Friction electricity material, friction nanometer generator and preparation method and application of friction nanometer generator

Abstract

The invention discloses a triboelectric material, a triboelectric nano-generator and a preparation method and application of the triboelectric material and the triboelectric nano-generator. During preparation, a first fiber membrane is spun from a first spinning solution containing a polymer and tetraalkyl ammonium hexafluorophosphate, pyrrole is loaded on the first fiber membrane, polymerization reaction is carried out, and a first triboelectric material is obtained; spinning a second spinning solution containing the polymer, tetraalkyl ammonium hexafluorophosphate and oxyacid zinc salt into a second fiber membrane, carrying out heat treatment, carrying out hydrothermal treatment in a growth solution containing oxyacid zinc salt, and modifying by using fluorinated alkylsilane to obtain a second triboelectric material; the friction nanometer generator prepared by matching the two special friction electricity materials can effectively adapt to two opposite extreme environments of hot and cold, and also shows excellent energy output performance, sensitivity, stability and the like, and the whole material is good in air permeability, light in weight, suitable for wearable equipment and wide in application range. And the wearing comfort is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of triboelectric nanogenerator, in particular to a triboelectric material, a triboelectric nanogenerator and a preparation method and application thereof. BACKGROUND

[0002] With the deep integration of Internet of Things technology and artificial intelligence, modern wearable devices are upgrading from single-function sensors to intelligent systems that integrate energy harvesting, environmental interaction, and health monitoring. Such devices have great application potential in extreme environment operations such as polar exploration and desert rescue, as well as medical scenarios such as chronic disease monitoring and sports rehabilitation. However, existing devices face two key contradictions in complex temperature environments: first, the use of hard materials and thick thermal insulation layers to maintain the performance of electronic components severely reduces air permeability, and long-term contact with the skin may cause allergic or inflammatory reactions; second, traditional batteries have a sharp drop in capacity in low-temperature environments, making it difficult to support continuous monitoring needs. How to develop an intelligent wearable platform that combines temperature regulation, self-power supply capability, and physiological monitoring functions has become a key research area.

[0003] The working mechanism of triboelectric nanogenerator (TENG) is based on the coupling effect of triboelectric effect and electrostatic induction between two friction materials. It is considered as an ideal solution for wearable self-powered systems due to its high voltage output, wide material selection, and environmental compatibility. However, TENG still faces some challenges in practical applications, such as the output performance being greatly affected by environmental temperature and humidity, making it difficult to maintain stable and efficient energy harvesting in complex environments; traditional TENG design focuses on mechanical-to-electrical energy conversion, lacking coordination and regulation with environmental factors such as heat, humidity, and light; air permeability is not good, and long-term wear can easily cause skin irritation.

[0004] In terms of thermal management technology, traditional solutions mainly rely on passive thermal insulation or phase change energy storage materials (such as paraffin-based composites). Although such strategies can alleviate short-term thermal shock, their fixed thermal resistance values cannot dynamically adapt to environmental temperature fluctuations, and they cannot meet the corresponding thermal management needs in rapidly changing environments, and the thick structure severely sacrifices wear comfort.

[0005] It should be noted that the information disclosed in the above background section is only for understanding the background of the present application, therefore the background section of the present application can contain background information about the problems or environment of the present application, and it is not necessarily a description of the prior art. Therefore, the content contained in the background section is not an admission by the applicant of prior art. SUMMARY

[0006] The application aims to overcome one or more deficiencies in the prior art, and provide a new preparation method of a triboelectric nanogenerator with a bidirectional thermal regulation function, which can switch the refrigeration / heating mode as needed, adapt to different environments, and realize the synergistic regulation with environmental factors such as heat, humidity and light.

[0007] Further, the triboelectric nanogenerator (TENG) prepared by the application also has excellent energy output and sensitivity, and can be applied to wearable devices to monitor the health status of the wearer and ensure safe operation.

[0008] The application also provides a triboelectric material.

[0009] The application also provides an application of the triboelectric material or the triboelectric nanogenerator (TENG) in a wearable device.

[0010] To achieve the above-mentioned purpose, one technical solution adopted by the application is a preparation method of a triboelectric nanogenerator, which comprises the following steps: The first spinning solution is spun into a first fiber membrane, then pyrrole (Py) is loaded on the first fiber membrane and a polymerization reaction is carried out in the presence of ferric chloride to obtain a first triboelectric material; The second spinning solution containing a zinc salt of an oxygen-containing acid is spun into a second fiber membrane, and the zinc salt of the oxygen-containing acid is converted into zinc oxide by heat treatment to obtain a third fiber membrane; the third fiber membrane is placed in a growth solution and subjected to hydrothermal treatment to obtain a fourth fiber membrane, and the fourth fiber membrane is modified by using a fluorinated alkylsilane to obtain a second triboelectric material; The first triboelectric material and the second triboelectric material are oppositely arranged; The first spinning solution comprises a first polymer, tetraalkylammonium hexafluorophosphate and a first solvent. The second spinning solution comprises a second polymer, tetraalkylammonium hexafluorophosphate, a zinc salt of an oxygen-containing acid and a second solvent, and the growth solution comprises a zinc salt of an oxygen-containing acid, hexamethylenetetramine and ammonia water.

[0011] In some embodiments of the application, in the process of preparing the first triboelectric material, the first fiber membrane is immersed in a pyrrole aqueous solution, then a ferric chloride aqueous solution is added, and the polymerization reaction is controlled at 0-5℃.

[0012] Further, the polymerization reaction is controlled for 2-6h.

[0013] Further, the polymerization reaction is carried out in an ice water bath.

[0014] In some embodiments of the application, the molar ratio of pyrrole to ferric chloride is 1:1.8-2.2.

[0015] According to some specific aspects of the present application, the molar ratio of pyrrole to ferric chloride can be 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, etc.

[0016] In some embodiments of the present application, the molar concentration of the aqueous pyrrole solution is 0.1-0.3 mol / L.

[0017] In some embodiments of the present application, the molar concentration of the aqueous ferric chloride solution is 0.3-0.5 mol / L.

[0018] In some embodiments of the present application, the first polymer is a combination of one or more selected from thermoplastic polyurethane (TPU), polyethylene terephthalate (PET) and nylon 6 (PA6).

[0019] In some embodiments of the present application, the tetraalkylammonium hexafluorophosphate in the first spinning solution or the second spinning solution is a combination of one or more selected from tetrabutylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrapentylammonium hexafluorophosphate and tetrahexylammonium hexafluorophosphate.

[0020] In some embodiments of the present application, the first solvent is a combination of one or more selected from N,N-dimethylformamide, trifluoroacetic acid, dichloromethane, formic acid and acetic acid.

[0021] In some embodiments of the present application, the concentration of the tetraalkylammonium hexafluorophosphate in the first spinning solution is 0.01-0.1 mol / L. According to some specific aspects of the present application, the concentration of the tetraalkylammonium hexafluorophosphate can be 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, etc.

[0022] In some embodiments of the present application, the first polymer is thermoplastic polyurethane, the first spinning solution comprises thermoplastic polyurethane, tetraalkylammonium hexafluorophosphate and N,N-dimethylformamide, and the thermoplastic polyurethane accounts for 8wt.%-12wt.% of the first spinning solution.

[0023] In some embodiments of the present application, the first polymer is polyethylene terephthalate, the first spinning solution comprises polyethylene terephthalate, tetraalkylammonium hexafluorophosphate, trifluoroacetic acid and dichloromethane, and the polyethylene terephthalate accounts for 12wt.%-15wt.% of the first spinning solution, and the volume ratio of the trifluoroacetic acid to the dichloromethane is 6-8:3.

[0024] In some embodiments of the present application, the first polymer is nylon 6, the first spinning solution comprises nylon 6, tetraalkylammonium hexafluorophosphate, formic acid, and the nylon 6 accounts for 18wt.%-24wt.% of the first spinning solution.

[0025] In some embodiments of the present application, the first spinning solution is spun into a first fiber membrane by using an electrospinning method, and the working parameters of the electrospinning are as follows: a spinning voltage of 20-35kV, a pushing rate of 0.5-2.0mL / h, a receiving distance of 12-18cm, an ambient temperature of 20-35℃, and a humidity of 20%-45%.

[0026] In some embodiments of the present application, the second polymer is polyvinylidene fluoride (PVDF) and / or polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP).

[0027] In some embodiments of the present application, the second solvent is composed of N,N-dimethylformamide and acetone in a volume ratio of 6-8:3.

[0028] In some embodiments of the present application, the second polymer accounts for 17wt.%-19wt.% of the second spinning solution.

[0029] In some embodiments of the present application, the concentration of the tetraalkylammonium hexafluorophosphate in the second spinning solution is 0.03-0.07mol / L. According to some specific aspects of the present application, the concentration of the tetraalkylammonium hexafluorophosphate in the second spinning solution can be 0.03mol / L, 0.04mol / L, 0.05mol / L, 0.06mol / L, 0.07mol / L, etc.

[0030] In some embodiments of the present application, the mass ratio of the second polymer to the zinc salt of oxygen-containing acid in the second spinning solution is 8-10:1. According to some specific aspects of the present application, the mass ratio of the second polymer to the zinc salt of oxygen-containing acid in the second spinning solution can be 8:1, 8.2:1, 8.5:1, 8.6:1, 8.8:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10:1, etc.

[0031] In some embodiments of the present application, the zinc salt of oxygen-containing acid in the second spinning solution is zinc acetate or a hydrate thereof.

[0032] In some embodiments of the present application, the zinc salt of oxygen-containing acid in the growth solution is zinc nitrate or a hydrate thereof, zinc sulfate or a combination of the two.

[0033] In some embodiments of the present invention, the molar ratio of zinc oxyacid salt to hexamethylenetetramine in the growth solution is 1-3:1. According to some specific aspects of the present invention, the molar ratio of zinc oxyacid salt to hexamethylenetetramine in the growth solution can be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, etc.

[0034] In some embodiments of the present invention, the mass concentration of ammonia in the growth solution is 10%-20%.

[0035] In some embodiments of the present invention, the heat treatment is controlled to be performed at 120-150°C. According to some specific aspects of the present invention, the heat treatment can be controlled to be performed at 120°C, 122°C, 125°C, 128°C, 130°C, 132°C, 135°C, 138°C, 140°C, 145°C, or 148°C.

[0036] In some embodiments of the present invention, the hydrothermal treatment is controlled to be performed at 90-100°C. According to some specific aspects of the present invention, the hydrothermal treatment can be controlled to be performed at 90°C, 92°C, 94°C, 95°C, 96°C, 97°C, or 98°C.

[0037] In some embodiments of the present invention, the fluorinated alkylsilane includes, but is not limited to, 1H,1H,2H,2H-perfluorooctyltriethyloxysilane.

[0038] In some embodiments of the present invention, the fourth fiber membrane is modified by immersing it in a fluorinated alkylsilanol solution with a concentration of 0.5 vol% to 2 vol%. According to some specific aspects of the present invention, the concentration of the fluorinated alkylsilanol solution can be 0.5 vol%, 0.6 vol%, 0.8 vol%, 1 vol%, 1.2 vol%, 1.3 vol%, 1.4 vol%, 1.5 vol%, 1.6 vol%, 1.7 vol%, 1.8 vol%, 1.9 vol%, 2 vol%, etc. Further, ethanol is used as the solvent for the fluorinated alkylsilanol solution, i.e., the fluorinated alkylsilanol solution is a fluorinated alkylsilane ethanol solution.

[0039] In some embodiments of the present invention, a second fiber membrane is spun from a second spinning solution containing zinc oxyacid salt using electrospinning. The electrospinning operating parameters are: spinning voltage 20~35kV, feed rate 0.5~1.0mL / h, receiving distance 12~18cm, ambient temperature 20~35℃, and humidity 20%~35%.

[0040] In some embodiments of the present invention, during the preparation of the first triboelectric material, the first polymer is first dissolved in a first solvent, and then tetraalkylammonium hexafluorophosphate is added, stirred and dissolved to form a first spinning solution.

[0041] In some embodiments of the present invention, during the preparation of the first triboelectric material, the first fiber membrane is first cleaned and dried before loading pyrrole. The cleaning can be done using ethanol.

[0042] In some embodiments of the present invention, during the preparation of the first triboelectric material, after the polymerization reaction, the material is sequentially washed with water and dried.

[0043] In some embodiments of the present invention, in the process of preparing the second triboelectric material, the second polymer is first dispersed in the second solvent and stirred to dissolve, and then tetraalkylammonium hexafluorophosphate and zinc oxyacid salt are added and stirred until completely dissolved to prepare the second spinning solution.

[0044] In some embodiments of the present invention, the heat treatment is performed in an oven during the preparation of the second triboelectric material.

[0045] In some embodiments of the present invention, during the preparation of the second triboelectric material, the hydrothermal treatment is carried out in a sealed container, and the sealed container is placed in an oven.

[0046] In some embodiments of the present invention, during the preparation of the second triboelectric material, before modifying the fourth fiber membrane with fluorinated alkylsilane, the fourth fiber membrane is first rinsed and dried; wherein rinsing can be performed using deionized water.

[0047] In some embodiments of the present invention, during the preparation of the second triboelectric material, after modifying the fourth fiber membrane with fluorinated alkylsilane, the modified membrane is dried at a temperature of 100-130°C for 1-5 hours.

[0048] Another technical solution provided by the present invention: a triboelectric nanogenerator prepared by the above-described method.

[0049] According to some specific aspects of the present invention, the triboelectric nanogenerator includes a first triboelectric material and a second triboelectric material disposed opposite to each other, a first conductive electrode connected to the first triboelectric material, and a second conductive electrode connected to the second triboelectric material.

[0050] Furthermore, the first triboelectric material and the second triboelectric material can come into contact with each other and separate.

[0051] Furthermore, in some embodiments, there is a separable contact gap between the first triboelectric material and the second triboelectric material, which can make full contact when under pressure and separate when not under pressure.

[0052] Another technical solution provided by the present invention: a triboelectric material, wherein the preparation method of the triboelectric material includes: spinning a first spinning solution into a first fiber membrane, then loading pyrrole onto the first fiber membrane and performing a polymerization reaction in the presence of ferric chloride to obtain the triboelectric material; wherein the first spinning solution comprises a first polymer, tetraalkylammonium hexafluorophosphate and a first solvent.

[0053] Another technical solution provided by the present invention: a triboelectric material, wherein the preparation method of the triboelectric material includes: spinning a second spinning solution containing an oxyacid zinc salt into a second fiber membrane, subjecting it to heat treatment to convert the oxyacid zinc salt into zinc oxide, thereby obtaining a third fiber membrane; placing the third fiber membrane in a growth solution and subjecting it to hydrothermal treatment to obtain a fourth fiber membrane; modifying the fourth fiber membrane with a fluorinated alkylsilane to obtain the triboelectric material; wherein the second spinning solution contains a second polymer, tetraalkyl hexafluorophosphate ammonium, an oxyacid zinc salt, and a second solvent, and the growth solution contains an oxyacid zinc salt, hexamethylenetetramine, and ammonia.

[0054] Another technical solution provided by the present invention is a triboelectric nanogenerator as described above, or the application of the triboelectric material as described above in the preparation of wearable devices.

[0055] Another technical solution provided by the present invention is a method of using the above-mentioned triboelectric nanogenerator, the method comprising: when heating is required, the first triboelectric material is oriented outward to achieve photothermal conversion by absorbing solar radiation; when cooling is required, the second triboelectric material is oriented outward to achieve cooling function by reflecting sunlight and enhancing infrared radiation.

[0056] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: Addressing the issues of existing triboelectric nanogenerators (TENGs) in their inability to dynamically adapt to environmental temperature fluctuations and the significant sacrifice of wearing comfort due to their bulky structure, this invention innovatively provides an improved triboelectric nanogenerator. By using two special triboelectric materials in combination, it can not only effectively adapt to both hot and cold extreme environments, but also exhibit excellent energy output performance and sensitivity. Furthermore, the overall material is breathable, lightweight, and suitable for use in wearable devices, thus improving wearing comfort. Attached Figure Description

[0057] Figure 1This is a schematic diagram of the structure of the triboelectric nanogenerator prepared in an embodiment of the present invention; wherein, in the figure, 1, first triboelectric material, 2, second triboelectric material, 3, polyimide tape, 4, conductive electrode, 5, wire; Figure 2 This is a scanning electron microscope (SEM) schematic diagram of the PPy@TPU / TBAHP nanofiber membrane prepared in Example 1 of this invention; Figure 3 This is a scanning electron microscope (SEM) schematic diagram of the P-ZnO@PVDF / TBAHP nanofiber membrane prepared in Example 1 of this invention; Figure 4 These are absorbance performance test graphs of the PPy@TPU / TBAHP nanofiber membrane prepared in Example 1 of this invention and the TPU / TBAHP nanofiber membrane prepared in Comparative Example 1. Figure 5 The PPy@TPU / TBAHP nanofiber membrane prepared in Example 1 and the TPU / TBAHP nanofiber membrane prepared in Comparative Example 1 are compared at 1 kW·m. -2 Surface temperature change curve under light intensity; Figure 6 The surface temperature change curves of the pure PVDF nanofiber membrane prepared in Comparative Example 2, the PVDF / TBAHP nanofiber membrane prepared in Comparative Example 3, the P-ZnO@PVDF nanofiber membrane prepared in Comparative Example 4, and the P-ZnO@PVDF / TBAHP nanofiber membrane prepared in Example 1 are shown. Figure 7 The voltage output performance test graphs of triboelectric nanogenerators (TENGs) made from the first triboelectric material PPy@TPU / TBAHP nanofiber membrane prepared in Example 1 of the present invention and different second triboelectric materials (pure PVDF nanofiber membrane of Comparative Example 2, PVDF / TBAHP nanofiber membrane of Comparative Example 3, P-ZnO@PVDF nanofiber membrane of Comparative Example 4 and P-ZnO@PVDF / TBAHP nanofiber membrane of Example 1) are shown. Figure 8 The current output performance test diagram of the triboelectric nanogenerator (TENG) made from the first triboelectric material PPy@TPU / TBAHP nanofiber membrane prepared in Example 1 of the present invention and different second triboelectric materials (pure PVDF nanofiber membrane of Comparative Example 2, PVDF / TBAHP nanofiber membrane of Comparative Example 3, P-ZnO@PVDF nanofiber membrane of Comparative Example 4 and P-ZnO@PVDF / TBAHP nanofiber membrane of Example 1) is shown. Figure 9 The output power density test diagram of the triboelectric nanogenerator (TENG) prepared in Example 1 of the present invention under different external load resistances; Figure 10This is a durability test image of the triboelectric nanogenerator (TENG) prepared in Example 1 of the present invention; Figure 11 This is a test diagram of the output performance of the triboelectric nanogenerator (TENG) of Embodiment 1 of the present invention under different human movement states. Detailed Implementation

[0058] This invention proposes a synergistic design concept of "spectral adaptive modulation + triboelectric enhancement": by constructing a dual-electrode material with bidirectional thermal regulation function, the cooling / heating modes can be switched on demand in the same triboelectric nanogenerator device.

[0059] Furthermore, this invention discloses a method for preparing a triboelectric nanogenerator (TENG) with bidirectional thermal regulation function and its application. The generator includes a first triboelectric material (also referred to as a first triboelectric layer) and a second triboelectric material (also referred to as a second triboelectric layer).

[0060] Methods for preparing triboelectric nanogenerators include: The first spinning solution is spun into a first fiber membrane, and then pyrrole (Py) is loaded onto the first fiber membrane and polymerized in the presence of ferric chloride to obtain a first triboelectric material. A second spinning solution containing zinc oxyacid salt is spun into a second fiber membrane, which is then heat-treated to convert the zinc oxyacid salt into zinc oxide, resulting in a third fiber membrane. The third fiber membrane is placed in a growth solution and subjected to hydrothermal treatment to obtain a fourth fiber membrane. The fourth fiber membrane is then modified with fluorinated alkylsilane to obtain a second triboelectric material. The first triboelectric material and the second triboelectric material are positioned opposite to each other; The first spinning solution comprises a first polymer, tetraalkylammonium hexafluorophosphate, and a first solvent; The second spinning solution comprises a second polymer, tetraalkyl hexafluorophosphate, zinc oxyacid salt, and a second solvent, and the growth solution comprises zinc oxyacid salt, hexamethylenetetramine, and ammonia.

[0061] Furthermore, the first triboelectric material (also referred to as the first triboelectric layer) prepared by this invention is a polymer nanofiber membrane containing thermoplastic polyurethane (TPU), polyester, polyamide, etc., loaded with polypyrrole (PPy) (abbreviated as PPy@polymer / TBAHP nanofiber membrane). It not only has high specific surface area and porosity, but also high solar absorptivity, which can achieve efficient photothermal conversion. In the preparation process, the specific spinning solution can be configured to spin a nanofiber membrane with small fiber size and large specific surface area - the first fiber membrane. Pyrrole is distributed in the pores and surface of the first fiber membrane. After polymerization to form polypyrrole, the polypyrrole is deeply and stably bonded to the first fiber membrane, and the polypyrrole particles are distributed along the fiber surface. Polypyrrole chains are formed between the polypyrrole particles, achieving efficient and uniform dispersion and high solar absorptivity.

[0062] The second triboelectric material (also known as the second triboelectric layer) is a polyvinylidene fluoride (PVDF) series polymer nanofiber membrane modified with fluorosilane-modified ZnO nanowires (P-ZnO@PVDF series polymer / TBAHP nanofiber membrane). It achieves radiative cooling through high solar reflectivity and high emissivity at atmospheric windows. The ZnO nanorods effectively reflect ultraviolet and visible light, exhibiting high solar reflectivity. Furthermore, the nanoscale size and array structure of the ZnO nanorods, along with the CF bonds in the PVDF series polymers, exhibit high infrared emissivity in the 8-13 μm atmospheric window band, enabling efficient dissipation of surface heat into outer space via infrared radiation, thus achieving radiative cooling. Further, during preparation, the specific spinning solution configuration allows for the spinning of nanofiber membranes—the second fiber membrane—with small fiber sizes and large specific surface areas. During heat treatment, the oxyacid zinc salt is converted into zinc oxide, which acts as seeds uniformly dispersed on the nanofibers. When grown in a growth solution, uniformly distributed nanofibers can be obtained. Zinc oxide nanorods (or zinc oxide nanowires) on nanofibers, with their small size, can be arrayed on the base fiber. For example, zinc oxide nanorods are densely distributed along the axis of the second polymer nanofiber, and these nanorods / wires penetrate the entire nanofiber membrane. At the same time, zinc oxide nanorods are distributed in all directions, forming a large number of porous structures and exhibiting a rough surface, thus obtaining a large specific surface area and thermal radiation surface, further enhancing the light scattering and reflection effects, and forming effective thermal radiation channels through the gaps between the nanorods, which is beneficial to the realization of the cooling function. Furthermore, the surface of the second triboelectric material of the present invention forms a stable hydrophobic film layer through physical adhesion and bonding, such as the physical adsorption of fluorinated alkylsilanes after hydrolysis and the condensation of silanol groups with hydroxyl groups on the zinc oxide surface to form covalent bonds. This helps to reduce the adhesion of water droplets. When pressure is applied, the pressure generated can make it easier for some water droplets on the surface to be discharged, thereby maintaining the effective contact area of ​​the triboelectric nanogenerator (TENG), improving charge transfer efficiency, and making it suitable for use in high humidity environments. At the same time, it reduces the interference of moisture on thermal radiation performance and prevents the adhesion of dust and contaminants, maintaining the long-term stable radiative cooling performance of the material.

[0063] In particular, the triboelectric nanogenerator fabricated by combining the aforementioned specific first triboelectric material (also referred to as the first triboelectric layer) and second triboelectric material (also referred to as the second triboelectric layer) of this invention has achieved unexpectedly excellent results in terms of energy output performance and sensitivity. Analysis suggests that this is due to the very high specific surface area of ​​the two triboelectric materials, and their unique surface structures allowing for a larger effective contact area and providing more frictional contact points. Simultaneously, zinc oxide, as a wide-bandgap semiconductor material, possesses excellent electron transport characteristics, effectively capturing and storing the charge generated during friction, thereby increasing the surface charge density. The interfacial effect between zinc oxide nanorods, polypyrrole particles, and the matrix improves charge distribution and migration, reducing charge recombination, thus enhancing the output performance of the triboelectric nanogenerator. The introduction of zinc oxide nanorods and polypyrrole particles increases the surface roughness of the material, further improving the contact efficiency of the friction layer and promoting charge generation and transfer. The combined effect of these aspects comprehensively improves the overall output performance and sensitivity of the triboelectric nanogenerator.

[0064] In this invention, when the first friction layer faces outward, the PPy@polymer / TBAHP nanofiber membrane effectively absorbs solar radiation to heat the surface; when worn in reverse, the P-ZnO@PVDF series polymer / TBAHP nanofiber membrane reflects sunlight and enhances infrared radiation heat dissipation, thus effectively adapting to two opposite extreme environments: hot and cold. Simultaneously, the fabricated triboelectric nanogenerator exhibits excellent energy output performance and sensitivity, capable of efficiently harvesting mechanical energy and accurately monitoring the wearer's health status, providing a guarantee for safe operation in extreme temperature environments.

[0065] Furthermore, such as Figure 1As shown, an exemplary structure of the triboelectric nanogenerator of the present invention includes a first triboelectric material 1 and a second triboelectric material 2 arranged opposite to each other. A conductive copper tape is used as a conductive electrode 4. The conductive copper tape can be bonded to the first triboelectric material 1 and the second triboelectric material 2. Of course, the first triboelectric material 1 and the second triboelectric material 2 correspond to their respective conductive electrodes 4. For example, the first triboelectric material 1 can be bonded to the first conductive electrode, such as the first conductive copper tape, and the second triboelectric material 2 can be bonded to the second conductive electrode, such as the second conductive copper tape. Then, the whole assembly can be placed on a polyimide tape 3, and a wire 5 is connected to the conductive copper tape and led out. There is a separable contact gap between the first triboelectric material and the second triboelectric material, which can make full contact when under pressure and separate when not under pressure.

[0066] certainly, Figure 1 This is just an example structure. Different structural settings can be used in different application scenarios, as long as the function of the triboelectric nanogenerator is met.

[0067] The above-mentioned solution will be further described below with reference to specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following embodiments; the implementation conditions used in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0068] Unless otherwise specified in the following examples, all raw materials were commercially available or prepared using conventional methods in the art. The sources of some raw materials in the examples are shown in Table 1.

[0069] Example 1

[0070] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator prepared therefrom. The method for preparing the triboelectric nanogenerator includes: (1) Preparation of the first triboelectric material (PPy@TPU / TBAHP nanofiber membrane): TPU particles were added to N,N-dimethylformamide (DMF) solvent and stirred continuously until the TPU particles were completely dissolved to prepare a TPU solution with a concentration of 8 wt.%; then TBAHP was added to the TPU solution with a concentration of 8 wt.% and stirred continuously until completely dissolved to obtain a TPU / TBAHP spinning solution (TBAHP concentration of 0.05 mol•L). −1TPU / TBAHP nanofiber membranes were prepared by electrospinning (spinning voltage 25 kV, receiving distance 15 cm, liquid supply rate 0.5 mL / h, temperature maintained at 25±5℃, relative humidity maintained at 35±10%). The prepared TPU / TBAHP nanofiber membranes were cleaned of surface impurities with anhydrous ethanol and dried in a 60℃ oven for 30 min. The dried TPU / TBAHP nanofiber membranes were then immersed in a 0.2 mol / L pyrrole (Py) aqueous solution for 1 h to allow Py to fully adsorb onto the fiber surface. Then, a 0.4 mol / L FeCl3 aqueous solution was added, and polymerization was carried out in an ice-water bath for 6 h, with a Py to FeCl3 molar ratio of 1:2. The polymerized membrane was washed three times with deionized water and dried in a 60℃ oven for 30 min to obtain the first triboelectric material – PPy@TPU / TBAHP nanofiber membrane. Its scanning electron microscope image is shown below. Figure 2 As shown.

[0071] (2) Preparation of the second triboelectric material (P-ZnO@PVDF / TBAHP nanofiber membrane): Zn(Ac)2, PVDF and TBAHP were added to a mixed solvent of DMF and acetone (volume ratio 7:3). The mixture was continuously magnetically stirred at room temperature for 6 h to completely dissolve the PVDF powder, resulting in a uniform and transparent PVDF spinning solution. The concentration of PVDF in the PVDF spinning solution was 18 wt.%, the mass ratio of PVDF to Zn(Ac)2 was 10:1, and the molar concentration of TBAHP was 0.05 mol·L⁻¹. -1 Electrospinning was employed (spinning voltage 27 kV, spinning solution extrusion rate 0.5 mL•h). -1A Zn(Ac)₂ / PVDF / TBAHP nanofiber membrane was prepared by controlling the receiving distance at 15 cm and the relative humidity and temperature at 25±5% and 25±5°C, respectively. The prepared Zn(Ac)₂ / PVDF / TBAHP nanofiber membrane was then heat-treated in a 130°C oven for 12 h to obtain a ZnO seed layer, thus obtaining the ZnO / PVDF / TBAHP nanofiber membrane. The heat-treated ZnO / PVDF / TBAHP nanofiber membrane was placed in a sealed container containing a growth solution composed of Zn(NO₃)₂•6H₂O, HMTA, and ammonia (the molar ratio of Zn(NO₃)₂•6H₂O to HMTA was 3:1, and the mass concentration of ammonia was 20%), and then subjected to low-temperature hydrothermal treatment in a 95°C oven for 3 h. Finally, a ZnO@PVDF / TBAHP composite nanofiber membrane was prepared. The nanofiber membrane was rinsed with a large amount of deionized water to remove surface residues and then dried for later use. The membrane was immersed in a 1 vol% 1H,1H,2H,2H-perfluorooctyltriethyloxysilane (POTS) ethanol solution for 24 h, and then dried at 120 °C for 2 h to obtain a POTS-coated ZnO@PVDF / TBAHP nanofiber membrane, namely the second triboelectric material -P-ZnO@PVDF / TBAHP nanofiber membrane. Its scanning electron microscope image is shown below. Figure 3 As shown.

[0072] (3) Cut the PPy@TPU / TBAHP nanofiber membrane obtained in step (1) and the P-ZnO@PVDF / TBAHP nanofiber membrane obtained in step (2) into 3×3 cm pieces respectively. 2 The size, then according to Figure 1 The structure shown is prepared by attaching copper tape as a conductive layer, placing it face-to-face on polyimide tape, and connecting wires to the conductive copper tape to fabricate a triboelectric nanogenerator. Example 2

[0073] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator prepared therefrom. The method for preparing the triboelectric nanogenerator includes: (1) Preparation of the first triboelectric material (PPy@TPU / TBAHP nanofiber membrane): TPU particles were added to N,N-dimethylformamide (DMF) solvent and stirred continuously until the TPU particles were completely dissolved to prepare a TPU solution with a concentration of 12 wt.%; then TBAHP was added to the above solution and stirred continuously until completely dissolved to obtain a TPU / TBAHP spinning solution (TBAHP concentration of 0.06 mol•L). −1 The electrospinning method was used (spinning voltage of 30 kV, spinning solution extrusion rate of 0.5 mL•h). -1TPU / TBAHP nanofiber membranes were prepared by maintaining a receiving distance of 15 cm, a temperature of 25±5℃, and a relative humidity of 35±10%. The prepared TPU / TBAHP nanofiber membranes were cleaned of surface impurities with anhydrous ethanol and dried in a 60℃ oven for 30 min. The dried TPU / TBAHP nanofiber membranes were then immersed in a 0.15 mol / L pyrrole (Py) aqueous solution for 1 h to allow Py to fully adsorb onto the fiber surface. Then, a 0.3 mol / L FeCl3 aqueous solution was added, and polymerization was carried out in an ice-water bath for 4 h, with a Py to FeCl3 molar ratio of 1:2. The polymerized membrane was washed three times with deionized water and dried in a 60℃ oven for 30 min, finally yielding the first triboelectric material – PPy@TPU / TBAHP nanofiber membrane.

[0074] (2) The preparation of the second triboelectric material (P-ZnO@PVDF / TBAHP nanofiber membrane) is the same as step (2) in Example 1.

[0075] (3) The preparation process of the triboelectric nanogenerator is the same as step (3) in Example 1. Example 3

[0076] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator prepared therefrom. The method for preparing the triboelectric nanogenerator includes: (1) The preparation of the first triboelectric material (PPy@TPU / TBAHP nanofiber membrane) is the same as step (1) in Example 1.

[0077] (2) Preparation of the second triboelectric material (P-ZnO@PVDF-HFP / TBAHP nanofiber membrane): PVDF-HFP was added to a composite solvent of N,N-dimethylformamide (DMF) and acetone in a volume ratio of 7:3. The mixture was stirred at 50°C until PVDF-HFP was completely dissolved, resulting in a PVDF-HFP solution with a concentration of 19 wt.%. Then, TBAHP and zinc acetate were added to the above solution and stirred continuously until completely dissolved to obtain a PVDF-HFP / TBAHP spinning solution. In the PVDF-HFP / TBAHP spinning solution, the mass ratio of PVDF-HFP to Zn(Ac)2 was 10:1, and the molar concentration of TBAHP was 0.07 mol•L. −1Zn(Ac)₂ / PVDF-HFP / TBAHP nanofiber membranes were prepared by electrospinning (spinning voltage 30 kV, receiving distance 15 cm, liquid supply rate 0.5 mL / h, temperature maintained at 25±5℃, relative humidity maintained at 35±10%). The prepared Zn(Ac)₂ / PVDF-HFP / TBAHP nanofiber membranes were then heat-treated in a 130°C oven for 12 h to obtain a ZnO seed layer and thus the ZnO / PVDF-HFP / TBAHP nanofiber membrane. The prepared ZnO / PVDF-HFP / TBAHP nanofiber membrane was placed in a sealed container filled with a growth solution consisting of Zn(NO3)2•6H2O, HMTA (molar ratio 1:1), and ammonia (the molar ratio of Zn(NO3)2•6H2O to HMTA in the growth solution was 1:1, and the mass concentration of ammonia was 10%), and then subjected to low-temperature hydrothermal treatment in a 95°C oven for 6 h. Finally, the ZnO@PVDF-HFP / TBAHP composite nanofiber membrane was prepared. The nanofiber membrane was rinsed with a large amount of deionized water to remove surface residues and then dried for later use. The ZnO@PVDF-HFP / TBAHP composite nanofiber membrane was immersed in a 1 vol% 1H,1H,2H,2H-perfluorooctyltriethyloxysilane (POTS) ethanol solution for 24 h, and then the membrane was dried at 120 °C for 2 h to obtain the POTS-coated ZnO@PVDF-HFP / TBAHP nanofiber membrane, which is the second triboelectric material -P-ZnO@PVDF-HFP / TBAHP nanofiber membrane.

[0078] (3) The preparation process of the triboelectric nanogenerator is the same as step (3) in Example 1. Example 4

[0079] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator prepared therefrom. The method for preparing the triboelectric nanogenerator includes: (1) Preparation of the first triboelectric material (PPy@PET / TBAHP nanofiber membrane): PET particles were added to a mixed solvent of trifluoroacetic acid / dichloromethane in a volume ratio of 7:3 and stirred continuously until completely dissolved to prepare a PET solution with a concentration of 13 wt.%; then TBAHP was added to the PET solution and stirred continuously until completely dissolved to obtain a PET / TBAHP spinning solution (wherein, the concentration of TBAHP was 0.05 mol•L). −1PET / TBAHP nanofiber membranes were prepared by electrospinning (spinning voltage 25 kV, receiving distance 15 cm, liquid supply rate 0.5 mL / h, temperature maintained at 25±5℃, relative humidity maintained at 35±10%). The prepared PET / TBAHP nanofiber membranes were cleaned of surface impurities with anhydrous ethanol and dried in a 60℃ oven for 30 min. Then, the dried PET / TBAHP nanofiber membranes were immersed in a 0.25 mol / L pyrrole (Py) aqueous solution for 1 h to allow Py to fully adsorb onto the fiber surface. Then, a 0.5 mol / L FeCl3 aqueous solution was added, and polymerization was carried out in an ice-water bath for 6 h, with a Py to FeCl3 molar ratio of 1:2. The polymerized membrane was washed three times with deionized water and dried in a 60℃ oven for 30 min, finally yielding the first triboelectric material – PPy@PET / TBAHP nanofiber membrane.

[0080] (2) The preparation of the second triboelectric material (P-ZnO@PVDF / TBAHP nanofiber membrane) is the same as step (2) in Example 1.

[0081] (3) The preparation process of the triboelectric nanogenerator is the same as step (3) in Example 1. Example 5

[0082] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator prepared therefrom. The method for preparing the triboelectric nanogenerator includes: (1) Preparation of the first triboelectric material (PPy@PA6 / TBAHP nanofiber membrane): PA6 was added to formic acid and stirred continuously until it was completely dissolved to prepare a PA6 solution with a concentration of 20 wt.%; then TBAHP was added to the PA6 solution and stirred continuously until it was completely dissolved to obtain a PA6 / TBAHP spinning solution (TBAHP concentration was 0.03 mol•L). −1PA6 / TBAHP nanofiber membranes were prepared by electrospinning (spinning voltage 30 kV, receiving distance 15 cm, liquid supply rate 0.5 mL / h, temperature maintained at 25±5℃, relative humidity maintained at 35±10%). The prepared PA6 / TBAHP nanofiber membranes were cleaned of surface impurities with anhydrous ethanol and dried in a 60℃ oven for 30 min. Then, the dried PA6 / TBAHP nanofiber membranes were placed in a 0.2 mol / L pyrrole (Py) aqueous solution for 1 h to allow Py to fully adsorb onto the fiber surface. Then, a 0.4 mol / L FeCl3 aqueous solution was added, and polymerization was carried out in an ice-water bath for 6 h, with a Py to FeCl3 molar ratio of 1:2. The polymerized membrane was washed three times with deionized water and dried in a 60℃ oven for 30 min, finally yielding the first triboelectric material – PPy@PA6 / TBAHP nanofiber membrane.

[0083] (2) The preparation of ZnO@PVDF / TBAHP nanofiber membrane is the same as step (2) in Example 1.

[0084] (3) The preparation process of the triboelectric nanogenerator is the same as step (3) in Example 1. Comparative Example 1:

[0085] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator made therefrom, which is basically the same as in Example 1, except that step (1) is different.

[0086] Specifically, step (1) is as follows: Preparation of the first triboelectric material – TPU / TBAHP nanofiber membrane: TPU particles were added to N,N-dimethylformamide (DMF) solvent and stirred continuously until the TPU particles were completely dissolved, preparing an 8 wt.% TPU solution; then TBAHP was added to the 8 wt.% TPU solution and stirred continuously until completely dissolved, obtaining a TPU / TBAHP spinning solution (TBAHP concentration was 0.05 mol•L). −1 TPU / TBAHP nanofiber membranes were prepared by electrospinning (spinning voltage 25 kV, receiving distance 15 cm, liquid supply rate 0.5 mL / h, temperature maintained at 25±5℃, and relative humidity maintained at 35±10%). The prepared TPU / TBAHP nanofiber membranes were cleaned of surface impurities with anhydrous ethanol and dried in a 60℃ oven for 30 min to obtain the TPU / TBAHP nanofiber membrane. Comparative Example 2:

[0087] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator made therefrom, which is basically the same as in Example 1, except that step (2) is different.

[0088] Specifically, the second triboelectric material in step (2) is a pure PVDF nanofiber membrane, and the steps are as follows: PVDF was added to a mixed solvent of DMF and acetone (volume ratio 7:3), and the mixture was continuously magnetically stirred at room temperature for 6 h to completely dissolve the PVDF powder, resulting in a uniform and transparent PVDF spinning solution with a PVDF concentration of 18 wt.%. Electrospinning was performed (spinning voltage 20 kV, spinning solution extrusion rate 0.5 mL•h). -1 A pure PVDF nanofiber membrane was prepared by controlling the receiving distance at 15 cm and the relative humidity and temperature at 25±5% and 25±5°C, respectively. Comparative Example 3:

[0089] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator made therefrom, which is basically the same as in Example 1, except that step (2) is different.

[0090] Specifically, step (2) is as follows: Preparation of the second triboelectric material – PVDF / TBAHP nanofiber membrane: PVDF and TBAHP were added to a mixed solvent of DMF and acetone (volume ratio 7:3). The mixture was continuously magnetically stirred at room temperature for 6 h to completely dissolve the PVDF powder, resulting in a uniform and transparent PVDF / TBAHP spinning solution. The concentration of PVDF in the PVDF / TBAHP spinning solution was 18 wt.%, and the molar concentration of TBAHP was 0.05 mol·L⁻¹. -1 Electrospinning was employed (spinning voltage 27 kV, spinning solution extrusion rate 0.5 mL•h). -1 A PVDF / TBAHP nanofiber membrane was prepared by controlling the receiving distance at 15 cm and the relative humidity and temperature at 25±5% and 25±5°C, respectively. Comparative Example 4:

[0091] This example provides a method for preparing a triboelectric nanogenerator and the triboelectric nanogenerator made therefrom, which is basically the same as in Example 1, except that step (2) is different.

[0092] Specifically, step (2) is as follows: Preparation of the second triboelectric material – P-ZnO@PVDF nanofiber membrane: Zn(Ac)₂ and PVDF were added to a mixed solvent of DMF and acetone (volume ratio 7:3). The mixture was continuously magnetically stirred at room temperature for 6 h to completely dissolve the PVDF powder, resulting in a uniform and transparent PVDF spinning solution. The concentration of PVDF in the spinning solution was 18 wt.%, and the mass ratio of PVDF to Zn(Ac)₂ was 10:1. Electrospinning was performed (spinning voltage 20 kV, spinning solution extrusion rate 0.5 mL•h). -1 A Zn(Ac)₂ / PVDF nanofiber membrane was prepared by controlling the receiving distance at 15 cm and the relative humidity and temperature at 25±5% and 25±5°C, respectively. The prepared Zn(Ac)₂ / PVDF nanofiber membrane was then heat-treated in a 130°C oven for 12 h to obtain a ZnO seed layer, thus obtaining the ZnO / PVDF nanofiber membrane. The heat-treated ZnO / PVDF nanofiber membrane was placed in a sealed container containing a growth solution composed of Zn(NO₃)₂•6H₂O, HMTA, and ammonia (the molar ratio of Zn(NO₃)₂•6H₂O to HMTA was 3:1, and the mass concentration of ammonia was 20%), and then subjected to low-temperature hydrothermal treatment in a 95°C oven for 3 h. Finally, a ZnO@PVDF composite nanofiber membrane was prepared. The nanofiber membrane was rinsed with a large amount of deionized water to remove surface residues and then dried for later use. The membrane was immersed in a 1 vol% 1H,1H,2H,2H-perfluorooctyltriethyloxysilane (POTS) ethanol solution for 24 h, and then dried at 120 °C for 2 h to obtain a POTS-coated ZnO@PVDF nanofiber membrane, namely the second triboelectric material - P-ZnO@PVDF nanofiber membrane. Performance testing:

[0093] (1) See Figure 2 As shown, it is a scanning electron microscope schematic diagram of the first triboelectric material - PPy@TPU / TBAHP nanofiber membrane prepared in Example 1. It can be seen that the membrane has a randomly oriented dendritic fiber matrix structure, with PPy particles distributed along the fiber surface, having a large comparative area and a rough surface. See Figure 3 As shown, this is a scanning electron microscope (SEM) schematic diagram of the second triboelectric material - P-ZnO@PVDF / TBAHP nanofiber membrane prepared in Example 1. It can be seen that ZnO nanorods / wires are densely distributed along the axial direction of PVDF nanofibers, and these nanorods / wires penetrate the entire PVDF nanofiber membrane. At the same time, zinc oxide nanorods are distributed in all directions, forming a large number of porous structures, and the surface exhibits a rough appearance, resulting in a large specific surface area and thermal radiation surface.

[0094] (2) The absorbance properties of the first triboelectric material (PPy@TPU / TBAHP nanofiber membrane) obtained in step (1) of Example 1 and the first triboelectric material-TPU / TBAHP nanofiber membrane obtained in step (1) of Comparative Example 1 were tested. like Figure 4 As shown, the absorbance of the TPU / TBAHP nanofiber membrane in Comparative Example 1 remained at a low value, not exceeding 20%, across the entire spectral range. In contrast, the PPy@TPU / TBAHP nanofiber membrane photothermal film of Example 1 exhibited excellent light absorption characteristics across the entire spectral range, especially in the ultraviolet-visible spectral range from 240 to 780 nm, where its absorbance peak reached 98.8%. This demonstrates the high-efficiency light absorption capability of the PPy@TPU / TBAHP nanofiber membrane of Example 1 of the present invention across the entire spectrum.

[0095] (3) The temperature rise performance of the first triboelectric material (PPy@TPU / TBAHP nanofiber membrane) obtained in step (1) of Example 1 and the first triboelectric material-TPU / TBAHP nanofiber membrane obtained in step (1) of Comparative Example 1 was tested. like Figure 5 As shown, at 1 kW•m -2 Under illumination, the surface temperature of the TPU / TBAHP nanofiber membrane in Comparative Example 1 rose relatively slowly, reaching a steady state of approximately 38.5°C after 70 seconds. In contrast, the surface temperature of the PPy@TPU / TBAHP nanofiber membrane in Example 1 rose sharply, reaching approximately 38°C in just 6 seconds, and continued to rise until reaching a maximum temperature of 51.7°C after 100 seconds, after which it stabilized. This result indicates that the PPy@TPU / TBAHP nanofiber membrane in Example 1 exhibits excellent surface heating rate and superior photothermal conversion efficiency.

[0096] (4) In order to intuitively evaluate the radiation cooling performance of the sample, the temperature change of the surface of the second triboelectric material (P-ZnO@PVDF / TBAHP nanofiber membrane) obtained in step (2) of Example 1 was tested under simulated light intensity indoors. At the same time, the temperature change of the surface of the second triboelectric material obtained in step (2) of Comparative Examples 2-4 was also tested. See Figure 6 As shown, the results indicate that at 1 kW•m -2Under illumination at the specified light intensity for 800 s, the surface temperature of the P-ZnO@PVDF / TBAHP nanofiber membrane in Example 1 was approximately 37.2 °C, while the surface temperature of the pure PVDF nanofiber membrane in Comparative Example 2 was approximately 42.1 °C, representing a temperature decrease of approximately 5.1 °C. The surface temperature of the PVDF / TBAHP nanofiber membrane in Comparative Example 3 was approximately 41.9 °C, and the surface temperature of the P-ZnO@PVDF membrane in Comparative Example 4 was approximately 38.1 °C.

[0097] (5) The voltage and current output performance of triboelectric nanogenerators (TENGs) made of the first triboelectric material PPy@TPU / TBAHP nanofiber membrane in Example 1 and different second triboelectric materials (pure PVDF nanofiber membrane in Comparative Example 2, PVDF / TBAHP nanofiber membrane in Comparative Example 3, P-ZnO@PVDF nanofiber membrane in Comparative Example 4 and P-ZnO@PVDF / TBAHP nanofiber membrane in Example 1) were tested.

[0098] like Figure 7 and Figure 8 As shown, the output voltage of the triboelectric nanogenerator (TENG) in Comparative Example 2 is 62V and the output current is 5.8μA; the output voltage of the triboelectric nanogenerator (TENG) in Comparative Example 3 is 70V and the output current is 10.7μA; the output voltage of the triboelectric nanogenerator (TENG) in Comparative Example 4 is 90V and the output current is 14.6μA; and the output voltage of the triboelectric nanogenerator (TENG) in Example 1 is 98V and the output current is 18.7μA. As can be seen, the triboelectric nanogenerator (TENG) of Example 1 has the highest voltage and current; this result indicates that the triboelectric nanogenerator made of the triboelectric material with the specific structure prepared by the method of the present invention can more effectively convert mechanical energy into electrical energy.

[0099] (6) The effect of external load resistance on the electrical output of the triboelectric nanogenerator (TENG) of Example 1 was tested. See Figure 9 As shown, when the external load resistance is 1 MΩ, the maximum output power density of the triboelectric nanogenerator reaches 25 µW / cm².

[0100] In addition, the test results were obtained through 1200 consecutive compression-release cycles (at a frequency of approximately 3.08 Hz). (See attached image for test results.) Figure 10 As shown, the open-circuit voltage of the triboelectric nanogenerator (TENG) in Example 1 remains stable, indicating that it has excellent mechanical durability and output reliability.

[0101] (7) The output performance of the triboelectric nanogenerator (TENG) of Example 1 under different human motion states was tested. See test results Figure 11 As shown, Figure 11 In the figure, Figure a shows the signal output when the finger is bent; Figure b shows the signal output when the wrist is bent; Figure c shows the signal output when the elbow is bent; Figure d shows the signal output when the finger is tapping; Figure e shows the signal output when the palm is slapping; and Figure f shows the signal output of the shoe sole in different motion states. The results showed that the triboelectric nanogenerator (TENG) of Example 1 exhibited high sensitivity to finger tapping, wrist flexion, arm movement and foot movement. The output voltage signal was positively correlated with the intensity of mechanical stimulation, indicating that it has application prospects in the field of motion monitoring and rehabilitation medicine.

[0102] As used throughout the specification and claims, the term "comprising" is an open-ended term and should be interpreted as "comprising but not limited to." "Substantially" means that within an acceptable margin of error, those skilled in the art can solve the technical problem and substantially achieve the technical effect. It should also be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a product or system comprising a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a product or system. Without further limitations, an element defined by the phrase "comprising one" does not exclude the presence of other identical elements in the product or system comprising said element.

[0103] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

[0104] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A method for preparing a triboelectric nanogenerator, characterized in that, The preparation method includes: The first spinning solution is spun into a first fiber membrane, and then pyrrole is loaded onto the first fiber membrane and polymerized in the presence of ferric chloride to obtain a first triboelectric material. A second spinning solution containing zinc oxyacid salt is spun into a second fiber membrane, which is then heat-treated to convert the zinc oxyacid salt into zinc oxide, resulting in a third fiber membrane. The third fiber membrane is placed in a growth solution and subjected to hydrothermal treatment to obtain a fourth fiber membrane. The fourth fiber membrane is then modified with fluorinated alkylsilane to obtain a second triboelectric material. The first triboelectric material and the second triboelectric material are positioned opposite to each other; The first spinning solution comprises a first polymer, tetraalkylammonium hexafluorophosphate, and a first solvent; The second spinning solution comprises a second polymer, tetraalkyl hexafluorophosphate, zinc oxyacid salt, and a second solvent, and the growth solution comprises zinc oxyacid salt, hexamethylenetetramine, and ammonia.

2. The method for preparing the triboelectric nanogenerator according to claim 1, characterized in that, In the process of preparing the first triboelectric material, the first fiber membrane is immersed in a pyrrole aqueous solution, then a ferric chloride aqueous solution is added, and the polymerization reaction is controlled at 0-5°C.

3. The method for preparing the triboelectric nanogenerator according to claim 2, characterized in that, The molar ratio of pyrrole to ferric chloride is 1:1.8-2.2; and / or, the molar concentration of the pyrrole aqueous solution is 0.1-0.3 mol / L; and / or, the molar concentration of the ferric chloride aqueous solution is 0.3-0.5 mol / L; and / or, the polymerization reaction is controlled to be carried out in an ice-water bath.

4. The method for preparing the triboelectric nanogenerator according to claim 1, characterized in that, The first polymer is selected from one or more of thermoplastic polyurethane, polyethylene terephthalate, and nylon 6; and / or, the tetraalkyl hexafluorophosphate is selected from one or more of tetrabutyl hexafluorophosphate, tetrapropyl hexafluorophosphate, tetrapentyl hexafluorophosphate, and tetrahexyl hexafluorophosphate; and / or, the first solvent is selected from one or more of N,N-dimethylformamide, trifluoroacetic acid, dichloromethane, formic acid, and acetic acid; and / or, the concentration of tetraalkyl hexafluorophosphate in the first spinning solution is 0.01-0.1 mol / L.

5. The method for preparing a triboelectric nanogenerator according to claim 1 or 4, characterized in that, The first polymer is thermoplastic polyurethane, and the first spinning solution contains thermoplastic polyurethane, tetraalkylammonium hexafluorophosphate, and N,N-dimethylformamide, with the thermoplastic polyurethane accounting for 8 wt.%-12 wt.% of the first spinning solution. Alternatively, the first polymer is polyethylene terephthalate, and the first spinning solution contains polyethylene terephthalate, tetraalkyl hexafluorophosphate, trifluoroacetic acid and dichloromethane, and polyethylene terephthalate accounts for 12wt.%-15wt.% of the first spinning solution, and the volume ratio of trifluoroacetic acid to dichloromethane is 6-8:3; Alternatively, the first polymer is nylon 6, and the first spinning solution contains nylon 6, tetraalkyl hexafluorophosphate ammonium, and formic acid, with nylon 6 accounting for 18 wt.%-24 wt.% of the first spinning solution; And / or, The first spinning solution was spun into a first fiber membrane using electrospinning. The electrospinning operating parameters were: spinning voltage 20~35kV, feed rate 0.5~2.0mL / h, receiving distance 12~18cm, ambient temperature 20~35℃, and humidity 20%~45%.

6. The method for preparing the triboelectric nanogenerator according to claim 1, characterized in that, The second polymer is polyvinylidene fluoride and / or polyvinylidene fluoride-hexafluoropropylene; and / or, the second solvent is composed of N,N-dimethylformamide and acetone in a volume ratio of 6-8:3; and / or, in the second spinning solution, the second polymer accounts for 17wt.%-19wt.%; and / or, in the second spinning solution, the concentration of tetraalkylhexafluorophosphate ammonium is 0.03-0.07mol / L; and / or, in the second spinning solution, the mass ratio of the second polymer to the oxyacid zinc salt is 8-10:1; and / or, in the second spinning solution, the oxyacid zinc salt is zinc acetate or its hydrate.

7. The method for preparing a triboelectric nanogenerator according to claim 1, characterized in that, In the growth solution, the oxyacid zinc salt is zinc nitrate or its hydrate, zinc sulfate or a combination of both; and / or, in the growth solution, the molar ratio of the oxyacid zinc salt to hexamethylenetetramine is 1-3:1; and / or, in the growth solution, the mass concentration of ammonia is 10%-20%.

8. The method for preparing a triboelectric nanogenerator according to claim 1, characterized in that, The heat treatment is controlled at 120-150℃; and / or, the hydrothermal treatment is controlled at 90-100℃; and / or, the fluorinated alkylsilane is 1H,1H,2H,2H-perfluorooctyltriethyloxysilane; and / or, the fourth fiber membrane is modified by immersing it in a fluorinated alkylsilanol solution with a concentration of 0.5 vol%-2 vol%; and / or, the second fiber membrane is spun from the second spinning solution containing zinc oxyacid salt by electrospinning, and the electrospinning operating parameters are: spinning voltage 20~35kV, feed rate 0.5~1.0mL / h, receiving distance 12~18cm, ambient temperature 20~35℃, and humidity 20%~35%.

9. A triboelectric nanogenerator prepared by the method of any one of claims 1-8.

10. The triboelectric nanogenerator according to claim 9, characterized in that, The first triboelectric material and the second triboelectric material can contact and separate from each other; and / or, The triboelectric nanogenerator includes a first triboelectric material and a second triboelectric material disposed opposite to each other, a first conductive electrode connected to the first triboelectric material, and a second conductive electrode connected to the second triboelectric material.

11. A triboelectric material, characterized in that, The method for preparing the triboelectric material includes: spinning a first spinning solution into a first fiber membrane, then loading pyrrole onto the first fiber membrane and performing a polymerization reaction in the presence of ferric chloride to obtain the triboelectric material; wherein the first spinning solution comprises a first polymer, tetraalkylammonium hexafluorophosphate and a first solvent.

12. A triboelectric material, characterized in that, The method for preparing the triboelectric material includes: spinning a second spinning solution containing a zinc oxyacid salt into a second fiber membrane, subjecting it to heat treatment to convert the zinc oxyacid salt into zinc oxide, thereby obtaining a third fiber membrane; placing the third fiber membrane in a growth solution and subjecting it to hydrothermal treatment to obtain a fourth fiber membrane; and modifying the fourth fiber membrane with a fluorinated alkylsilane to obtain the second triboelectric material; wherein the second spinning solution contains a second polymer, tetraalkylammonium hexafluorophosphate, a zinc oxyacid salt, and a second solvent, and the growth solution contains a zinc oxyacid salt, hexamethylenetetramine, and ammonia.

13. The triboelectric nanogenerator of claim 9 or 10, or the triboelectric material of claim 11 or 12, in the fabrication of wearable devices.

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