A triboelectric specialty paper and its applications

Abstract

The application discloses a triboelectric special paper for high-efficiency energy collection and power generation. The triboelectric special paper is prepared by using a cellulose nanofibril membrane formed through water flow assisted self-assembly as a base material, and then coating and modifying the base material with an amino silane solution to enhance electron donating capability. The triboelectric special paper has the characteristics of high thermal stability and high surface charge density, and the surface charge density reaches 196 muC m ‑2 at high temperature. The output power of a triboelectric nanogenerator based on the triboelectric special paper is one order of magnitude higher than that of an existing triboelectric nanogenerator device (2750 mW m ‑2 at 200 DEG C). The process flow is short, the equipment is simple, the cost is low, the electric output performance is significantly improved at high temperature, and the triboelectric special paper has a wide application prospect in the field of energy collection.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high-value utilization of cellulose biomass and friction nanogenerator, and in particular to an advanced cellulose material for energy collection, and a preparation method and application thereof. BACKGROUND

[0002] Since the industrial revolution, obtaining clean, affordable and reliable energy has been the cornerstone of the world's growing prosperity. In the 21st century, human exploration of space, the seabed and the depths of the earth has continuously driven the development of energy equipment, especially in the field of portable energy devices that work in extreme environments. In this context, friction nanogenerator emerged as the times require, and is widely used to collect and directly convert distributed energy in nature to generate electricity. Due to the characteristics of maintenance-free, self-powered and strong environmental adaptability, friction nanogenerator is expected to become a sustainable energy technology in extreme environments.

[0003] Polytetrafluoroethylene and polycarbonate polymers have become the first choice for high-performance friction nanogenerator due to their inherent advantages, such as low cost, easy processing, flexibility and high surface charge density. Due to the surge in demand for electrical energy in high-temperature applications such as deep-sea exploration, underground oil / gas exploration and aerospace systems, there is a need for polymer triboelectric materials that can work at high temperatures. However, typical polymer positive triboelectric materials suffer from severe structural degradation and rapid decline in charge density at high temperatures, severely damaging the power supply capability of the friction nanogenerator and possibly leading to serious consequences. In recent years, considerable efforts have been made to develop intrinsically temperature-resistant polymers for high-temperature environments, but the integration of high thermal stability and high surface charge density in polymer positive triboelectric materials has not been achieved, and the output power of the friction nanogenerator has not exceeded 200 mW m -2 .

[0004] Therefore, it is of great significance to introduce groups with higher electron-donating ability into cellulose nanofibers using chemical reaction methods, while enhancing the high-temperature resistance and power generation capacity of cellulose paper, to prepare a friction electric special paper that can maintain high and stable power generation performance in high-temperature environments. SUMMARY

[0005] The purpose of the present application is to design an advanced friction electric special paper, and use it as a positive triboelectric material for friction nanogenerator, to greatly improve the output performance and stability of the friction nanogenerator under high-temperature conditions.

[0006] The technical problem to be solved by the present application is solved by the following technical solution:

[0007] The frictional electricity special paper is prepared by using cellulose nanofibril membrane formed by water flow assisted self-assembly as a base material, and coating and modifying the base material by using an amino silane solution with enhanced electron donating ability.

[0008] Further, the preparation process of the cellulose nanofibril membrane is as follows: cellulose nanofibrils with a diameter of 20-100 nm are selected, the cellulose nanofibril solution is fully dispersed by magnetic stirring and ultrasonic treatment, and the cellulose nanofibril membrane is formed by water flow assisted self-assembly under vacuum conditions.

[0009] Further, the preparation process of the amino silane solution is as follows: an amino silane containing compound is dissolved in an ethanol / water solution, the concentration of the amino silane containing compound in the solution is 10-50 mg / mL, and the solution is stored after stirring at 30-90 DEG C for 1-5 h.

[0010] Further, the coating and modifying process is as follows: the amino silane solution is taken by using a pipette, and is spin-coated on the surface of the cellulose nanofibril membrane base material at a spin-coating speed of 5-30 r / min, and the frictional electricity special paper is obtained after drying for 2-8 h.

[0011] Further, the loading amount of the coating of the base material is 32-95 mg / cm 2 .

[0012] Further, the amino silane containing compound is 3-aminopropyl triethoxysilane.

[0013] Further, the thickness of the frictional electricity special paper is 30-100 mu m.

[0014] The frictional electricity special paper of the application can be used as the positive and negative frictional electricity materials of a triboelectric nanogenerator respectively together with a perfluoroethylene propylene copolymer film, and the triboelectric nanogenerator based on the frictional electricity special paper is suitable for a 200 DEG C high temperature environment.

[0015] The application has the following beneficial effects:

[0016] (1) The application endows cellulose nanofibrils with stronger electron donating ability, so that the cellulose nanofibrils become a material that can replace strong positive frictional materials such as nylon.

[0017] (2) The frictional electricity special paper of the application can work stably at 200 DEG C, the charge amount is increased by 10-500% compared with general paper based frictional electricity materials, the short circuit current is increased by 20-400%, and the open circuit voltage is increased by 10-500%.

[0018] (3) The process has short flow, simple equipment, low cost, and the output performance of electricity is significantly improved under high temperature environment, and has wide application prospect in the field of energy collection. DETAILED DESCRIPTION

[0019] The application will be further described below with reference to examples.

[0020] Example 1: A triboelectric special paper according to the application

[0021] (I) Preparation of the triboelectric special paper

[0022] Cellulose nanofibril with a diameter of 97±4 nm was selected, and cellulose nanofibril solution with an absolute dry mass of 0.4 g was completely dispersed by magnetic stirring and ultrasonic treatment. The cellulose nanofibril was subjected to vacuum filtration, and a cellulose nanofibril membrane matrix material was formed by water-assisted self-assembly. 3-aminopropyl triethoxysilane was dissolved in an ethanol / water solution, and the concentration of 3-aminopropyl triethoxysilane in the solution was 10 mg / mL. The solution was stirred at 30°C for 1 h to obtain an amino silane solution, which was stored in the form of a solution. The amino silane solution was taken by a pipette and spin-coated on the surface of the cellulose nanofibril membrane matrix material at a spin-coating speed of 5 r / min. After drying for 2 h, a triboelectric special paper was obtained. The thickness of the triboelectric special paper was 30 μm, and the loading of the coating of the matrix material was 32 mg / cm 2 .

[0023] (II) Preparation of the triboelectric nanogenerator

[0024] The triboelectric special paper prepared above was taken as a positive triboelectric film rubbing layer, and a perfluoroethylene propylene copolymer film was taken as a negative triboelectric film rubbing layer. The triboelectric special paper and the perfluoroethylene propylene copolymer film were the same size, 4 cm 2 in length, 2 cm in width and 0.02 cm in thickness. Copper tape was pasted on the back of each triboelectric material, and then the two triboelectric materials were fixed on a ceramic support plate. The wires were connected to the upper and lower electrodes. The contact separation power generation test of the triboelectric nanogenerator was carried out, and the pressure was 50 N and the frequency was 1 Hz.

[0025] The surface charge density of the triboelectric nanogenerator with untreated cellulose nanofiber paper as the positive rubbing layer was 20 μC m -2 , the short-circuit current was 1.9 μA, and the open-circuit voltage was 21 V. The surface charge density of the triboelectric nanogenerator based on the triboelectric special paper of the present application was 98 μC m -2 , the short-circuit current was 9.3 μA, and the open-circuit voltage was 116 V. It can be seen that the output performance of electricity of the triboelectric nanogenerator of the present application is significantly improved.

[0026] Example 2: A triboelectric special paper according to the application

[0027] Preparation of triboelectric special paper

[0028] Cellulose nanofibril with diameter of 57±5 nm was selected, and cellulose nanofibril solution with absolute dry mass of 1.2 g was completely dispersed by magnetic stirring and ultrasonic treatment. The cellulose nanofibril membrane matrix material was formed by water-assisted self-assembly under vacuum condition. 3-aminopropyl triethoxysilane was dissolved in an ethanol / water solution, and the concentration of 3-aminopropyl triethoxysilane in the solution was 50 mg / mL. The amino silane solution was obtained by stirring at 90°C for 5 h and was stored in the form of a solution. The amino silane solution was taken by using a pipette, and was spin-coated on the surface of the cellulose nanofibril membrane matrix material at a spin-coating speed of 30 r / min. The triboelectric special paper was obtained after drying for 8 h. The thickness of the triboelectric special paper was 100 μm, and the loading of the coating of the matrix material was 69 mg / cm 2 .

[0029] Preparation of high-temperature triboelectric nanogenerator

[0030] The triboelectric special paper prepared above was taken as a triboelectric positive film rubbing layer, and a perfluoroethylene propylene copolymer film was taken as a triboelectric negative film rubbing layer. The triboelectric special paper and the perfluoroethylene propylene copolymer film were the same size, 4 cm 2 × 4 cm. Copper adhesive tape was pasted on the back of each of the two triboelectric materials, and then the two triboelectric materials were fixed on ceramic support sheets, respectively. The wires were connected to the upper and lower electrodes. The triboelectric nanogenerator was placed in a high-temperature environment (200°C) for contact-separation power generation test, with a pressure of 50 N and a frequency of 1 Hz.

[0031] The surface charge density of the triboelectric special paper of the embodiment was 105 μC m -2 at an environmental temperature of 200°C. The output power of the triboelectric nanogenerator based on the triboelectric special paper was 310 mW m -2 , and the triboelectric nanogenerator could stably operate for 24 h. It can be seen that the triboelectric special paper of the embodiment can stably collect energy and generate electricity in a high-temperature environment of 200°C.

[0032] Example 3: A triboelectric special paper of the present application

[0033] Preparation of triboelectric special paper

[0034] The cellulose nanofibril solution with an absolute dry mass of 0.4 g was subjected to magnetic stirring and ultrasonic treatment to completely disperse the cellulose nanofibrils, and then subjected to vacuum filtration to form a cellulose nanofibril membrane matrix material through water-assisted self-assembly. 3-Aminopropyl triethoxysilane was dissolved in an ethanol / water solution, and the concentration of 3-aminopropyl triethoxysilane in the solution was 30 mg / mL. The solution was stirred at 60°C for 2 h to obtain an aminosilane solution, which was stored in the form of a solution. The aminosilane solution was taken by using a pipette and spin-coated on the surface of the cellulose nanofibril membrane matrix material at a spin-coating speed of 10 r / min. After drying for 6 h, a triboelectric special paper was obtained. The thickness of the triboelectric special paper was 50 μm, and the loading of the coating of the matrix material was 95 mg / cm 2 .

[0035] (ii) Preparation of a temperature difference triboelectric nanogenerator

[0036] The triboelectric special paper prepared above was taken as a triboelectric positive film rubbing layer, and a perfluoroethylene propylene copolymer film was taken as a triboelectric negative film rubbing layer. The triboelectric special paper and the perfluoroethylene propylene copolymer film were the same size, 4 cm 2 in length and 4 cm in width. Copper adhesive tape was pasted on the back of each of the two triboelectric materials, and then each was fixed on a ceramic support sheet. The wires were connected to the upper and lower electrodes. The triboelectric nanogenerator was placed under a temperature difference condition for contact separation power generation test. A high-temperature heating device was added to the side of the triboelectric special paper to maintain a temperature of 200°C, and a cooling device was added to the side of the perfluoroethylene propylene copolymer film to maintain a temperature of 25°C. The pressure was 50 N, and the frequency was 1 Hz.

[0037] The triboelectric special paper of the present embodiment reached a surface charge density of 196 μC m -2 under a temperature difference condition of 175°C. The output power of the triboelectric nanogenerator based on the triboelectric special paper was 2750 mW m -2 . It can be seen that the triboelectric special paper of the present embodiment is suitable for a triboelectric nanogenerator in a temperature difference environment.

Claims

1. A triboelectric specialty paper, characterized in that, The cellulose nanofibril film is formed by water flow assisted self-assembly, and the base material is coated and modified by an amino silane solution with enhanced electron donating capacity; The preparation process of the cellulose nanofibril film is as follows: cellulose nanofibrils with a diameter of 20-100 nm are selected, the cellulose nanofibril solution is fully dispersed by magnetic stirring and ultrasonic treatment, and the cellulose nanofibril film is formed by water flow assisted self-assembly under vacuum condition; The preparation process of the amino silane solution is as follows: an amino silane containing compound is dissolved in an ethanol / water solution, the concentration of the amino silane containing compound in the solution is 10-50 mg / mL, and the solution is stored after stirring at 30-90℃ for 1-5 h; the amino silane containing compound is 3-aminopropyl triethoxysilane; The coating modification process is as follows: the amino silane solution is taken by a pipette and spin-coated on the surface of the cellulose nanofibril film base material at a spin-coating speed of 5-30 r / min, and the triboelectric special paper is obtained after drying for 2-8 h; The triboelectric special paper can work stably at 200℃.

2. The triboelectric specialty paper of claim 1, wherein, The coating of the base material has a load of 32 to 95 mg / cm 2 .

3. The triboelectric specialty paper of claim 1, wherein, The thickness of the triboelectric special paper is 30-100 μm.

4. Application of the triboelectric special paper according to any one of claims 1-3 as a positive triboelectric material of a triboelectric nanogenerator.