A multilayer structure triboelectric nanogenerator with three-dimensional dielectric functional layer and a preparation method thereof

Abstract

A multilayer structure friction nanogenerator with a three-dimensional dielectric functional layer, comprising a positive electrode friction part and a negative electrode friction part in cyclic contact-separation with the positive electrode friction part, the positive electrode friction part comprising a fabric substrate-electrode layer-positive electrode friction material arranged in layers, and the negative electrode friction part comprising a fabric substrate-electrode layer-dielectric functional layer with a three-dimensional structure-negative electrode friction material arranged in layers; the preparation method comprises in-situ polymerization to prepare the electrode layer, preparation of the positive electrode friction part, preparation of the negative electrode friction part, fixing the positive electrode friction part and the negative electrode friction part to two substrates respectively, reciprocating movement of the two substrates to realize contact-separation of the positive and negative electrode friction parts, friction power generation during contact, and preparation of the multilayer structure friction nanogenerator with the three-dimensional dielectric functional layer; the application improves the electrical output performance of the friction nanogenerator, and has the characteristics of high electrical output performance, good air permeability, flexible wearable, and simple process.

Description

Technical Field

[0001] This invention belongs to the field of nanogenerator technology, specifically relating to a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer and its preparation method. Background Technology

[0002] With the increasing depletion of non-renewable energy sources, energy issues have become a significant factor influencing and constraining social development. Triboelectricity is a physical phenomenon discovered long ago. Friction is ever-present in daily life, containing a considerable amount of energy. Triboelectric nanogenerators (TENGs) utilize the principles of triboelectricity and electrostatic induction to directly convert frictional energy, which cannot be collected by traditional power generation methods, into electrical energy, achieving effective collection and utilization of frictional energy.

[0003] Introducing a dielectric functional layer between the electrode and the negative electrode friction layer to construct a multilayer triboelectric nanogenerator is an effective method to improve electrical output performance. The dielectric functional layer interacts with the friction layer to reduce electron attenuation, increase charge density, and ultimately improve electrical output performance. Existing technology [Nuanyang Cui, et al. ACS Nano 2016, 10, 6131-6138] reports a multilayer triboelectric nanogenerator with a polystyrene dielectric functional layer introduced between the electrode and the negative electrode friction layer. The positive electrode portion of this generator adopts a glass substrate-aluminum foil structure, where the aluminum foil serves as both the electrode and the positive electrode friction material. The negative electrode portion adopts a glass substrate-aluminum foil-polystyrene-polyvinylidene fluoride structure, where the aluminum foil serves as the electrode, polystyrene as the dielectric functional layer, and polyvinylidene fluoride as the negative electrode friction material. These components are then assembled into a vertically contacted, separated multilayer triboelectric nanogenerator. The negative part uses a glass substrate-aluminum foil-polystyrene-polyvinylidene fluoride structure, in which aluminum foil is used as the electrode, polystyrene as the dielectric functional layer, and polyvinylidene fluoride as the negative friction material. Subsequently, a vertically contact-separated multilayer friction nanogenerator was assembled. This technology investigated the effect of introducing a polystyrene dielectric functional layer on improving the performance of this multilayer TENG, increasing the electrical output performance by 11.2 times. However, this technology uses a glass substrate as the base and aluminum foil as the electrode, resulting in poor practicality, and the electrical output performance still needs further improvement.

[0004] [ZhiqingBai, et al. NanoEnergy 2019, 65, 104012] reported a multi-level triboelectric nanogenerator with an Ecoflex dielectric functional layer introduced between the electrode and the negative electrode triboelectric layer. The positive part of the TENG uses a laminated structure of conductive fabric-NBR layer, where the conductive fabric serves as the substrate and electrode, and the NBR serves as the positive friction layer. The negative part of the TENG uses a laminated structure of conductive fabric-elastomer Ecoflex layer-LTV layer, where the conductive fabric serves as the substrate and electrode, the Ecoflex layer serves as the dielectric functional layer, and the LTV serves as the negative friction layer. These are then assembled into a vertically contacted, discrete multilayer triboelectric nanogenerator. This technology, by introducing an Ecoflex dielectric functional layer, fabricated a high-performance multilayer triboelectric nanogenerator with a maximum open-circuit voltage of 370V and a short-circuit current of 27μA. The substrate used in this technology is a conductive fabric; however, the layered structure process loses the fabric's texture characteristics, resulting in poor breathability and wearing comfort. Including the two examples mentioned above, currently reported multilayer TENGs, while the introduction of dielectric functional layers can significantly improve output performance, all utilize planar structures for the dielectric functional layers, resulting in a two-dimensional planar contact between the layers and the triboelectric layer. This design has limited impact on improving electrical output performance. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention aims to provide a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer and its preparation method. By using a fabric as a substrate, an electrode layer is prepared by in-situ polymerization on the fabric surface. The electron-losing polymer is used as the positive electrode friction material, and the electron-gaining polymer is used as the negative electrode friction material. A three-dimensional dielectric functional layer with a micro-nano structure on its surface is introduced between the electrode layer and the negative electrode friction material, so that a three-dimensional contact is formed between the three-dimensional dielectric functional layer and the negative electrode friction material, resulting in a stronger interaction and improving the electrical output performance of the triboelectric nanogenerator. It has the characteristics of high electrical output performance, good breathability, flexible wearability, and simple process.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes a positive electrode friction part and a negative electrode friction part that cyclically contacts and separates from the positive electrode friction part. The positive electrode friction part includes a fabric substrate, an electrode layer, and a positive electrode friction material stacked together. The negative electrode friction part includes a fabric substrate, an electrode layer, a three-dimensional dielectric functional layer, and a negative electrode friction material stacked together.

[0008] The dielectric functional layer with a three-dimensional structure is specifically a polymer with a surface microporous structure.

[0009] The three-dimensional dielectric functional layer material is one of SEBS, polystyrene, or polycaprolactone.

[0010] The electrode layer in the positive electrode friction part is a polyaniline electrode, and the positive electrode friction material is an electron-depleting tribopolymer.

[0011] The electrode layer in the negative electrode friction part is a polyaniline electrode, and the negative electrode friction material is an electron-gaining tribopolymer.

[0012] The electron-loss tribopolymer is a polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) or polystyrene.

[0013] The electron-gaining tribopolymer is polyvinylidene fluoride.

[0014] The fabric substrate is preferably a nylon substrate, and the fabric material is a single-layer fabric structure with a pore size of 250-800 mesh.

[0015] The microporous structure on the surface of the three-dimensional dielectric functional layer enables the formation of a three-dimensional structure between the electrode layer and the negative electrode friction material, achieving three-dimensional contact.

[0016] A method for fabricating a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer, characterized by comprising the following steps:

[0017] Step 1: Prepare the electrode layer by in-situ polymerization on the fabric substrate. Place the fabric substrate in the reaction vessel, and then add deionized water, aniline, perchloric acid and ammonium persulfate in sequence. React at a temperature of 0-5℃ for 24-36 hours. After the reaction is completed, wash the fabric with deionized water to obtain the surface-modified fabric substrate---electrode layer. Among them, add 20-30mL of deionized water, 20-30μL of aniline, 2-3mL of perchloric acid and 40-50mg of ammonium persulfate to each (4×4)-(5×5)cm of fabric.

[0018] Step 2: Prepare the positive electrode friction part. Immerse the fabric substrate-electrode layer prepared in Step 1 in a chloroform solution with a polymer concentration of 10-100 mg / mL for 10-30 min. After drying for 1-2 hours, the polymer is obtained. Then, it is treated with plasma for 1-3 min to obtain a positive electrode friction part with solvent resistance: fabric substrate-electrode layer-positive electrode friction material.

[0019] Step 3: Immerse the substrate-electrode layer prepared in Step 1 in a chloroform solution of polymer with a concentration of 10-100 mg / mL for 10-30 min, then remove and dry for 1-2 hours to obtain the dielectric functional layer of the substrate-electrode layer-three-dimensional structure.

[0020] Step 4: Prepare the negative electrode friction component. At 60-80℃, spray a negative electrode friction material with a concentration of 10-30 mg / mL onto the surface of the substrate-electrode layer-three-dimensional dielectric functional layer prepared in Step 3. The amount of material sprayed is 0.012-0.032 mL / cm². 2 The negative electrode friction part is obtained as follows: fabric substrate - electrode layer - dielectric functional layer - negative electrode friction material;

[0021] Step 5: Fix the positive electrode friction part prepared in Step 2 and the negative electrode friction part prepared in Step 4 onto two substrates respectively, and make the two substrates reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the preparation of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] 1. The present invention proposes a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer. For the first time, a three-dimensional dielectric functional layer with a surface micro-nano structure is introduced between the electrode and the negative electrode triboelectric material. Compared with the existing two-dimensional dielectric functional layer, the electrical output performance of the triboelectric nanogenerator is significantly improved.

[0024] 2. The dielectric functional layer of this invention has a three-dimensional structure, which makes a three-dimensional contact between the dielectric functional layer and the electron-gaining polymer polyvinylidene fluoride. This fully utilizes the function of the dielectric functional layer and has the characteristics of large contact area, high triboelectric charge density and low charge loss compared with traditional planar contact.

[0025] 3. This invention prepares a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer by using fabric as a substrate, which retains the texture characteristics of the fabric itself, thus having the characteristics of good breathability and flexible wearability.

[0026] In summary, by using fabric as a substrate and preparing polyaniline electrodes through in-situ polymerization on the fabric surface, electron-depleting polymers are used as positive electrode friction materials, and electron-gaining polymers are used as negative electrode friction materials. A three-dimensional dielectric functional layer with micro-nano structures is introduced between the polyaniline electrode and the negative electrode friction material, enabling a three-dimensional contact between the dielectric functional layer and the negative electrode friction material, resulting in stronger interaction and improving the electrical output performance of the triboelectric nanogenerator. This method features high electrical output performance, good breathability, flexible wearability, and simple processing. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the structure of the triboelectric nanogenerator with a multi-level structure and a three-dimensional dielectric functional layer prepared according to the present invention.

[0028] Figure 2 Scanning electron microscope image of the negative electrode portion of the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared for this invention, which is composed of nylon-polyaniline-SEBS-polyvinylidene fluoride.

[0029] Figure 3 Figure 1 shows the electrical output performance of the triboelectric nanogenerator with a multi-level structure and a three-dimensional dielectric functional layer prepared in this invention. Figure 2 shows the short-circuit current of the triboelectric nanogenerator and Figure 3 shows the open-circuit voltage of the triboelectric nanogenerator.

[0030] Figure 4 This image illustrates the excellent flexibility of the multi-level triboelectric nanostructure with a three-dimensional dielectric functional layer prepared according to the present invention.

[0031] Figure 5 The figure shows the water vapor diffusion test results of the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in this invention.

[0032] Figure 6 The image shows the air permeability test results of the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared according to the present invention. Detailed Implementation

[0033] The present invention will now be described in detail with reference to the accompanying drawings.

[0034] Example 1

[0035] See Figure 1 A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes a positive electrode triboelectric part and a negative electrode triboelectric part that cyclically contacts and separates from the positive electrode triboelectric part; the positive electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS; the negative electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride.

[0036] A method for fabricating a multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer includes the following steps:

[0037] Step 1: Place a nylon substrate with a pore size of 250 mesh and a diameter of 4×4 cm into a reaction vessel, and then add 20 mL of deionized water, 20 μL of aniline, 2 mL of perchloric acid and 40 mg of ammonium persulfate in sequence. React at 0°C for 24 hours. After the reaction is completed, wash the nylon substrate with deionized water to obtain a surface-modified nylon substrate-polyaniline electrode.

[0038] Step 2: Prepare the positive electrode friction part. Immerse the nylon substrate-polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 100 mg / mL SEBS for 10 min. After drying for 1 hour, the polymer is obtained. Then, it is subjected to plasma treatment for 1 min to form a cross-linked layer on the polymer surface, thus obtaining a solvent-resistant positive electrode friction part: nylon substrate-polyaniline electrode-SEBS.

[0039] Step 3: Immerse the nylon-based polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 100 mg / mL SEBS for 10 min, then remove and dry for 1 hour to obtain the nylon-based polyaniline electrode-SEBS.

[0040] Step 4: Prepare the negative electrode friction part. At 60°C, spray a 10 mg / mL polyvinylidene fluoride dimethylformamide solution onto the nylon substrate-polyaniline electrode-SEBS surface prepared in Step 3. The spraying amount is 0.012 mL / cm². 2 The negative electrode friction part is obtained as follows: nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride;

[0041] Step 5: Use the nylon substrate-polyaniline electrode-SEBS prepared in Step 2 as the positive electrode friction part of the vertically separated triboelectric nanogenerator, and use the nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride prepared in Step 4 as the negative electrode friction part of the vertically separated triboelectric nanogenerator. Fix the positive and negative electrode friction parts to the two substrates respectively, and use a motor to make the two substrates reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the fabrication of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

[0042] Example 2

[0043] See Figure 1 A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes a positive electrode triboelectric part and a negative electrode triboelectric part that cyclically contacts and separates from the positive electrode triboelectric part; the positive electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS; the negative electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride.

[0044] A method for fabricating a multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer includes the following steps:

[0045] Step 1: Place a nylon substrate with an 800-mesh pore size of 5×5cm into a reaction vessel, then add 30mL of deionized water, 30μL of aniline, 3mL of perchloric acid and 50mg of ammonium persulfate in sequence, and react at 1℃ for 36 hours. After the reaction is completed, wash the nylon substrate with deionized water to obtain a surface-modified nylon substrate-polyaniline electrode.

[0046] Step 2: Prepare the positive electrode friction part. Immerse the nylon substrate-polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 10 mg / mL SEBS for 30 min. After drying for 2 hours, the polymer is obtained. Then, it is plasma treated for 3 min to form a cross-linked layer on the polymer surface, thus obtaining a solvent-resistant positive electrode friction part: nylon substrate-polyaniline electrode-SEBS.

[0047] Step 3: Immerse the nylon-based polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 10 mg / mL SEBS for 30 min, then remove and dry for 2 hours to obtain the nylon-based polyaniline electrode-SEBS.

[0048] Step 4: Prepare the negative electrode friction part. At 80°C, spray a 30 mg / mL polyvinylidene fluoride dimethylformamide solution onto the nylon substrate-polyaniline electrode-SEBS surface prepared in Step 3. The spraying amount is 0.032 mL / cm². 2The negative electrode friction part is obtained as follows: nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride;

[0049] Step 5: Use the nylon substrate-polyaniline electrode-SEBS prepared in Step 2 as the positive electrode friction part of the vertically separated triboelectric nanogenerator, and use the nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride prepared in Step 4 as the negative electrode friction part of the vertically separated triboelectric nanogenerator. Fix the positive and negative electrode friction parts to the two substrates respectively, and use a motor to make the two substrates reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the fabrication of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

[0050] Example 3

[0051] See Figure 1 A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes a positive electrode triboelectric part and a negative electrode triboelectric part that cyclically contacts and separates from the positive electrode triboelectric part; the positive electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS; the negative electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-polystyrene-polyvinylidene fluoride.

[0052] A method for fabricating a multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer includes the following steps:

[0053] Step 1: Place a 400-mesh, 4×5cm nylon substrate in a reaction vessel, then add 23mL of deionized water, 23μL of aniline, 2.5mL of perchloric acid and 43mg of ammonium persulfate in sequence, and react at 2℃ for 28 hours. After the reaction is complete, wash the nylon substrate with deionized water to obtain surface-modified nylon-polyaniline.

[0054] Step 2: Prepare the positive electrode friction part. Immerse the nylon substrate-polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 20 mg / mL SEBS for 15 min. After drying for 1.5 hours, a polymer is obtained. Then, it is subjected to plasma treatment for 2 min to form a cross-linked layer on the polymer surface, thus obtaining a solvent-resistant positive electrode friction part: nylon substrate-polyaniline electrode-SEBS.

[0055] Step 3: Immerse the nylon-based polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 20 mg / mL polystyrene for 15 min, then remove and dry for 1.5 hours to obtain the nylon-based polyaniline electrode-polystyrene.

[0056] Step 4: Prepare the negative electrode friction part. At 75°C, spray a 15 mg / mL polyvinylidene fluoride dimethylformamide solution onto the nylon substrate-polyaniline electrode-polystyrene surface prepared in Step 3. The spraying amount is 0.020 mL / cm². 2 The negative electrode friction part is obtained as follows: nylon substrate - polyaniline electrode - polystyrene - polyvinylidene fluoride;

[0057] Step 5: Use the nylon substrate-polyaniline electrode-SEBS prepared in Step 2 as the positive electrode friction part of the vertically separated triboelectric nanogenerator, and use the nylon substrate-polyaniline electrode-polystyrene-polyvinylidene fluoride prepared in Step 4 as the negative electrode friction part of the vertically separated triboelectric nanogenerator. Fix the positive and negative electrode friction parts to the two substrates respectively, and use a motor to make the two substrates reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the preparation of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

[0058] Example 4

[0059] See Figure 1 A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes a positive electrode triboelectric part and a negative electrode triboelectric part that cyclically contacts and separates from the positive electrode triboelectric part; the positive electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS; the negative electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-polycaprolactone-polyvinylidene fluoride.

[0060] A method for fabricating a multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer includes the following steps:

[0061] Step 1: Place a 500-mesh, 5×4cm nylon substrate in a reaction vessel, then add 25mL of deionized water, 25μL of aniline, 2.7mL of perchloric acid and 45mg of ammonium persulfate in sequence, and react at 3℃ for 30 hours. After the reaction is complete, wash the nylon substrate with deionized water to obtain surface-modified nylon-polyaniline.

[0062] Step 2: Prepare the positive electrode friction part. Immerse the nylon substrate-polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 50 mg / mL SEBS for 20 min. After drying for 1 hour, a polymer is obtained. Then, it is plasma treated for 2.5 min to form a cross-linked layer on the polymer surface, thus obtaining a solvent-resistant positive electrode friction part: nylon substrate-polyaniline electrode-SEBS.

[0063] Step 3: Immerse the nylon-based polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 50 mg / mL polycaprolactone for 20 min, then remove and dry for 1 hour to obtain the nylon-based polyaniline electrode-polycaprolactone.

[0064] Step 4: Prepare the negative electrode friction material. Spray a 20 mg / mL polyvinylidene fluoride dimethylformamide solution onto the surface of the nylon-polyaniline-polycaprolactone prepared in Step 3 at 70°C. The spraying amount is 0.025 mL / cm². 2 The negative electrode friction part is obtained as follows: nylon-polyaniline-polycaprolactone-polyvinylidene fluoride;

[0065] Step 5: Prepare a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer. Use the nylon substrate-polyaniline-SEBS prepared in Step 2 as the positive electrode friction part of the vertically separated triboelectric nanogenerator, and use the nylon-polyaniline-polycaprolactone-polyvinylidene fluoride prepared in Step 4 as the negative electrode friction part of the vertically separated triboelectric nanogenerator. Fix the positive and negative electrode friction parts to two substrates respectively, and use a motor to reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the preparation of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

[0066] Example 5

[0067] A method for fabricating a multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer includes the following steps:

[0068] See Figure 1 A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes a positive electrode triboelectric part and a negative electrode triboelectric part that cyclically contacts and separates from the positive electrode triboelectric part; the positive electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-polystyrene; the negative electrode triboelectric part is specifically a nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride.

[0069] Step 1: Place a nylon substrate with a pore size of 600 mesh and a diameter of 4.5×4.5cm into a reaction vessel, then add 28mL of deionized water, 28μL of aniline, 2.8mL of perchloric acid and 48mg of ammonium persulfate in sequence, and react at a temperature of 4℃ for 33 hours. After the reaction is completed, wash the nylon substrate with deionized water to obtain a surface-modified nylon substrate-polyaniline electrode.

[0070] Step 2: Prepare the positive electrode friction part. Immerse the nylon substrate-polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 80 mg / mL polystyrene for 25 min. After drying for 1 hour, the polymer is obtained. Then, it is subjected to plasma treatment for 2.5 min to form a cross-linked layer on the polymer surface, thus obtaining a solvent-resistant positive electrode friction part: nylon substrate-polyaniline electrode-polystyrene.

[0071] Step 3: Immerse the nylon-based polyaniline electrode prepared in Step 1 in a chloroform solution with a concentration of 80 mg / mL SEBS for 25 min, then remove and dry for 1 hour to obtain the nylon-based polyaniline electrode-SEBS.

[0072] Step 4: Prepare the negative electrode friction part. At 60°C, spray a dimethylformamide solution of polyvinylidene fluoride at a concentration of 80 mg / mL onto the surface of the nylon substrate-polyaniline electrode-SEBS prepared in Step 3. The spraying amount is 0.028 mL / cm². 2 The negative electrode friction part is obtained as follows: nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride;

[0073] Step 5: Use the nylon substrate-polyaniline electrode-polystyrene prepared in Step 2 as the positive electrode friction part of the vertically separated triboelectric nanogenerator, and use the nylon substrate-polyaniline electrode-SEBS-polyvinylidene fluoride prepared in Step 4 as the negative electrode friction part of the vertically separated triboelectric nanogenerator. Fix the positive and negative electrode friction parts to the two substrates respectively, and use a motor to make the two substrates reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the preparation of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

[0074] Figure 2 Scanning electron microscope images of the negative electrode portion of the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in this invention, consisting of nylon-polyaniline-SEBS-polyvinylidene fluoride, show that it has a good microporous structure with a pore size of about 10 μm, and retains the fabric morphology and texture characteristics of nylon itself.

[0075] See Figure 3 The multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in Example 1 has an open-circuit voltage of 515.5V, a short-circuit current of 13.7μA, and a power density of 4.4W / m³. 2 Example 2 shows a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer. The open-circuit voltage is 344V, the short-circuit current is 17.1μA, and the power density is 3.7W / m³. 2The multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in Example 3 had an open-circuit voltage of 332.1 V, a short-circuit current of 15.4 μA, and a power density of 3.2 W / m³. 2 The multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in Example 4 has an open-circuit voltage of 202.7V, a short-circuit current of 6.2μA, and a power density of 3.9W / m³. 2 The multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in Example 5 has an open-circuit voltage of 353.2V, a short-circuit current of 12.1μA, and a power density of 2.7W / m³. 2 The power density was increased by about 43 times compared to the multi-level triboelectric nanogenerator without a dielectric functional layer. Therefore, it can be seen that introducing a dielectric functional layer with a three-dimensional structure between the electrode and the negative electrode triboelectric material can significantly improve the output performance of the triboelectric nanogenerator.

[0076] Figure 4 The image shows the excellent flexibility of the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in this invention. It can be seen that the triboelectric nanogenerator does not break when bent, proving that it has excellent flexibility.

[0077] Figure 5 The image shows the water vapor diffusion test results for a multilevel triboelectric nanogenerator with a three-dimensional dielectric functional layer. A certain mass of water was placed in a bottle, with the cap open and the bottle opening tightly wrapped with different polymer films. The water vapor diffusion rate was tested, and the amount of water vapor permeating per 100 hours is as follows: Open cap (None): 0.45 g / cm³ -2 The nylon base (NY) is 0.46 g / cm³. -2 The nylon-polyaniline (NY-PANI) content is 0.47 g / cm³. -2 The nylon-polyaniline-SEBS (NY-PANi-SEBS) content is 0.22 g / cm³. -2 Pure SEBS film has a content of 0.04 g / cm³. -2 It can be seen that the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared by the present invention has good air permeability.

[0078] Figure 6 The image shows the air permeability test results of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer. When the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer is wrapped around a humidifier, water vapor passes through the triboelectric nanogenerator very smoothly, proving that the multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer prepared in this invention has good air permeability.

Claims

1. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer, comprising a positive electrode friction portion and a negative electrode friction portion that cyclically contacts and separates from the positive electrode friction portion, characterized in that, The positive electrode friction portion includes a fabric substrate, an electrode layer, and a positive electrode friction material stacked together; the negative electrode friction portion includes a fabric substrate, an electrode layer, a dielectric functional layer with a three-dimensional structure, and a negative electrode friction material stacked together. The method for fabricating a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer includes the following steps: Step 1: Prepare an electrode layer by in-situ polymerization on a fabric substrate. Place the fabric substrate in a reaction vessel, and then add deionized water, aniline, perchloric acid and ammonium persulfate in sequence. React at a temperature of 0-5℃ for 24-36 hours. After the reaction is completed, wash the fabric with deionized water to obtain the surface-modified fabric substrate---electrode layer. Among them, add 20-30 mL of deionized water, 20-30 μL of aniline, 2-3 mL of perchloric acid and 40-50 mg of ammonium persulfate per (4×4)-(5×5) cm of fabric. Step 2: Prepare the positive electrode friction part. Immerse the fabric substrate-electrode layer prepared in Step 1 in a chloroform solution with a polymer concentration of 10-100 mg / mL for 10-30 min. After drying for 1-2 hours, the polymer is obtained. Then, it is treated with plasma for 1-3 min to obtain a positive electrode friction part with solvent resistance: fabric substrate-electrode layer-positive electrode friction material. Step 3: Immerse the substrate-electrode layer prepared in Step 1 in a chloroform solution of polymer with a concentration of 10-100 mg / mL for 10-30 min, then remove and dry for 1-2 hours to obtain the dielectric functional layer of the substrate-electrode layer-three-dimensional structure. Step 4: Prepare the negative electrode friction component. At 60-80℃, spray a negative electrode friction material with a concentration of 10-30 mg / mL onto the surface of the substrate-electrode layer-three-dimensional dielectric functional layer prepared in Step 3. The amount of material sprayed is 0.012-0.032 mL / cm². 2 The negative electrode friction part is obtained as follows: fabric substrate - electrode layer - dielectric functional layer - negative electrode friction material; Step 5: Fix the positive electrode friction part prepared in Step 2 and the negative electrode friction part prepared in Step 4 onto two substrates respectively, and make the two substrates reciprocate to achieve contact and separation of the positive and negative electrode friction parts. When in contact, triboelectric power generation is achieved, thereby realizing the preparation of a multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer.

2. The multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 1, characterized in that, The dielectric functional layer with a three-dimensional structure is specifically a polymer with a surface microporous structure.

3. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 1 or 2, characterized in that, The three-dimensional dielectric functional layer material is one of SEBS, polystyrene, or polycaprolactone.

4. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 1, characterized in that, The electrode layer in the positive electrode friction part is a polyaniline electrode, and the positive electrode friction material is an electron-depleting tribopolymer.

5. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 1, characterized in that, The electrode layer in the negative electrode friction part is a polyaniline electrode, and the negative electrode friction material is an electron-gaining tribopolymer.

6. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 4, characterized in that, The electron-loss tribopolymer is a polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) or polystyrene.

7. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 5, characterized in that, The electron-gaining tribopolymer is polyvinylidene fluoride.

8. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 1, characterized in that, The fabric substrate is a nylon substrate, and the fabric material is a single-layer fabric structure with a pore size of 250-800 mesh.

9. A multi-level triboelectric nanogenerator with a three-dimensional dielectric functional layer according to claim 3, characterized in that, The microporous structure on the surface of the three-dimensional dielectric functional layer enables the formation of a three-dimensional structure between the electrode layer and the negative electrode friction material, achieving three-dimensional contact.

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