Composite carbon fiber cloth for friction power generation and preparation method thereof

Abstract

The invention provides a composite carbon fiber cloth for friction power generation and a preparation method thereof, the composite carbon fiber cloth comprises a carbon fiber cloth layer, a bonding layer and an electrostatic spinning film layer, the carbon fiber cloth layer, the bonding layer and the electrostatic spinning film layer are compounded through interlayer bonding, the bonding layer comprises acyl chloride grafted PEI and PEDOT: PSS aqueous dispersoid, and the electrostatic spinning film layer is an electrostatic spinning film layer. The electrostatic spinning membrane layer is a PMIA / ZrO2 composite electrostatic spinning membrane with a hollow structure, and ZrO2 is loaded on the surface of the composite electrostatic spinning membrane through phase separation.

Description

Technical Field

[0001] This invention relates to the field of functional carbon fiber cloth, and specifically to a composite carbon fiber cloth for triboelectric power generation and its preparation method. Background Technology

[0002] The rapid development of wearable electronic devices has created an urgent need for flexible and sustainable energy supply systems. Traditional chemical batteries suffer from limited capacity, large rigidity, and the need for frequent replacement or charging, making them unsuitable for the long-term operation requirements of distributed sensor networks and portable devices. Especially for invisible energy sources embedded in clothing or structures, there is a pressing need for materials and devices that can directly and efficiently convert environmental mechanical energy (such as human movement, wind-induced vibration, and water flow) into electrical energy. Triboelectric nanogenerators (TENGs) have become an ideal choice due to their advantages such as low frequency, high efficiency, wide material selection, and flexible structure; however, achieving integrated power generation and energy storage with seamless integration into flexible substrates remains a technological bottleneck.

[0003] Carbon fiber materials, due to their high conductivity, mechanical strength, corrosion resistance, and lightweight properties, have become an ideal substrate for functionalized fabrics used in triboelectric generation. In existing technologies, carbon fiber cloth or filaments can be used directly as triboelectric electrodes or as the conductive framework of supercapacitors. However, the triboelectric output power of a single carbon fiber structure is limited, and the lack of energy storage units leads to discontinuous power supply. Although some research has attempted to couple TENGs with supercapacitors (such as the CN120320633A patent which uses a woven structure to realize a fibrous power generation-storage unit), or to composite graphene on the surface of carbon cloth to improve capacitance performance, multiple challenges remain, including energy conversion efficiency, structural flexibility, large-scale fabrication, and adaptability to complex operating conditions.

[0004] This patent aims to propose an innovative composite carbon fiber fabric structure that overcomes the aforementioned limitations through multi-level material design and integrated process optimization. The core technology involves in-situ composite of a carbon fiber substrate, a friction layer with high charge capture properties, and a fast ion storage medium to construct a "triboelectric-conduction-storage" synergistic unit. This provides self-powered solutions for wearable electronics, bridge health monitoring, and other scenarios, promoting the deep integration of green energy and the Internet of Things. Summary of the Invention

[0005] The technical problem to be solved: This invention provides a composite carbon fiber cloth for triboelectric power generation and its preparation method. The carbon fiber cloth is combined with a PMIA / ZrO2 composite electrospun film with a hollow structure, thereby increasing the contact area between the two and improving the triboelectric power generation performance of the composite material.

[0006] Technical solution: A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0007] Preferably, the preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and a composite carbon fiber cloth for triboelectric power generation is obtained by interlayer bonding.

[0008] Preferably, the method for preparing the acyl chloride-grafted PEI in S1 includes the following steps: S11. Add succinic anhydride / DMF solution to PEI / DMF solution, and react by heating to obtain carboxylated PEI; S12. The carboxylated PEI obtained in S1 is dispersed in toluene, and SOCl2 is added. After heating and reaction, the mixture is rotary evaporated to obtain acyl chloride-grafted PEI.

[0009] Preferably, the method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC, stir until dissolved, then add PMIA, heat in a constant temperature water bath until dissolved, then add ZrO2 particles and a certain amount of ethanol, and disperse by ultrasonication to obtain solution A; add PVP to the ethanol / DMF mixed solution, stir until dissolved to obtain solution B; S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospun membrane is then immersed in an ethanol / acetone solution to obtain a PMIA / ZrO2 composite electrospun membrane with a hollow structure.

[0010] Preferably, the temperature for interlayer bonding in S2 is 100~120℃, and the time is 5~15min.

[0011] Preferably, the mass fraction of the succinic anhydride / DMF solution in S11 is 4~8 wt%; The PEI / DMF solution has a mass fraction of 3-6 wt%. The volume ratio of the succinic anhydride / DMF solution to the PEI / DMF solution is 1:1~4; The heating reaction is carried out at a temperature of 60-80°C for 2-4 hours.

[0012] Preferably, the mass-to-volume ratio of carboxylated PEI to toluene in S12 is 1:15~25 g / mL; The amount of SOCl2 added is 15-30 wt% of the mass of carboxylated PEI. The heating reaction is carried out at a temperature of 70~90℃ for 3~5 hours. The rotary evaporation temperature is 30~45℃ and the pressure is -0.15~-0.1MPa.

[0013] Preferably, the mass ratio of LiCl to PMIA in S21 is 1:0.2~0.9; The temperature of the constant temperature water bath is 50~60℃, and the time is 30~60min; The amount of ZrO2 particles added is 1-4 wt% of the PMIA mass; The mass fraction of solution A is 10~16 wt%; The volume ratio of ethanol to DMF is 5~7:5~7, and the mass fraction of solution B is 10~15wt%.

[0014] Preferably, the electrospinning parameters of the shell layer in S22 are: spinning voltage of 15~20kV, spinning speed of 0.2~1.2mL / min, and receiving distance of 18~22cm; The electrospinning parameters of the core layer are as follows: spinning voltage is 10~15kV; spinning speed is 0.1~0.5mL / min; and receiving distance is 18~22cm. The volume ratio of ethanol to acetone in the ethanol / acetone solution is 1:0.4~0.6; The mass-to-volume ratio of the electrospun membrane to the ethanol / acetone solution is 1:20~40 g / mL.

[0015] Beneficial effects: This invention has the following advantages: 1. In this invention, the amino group of PEI is protonated to -NH3⁺ under acidic conditions, making it positively charged as a whole. It forms self-assembled micelles through electrostatic cross-linking with the -SO3⁻ group of PEDOT:PSS. The self-assembled micelles contain granular protrusions, which increases the contact area between the binder and the carbon fiber cloth and the electrospun film. The electrostatic self-assembly strongly binds the two components and reduces interface defects. In addition, the amino group has a very strong electron-donating (Lewis base) ability, which captures and stabilizes the negative charge generated by friction. 2. The binder prepared in this invention has strong adhesion and can penetrate into the interior of the electrospun fiber membrane and carbon fiber cloth, forming a continuous polymer membrane on the cross-section of the composite membrane, thereby forming a complete conductive network structure, acting as a charge transfer channel, and improving the output power of the composite material. 3. In this invention, hydrophilic ZrO2 particles are added to the shell electrospinning solution while PMIA is a hydrophobic material. Due to the spontaneous phase selection and phase separation phenomenon between hydrophilic and hydrophobic materials, the rapid evaporation of ethanol during the spinning process causes phase separation between PMIA and ZrO2 particles. The ZrO2 particles are squeezed onto the fiber surface, forming a micro-nano structure on the fiber surface. 4. The PMIA fiber membrane in this invention contains a large number of benzene rings and amide bonds, which have a strong electron-acquiring ability due to the conjugation phenomenon between them, and can be used as a triboelectric negative electrode material. The micro-nano structure surface of the electrospun membrane in this invention, brought about by ZrO2 particles, is similar to the velvety structure of a gecko's foot. Compared with traditional fiber membranes, it can provide more triboelectric contact sites, thereby increasing the surface charge density. After the PVP in the core layer is eluted, it forms a through-hole nanopore, and the air and aramid form a dielectric constant difference interface, which inhibits charge neutralization. Under the action of external force, the micro-nano structure surface of the shell layer first contacts and generates charge, and then the pores are compressed to expand the contact area. The two work together to improve the charge transfer efficiency. Detailed Implementation

[0016] The present invention will be further described below with reference to embodiments. These embodiments are illustrative of the present invention, but the present invention is not limited to these embodiments: Example 1

[0017] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0018] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the interlayer bonding time is 5 minutes at 100°C to obtain a composite carbon fiber cloth for triboelectric power generation.

[0019] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 4 wt% succinic anhydride / DMF solution was added to a 3 wt% PEI / DMF solution, and the mixture was heated at 60°C for 2 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:20 g / mL. 15 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 70 °C for 3 h and then rotary evaporated at -0.15 MPa and 30 °C to obtain acyl chloride-grafted PEI.

[0020] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.2. Heat in a 50°C water bath for 30 minutes until dissolved. Add 1 wt% ZrO2 particles (based on the mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 10 wt% solution A. Add PVP to an ethanol / DMF mixed solution with a volume ratio of 5:5 and stir until dissolved to obtain a 12 wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane was obtained by coaxial electrospinning. The electrospinning parameters for the shell layer were: spinning voltage of 15 kV, spinning speed of 0.2 mL / min, and receiving distance of 18 cm. The electrospinning parameters for the core layer were: spinning voltage of 12 kV, spinning speed of 0.2 mL / min, and receiving distance of 18 cm. Subsequently, the electrospun membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.4 and a mass-to-volume ratio of 1:20 g / mL to the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospun membrane with a hollow structure. Example 2

[0021] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0022] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the bonding time is 120℃ and 12min to obtain a composite carbon fiber cloth for triboelectric power generation.

[0023] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 5 wt% succinic anhydride / DMF solution was added to a 4 wt% PEI / DMF solution, and the mixture was heated at 65°C for 3 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:20 g / mL. 25 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 75 °C for 3 h and then rotary evaporated at -0.1 pressure and 40 °C to obtain acyl chloride-grafted PEI.

[0024] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.9. Heat in a 60℃ water bath for 40 minutes until dissolved. Add 2wt% ZrO2 particles (by mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 12wt% solution A. Add PVP to an ethanol / DMF mixed solution with a volume ratio of 5:7 and stir until dissolved to obtain a 15wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospinning parameters of the shell are: spinning voltage of 15kV, spinning speed of 0.5mL / min, and receiving distance of 20cm. The electrospinning parameters for the core layer were: spinning voltage of 15kV, spinning speed of 0.5mL / min, and receiving distance of 20cm. Subsequently, the electrospinned membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.5 and a mass-volume ratio of 1:30g / mL between the electrospinned membrane and the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospinned membrane with a hollow structure. Example 3

[0025] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0026] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the bonding time is 12 min at 110℃ to obtain a composite carbon fiber cloth for triboelectric power generation.

[0027] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 5 wt% succinic anhydride / DMF solution was added to a 4 wt% PEI / DMF solution, and the mixture was heated at 75°C for 3 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:20 g / mL. 20 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 75 °C for 4 h and then rotary evaporated at -0.15 pressure and 30 °C to obtain acyl chloride-grafted PEI.

[0028] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.7. Heat in a 50°C water bath for 40 minutes until dissolved. Add 2wt% ZrO2 particles (by mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 15wt% solution A. Add PVP to an ethanol / DMF mixed solution with a volume ratio of 7:5 and stir until dissolved to obtain a 12wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospinning parameters of the shell are: spinning voltage of 16kV, spinning speed of 0.2mL / min, and receiving distance of 18cm. The electrospinning parameters for the core layer were: spinning voltage of 14 kV, spinning speed of 0.2 mL / min, and receiving distance of 18 cm. Subsequently, the electrospinned membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.6 and a mass-volume ratio of 1:35 g / mL between the electrospinned membrane and the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospinned membrane with a hollow structure. Example 4

[0029] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0030] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the bonding time is 12 min at 110℃ to obtain a composite carbon fiber cloth for triboelectric power generation.

[0031] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 6 wt% succinic anhydride / DMF solution was added to a 4 wt% PEI / DMF solution, and the mixture was heated at 70°C for 3 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:20 g / mL. 18 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 80 °C for 4 h and then rotary evaporated at -0.1 MPa pressure and 35 °C to obtain acyl chloride-grafted PEI.

[0032] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.5. Heat in a 50°C water bath for 40 minutes until dissolved. Add 3wt% ZrO2 particles (by mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 15wt% solution A. Add PVP to an ethanol / DMF mixed solution at a volume ratio of 6:5 and stir until dissolved to obtain a 12wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospinning parameters of the shell are: spinning voltage of 15kV, spinning speed of 0.3mL / min, and receiving distance of 20cm. The electrospinning parameters for the core layer were: spinning voltage of 15kV, spinning speed of 0.3mL / min, and receiving distance of 20cm. Subsequently, the electrospinned membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.6 and a mass-volume ratio of 1:25g / mL between the electrospinned membrane and the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospinned membrane with a hollow structure. Example 5

[0033] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0034] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the bonding time is 12 min at 110℃ to obtain a composite carbon fiber cloth for triboelectric power generation.

[0035] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 5 wt% succinic anhydride / DMF solution was added to a 4 wt% PEI / DMF solution, and the mixture was heated at 65°C for 3 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:20 g / mL. 18 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 80 °C for 4 h and then rotary evaporated at -0.15 MPa and 30 °C to obtain acyl chloride-grafted PEI.

[0036] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.5. Heat in a 55°C water bath for 40 minutes until dissolved. Add 3wt% ZrO2 particles (by mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 14wt% solution A. Add PVP to an ethanol / DMF mixed solution at a volume ratio of 5:5 and stir until dissolved to obtain a 12wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospinning parameters of the shell are: spinning voltage of 18kV, spinning speed of 0.2mL / min, and receiving distance of 18cm. The electrospinning parameters for the core layer were: spinning voltage of 15kV, spinning speed of 0.1mL / min, and receiving distance of 18cm. Subsequently, the electrospinned membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.6 and a mass-volume ratio of 1:30g / mL between the electrospinned membrane and the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospinned membrane with a hollow structure. Example 6

[0037] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0038] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the interlayer bonding time is 12 min at 110°C to obtain a composite carbon fiber cloth for triboelectric power generation.

[0039] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 5 wt% succinic anhydride / DMF solution was added to a 4 wt% PEI / DMF solution, and the mixture was heated at 70°C for 3 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:15 g / mL. 15 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 70 °C for 3 h and then rotary evaporated at -0.15 MPa and 35 °C to obtain acyl chloride-grafted PEI.

[0040] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.5. Heat in a 50°C water bath for 40 minutes until dissolved. Add 2wt% ZrO2 particles (by mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 12wt% solution A. Add PVP to an ethanol / DMF mixed solution with a volume ratio of 5:6 and stir until dissolved to obtain a 13wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospinning parameters of the shell are: spinning voltage of 15kV, spinning speed of 0.2mL / min, and receiving distance of 18cm. The electrospinning parameters for the core layer were: spinning voltage of 10 kV, spinning speed of 0.1 mL / min, and receiving distance of 18 cm. Subsequently, the electrospinned membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.5 and a mass-volume ratio of 1:35 g / mL between the electrospinned membrane and the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospinned membrane with a hollow structure. Example 7

[0041] A composite carbon fiber cloth for triboelectric power generation, characterized in that: the composite carbon fiber cloth comprises a carbon fiber cloth layer, an adhesive layer, and an electrospinning film layer, wherein the carbon fiber cloth layer, adhesive layer, and electrospinning film layer are bonded together by interlayer bonding; the adhesive layer is an aqueous dispersion of PEI and PEDOT:PSS grafted with acyl chloride; the electrospinning film layer is a PMIA / ZrO2 composite electrospinning film with a hollow structure; and the ZrO2 is loaded onto the surface of the composite electrospinning film through phase separation.

[0042] The preparation method of the composite carbon fiber cloth for triboelectric power generation includes the following steps: S1. Apply the PEI and PEDOT:PSS aqueous dispersion binder containing acyl chloride grafts to the surface of carbon fiber cloth to form an adhesive layer on the surface of carbon fiber cloth. S2. A PMIA / ZrO2 composite electrospun film with a hollow structure is covered on the surface of the adhesive layer, and the interlayer bonding time is 10 minutes at 100°C to obtain a composite carbon fiber cloth for triboelectric power generation.

[0043] The preparation method of PEI grafted with acyl chloride in S1 includes the following steps: S11. A 5 wt% succinic anhydride / DMF solution was added to a 4 wt% PEI / DMF solution, and the mixture was heated at 70°C for 3 hours to obtain carboxylated PEI. S12. The carboxylated PEI obtained in S1 was dispersed in toluene at a mass-to-volume ratio of 1:22 g / mL. 18 wt% SOCl2 of the mass of the carboxylated PEI was added. The mixture was heated at 80 °C for 4 h and then rotary evaporated at -0.1 MPa pressure and 45 °C to obtain acyl chloride-grafted PEI.

[0044] The method for preparing the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 includes the following steps: S21. Add LiCl to DMAC and stir until dissolved. Then add PMIA at a mass ratio of 1:0.5. Heat in a 55°C water bath for 55 minutes until dissolved. Add 2wt% ZrO2 particles (by mass of PMIA) and a certain amount of ethanol. After ultrasonic dispersion, obtain a 12wt% solution A. Add PVP to an ethanol / DMF mixed solution with a volume ratio of 6:7 and stir until dissolved to obtain a 10wt% solution B. S22. Using solution A as the shell solution and solution B as the core solution, an electrospun membrane is obtained by coaxial electrospinning. The electrospinning parameters of the shell are: spinning voltage of 18kV, spinning speed of 0.3mL / min, and receiving distance of 18cm. The electrospinning parameters for the core layer were: spinning voltage of 15kV, spinning speed of 0.2mL / min, and receiving distance of 18cm. Subsequently, the electrospinned membrane was immersed in an ethanol / acetone solution with a volume ratio of 1:0.6 and a mass-volume ratio of 1:35g / mL between the electrospinned membrane and the ethanol / acetone solution, resulting in a PMIA / ZrO2 composite electrospinned membrane with a hollow structure. Comparative Example 1

[0045] The difference between this comparative example and Example 7 is that hydrophilic ZrO2 particles were not added. Comparative Example 2

[0046] The difference between this comparative example and Example 7 is that hydrophobic ZrO2 particles were added instead of hydrophilic ZrO2 particles.

[0047] The method for preparing the hydrophobic ZrO2 particles includes the following steps: Step 1: Dry ZrO2 particles at 120℃ for 2 hours, then add them to toluene and disperse them by ultrasonication. The mass-to-volume ratio of ZrO2 particles to toluene solution is 1:100 g / mL to obtain a suspension. Step 2: Under nitrogen protection, add octadecyltrimethoxysilane to the suspension obtained in Step 1. The amount of octadecyltrimethoxysilane added is 10 wt% of the ZrO2 particles. Heat in an oil bath at 80°C for 8 hours to obtain hydrophobic ZrO2 particles. Comparative Example 3

[0048] The difference between this comparative example and Example 7 is that only solution A was used for electrospinning, instead of coaxial electrospinning of solution A and solution B. Comparative Example 4

[0049] The difference between this comparative example and Example 7 is that PEI was not grafted or modified. Comparative Example 5

[0050] The difference between this comparative example and Example 7 is that the electrospun membrane in S22 was not soaked in an ethanol / acetone solution.

[0051] Performance testing The triboelectric properties of the embodiments and comparative examples obtained in this invention were tested under strong acid and strong alkali environments: the acid and alkali triboelectric test conditions were in accordance with GB 24539-2021 (China) standard. The samples were immersed in strong acid and strong alkali solutions for a certain period of time, and then removed. According to GB 24540-2021 standard, immersion for 5 minutes was counted as one immersion. After immersion, the samples were repeatedly washed with water and finally dried at room temperature. The dried samples were then tested under 40 N and 1.5 Hz conditions using a Keithley 6514 electrometer to measure the open-circuit voltage V of the triboelectric output performance of the samples after 0-14 acid and alkali immersion cycles. OC The durability of the samples in strong acid and strong alkali environments was evaluated, and the results are shown in the table below.

[0052] Table 1 shows the V of TENG after immersion in NaOH solution (pH 8) for 1, 5, 9, and 14 times. OC change

[0053] Table 2. V of TENG after immersion in HNO3 solution (pH 4) for 1, 5, 9, and 14 times. OC change

[0054] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A composite carbon fiber cloth for a triboelectric generator, characterized by: The composite carbon fiber cloth comprises a carbon fiber cloth layer, a bonding layer and an electrospun membrane layer, the carbon fiber cloth layer, the bonding layer and the electrospun membrane layer are combined by interlayer adhesion, the bonding layer is composed of acyl chloride grafted PEI and PEDOT:PSS aqueous dispersion, and the electrospun membrane layer is a PMIA / ZrO2 composite electrospun membrane with a hollow structure, and ZrO2 is loaded on the surface of the composite electrospun membrane by phase separation.

2. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 1, characterized in that: The preparation method of the composite carbon fiber cloth for friction power generation comprises the following steps: S1. The acyl chloride grafted PEI and the PEDOT:PSS aqueous dispersion binder are coated on the surface of the carbon fiber cloth to form a bonding layer on the surface of the carbon fiber cloth; S2. The PMIA / ZrO2 composite electrospun membrane with a hollow structure is covered on the surface of the bonding layer to obtain the composite carbon fiber cloth for friction power generation by interlayer adhesion.

3. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 2, characterized in that: The preparation method of the acyl chloride grafted PEI in S1 comprises the following steps: S11. The succinic anhydride / DMF solution is added to the PEI / DMF solution, and a heating reaction is performed to obtain carboxylated PEI; S12. The carboxylated PEI obtained in S1 is dispersed in toluene, SOCl2 is added, a heating reaction is performed, and rotary evaporation is performed to obtain the acyl chloride grafted PEI.

4. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 2, characterized in that: The preparation method of the PMIA / ZrO2 composite electrospun membrane with a hollow structure in S2 comprises the following steps: S21. LiCl is added to DMAC, stirred until dissolved, then PMIA is added, a constant temperature water bath is performed until dissolved, then ZrO2 particles are added, a certain amount of ethanol is added, ultrasonic dispersion is performed to obtain solution A; PVP is added to the ethanol / DMF mixed solution, stirred until dissolved to obtain solution B; S22. Solution A is used as the shell layer solution, and solution B is used as the core layer solution, a coaxial electrospinning is performed to obtain an electrospun membrane, then the electrospun membrane is soaked in an ethanol / acetone solution to obtain the PMIA / ZrO2 composite electrospun membrane with a hollow structure.

5. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 2, characterized in that: The temperature of the interlayer adhesion in S2 is 100-120℃, and the time is 5-15min.

6. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 3, characterized in that: The mass fraction of the succinic anhydride / DMF solution in S11 is 4-8wt%; And / or, the mass fraction of the PEI / DMF solution is 3-6wt%; And / or, the volume ratio of the succinic anhydride / DMF solution to the PEI / DMF solution is 1:1-4; And / or, the temperature of the heating reaction is 60-80℃, and the time is 2-4h.

7. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 3, characterized in that: The mass-volume ratio of the carboxylated PEI to toluene in S12 is 1:15-25g / mL; And / or, the addition amount of SOCl2 is 15-30wt% of the mass of the carboxylated PEI; And / or, the temperature of the heating reaction is 70-90℃, and the time is 3-5h; And / or, the temperature of the rotary evaporation is 30-45℃, and the pressure is -0.15--0.1MPa.

8. The method for preparing composite carbon fiber cloth for triboelectric power generation according to claim 4, characterized in that: The mass ratio of LiCl to PMIA in S21 is 1:0.2-0.9; And / or, the temperature of the constant temperature water bath is 50-60℃, and the time is 30-60min; And / or, the added amount of ZrO2 particles is 1-4 wt% of the mass of PMIA; And / or, the mass fraction of the solution A is 10-16 wt%; And / or, the volume ratio of ethanol to DMF is 5-7:5-7, and the mass fraction of the solution B is 10-15 wt%.

9. The method for preparing the composite carbon fiber cloth for triboelectric power generation according to claim 4, characterized in that: The electrospinning parameters of the S22 middle shell layer are as follows: the spinning voltage is 15-20 kV, the spinning speed is 0.2-1.2 mL / min, and the receiving distance is 18-22 cm; And / or, the electrospinning parameters of the core layer are as follows: the spinning voltage is 10-15 kV, the spinning speed is 0.1-0.5 mL / min, and the receiving distance is 18-22 cm; And / or, the volume ratio of ethanol to acetone in the ethanol / acetone solution is 1:0.4-06; And / or, the mass-volume ratio of the electrospinning membrane to the ethanol / acetone solution is 1:20-40 g / mL.

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