability. To promote the effective composite of ternary materials, this invention improves PPy by adding an appropriate amount of PANI copolymerization during the PPy synthesis process. This composite material can significantly improve the specific capacitance and energy density of the capacitor electrode material. By optimizing the material design and synthesis process, PPy-Cu2O-C 60 Composite materials are expected to become a new type of high-performance capacitor electrode material and provide new ideas for the design of supercapacitor electrode materials. Attached Figure Description

[0017] Figure 1 The images show SEM images of the prepared materials. Specifically, a1 and a2 are SEM images of the morphology of PPy under different magnifications; b1 and b2 are SEM images of the morphology of PPy-Cu2O under different magnifications; c1 and c2 are SEM images of the morphology of PPy-C under different magnifications. 60 SEM images of the morphology and structure; d1 and d2 are PPy-Cu2O-C at different magnification ratios. 60 (d) SEM image of morphological structure.

[0018] Figure 2 For PPy (a), PPy-Cu2O (b), PPy-C 60 (c) and PPy-Cu2O-C 60 (d) CV curves at different scan rates in 1 M Na2SO4 solution.

[0019] Figure 3 PPy-Cu2O-C 60 CV curves of a series of electrodes in 1 M Na2SO4 solution.

[0020] Figure 4 PPy-Cu2O-C 60 The specific capacity versus scan rate curves of a series of electrodes when subjected to CV testing in 1 M Na2SO4 solution.

[0021] Figure 5 For PPy (a), PPy-Cu2O (b), PPy-C 60 (c) and PPy-Cu2O-C 60 (d) GCD curves at different current densities in 1 M Na2SO4 solution.

[0022] Figure 6 PPy-Cu2O-C 60GCD curves of a series of electrodes at a current density of 2 A / g in 1 M Na2SO4 solution.

[0023] Figure 7 PPy-Cu2O-C 60 The relationship between energy density and current density when the series of electrodes are tested for GCD in 1 M Na2SO4 solution. Detailed Implementation

[0024] The present invention will now be described in further detail with reference to the embodiments.

[0025] Preparation of Comparative Example 1 PPy Powder Add 50 mL of pure water and 10 mL of dichloromethane to a 200 mL beaker. After sonicating for 15 min to form a homogeneous oil-water mixture, add 200 μL of pyrrole monomer and 50 μL of aniline monomer to the mixture. Sonicate for another 15 min and continue stirring for 30 min to ensure thorough mixing. During this process, the solution forms oil-in-water droplets and dissolves the polymer monomers, which is used to control the size of the polymer product. Take 0.3 g of (NH4)2S2O8, dissolve it completely in pure aqueous solution, and slowly add it dropwise to the above solution. Stir the reaction for 1 h. At this point, (NH4)2S2O8 dissolves in the aqueous phase and diffuses to the surface of the polymer monomer droplets, completing the polymerization reaction. After the reaction, filter the product and wash it alternately with water and ethanol to demulsify and remove the dichloromethane solvent from the product surface. Finally, centrifuge the product, wash it with water and ethanol, and allow it to air dry to obtain PANI copolymerized modified PPy powder (referred to as PPy in the examples).

[0026] Preparation of 2PPy-Cu2O powder (comparative example) (1) Preparation of Cu2O powder Add 5 mL of pure water to 30 mL of ethylene glycol, mix well, then add 0.15 g of copper sulfate pentahydrate, 3 g of glucose, and 0.1 g of sodium hydroxide. After fully dissolving by sonication, transfer the mixture to a hydrothermal reactor and heat at 120 °C for 3 h. After cooling, filter, wash the solid product with water and ethanol, and air dry to obtain Cu₂O nanoparticles with a diameter of approximately 10 nm.

[0027] (2) Preparation of PPy-Cu2O powder Add 50 mL of pure water and 10 mL of dichloromethane to a 200 mL beaker. After sonicating for 15 min to form a homogeneous oil-water mixture, add 200 μL of pyrrole monomer, 50 μL of aniline monomer, and 50 mg of Cu₂O powder to the mixture. Sonicate for 15 min and then stir for another 30 min to ensure thorough mixing. The Cu₂O powder can adsorb at the oil-water interface as a Pickering emulsifier, reducing interfacial tension and preventing droplet aggregation. Under thorough stirring, the size of the oil-in-water droplets formed is significantly reduced, effectively controlling the size of the polymer product. Dissolve 0.3 g of (NH₄)₂S₂O₈ completely in pure aqueous solution and slowly add it dropwise to the above solution. Stir the reaction for 1 h. At this point, (NH₄)₂S₂O₈ dissolves in the aqueous phase and diffuses to the surface of the polymer monomer droplets, completing the polymerization reaction. After the reaction, filter the solution and wash alternately with water and ethanol to demulsify and remove the dichloromethane solvent from the product surface. Finally, the product was centrifuged, washed with water and ethanol, and naturally dried to obtain PANI copolymerized modified PPy-Cu2O powder (referred to as PPy-Cu2O in the examples).

[0028] Comparative example 3PPy-C 60 Powder preparation Add 50 mL of pure water and 10 mL of dichloromethane to a 200 mL beaker, sonicate for 15 min to form a homogeneous oil-water mixture, then add 200 μL of pyrrole monomer, 50 μL of aniline monomer, and 50 mg of C. 60 Add to the above mixture, sonicate for 15 minutes, and then continue stirring for 30 minutes to ensure the solution is thoroughly mixed. Due to the addition of C... 60 It is a hydrophobic powder, insoluble in both water and dichloromethane, dispersed in the system as nano-aggregates. These aggregates preferentially distribute within the oil droplets or near the interface, confining the polymerization space and assisting in droplet breakage. Under thorough stirring, the size of the oil-in-water droplets formed is significantly reduced, resulting in a drastically smaller final polymer product. 0.3 g of (NH4)2S2O8 was completely dissolved in a pure aqueous solution and then slowly added dropwise to the above solution, with stirring for 1 h. At this point, (NH4)2S2O8 dissolves in the aqueous phase and reaches the surface of the dissolved polymer monomer droplets through diffusion, completing the polymerization reaction. After the reaction, the mixture was filtered, and washed alternately with water and ethanol to demulsify and remove the dichloromethane solvent from the product surface. Finally, the product was centrifuged, washed with water and ethanol, and allowed to air dry to obtain PANI copolymerized modified PPy-C. 60 Powder (described as PPy-C in the examples) 60 ).

[0029] Example 1 PPy-Cu2O-C 60 Powder preparation The preparation of Cu2O powder was the same as in Comparative Example 2.

[0030] Add 50 mL of pure water and 10 mL of dichloromethane to a 200 mL beaker, and sonicate for 15 min to form a homogeneous oil-water mixture. Then add 200 μL of pyrrole monomer, 50 μL of aniline monomer, 50 mg of Cu2O, and 50 mg of C. 60 Add to the above mixture, sonicate for 15 min, and continue stirring for 30 min to ensure thorough mixing. This is because hydrophilic Cu₂O inorganic powder and hydrophobic C are added simultaneously. 60 In the powder, Cu2O adsorbs at the oil-water interface and acts as a pickering stabilizer, while C... 60 Aggregates distributed within oil droplets restrict polymerization growth, and both aggregates and droplets synergistically regulate droplet size. Under thorough stirring, the size of the oil-in-water droplets formed in the solution significantly decreases, ultimately resulting in a drastically reduced polymer product size. 0.3 g of (NH4)2S2O8 was completely dissolved in a pure aqueous solution and then slowly added dropwise to the above solution, with stirring for 1 h. At this point, (NH4)2S2O8 dissolves in the aqueous phase and diffuses to the surface of the dissolved polymer monomer droplets, completing the polymerization reaction. After the reaction, the mixture was filtered, and washed alternately with water and ethanol to demulsify and remove dichloromethane solvent from the product surface. Finally, the product was centrifuged, washed with water and ethanol, and allowed to air dry to obtain PANI copolymerized modified PPy-Cu2O-C. 60 Powder (described in the examples as PPy-Cu2O-C) 60 ).

[0031] Test case Using Nafion as a binder, the prepared powder material was loaded onto the surface of a 5 mm glassy carbon electrode to prepare a capacitor electrode. A graphite electrode was selected as an auxiliary electrode, and a saturated calomel electrode (SCE) was used as a reference electrode. Using an electrochemical workstation (CHI660D), cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) tests were performed on a series of capacitor electrode materials in 1 M Na2SO4 solution. The CV test voltage range was -0.5 V to 0.5 V (vs. SCE), and the GCD test current density was 2 to 10 A / g.

[0032] Results and Discussion Figure 1 SEM images of the prepared material are shown. Figure 1 In (a1) and (a2), it can be observed that PPy prepared by our experimental method presents as irregular spherical particles of approximately 200-300 nm. Compared with PPy, Figure 1 The PPy-Cu2O particle size in (b1) and (b2) is significantly reduced, to approximately 40-60 nm. (Observation) Figure 1 From (c1) and (c2), it can be found that PPy and C 60 The particle size after composite formation has been reduced to approximately 10-15 nm. Furthermore, when PPy is combined with Cu2O and C... 60 After nanomaterials are combined, Figure 1 The composite material particles in (d1) and (d2) have a diameter of approximately 15-30 nm. This demonstrates that the method of the present invention can effectively change the size of the polymer product by adjusting the oil-water ratio of the system and by adding hydrophilic or oleophilic materials.

[0033] PPy-Cu2O-C 60 The synthesis mechanism of composite materials is as follows: This synthetic system is based on an oil-in-water emulsion template mechanism: dichloromethane acts as the oil phase, dissolving pyrrole and aniline monomers, which disperse in the aqueous phase to form oil droplets. The oxidant (NH4)2S2O8 dissolves in the aqueous phase and diffuses to the oil-water interface, initiating polymerization. The diameter of the final polymer particles is related to the size of the oil droplets. In the PPy system, no additional additives are used, resulting in high oil-water interfacial tension. Under stirring, larger oil droplets are formed, leading to irregular spherical particles of 200–300 nm after polymerization. When hydrophilic Cu2O nanoparticles are introduced, Cu2O, insoluble in water and dichloromethane, exhibits appropriate wettability and therefore irreversibly adsorbs at the oil-water interface, acting as a Pickering emulsifier. The solid particles at the interface significantly reduce interfacial tension and form a steric barrier, effectively preventing oil droplet aggregation and making it easier for the oil droplets to break into smaller, stable droplets during stirring, thus reducing the size of the polymerized product to 40–60 nm. For PPy-C... 60 System, C 60 It is insoluble in both water and dichloromethane, and is dispersed in the system as nanoscale aggregates. Due to C... 60 Exhibiting strong hydrophobicity, these aggregates preferentially distribute within the oil phase (dichloromethane droplets) or near the oil-water interface. Cp distributed within the oil droplets... 60 Aggregates act as physical barriers, limiting the effective space for polymer monomers within individual oil droplets and potentially serving as additional polymerization nucleation sites, allowing the polymer to... 60 The aggregates grow around each other, thus preventing the formation of large particles; simultaneously, the C of the solid... 60 Aggregates may assist in the breakup of oil droplets during shearing and pinnate at the oil-water interface, playing a supporting stabilizing role. These synergistic effects significantly reduce the droplet diameter, resulting in a drastic reduction in the final product size to 10–15 nm. When Cu₂O and C are added simultaneously... 60 Preparation of ternary composite PPy-Cu2O-C 60 At the same time, two nanomaterials jointly regulate the emulsion template: Cu2O, as a Pickering emulsifier, is adsorbed at the oil-water interface, reducing interfacial tension and stabilizing oil droplets; C60 Aggregates are mainly distributed inside oil droplets, limiting the growth space of the polymer and providing additional nucleation sites. However, C 60 The presence of aggregates occupies the internal volume of the oil droplet, competing for space with Cu2O particles at the interface, making it difficult for the oil droplet to achieve pure C. 60 The system exhibits extremely small size (10–15 nm); simultaneously, the adsorption layer of Cu2O particles at the interface may also hinder C 60 The aggregates are fully distributed into the interior of the oil droplets. Therefore, the final particle diameter of the ternary composite is approximately 15–30 nm, between that of PPy-Cu2O (40–60 nm) and PPy-C. 60 (10–15 nm). The above results indicate that by selecting nano-additives with different hydrophilic / hydrophobic properties and steric effects (hydrophilic Pickering emulsifier Cu2O, hydrophobic internal nucleating / barrier agent C...), the nanoparticles can achieve the desired effect. 60 Aggregates can precisely adjust the droplet size and polymerization growth space of the emulsion template, thereby effectively controlling the particle diameter of conductive polymer composite materials.

[0034] exist Figure 2 The figure shows the effects of different scan rates on PPy, PPy-Cu2O, and PPy-C in 1 M Na2SO4 solution. 60 and PPy-Cu2O-C 60 The CV curves are shown. Observing these curves, it is clear that as the CV scan rate increases, the response current density of all electrode materials also shows an increasing trend. Comparing these four graphs, we can find that the current density of PPy is relatively low. When PPy forms a binary composite material with Cu2O, its current density decreases because the energy density of Cu2O is slightly lower than that of PPy. When PPy forms a binary composite material with C... 60 When forming binary composite materials, the current density is increased. When Cu₂O and C... 60 When combined with PPy, the current density is significantly enhanced, demonstrating the excellent capacitance performance of the composite material.

[0035] Figure 3 The comparison of CV curves for different composite materials in 1 M Na₂SO₄ solution at a scan rate of 50 mV / s is shown. At 0.2 V, PPy-Cu₂O-C... 60 The composite material achieved a current density of 25 A / g, while the other three electrode materials had current densities of 12.5 A / g, 12.5 A / g, and 17 A / g, respectively. Compared to PPy, the binary composite material did not show a significant improvement in current density. However, the PPy-Cu2O-C... 60The current density of the ternary composite material is twice that of PPy, which clearly demonstrates that PPy-Cu2O-C 60 Ternary composite materials have a significant advantage in capacitance performance compared to other materials.

[0036] Figure 4 The graph shows the relationship between specific capacitance and scan rate obtained from CV testing of the prepared material in 1 M Na₂SO₄ solution. According to the data in the figure, the specific capacitance of PPy reaches 271 F / g at a scan rate of 50 mV / s. Compared to PPy, the specific capacitance of the electrode material composited with Cu₂O decreases slightly; while that composited with C₂O… 60 The specific capacitance of the electrode material was increased to 358 F / g, an increase of 32.1%. This was achieved when the electrode material simultaneously incorporated Cu₂O and C. 60 At that time, the specific capacitance increased significantly to 505 F / g, an increase of 86.3%. Therefore, it can be found that the specific capacitance performance of ternary materials is better than that of others.

[0037] Figure 5 The GCD curves of the prepared materials in 1 M Na₂SO₄ solution at current densities of 2–10 A / g are shown. GCD curve analysis reveals that PPy and PPy-Cu₂O exhibit the shortest single charge-discharge times. In contrast, the composite C… 60 The charge / discharge time of the material is extended, especially for materials that simultaneously combine Cu2O and C. 60 The electrode material exhibits the most significant increase in charge-discharge time.

[0038] Figure 6 The GCD curves of the prepared material in 1 M Na₂SO₄ solution at a current density of 2 A / g are shown. The figure shows that the single charge-discharge time of PPy at 2 A / g is 284 s. When PPy is combined with Cu₂O, the single charge-discharge time is slightly shortened, while when combined with C… 60 After recombination, the single charge-discharge time was further extended to 351 s, an improvement of 25%. This demonstrates that when PPy is combined with Cu2O or C... 60 When forming binary composites, although these improvements are positive, their advantages are not very significant. However, when PPy is combined with Cu2O and C... 60 Simultaneous recombination significantly increased the single charge-discharge time to 498 s, reaching 1.8 times that of the original PPy, indicating that PPy-Cu2O-C 60 Ternary composite materials have better capacitor performance.

[0039] Figure 7The specific capacity versus current density curves obtained by GCD testing of the prepared materials in 1 M Na₂SO₄ solution are shown. At a current density of 2 A / g, the energy densities of the PPy and PPy-Cu₂O electrode materials are 120 Wh / kg and 106 Wh / kg, respectively. When PPy reacts with C… 60 During recombination, PPy-C is formed. 60 The energy density of the binary composite material was increased to 151 Wh / kg. And PPy-Cu2O-C 60 The energy density of the ternary composite material has been further increased to 216 Wh / kg. The figure shows that PPy-Cu2O-C 60 Ternary composite materials have a significant advantage in energy density. As the current density increases, the energy density of the resulting electrode materials decreases.

[0040] Table 1 clearly shows the specific capacitance and energy density data of the prepared materials. Under a scan rate of 50 mV / s, PPy and C... 60 The specific capacitance of the composite electrode material was improved by 32.1%, while PPy simultaneously reacted with Cu2O and C. 60 The specific capacitance of the composite electrode material increased by 86.3%. This demonstrates that Cu₂O and C… 60 The synergistic effect between PPy and C in the ternary composite material effectively enhances the specific capacitance of the composite system. At a current density of 2 A / g, it can be seen that PPy and C... 60 After compositing, the energy density of the electrode material increased by 25.8%, while simultaneously improving upon the effects of Cu2O and C. 60 After recombination, the energy density increased by 80%, which further confirms the effectiveness of PPy in combining with Cu2O and C. 60 The synergistic effect among the three can effectively improve the electrochemical performance of electrode materials.

[0041] Table 1 PPy-Cu2O-C 60 Electrode specific capacitance and energy density

[0042] Obviously, the above experimental examples are merely illustrative and not intended to limit the implementation methods. Those skilled in the art will recognize that various variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementation methods. However, any obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A PPy-Cu2O-C 60 The method for preparing ternary composite materials is characterized by, Includes the following steps: (1) Water and dichloromethane are mixed and ultrasonically treated to form a homogeneous oil-water mixture; pyrrole monomer, aniline monomer, Cu2O powder and C are added to the oil-water mixture. 60 The powder, after being subjected to ultrasonication and stirring, forms a mixture containing polymer monomers, Cu2O, and C. 60 Oil-in-water emulsion system; (2) Add an oxidant solution to the emulsion system obtained in step (1) to carry out an oxidative polymerization reaction to obtain a composite product containing polymer; (3) The composite product obtained in step (2) is filtered, washed, then centrifuged, washed and dried to obtain the PPy-Cu2O-C 60 Ternary composite materials.

2. The preparation method according to claim 1, characterized in that, In step (1), the water, dichloromethane, pyrrole monomer, aniline monomer, Cu2O powder, and C... 60 The powder addition ratio is 40-60 mL: 8-12 mL: 180-220 μL: 40-60 μL: 40-60 mg: 40-60 mg.

3. The preparation method according to claim 1, characterized in that, In step (1), the ultrasonic treatment time is 10 to 20 minutes and the stirring time is 20 to 40 minutes.

4. The preparation method according to claim 1, characterized in that, In step (2), the oxidant is ammonium persulfate ((NH4)2S2O8); the ammonium persulfate is dissolved in pure water to form a solution and then slowly added dropwise to the emulsion system; the time for the oxidative polymerization reaction is 0.5 to 2 h; the ammonium persulfate is dissolved in the aqueous phase and reaches the surface of the dissolved polymer monomer droplets through diffusion, and the polymerization reaction is completed at the droplet interface.

5. The preparation method according to claim 1, characterized in that, In step (3), the cleaning step uses water and ethanol alternately to remove the dichloromethane solvent remaining on the surface of the product.

6. The preparation method according to claim 1, characterized in that, The preparation method of the Cu2O powder includes the following steps: ethylene glycol is mixed with water, copper sulfate pentahydrate, glucose and sodium hydroxide are added, the mixture is dissolved by ultrasonication and then transferred to a hydrothermal reactor, heated at 100-140℃ for 15-30 h, cooled and filtered, washed with water and ethanol, and dried to obtain Cu2O nanoparticles with a diameter of 8-12 nm.

7. The preparation method according to claim 6, characterized in that, The ratio of ethylene glycol, water, copper sulfate pentahydrate, glucose, and sodium hydroxide is 20–40 mL: 4–6 mL: 0.1–0.2 g: 2–4 g: 0.05–0.2 g.

8. A PPy-Cu2O-C 60 Ternary composite material, characterized in that... The composite material is prepared by the method according to any one of claims 1 to 7; the composite material uses polypyrrole (PPy) copolymerized with polyaniline as the matrix, Cu2O nanoparticles and C 60 Fullerene composites are loaded onto the PPy matrix with particle diameters of 15–30 nm; at a scan rate of 50 mV / s, the specific capacitance of the composite material is not less than 500 F / g; at a current density of 2 A / g, the energy density of the composite material is not less than 210 Wh / kg.

9. The PPy-Cu2O-C according to claim 8 60 Ternary composite material, characterized in that... In the polypyrrole copolymerized with aniline, the volume ratio of pyrrole monomer to aniline monomer is 4:1; the polyaniline component is used to promote the reaction of PPy with Cu2O and C. 60 The effective combination between the components enhances the interfacial interaction between the ternary components; in the composite material, PPy provides energy storage through the pseudocapacitive effect, Cu2O enhances the charge and discharge efficiency, and C... 60 The three components exhibit a synergistic enhancement effect, improving electron transport performance.

10. A PPy-Cu2O-C according to claim 8 or 9 60 The application of ternary composite materials in the fabrication of supercapacitor electrodes is characterized by... With the aforementioned PPy-Cu2O-C 60 Ternary composite material is used as the active electrode material, with Nafion as the binder, and is loaded onto the surface of the current collector.

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