A method for preparing a paper-based triboelectric nanogenerator by integrating a friction material and an electrode material

Abstract

The application discloses a method for preparing a paper-based friction nanogenerator by integrating ODCP and PCP through a laminating net forming process. The method comprises the following steps: preparing paper ODCP with hydrophobic and acid and alkali resistant properties through Schiff base reaction of dialdehyde cellulose and octadecylamine; preparing polypyrrole conductive paper PCP through an in-situ polymerization reaction; and obtaining the full paper-based friction nanogenerator by integrating ODCP and PCP through the laminating net forming process. In the application, aldehyde groups are introduced into cellulose fibers through sodium periodate oxidation, and octadecylamine is introduced into the surface of the cellulose fibers through Schiff base reaction of the aldehyde groups and octadecylamine, so as to improve the hydrophobic and acid and alkali resistant properties of the paper. In the process of integrating ODCP and PCP through the laminating net forming process, hydrogen bonds are generated on the surface of ODCP and PCP, which is conducive to the integration of ODCP and PCP. Hydrogen bond force exists between PCP and PDMS, so that PCP and PDMS can be tightly combined. The method greatly improves the output performance, moisture resistance and acid and alkali resistance of the full paper-based friction nanogenerator.

Description

Technical Field

[0001] This invention relates to the field of high-value utilization of cellulose and triboelectric nanogenerators, specifically to a method for preparing a paper-based triboelectric nanogenerator by integrating a lamination-molded friction material and an electrode material. Background Technology

[0002] Triboelectric nanogenerators (TGNs) are a highly efficient and environmentally friendly energy conversion technology based on triboelectricity and electrostatic induction, capable of converting mechanical energy from the natural environment into electrical energy. The structure of a TGN mainly consists of triboelectric materials, electrode materials, a substrate support material, and external circuitry. The properties of the triboelectric materials determine the output performance of the TGN, while the electrode materials are crucial for electron transfer, meaning they need to possess excellent electrical conductivity. The electrode materials of TGNs are mostly metals or metal oxides, such as Au, Ag, Al, Cu, and ITO. However, metals or metal oxides are easily corroded or oxidized in acidic and alkaline environments, affecting the output performance and stability of the TGN.

[0003] Paper, a material composed of interwoven cellulose fibers, loses electrons and acquires a positive charge during friction, making it widely applicable as an electropositive triboelectric material in triboelectric nanogenerators. However, cellulose is almost neutral in relative polarity, occupying a slightly positive position in the triboelectric sequence. Furthermore, cellulose is highly hydrophilic, absorbing moisture from the environment and weakening its triboelectric properties. This limits the triboelectric output performance and applications of paper-based triboelectric nanogenerators.

[0004] To date, the output performance of paper-based triboelectric nanogenerators has primarily been improved through chemical modification of the hydroxyl groups on the paper surface to alter the functional group structure and thus the surface potential, or by introducing nanoparticles and conductive polymers into the paper to increase its effective contact area and conductivity. However, these methods are typically carried out on commercial paper, and their preparation processes are complex with limited improvement in output performance. Therefore, developing a fully paper-based triboelectric nanogenerator with excellent output performance and strong environmental adaptability by improving the ability of paper to generate surface charges, reducing the harmful effects of water molecules on the output performance of paper-based triboelectric nanogenerators, and leveraging the advantages of papermaking processes is of great significance for realizing the practical application of paper-based triboelectric nanogenerators. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a method for preparing paper-based triboelectric nanogenerators by integrating friction materials and electrode materials through a stacked mesh forming process.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing a paper-based triboelectric nanogenerator by stacking and integrating triboelectric materials and electrode materials includes the following steps: 1) The cellulose fibers that have been split and dispersed are dispersed in deionized water to form a cellulose fiber dispersion. The pH value of the reaction system is adjusted with dilute sulfuric acid solution, sodium periodate is added, the mixture is stirred evenly and heated to react, and then filtered and washed to obtain dialdehyde cellulose fibers. Dialdehyde cellulose fibers were dispersed in deionized water to form a dialdehyde cellulose fiber dispersion. Octadecylamine / ethanol solution was added, stirred evenly, heated to react, and then filtered and washed to obtain octadecylamine-modified dialdehyde cellulose fibers. 2) Disperse the cellulose fibers into deionized water and shake vigorously to make the cellulose fibers evenly dispersed to form a cellulose fiber dispersion. Add pyrrole, pre-cool, then add a mixed solution of ferric chloride and hydrochloric acid, shake vigorously again, let stand to react, and finally filter and wash to obtain polypyrrole conductive cellulose fibers. 3) Disperse the octadecylamine-modified dialdehyde cellulose fiber described in step 1) in deionized water to form an octadecylamine-modified dialdehyde cellulose fiber dispersion, fully dissociate it using a standard fiber dissociator, and then form it into wet paper, which is paper with hydrophobic and acid and alkali resistant properties (ODCP). The polypyrrole conductive cellulose fibers described in step 2) are dispersed in deionized water to form a polypyrrole conductive cellulose fiber dispersion, which is then fully dissociated using a standard fiber dissociator and then formed into wet paper, i.e., polypyrrole conductive paper (PCP). Wet PCP is covered on one side of wet ODCP, and finally pressed and dried to obtain ODCP / PCP electrode; 4) Mix the polydimethylsiloxane (PDMS) precursor and curing agent, pour into a disposable petri dish, pre-cur in an oven, then attach the pressed and dried PCP onto the PDMS surface, and further cure in a vacuum drying oven to obtain a PDMS / PCP electrode; 5) Using printing paper as the substrate support material, ODCP / PCP electrodes and PDMS / PCP electrodes are assembled into a paper-based triboelectric nanogenerator.

[0007] This invention utilizes Schiff base reaction fibers of dialdehyde cellulose and octadecylamine to introduce octadecylamine onto the surface of cellulose fibers, imparting hydrophobic and acid / alkali resistant properties to the paper. Then, polypyrrole is introduced into the paper through in-situ polymerization, giving it conductive properties. Simultaneously, by using a lamination process to integrate the hydrophobic, acid / alkali resistant paper and the conductive double-layer paper, the output performance, moisture resistance, and acid / alkali resistance of the all-paper-based triboelectric nanogenerator can be significantly improved.

[0008] Preferably, in step 1), the concentration of the cellulose fiber dispersion is 1 wt%, and the concentration of the dilute sulfuric acid solution is 0.1 mol·L⁻¹.-1 The pH of the reaction system was 4, the reaction temperature was 50℃, and the reaction time was 3 h.

[0009] Preferably, in step 1), the concentration of the dialdehyde cellulose fiber dispersion is 1 wt%, the concentration of the octadecylamine / ethanol solution is 0~0.2 g / mL, the reaction temperature is 50℃, and the reaction time is 1~3 h.

[0010] Preferably, in step 2), the concentration of the cellulose fiber dispersion is 2 wt%, the concentration of pyrrole is 4% (v / v), the pre-cooling equipment is a refrigerator, the pre-cooling temperature is 4°C, and the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L⁻¹. -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 The violent shaking time was 5 minutes, and the static reaction temperature was 4℃.

[0011] Preferably, in step 3), the concentrations of both the polypyrrole conductive cellulose fiber dispersion and the octadecylamine-modified dialdehyde cellulose fiber dispersion are 0.1 wt%, the propeller speed of the standard fiber dissociator is 1000~3000 rpm, and the basis weight of the paper is 40 g·m³. -2 The pressing and drying temperature is 80~90℃, and the drying time is 15~20 min.

[0012] Preferably, in step 4), the mass ratio of PDMS precursor to curing agent is 1:10, and the quantitative amount of PDMS is 10~11 g·m³. -2 The pre-curing temperature is 70~80℃, the pre-curing time is 5~10 min, the curing temperature is 70~80℃, and the curing time is 2~3 h.

[0013] Further, step 5) is as follows: Cut the printing paper into 5 × 13 cm pieces. 2 A rectangular shape is formed by gluing the shorter side together to create an arched structure. Then, ODCP / PCP and PDMS / PCP electrodes are glued to the center of both sides of the arched structure. The ODCP / PCP and PDMS / PCP electrodes are connected by copper wires, with the surface of ODCP facing the surface of PDMS, resulting in a paper-based triboelectric nanogenerator. In this process, ODCP is an electropositive triboelectric material, PDMS is an electronegative triboelectric material, and PCP is the electrode material. The prepared paper-based triboelectric nanogenerator significantly improves the output performance, moisture resistance, and acid and alkali resistance of the paper-based triboelectric nanogenerator.

[0014] Preferably, the cellulose fiber is selected from one or more of softwood pulp, hardwood pulp, bamboo pulp, and wheat straw pulp. Further, the cellulose fiber is selected from bleached chemical pulp commonly used in the papermaking industry, preferably bleached softwood chemical pulp.

[0015] Preferably, the preparation process of the split cellulose fiber is as follows: ① the plant fiber soaked in water is loosened into a uniformly dispersed single fiber state; ② the loosened plant fiber is subjected to high-speed shearing treatment to obtain split cellulose fiber.

[0016] Preferably, in the preparation process of the fibrillated cellulose fibers, the concentration of cellulose fibers during soaking is 3 wt%, the soaking time is 4-6 h, and the soaking temperature is 20-30℃; the concentration of cellulose fibers for disintegration is 1-2 wt%, the disintegration temperature is 20-30℃, and the disintegration time is 15-20 min; the propeller speed of the standard fiber disintegrator used for disintegration is 1000-3000 rpm. The temperature of the high-speed mechanical shearing treatment is 25-30℃, and the concentration of cellulose fibers is 10 wt%. The high-speed shearing equipment is a PFI mill, a Jokro mill, etc., with a PFI mill preferred. The degree of beating of the fibrillated cellulose fibers is 89. o SR. The cellulose fibers used in this invention undergo a fibrillation process to increase the specific surface area of ​​the cellulose fibers, thereby increasing the loading of octadecylamine and the effective friction area of ​​the paper.

[0017] This invention innovatively employs a lamination process to prepare a paper-based triboelectric nanogenerator with high output performance, high moisture resistance, and acid and alkali resistance. (1) Aldehyde groups are introduced into cellulose fibers by oxidation with sodium periodate. The Schiff base reaction between the aldehyde groups and octadecylamine can introduce octadecylamine into the surface of the cellulose fibers, which is beneficial to increasing the hydrophobicity and acid and alkali resistance of the paper. (2) During the lamination process of integrating ODCP and PCP, hydrogen bonding occurs between the ODCP and PCP surfaces, which is beneficial to promoting the integration of ODCP and PCP. (3) Hydrogen bonding exists between the PCP and PDMS surfaces, which allows PCP and PDMS to be tightly bonded, which is beneficial to the preparation of the paper-based triboelectric nanogenerator. (4) Using printing paper as the substrate support material, ODCP as the electropositive triboelectric material, PDMS as the electronegative triboelectric material, and PCP as the electrode material to prepare a paper-based triboelectric nanogenerator greatly improves the output performance, moisture resistance, and acid and alkali resistance of the paper-based triboelectric nanogenerator.

[0018] Compared with the prior art, the beneficial effects of the technical solution of the present invention are: 1. Polypyrrole is synthesized in situ on the surface of cellulose fibers to enhance the conductivity of cellulose fibers, thereby improving the conductivity of paper. This allows paper to be used as an electrode material for triboelectric nanogenerators, increasing the environmental adaptability of paper-based triboelectric nanogenerators.

[0019] 2. The Schiff base reaction between dialdehyde cellulose fibers and octadecylamine enhances the bonding strength between octadecylamine and cellulose fibers, giving the paper excellent hydrophobic and acid and alkali resistance properties.

[0020] 3. A method of lamination molding is used to integrate polypyrrole conductive paper and hydrophobic and acid-alkali resistant paper modified by reaction of dialdehyde fiber with octadecylamine Schiff base, which makes the two different types of paper tightly bonded, significantly improving the output performance, moisture resistance and acid and alkali resistance of paper-based triboelectric nanogenerator.

[0021] 4. The cellulose fibers selected in this invention undergo a fibrillation process. High-speed shearing refines the surface of the cellulose fibers, exposing more hydroxyl groups, thereby increasing the effective friction area of ​​the paper and the bonding strength between the polypyrrole conductive paper and the hydrophobic and acid- and alkali-resistant paper modified by the reaction of dialdehyde fibers with octadecylamine Schiff base.

[0022] 5. The technology of stacking and forming integrated paper-based friction materials and electrode materials can be directly applied to industrial production to obtain all-paper-based triboelectric nanogenerators with high output performance, high moisture resistance, and acid and alkali resistance. One embodiment of this invention shows that the all-paper-based triboelectric nanogenerator prepared by this method has an open-circuit voltage of 227.1 V, a short-circuit current of 6.9 μA, and a surface charge density of 41.9 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator remains as high as 177.2V, the short-circuit current is 5.0 μA, and the surface charge density is 36.8 μC·m. -2 0.1 mol·L -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 226.1 V, the short-circuit current was 6.7 μA, and the surface charge density was 40.6 μC·m. -2 0.1 mol·L -1 After sodium hydroxide treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 225.4 V, the short-circuit current was 6.8 μA, and the surface charge density was 40.8 μC·m. -2 After being soaked in hydrochloric acid and sodium hydroxide, the output performance of the triboelectric nanogenerator remained almost unchanged, promoting the development of environmentally friendly triboelectric nanogenerators.

[0023] 6. The all-paper-based triboelectric nanogenerator prepared by this invention can be applied in high humidity, strong acid and strong alkali environments, as well as in the fields of mechanical energy harvesting, flexible sensors and self-powered energy storage systems. Attached Figure Description

[0024] Figure 1 This is a process flow diagram for the integrated friction material and electrode material formed by lamination.

[0025] Figure 2Scanning electron microscope images of hydrophobic and acid- and alkali-resistant paper prepared by the Schiff base reaction of dialdehyde cellulose and octadecylamine in Example 1; (a) paper prepared from cellulose fibers after high-speed shearing treatment; (b) paper prepared from dialdehyde cellulose fibers; (c) paper prepared from dialdehyde cellulose fibers after the Schiff base reaction of octadecylamine.

[0026] Figure 3 The image shows a scanning electron microscope (cross-sectional view) of the paper-based friction material and electrode material integrated by the overlay forming process in Example 1.

[0027] Figure 4 The contact angle of the paper prepared by reacting dialdehyde cellulose fibers with octadecylamine in Example 1 with water, hydrochloric acid, and sodium hydroxide solution is given.

[0028] Figure 5 This is a schematic diagram of the structure of the all-paper-based triboelectric nanogenerator in Example 1.

[0029] Figure 6 This is a scanning electron microscope image of the paper prepared by reacting dialdehyde cellulose with octadecylamine as a Schiff base in Example 2.

[0030] Figure 7 This is a scanning electron microscope image of the paper prepared by reacting dialdehyde cellulose with an octadecylamine Schiff base in Example 3. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is further described below through specific embodiments. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0032] A method for preparing a paper-based triboelectric nanogenerator by stacking and integrating triboelectric materials and electrode materials includes the following steps: 1) Preparation of cellulose fibers with fibrillation 1-1) Weigh a certain amount of cellulose fiber and add it to an appropriate amount of deionized water to make the concentration of cellulose fiber 3 wt%. Soak it at 20~30℃ for 4~6 h, then add an appropriate amount of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1~2wt%. Use a standard fiber dissociator to dissociate it at 20~30℃ for 15~20 min, with the propeller speed at 10000~30000 rpm, so that the cellulose fiber is dispersed into a single fiber state. 1-2) The loosened cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 20~30℃ and a rotation speed of 21000 rpm to make the cellulose fiber freeness 89°SR, thereby obtaining cellulose fibers with a fiber surface fibrillation.

[0033] 2) Preparation of polypyrrole conductive cellulose fibers: Weigh a certain mass of fibrillated cellulose fibers, add an appropriate amount of deionized water to form a cellulose fiber dispersion with a fiber concentration of 2 wt%. Vigorously shake for 5-10 min to ensure uniform fiber dispersion. Add a certain volume of pyrrole with a concentration of 4% (V / V). Pre-cool to 4℃ in a refrigerator. Then, add a pre-cooled ferric chloride and hydrochloric acid mixture to the cellulose fiber and pyrrole suspension. Vigorously shake for 5 min and react at 4℃ for 2 h. The concentration of ferric chloride in the ferric chloride and hydrochloric acid mixture is 0.5 mol·L⁻¹. -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 The volume of the mixed solution of ferric chloride and hydrochloric acid is equal to the volume of deionized water in the cellulose fiber dispersion. Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0034] 3) Preparation of octadecylamine-modified dialdehyde cellulose fibers 3-1) Weigh a certain mass of fibrillated cellulose fibers, add an appropriate amount of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1 wt%, and then use 0.1 mol·L⁻¹ water. -1 The pH of the reaction system was adjusted to 4 with sulfuric acid solution, sodium periodate was added, and the mass ratio of sodium periodate to cellulose fiber was 1:1. The reaction was then magnetically stirred at 50°C for 3 h. Anhydrous ethanol was added to terminate the reaction. Finally, the product was filtered and washed until the filtrate was colorless when dropped onto starch-potassium iodide test paper, thus obtaining dialdehyde cellulose fiber. 3-2) Weigh a certain mass of dialdehyde cellulose fiber and add a certain volume of deionized water to form a dialdehyde cellulose fiber dispersion with a fiber concentration of 1 wt%. Then dissolve octadecylamine in 25 mL of anhydrous ethanol to make the concentration of the octadecylamine / ethanol solution 0~0.2 g·mL. -1 The mixture was added dropwise to the dialdehyde cellulose fiber dispersion using a dropper, and then magnetically stirred at 50°C for 1-3 hours. After washing with anhydrous ethanol and deionized water, octadecylamine-modified dialdehyde cellulose fiber was obtained.

[0035] 4) Stacked mesh forming of integrated paper-based friction materials and electrode materials A certain mass of polypyrrole conductive cellulose fiber was weighed and added to an appropriate amount of deionized water to achieve a fiber concentration of 0.1 wt%. Then, it was dissociated using a standard fiber dissociator at room temperature for 10–15 min (propeller speed 10,000–30,000 rpm). The resulting wet PCP was then formed using a paper forming machine, with a paper basis weight of 40 g·m³. -2 ; A certain mass of octadecylamine-modified dialdehyde cellulose fiber was weighed and added to an appropriate amount of deionized water to achieve a fiber concentration of 0.1 wt%. The fiber was then dissociated at room temperature for 10–15 min using a standard fiber dissociator with a propeller speed of 10,000–30,000 rpm. The resulting wet OPCP was then formed using a paper forming machine, producing a paper basis weight of 40 g·m³. -2 ; Wet PCP is covered on one side of wet ODCP, and then pressed and dried at 80~90℃ for 15~20 min to obtain ODCP / PCP electrode. At the same time, wet PCP is pressed and dried at 80~90℃ for 15~20 min and used as electrode material for PDMS.

[0036] 5) Fabrication of PDMS / PCP electrode The PDMS precursor and curing agent were mixed at a mass ratio of 1:10, then poured into disposable petri dishes and pre-cured in an oven at 70-80℃ for 5-10 min. The quantitative amount of PDMS was 10-11 g·m³. -2 Then, the pressed and dried PCP is attached to the surface of PDMS and pressed to make the PCP and PDMS tightly bonded. Finally, it is further cured in a vacuum drying oven at 70~80℃ for 2~3 h to obtain the PDMS / PCP electrode.

[0037] 6) Fabrication of an all-paper-based triboelectric nanogenerator: The printing paper was cut into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding two 5 cm sides together with 3M tape to create an arched structure. The ODCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample was attached to the center of both sides of the arched structure of the above-mentioned printing paper. The ODCP / PCP electrode and the PDMS / PCP electrode were connected by copper wires, with the surface of ODCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator. Example 1

[0038] A method for preparing a paper-based triboelectric nanogenerator by stacking and integrating triboelectric materials and electrode materials includes the following steps: (1) Weigh 30 g (octane dry weight) of bleached spruce coniferous chemical pulp, add 970 mL of deionized water to make the concentration of cellulose fiber 3 wt%, soak at 25℃ for 6 h, then add 500 mL of deionized water to adjust the concentration of cellulose fiber to 2 wt%, and use a standard fiber dissociator to dissociate at 25℃ for 15 min, with the propeller speed at 20000 rpm, so that the cellulose fiber is dispersed into a single fiber state.

[0039] The dissolved cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 25°C and a rotation speed of 21,000 rpm. The cellulose fibers after high-speed shearing treatment had a beating degree of 89°SR, thus obtaining cellulose fibers with a fiber surface fibrillation.

[0040] (2) Weigh 5 g (dry weight) of the cellulose fibers separated in step (1), add 245 mL of deionized water to obtain a cellulose fiber dispersion with a fiber concentration of 2 wt%, shake vigorously for 5 min to make the fibers uniformly dispersed, add 10 mL of pyrrole, place in a refrigerator to pre-cool to 4℃, then add 250 mL of a mixed solution of ferric chloride and hydrochloric acid pre-cooled to 4℃ to the suspension of cellulose fibers and pyrrole, shake vigorously for 5 min, react at 4℃ for 2 h, the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0041] (3) Weigh 15 g (dry weight) of the cellulose fibers separated in step (1), add 1485 mL of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1 wt%, and then use 0.1 mol·L⁻¹ water. -1 The pH of the reaction system was adjusted to 4 with sulfuric acid solution, 15 g of sodium periodate was added, and the reaction was magnetically stirred at 50 °C for 3 h. The reaction was terminated by adding 75 mL of anhydrous ethanol. Finally, the product was filtered and washed until the filtrate was colorless when dropped onto starch-potassium iodide test paper, thus obtaining dialdehyde cellulose fiber.

[0042] Weigh 2.5 g (octahydrate weight) of dialdehyde cellulose fiber and add 247.5 mL of deionized water to form a dialdehyde cellulose fiber dispersion with a fiber concentration of 1 wt%. Then, dissolve 2.5 g of octadecylamine in 25 mL of anhydrous ethanol and add the octadecylamine / ethanol solution dropwise to the dialdehyde cellulose fiber dispersion using a dropper. Stir the mixture magnetically at 50 °C for 1 h. Wash the mixture with anhydrous ethanol and deionized water respectively to obtain octadecylamine-modified dialdehyde cellulose fiber.

[0043] (4) Weigh 1.25 g of the polypyrrole conductive cellulose fiber from step (2), add 1248.8 mL of deionized water to make the fiber concentration 0.1 wt%, then dissociate it using a standard fiber dissociator at room temperature for 15 min. The propeller speed of the standard fiber dissociator is 20000 rpm. Then, use a paper forming machine to form wet PCP with a basis weight of 40 g·m -2 Then, wet ODCP was obtained using the same method, and the basis weight of the paper was also 40 g·m. -2 Finally, wet PCP is covered on one side of wet ODCP, and the mixture is pressed and dried at 80°C for 15 min to obtain the ODCP / PCP electrode. At the same time, the wet PCP is pressed and dried at 80°C for 15 min and used as the electrode material for PDMS.

[0044] (5) Mix the PDMS precursor and curing agent at a mass ratio of 1:10, then pour 3 g of the mixture into a 60 mm disposable petri dish, pre-cur it at 80°C in an oven for 8 min, then press and dry the PCP onto the PDMS surface and press it to make the PCP and PDMS tightly bonded. Finally, further cure it at 80°C in a vacuum drying oven for 2 h to obtain the PDMS / PCP electrode.

[0045] (6) Cut the printing paper into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding two 5 cm sides together with 3M tape to create an arched structure. The ODCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample was attached to the center of both sides of the arched structure of the above-mentioned printing paper. The ODCP / PCP electrode and the PDMS / PCP electrode were connected by copper wires, with the surface of ODCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

[0046] The above process flow for using stacked mesh forming integrated friction material and electrode material is as follows: Figure 1 As shown, paper prepared by the Schiff base reaction of dialdehyde cellulose and octadecylamine, and ODCP / PCP were observed using a scanning electron microscope, as follows: Figure 2 and Figure 3 As shown. The results show that high-speed shearing treatment forms a fine fibrous structure on the fiber surface, exhibiting filament splitting and broom-like phenomena, increasing the effective friction area of ​​the paper; after Schiff base modification with octadecylamine and dialdehyde cellulose fibers, the fiber surface is loaded with a large amount of octadecylamine, which improves the surface roughness, hydrophobicity, and acid and alkali resistance of the paper (e.g. Figure 4 As shown), ultimately a high-output, moisture-resistant, and acid-alkali-resistant all-paper-based triboelectric nanogenerator (such as...) was obtained. Figure 5 (As shown).

[0047] The sheet resistance of the PCP prepared above is 662.3 Ω / □, and the ODCP resists water and 0.1 mol·L⁻¹. -1 Hydrochloric acid and 0.1 mol·L -1 The contact angles of the sodium hydroxide solution were 141.6°, 139.6° and 140.4°, respectively.

[0048] The all-paper-based triboelectric nanogenerator has an open-circuit voltage of 227.1 V, a short-circuit current of 6.9 μA, and a surface charge density of 41.9 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator is 177.2 V, the short-circuit current is 5.0 μA, and the surface charge density is 36.8 μC·m. -2 They retained 78%, 72.5%, and 87.8% of their initial state, respectively. 0.1 mol·L⁻¹ -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 226.1 V, the short-circuit current was 6.7 μA, and the surface charge density was 40.6 μC·m. -2 They maintained 99.6%, 97.1%, and 96.9% of their initial states, respectively; 0.1 mol·L -1 After treatment with sodium hydroxide, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 225.4 V, the short-circuit current was 6.8 μA, and the surface charge density was 40.8 μC·m. -2 They maintained 99.2%, 98.6%, and 97.4% of their initial states, respectively. Example 2

[0049] A method for preparing a paper-based triboelectric nanogenerator by stacking and integrating triboelectric materials and electrode materials includes the following steps: (1) Weigh 30 g (octane dry weight) of bleached spruce coniferous chemical pulp, add 970 mL of deionized water to make the concentration of cellulose fiber 3 wt%, soak at 25℃ for 6 h, then add 500 mL of deionized water to adjust the concentration of cellulose fiber to 2 wt%, and use a standard fiber dissociator to dissociate at 25℃ for 15 min, with the propeller speed at 20000 rpm, so that the cellulose fiber is dispersed into a single fiber state.

[0050] The dissolved cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 25°C and a rotation speed of 21,000 rpm. The cellulose fibers after high-speed shearing treatment had a beating degree of 89°SR, thus obtaining cellulose fibers with a fiber surface fibrillation.

[0051] (2) Weigh 5 g (dry weight) of the cellulose fibers separated in step (1), add 245 mL of deionized water to obtain a cellulose fiber dispersion with a fiber concentration of 2 wt%, shake vigorously for 5 min to make the fibers uniformly dispersed, add 10 mL of pyrrole, place in a refrigerator to pre-cool to 4℃, then add 250 mL of a mixed solution of ferric chloride and hydrochloric acid pre-cooled to 4℃ to the suspension of cellulose fibers and pyrrole, shake vigorously for 5 min, react at 4℃ for 2 h, the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0052] (3) Weigh 15 g (dry weight) of the cellulose fibers separated in step (1), add 1485 mL of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1 wt%, and then use 0.1 mol·L⁻¹ water. -1 The pH of the reaction system was adjusted to 4 with sulfuric acid solution, 15 g of sodium periodate was added, and the reaction was magnetically stirred at 50 °C for 3 h. The reaction was terminated by adding 75 mL of anhydrous ethanol. Finally, the product was filtered and washed until the filtrate was colorless when dropped onto starch-potassium iodide test paper, thus obtaining dialdehyde cellulose fiber.

[0053] Weigh 2.5 g (octahydrate weight) of dialdehyde cellulose fiber and add 247.5 mL of deionized water to form a dialdehyde cellulose fiber dispersion with a fiber concentration of 1 wt%. Then, dissolve 0.5 g of octadecylamine in 25 mL of anhydrous ethanol and add the octadecylamine / ethanol solution dropwise to the dialdehyde cellulose fiber dispersion using a dropper. Stir the mixture magnetically at 50 °C for 2 h. Wash the mixture with anhydrous ethanol and deionized water respectively to obtain octadecylamine-modified dialdehyde cellulose fiber.

[0054] (4) Weigh 1.25 g of the polypyrrole conductive cellulose fiber from step (2), add 1248.8 mL of deionized water to make the fiber concentration 0.1 wt%, then dissociate it using a standard fiber dissociator at room temperature for 15 min. The propeller speed of the standard fiber dissociator is 20000 rpm. Then, use a paper forming machine to form wet PCP with a basis weight of 40 g·m -2 Then, wet ODCP was obtained using the same method, and the basis weight of the paper was also 40 g·m. -2 Finally, wet PCP is covered on one side of wet ODCP, and the mixture is pressed and dried at 80°C for 15 min to obtain the ODCP / PCP electrode. At the same time, the wet PCP is pressed and dried at 80°C for 15 min and used as the electrode material for PDMS.

[0055] (5) Mix the PDMS precursor and curing agent at a mass ratio of 1:10, then pour 3 g of the mixture into a 60 mm disposable petri dish, pre-cur it at 80°C in an oven for 8 min, then press and dry the PCP onto the PDMS surface and press it to make the PCP and PDMS tightly bonded. Finally, further cure it at 80°C in a vacuum drying oven for 2 h to obtain the PDMS / PCP electrode.

[0056] (6) Cut the printing paper into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding two 5 cm sides together with 3M tape to create an arched structure. The ODCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample was attached to the center of both sides of the arched structure of the above-mentioned printing paper. The ODCP / PCP electrode and the PDMS / PCP electrode were connected by copper wires, with the surface of ODCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

[0057] The paper prepared by the Schiff base reaction of dialdehyde cellulose and octadecylamine described above was observed under a scanning electron microscope as follows: Figure 6 As shown.

[0058] The sheet resistance of the PCP prepared above is 662.3 Ω / □, and the ODCP resists water and 0.1 mol·L⁻¹. -1 Hydrochloric acid and 0.1 mol·L -1 The contact angles of the sodium hydroxide solution were 136.5°, 136.3° and 136.8°, respectively.

[0059] The all-paper-based triboelectric nanogenerator has an open-circuit voltage of 173.4 V, a short-circuit current of 4.8 μA, and a surface charge density of 31.1 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator is 114.2 V, the short-circuit current is 3.5 μA, and the surface charge density is 25.8 μC·m. -2 They retained 65.9%, 72.9%, and 83.0% of their initial states, respectively. 0.1 mol·L⁻¹ -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 172.9 V, the short-circuit current was 4.7 μA, and the surface charge density was 30.8 μC·m. -2 They maintained 99.7%, 97.9%, and 99.0% of their initial states, respectively; 0.1 mol·L -1 After treatment with sodium hydroxide, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 173.2 V, the short-circuit current was 4.8 μA, and the surface charge density was 30.9 μC·m. -2 They maintain 99.9%, 100%, and 99.4% of their initial states, respectively. Example 3

[0060] A method for preparing a paper-based triboelectric nanogenerator by stacking and integrating triboelectric materials and electrode materials includes the following steps: (1) Weigh 30 g (octane dry weight) of bleached spruce coniferous chemical pulp, add 970 mL of deionized water to make the concentration of cellulose fiber 3 wt%, soak at 25℃ for 6 h, then add 500 mL of deionized water to adjust the concentration of cellulose fiber to 2 wt%, and use a standard fiber dissociator to dissociate at 25℃ for 15 min, with the propeller speed at 20000 rpm, so that the cellulose fiber is dispersed into a single fiber state.

[0061] The dissolved cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 25°C and a rotation speed of 21,000 rpm. The cellulose fibers after high-speed shearing treatment had a beating degree of 89°SR, thus obtaining cellulose fibers with a fiber surface fibrillation.

[0062] (2) Weigh 5 g (dry weight) of the cellulose fibers separated in step (1), add 245 mL of deionized water to obtain a cellulose fiber dispersion with a fiber concentration of 2 wt%, shake vigorously for 5 min to make the fibers uniformly dispersed, add 10 mL of pyrrole, place in a refrigerator to pre-cool to 4℃, then add 250 mL of a mixed solution of ferric chloride and hydrochloric acid pre-cooled to 4℃ to the suspension of cellulose fibers and pyrrole, shake vigorously for 5 min, react at 4℃ for 2 h, the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0063] (3) Weigh 15 g (dry weight) of the cellulose fibers separated in step (1), add 1485 mL of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1 wt%, and then use 0.1 mol·L⁻¹ water. -1 The pH of the reaction system was adjusted to 4 with sulfuric acid solution, 15 g of sodium periodate was added, and the reaction was magnetically stirred at 50 °C for 3 h. The reaction was terminated by adding 75 mL of anhydrous ethanol. Finally, the product was filtered and washed until the filtrate was colorless when dropped onto starch-potassium iodide test paper, thus obtaining dialdehyde cellulose fiber.

[0064] Weigh 2.5 g (octahydrate weight) of dialdehyde cellulose fiber and add 247.5 mL of deionized water to form a dialdehyde cellulose fiber dispersion with a fiber concentration of 1 wt%. Then, dissolve 5 g of octadecylamine in 25 mL of anhydrous ethanol and add the octadecylamine / ethanol solution dropwise to the dialdehyde cellulose fiber dispersion using a dropper. Stir the mixture magnetically at 50 °C for 1 h. Wash the mixture with anhydrous ethanol and deionized water respectively to obtain octadecylamine-modified dialdehyde cellulose fiber.

[0065] (4) Weigh 1.25 g of the polypyrrole conductive cellulose fiber from step (2), add 1248.8 mL of deionized water to make the fiber concentration 0.1 wt%, then dissociate it using a standard fiber dissociator at room temperature for 15 min. The propeller speed of the standard fiber dissociator is 20000 rpm. Then, use a paper forming machine to form wet PCP with a basis weight of 40 g·m -2 Then, wet ODCP was obtained using the same method, and the basis weight of the paper was also 40 g·m. -2 Finally, wet PCP is covered on one side of wet ODCP, and the mixture is pressed and dried at 80°C for 15 min to obtain the ODCP / PCP electrode. At the same time, the wet PCP is pressed and dried at 80°C for 15 min and used as the electrode material for PDMS.

[0066] (5) Mix the PDMS precursor and curing agent at a mass ratio of 1:10, then pour 3 g of the mixture into a 60 mm disposable petri dish, pre-cur it at 80°C in an oven for 8 min, then press and dry the PCP onto the PDMS surface and press it to make the PCP and PDMS tightly bonded. Finally, further cure it at 80°C in a vacuum drying oven for 2 h to obtain the PDMS / PCP electrode.

[0067] (6) Cut the printing paper into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding two 5 cm sides together with 3M tape to create an arched structure. The ODCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample was attached to the center of both sides of the arched structure of the above-mentioned printing paper. The ODCP / PCP electrode and the PDMS / PCP electrode were connected by copper wires, with the surface of ODCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

[0068] The paper prepared by the Schiff base reaction of dialdehyde cellulose and octadecylamine described above was observed under a scanning electron microscope as follows: Figure 7 As shown.

[0069] The sheet resistance of the PCP prepared above is 662.3 Ω / □, and the ODCP resists water and 0.1 mol·L⁻¹. -1 Hydrochloric acid and 0.1 mol·L -1 The contact angles of the sodium hydroxide solution were 142.5°, 141.4°, and 141.6°, respectively.

[0070] The all-paper-based triboelectric nanogenerator has an open-circuit voltage of 226.9 V, a short-circuit current of 6.9 μA, and a surface charge density of 41.2 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator is 175.3 V, the short-circuit current is 5.1 μA, and the surface charge density is 37.0 μC·m. -2 They retained 77.3%, 73.9%, and 89.8% of their initial states, respectively. 0.1 mol·L⁻¹ -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 222.5 V, the short-circuit current was 6.8 μA, and the surface charge density was 40.8 μC·m. -2 They maintained 98.1%, 98.6%, and 99.0% of their initial states, respectively; 0.1 mol·L -1 After sodium hydroxide treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 221.8 V, the short-circuit current was 6.8 μA, and the surface charge density was 40.6 μC·m.-2 They maintained 97.8%, 98.6%, and 98.5% of their initial states, respectively. Comparative Example 1

[0071] A method for preparing an all-paper-based triboelectric nanogenerator by lamination and forming includes the following steps: (1) Weigh 30 g (octane dry weight) of bleached spruce coniferous chemical pulp, add 970 mL of deionized water to make the concentration of cellulose fiber 3 wt%, soak at 25℃ for 6 h, then add 500 mL of deionized water to adjust the concentration of cellulose fiber to 2 wt%, and use a standard fiber dissociator to dissociate at 25℃ for 15 min, with the propeller speed at 20000 rpm, so that the cellulose fiber is dispersed into a single fiber state.

[0072] The dissolved cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 25°C and a rotation speed of 21,000 rpm. The cellulose fibers after high-speed shearing treatment had a beating degree of 89°SR, thus obtaining cellulose fibers with a fiber surface fibrillation.

[0073] (2) Weigh 5 g (dry weight) of the cellulose fibers separated in step (1), add 245 mL of deionized water to obtain a cellulose fiber dispersion with a fiber concentration of 2 wt%, shake vigorously for 5 min to make the fibers uniformly dispersed, add 10 mL of pyrrole, place in a refrigerator to pre-cool to 4℃, then add 250 mL of a mixed solution of ferric chloride and hydrochloric acid pre-cooled to 4℃ to the suspension of cellulose fibers and pyrrole, shake vigorously for 5 min, react at 4℃ for 2 h, the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0074] (3) Weigh 1.25 g of the polypyrrole conductive cellulose fiber from step (2), add 1248.8 mL of deionized water to make the fiber concentration 0.1 wt%, then dissociate it using a standard fiber dissociator at room temperature for 15 min. The propeller speed of the standard fiber dissociator is 20000 rpm. Then, use a paper forming machine to form wet PCP with a basis weight of 40 g·m -2 Then, wet paper (BCP) was produced from cellulose fibers using the same method, with a basis weight of 40 g·m³. -2Finally, wet PCP is covered on one side of wet BCP, and the mixture is pressed and dried at 80°C for 15 min to obtain the BCP / PCP electrode. At the same time, the wet PCP is pressed and dried at 80°C for 15 min and used as the electrode material for PDMS.

[0075] (4) Mix the PDMS precursor and curing agent at a mass ratio of 1:10, then pour 3 g of the mixture into a 60 mm disposable petri dish, pre-cur it at 80°C in an oven for 8 min, then press and dry the PCP onto the PDMS surface and press it to make the PCP and PDMS tightly bonded. Finally, further cure it at 80°C in a vacuum drying oven for 2 h to obtain the PDMS / PCP electrode.

[0076] (5) Cut the printing paper into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding the two 5 cm sides together with 3M tape to create an arched structure. The BCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample is attached to the center of both sides of the above-mentioned printing paper arch structure. The BCP / PCP electrode and the PDMS / PCP electrode are connected by copper wires, with the surface of BCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

[0077] The sheet resistance of the PCP prepared above is 662.3 Ω / □. BCP resists water and 0.1 mol·L⁻¹. -1 Hydrochloric acid and 0.1 mol·L -1 The contact angles of the sodium hydroxide solution were 22.6°, 18.5°, and 18.2°, respectively.

[0078] The all-paper-based triboelectric nanogenerator has an open-circuit voltage of 120.7 V, a short-circuit current of 3.2 μA, and a surface charge density of 21.8 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator is 31.9 V, the short-circuit current is 1.0 μA, and the surface charge density is 6.3 μC·m. -2 They retained 26.4%, 31.3%, and 28.9% of their initial states, respectively. 0.1 mol·L⁻¹ -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 58.2 V, the short-circuit current was 1.5 μA, and the surface charge density was 10.2 μC·m. -2 They maintained 48.2%, 46.9%, and 46.8% of their initial states, respectively; 0.1 mol·L -1After sodium hydroxide treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 57.4 V, the short-circuit current was 1.3 μA, and the surface charge density was 9.8 μC·m. -2 They maintained 47.6%, 40.6%, and 45.0% of their initial states, respectively.

[0079] As can be seen from Comparative Example 1 and Example 1, the present invention introduces aldehyde groups into cellulose fibers through sodium periodate oxidation, and introduces octadecylamine onto the surface of cellulose fibers by Schiff base reaction of aldehyde groups with octadecylamine, which is beneficial to enhancing the output performance, moisture resistance and acid and alkali resistance of the all-paper-based triboelectric nanogenerator. Comparative Example 2

[0080] A method for preparing an all-paper-based triboelectric nanogenerator by lamination and forming includes the following steps: (1) Weigh 30 g (octane dry weight) of bleached spruce coniferous chemical pulp, add 970 mL of deionized water to make the concentration of cellulose fiber 3 wt%, soak at 25℃ for 6 h, then add 500 mL of deionized water to adjust the concentration of cellulose fiber to 2 wt%, and use a standard fiber dissociator to dissociate at 25℃ for 15 min, with the propeller speed at 20000 rpm, so that the cellulose fiber is dispersed into a single fiber state.

[0081] The dissolved cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 25°C and a rotation speed of 21,000 rpm. The cellulose fibers after high-speed shearing treatment had a beating degree of 89°SR, thus obtaining cellulose fibers with a fiber surface fibrillation.

[0082] (2) Weigh 5 g (dry weight) of the cellulose fibers separated in step (1), add 245 mL of deionized water to obtain a cellulose fiber dispersion with a fiber concentration of 2 wt%, shake vigorously for 5 min to make the fibers uniformly dispersed, add 10 mL of pyrrole, place in a refrigerator to pre-cool to 4℃, then add 250 mL of a mixed solution of ferric chloride and hydrochloric acid pre-cooled to 4℃ to the suspension of cellulose fibers and pyrrole, shake vigorously for 5 min, react at 4℃ for 2 h, the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0083] (3) Weigh 15 g (dry weight) of the cellulose fibers separated in step (1), add 1485 mL of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1 wt%, and then use 0.1 mol·L⁻¹ water. -1 The pH of the reaction system was adjusted to 4 with sulfuric acid solution, 15 g of sodium periodate was added, and the reaction was magnetically stirred at 50 °C for 3 h. The reaction was terminated by adding 75 mL of anhydrous ethanol. Finally, the product was filtered and washed until the filtrate was colorless when dropped onto starch-potassium iodide test paper, thus obtaining dialdehyde cellulose fiber.

[0084] (4) Weigh 1.25 g of the polypyrrole conductive cellulose fiber from step (2), add 1248.8 mL of deionized water to make the fiber concentration 0.1 wt%, then dissociate it using a standard fiber dissociator at room temperature for 15 min. The propeller speed of the standard fiber dissociator is 20000 rpm. Then, use a paper forming machine to form wet PCP with a basis weight of 40 g·m -2 Then, using the same method, wet paper DCP was obtained from dialdehyde cellulose fibers, with a basis weight of 40 g·m³. -2 Finally, wet PCP is covered on one side of wet DCP, and pressed and dried at 80°C for 15 min to obtain DCP / PCP electrode. At the same time, wet PCP is pressed and dried at 80°C for 15 min to be used as electrode material for PDMS.

[0085] (5) Mix the PDMS precursor and curing agent at a mass ratio of 1:10, then pour 3 g of the mixture into a 60 mm disposable petri dish, pre-cur it at 80°C in an oven for 8 min, then press and dry the PCP onto the PDMS surface and press it to make the PCP and PDMS tightly bonded. Finally, further cure it at 80°C in a vacuum drying oven for 2 h to obtain the PDMS / PCP electrode.

[0086] (6) Cut the printing paper into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding the two 5 cm sides together with 3M tape to create an arched structure. The DCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample is attached to the center of both sides of the above-mentioned printing paper arch structure. The DCP / PCP electrode and the PDMS / PCP electrode are connected by copper wires, with the surface of DCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

[0087] The sheet resistance of the PCP prepared above is 662.3 Ω / □, and the DCP resists water and 0.1 mol·L⁻¹. -1 Hydrochloric acid and 0.1 mol·L-1 The contact angles of the sodium hydroxide solution were 56.8°, 55.5.4°, and 53.4°, respectively.

[0088] The all-paper-based triboelectric nanogenerator has an open-circuit voltage of 120.6 V, a short-circuit current of 3.2 μA, and a surface charge density of 22.0 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator remains as high as 34.3V, the short-circuit current is 1.3 μA, and the surface charge density is 7.7 μC·m. -2 They retained 28.4%, 40.6%, and 35.0% of their initial states, respectively. 0.1 mol·L⁻¹ -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 62.2 V, the short-circuit current was 1.7 μA, and the surface charge density was 11.6 μC·m. -2 They maintained 51.6%, 53.1%, and 52.7% of their initial states, respectively; 0.1 mol·L -1 After treatment with sodium hydroxide, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 61.9 V, the short-circuit current was 1.6 μA, and the surface charge density was 10.8 μC·m. -2 They maintained 51.3%, 50.0%, and 49.1% of their initial states, respectively.

[0089] Compared to Comparative Example 2, which did not undergo octadecylamine-modified dialdehyde cellulose fiber, Example 1 utilizes the Schiff base reaction between dialdehyde cellulose and octadecylamine to improve the hydrophobicity and acid and alkali resistance of paper, thereby enhancing the output performance, moisture resistance, and acid and alkali resistance of the all-paper-based triboelectric nanogenerator. Comparative Example 3

[0090] A method for preparing an all-paper-based triboelectric nanogenerator by lamination and forming includes the following steps: (1) Weigh 30 g (octane dry weight) of bleached spruce coniferous chemical pulp, add 970 mL of deionized water to make the concentration of cellulose fiber 3 wt%, soak at 25℃ for 6 h, then add 500 mL of deionized water to adjust the concentration of cellulose fiber to 2 wt%, and use a standard fiber dissociator to dissociate at 25℃ for 15 min, with the propeller speed at 20000 rpm, so that the cellulose fiber is dispersed into a single fiber state.

[0091] The dissolved cellulose fibers were filtered through a Buchner funnel to concentrate the fiber concentration to 10 wt%. Then, they were placed in a PFI mill for high-speed shearing treatment at a temperature of 25°C and a rotation speed of 21,000 rpm. The cellulose fibers after high-speed shearing treatment had a beating degree of 89°SR, thus obtaining cellulose fibers with a fiber surface fibrillation.

[0092] (2) Weigh 5 g (dry weight) of the cellulose fibers separated in step (1), add 245 mL of deionized water to obtain a cellulose fiber dispersion with a fiber concentration of 2 wt%, shake vigorously for 5 min to make the fibers uniformly dispersed, add 10 mL of pyrrole, place in a refrigerator to pre-cool to 4℃, then add 250 mL of a mixed solution of ferric chloride and hydrochloric acid pre-cooled to 4℃ to the suspension of cellulose fibers and pyrrole, shake vigorously for 5 min, react at 4℃ for 2 h, the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 Finally, the polypyrrole conductive cellulose fiber is obtained by washing with anhydrous ethanol and deionized water.

[0093] (3) Weigh 1.25 g (dry weight) of the cellulose fiber that was split in step (1), add 247.5 mL of deionized water to form a cellulose fiber dispersion with a fiber concentration of 1 wt%. Then dissolve 2.5 g of octadecylamine in 25 mL of anhydrous ethanol and add the octadecylamine / ethanol solution to the dialdehyde cellulose fiber dispersion with a dropper. Stir the reaction magnetically at 50 °C for 1 h. Wash with anhydrous ethanol and deionized water respectively to obtain octadecylamine modified cellulose fiber.

[0094] (4) Weigh 1.25 g of the polypyrrole conductive cellulose fiber from step (2), add 1248.8 mL of deionized water to make the fiber concentration 0.1 wt%, then dissociate it using a standard fiber dissociator at room temperature for 15 min. The propeller speed of the standard fiber dissociator is 20000 rpm. Then, use a paper forming machine to form wet PCP with a basis weight of 40 g·m -2 Then, using the same method, wet paper OCP was prepared from octadecylamine-modified cellulose fibers, with a basis weight of 40 g·m³. -2 Finally, wet PCP is covered on one side of wet OCP, and pressed and dried at 80°C for 15 min to obtain OCP / PCP electrode. At the same time, wet PCP is pressed and dried at 80°C for 15 min to be used as electrode material for PDMS.

[0095] (5) Mix the PDMS precursor and curing agent at a mass ratio of 1:10, then pour 3 g of the mixture into a 60 mm disposable petri dish, pre-cur it at 80°C in an oven for 8 min, then press and dry the PCP onto the PDMS surface and press it to make the PCP and PDMS tightly bonded. Finally, further cure it at 80°C in a vacuum drying oven for 2 h to obtain the PDMS / PCP electrode.

[0096] (6) Cut the printing paper into 5 × 13 cm pieces. 2 The rectangle was then formed by bonding the two 5 cm sides together with 3M tape to create an arched structure. The OCP / PCP and PDMS / PCP electrodes were then cut into 3 × 3 cm pieces. 2 The sample is attached to the center of both sides of the above-mentioned printing paper arch structure. The OCP / PCP electrode and the PDMS / PCP electrode are connected by copper wires, with the surface of OCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

[0097] The sheet resistance of the PCP prepared above is 662.3 Ω / □, and the OCP is effective against water and 0.1 mol·L⁻¹. -1 Hydrochloric acid and 0.1 mol·L -1 The contact angles of the sodium hydroxide solution were 98.1°, 62.4°, and 91.2°, respectively.

[0098] The all-paper-based triboelectric nanogenerator has an open-circuit voltage of 150.8 V, a short-circuit current of 3.9 μA, and a surface charge density of 27.1 μC·m. -2 At an ambient relative humidity of 90%, the open-circuit voltage of the all-paper-based triboelectric nanogenerator remains as high as 57.6V, the short-circuit current is 2.0 μA, and the surface charge density is 14.3 μC·m. -2 They retained 38.2%, 51.3%, and 52.8% of their initial states, respectively. 0.1 mol·L⁻¹ -1 After hydrochloric acid treatment, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 65.2 V, the short-circuit current was 1.8 μA, and the surface charge density was 12.8 μC·m. -2 They maintained 43.2%, 46.2%, and 47.2% of their initial states, respectively; 0.1 mol·L -1 After treatment with sodium hydroxide, the open-circuit voltage of the all-paper-based triboelectric nanogenerator was 150.2 V, the short-circuit current was 3.8 μA, and the surface charge density was 26.8 μC·m. -2 They maintained 99.6%, 97.4%, and 98.9% of their initial states, respectively.

[0099] In Comparative Example 3, no aldehyde groups were introduced into the cellulose fibers. A small amount of octadecylamine was adsorbed onto the surface of the cellulose fibers through hydrogen bonding and electrostatic interactions. Furthermore, octadecylamine would form water-soluble octadecylamine hydrochloride under acidic conditions, resulting in poor acid resistance of the paper. In contrast, in Example 1, aldehyde groups were introduced into the cellulose fibers through oxidation with sodium periodate. These aldehyde groups could then undergo a Schiff base reaction with the amino group of octadecylamine, enhancing the hydrophobicity and acid / alkali resistance of the paper. This resulted in a high-output, highly moisture-resistant, and acid / alkali-resistant all-paper-based triboelectric nanogenerator.

[0100] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. 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 describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming process with friction materials and electrode materials, characterized in that, Includes the following steps: 1) The cellulose fibers that have been split and dispersed are dispersed in water to form a cellulose fiber dispersion. The pH value of the reaction system is adjusted with dilute sulfuric acid solution, sodium periodate is added, the mixture is stirred evenly and heated to react, and then filtered and washed to obtain dialdehyde cellulose fibers. Dialdehyde cellulose fibers were dispersed in water to form a dialdehyde cellulose fiber dispersion. Octadecylamine / ethanol solution was added, stirred evenly, heated to react, and then filtered and washed to obtain octadecylamine-modified dialdehyde cellulose fibers. 2) Disperse the cellulose fibers into water and shake vigorously to make the cellulose fibers evenly dispersed to form a cellulose fiber dispersion. Add pyrrole, pre-cool, then add a mixed solution of ferric chloride and hydrochloric acid, shake vigorously again, let stand to react, and finally filter and wash to obtain polypyrrole conductive cellulose fibers. 3) Disperse the octadecylamine-modified dialdehyde cellulose fiber described in step 1) in water to form an octadecylamine-modified dialdehyde cellulose fiber dispersion, fully dissociate it using a standard fiber dissociator, and then form it into wet paper ODCP; The polypyrrole conductive cellulose fibers described in step 2) are dispersed in deionized water to form a polypyrrole conductive cellulose fiber dispersion, which is then fully dissociated using a standard fiber dissociator and then formed into wet paper PCP. Wet PCP is covered on one side of wet ODCP, and finally pressed and dried to obtain ODCP / PCP electrode; 4) Mix the PDMS precursor and curing agent, pour into a disposable petri dish, pre-cur in an oven, then attach the pressed and dried PCP onto the PDMS surface, and further cure in a vacuum drying oven to obtain the PDMS / PCP electrode; 5) Using printing paper as the substrate support material, ODCP / PCP electrodes and PDMS / PCP electrodes are assembled into a paper-based triboelectric nanogenerator.

2. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, In step 1), the concentration of the cellulose fiber dispersion is 1 wt%, and the concentration of the dilute sulfuric acid solution is 0.1 mol·L⁻¹. -1 The pH of the reaction system was 4, the reaction temperature was 50℃, and the reaction time was 3 h. In step 1), the concentration of the dialdehyde cellulose fiber dispersion is 1 wt%, the concentration of the octadecylamine / ethanol solution is 0~0.2 g / mL, the reaction temperature is 50℃, and the reaction time is 1~3 h.

3. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, In step 2), the concentration of the cellulose fiber dispersion is 2 wt%, the concentration of pyrrole is 4% (v / v), the pre-cooling equipment is a refrigerator, the pre-cooling temperature is 4℃, and the concentration of ferric chloride in the mixed solution of ferric chloride and hydrochloric acid is 0.5 mol·L⁻¹. -1 The hydrochloric acid concentration is 1 mol·L⁻¹ -1 The violent shaking time was 5 minutes, and the static reaction temperature was 4℃.

4. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, In step 3), the concentrations of both the polypyrrole conductive cellulose fiber dispersion and the octadecylamine-modified dialdehyde cellulose fiber dispersion were 0.1 wt%, the propeller speed of the standard fiber dissociator was 1000–3000 rpm, and the basis weight of the paper was 40 g·m³. -2 The pressing and drying temperature is 80~90℃, and the drying time is 15~20 min.

5. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, In step 4), the mass ratio of PDMS precursor to curing agent is 1:10, and the quantitative amount of PDMS is 10~11 g·m³. -2 The pre-curing temperature is 70~80℃, the pre-curing time is 5~10 min, the curing temperature is 70~80℃, and the curing time is 2~3 h.

6. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, Step 5) is as follows: Cut the printing paper into 5 × 13 cm pieces. 2 The rectangular shape is formed by pasting the shorter side together to create an arch structure. Then, ODCP / PCP electrodes and PDMS / PCP electrodes are pasted at the center of both sides of the arch structure. The ODCP / PCP electrodes and PDMS / PCP electrodes are connected by copper wires, with the surface of ODCP facing the surface of PDMS, thus obtaining an all-paper-based triboelectric nanogenerator.

7. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, The cellulose fibers are selected from one or more of softwood pulp, hardwood pulp, bamboo pulp, and wheat straw pulp.

8. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 1, characterized in that, The preparation process of the split cellulose fiber is as follows: ① The plant fiber soaked in water is loosened into a uniformly dispersed single fiber state; ② The loosened plant fiber is subjected to high-speed shearing to obtain the split cellulose fiber.

9. The method for preparing a paper-based triboelectric nanogenerator by integrating a stacked mesh forming friction material and an electrode material according to claim 8, characterized in that, In the preparation process of fractionated cellulose fibers, the concentration of cellulose fibers during soaking is 3 wt%, the soaking time is 4-6 h, and the soaking temperature is 20-30℃; the disintegration concentration of cellulose fibers is 1-2 wt%, the disintegration temperature is 20-30℃, and the disintegration time is 15-20 min; the propeller speed of the standard fiber disintegrator used for disintegration is 1000-3000 rpm, the temperature of the high-speed mechanical shearing treatment is 25-30℃, and the freeness of the fractionated cellulose fibers is 89%. o SR.

10. The paper-based triboelectric nanogenerator obtained by the method according to any one of claims 1 to 9.

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