Fabric-based triboelectric nanogenerator and preparation method thereof

Abstract

A fabric-based triboelectric nanogenerator and a preparation method thereof. The fabric-based triboelectric nanogenerator comprises a positive electrode friction part and a negative electrode friction part in cyclic contact and separation with the positive electrode friction part; the positive electrode friction part comprises a positive electrode substrate, a positive electrode layer and a positive electrode friction layer arranged in layers; the negative electrode friction part comprises a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer arranged in layers; the preparation method comprises the following steps: preparing a positive electrode part, preparing a negative electrode part, reciprocating the positive electrode friction part and the negative electrode friction part to realize contact and separation of the positive electrode friction layer and the negative electrode friction layer, and generating electricity by friction when the positive electrode friction layer and the negative electrode friction layer are in contact. The fabric-based triboelectric nanogenerator has the characteristics of simple preparation process, low cost, good air permeability, strong wearability and high electric output performance.

Description

Technical Field

[0001] This invention relates to the field of nanogenerator technology, specifically to a fabric-based triboelectric nanogenerator and its preparation method. Background Technology

[0002] Triboelectric nanogenerators (TENGs) directly convert mechanical energy into electrical energy, making them a promising power source for efficiently powering electronic devices and potentially replacing traditional batteries. High electrical output performance is key to the effective application of TENGs, and numerous studies have shown that micro / nano structures can significantly improve their output performance. On the other hand, wearable devices have become an integral part of daily life. Smart textiles, due to their lightweight, high elasticity, breathability, and washability, are more suitable for wearable devices. Therefore, the fabrication of fabric-based TENGs with micro / nano structures is an important research topic for high-performance wearable power sources.

[0003] Wang et al. reported a method for preparing fabric-based TENGs with surface microstructures via direct imprinting thermal drawing technology in Nat. Commun. 2020 [Zhe Wang, et al. Nat. Commun. 2020, 11(1), 3842], demonstrating its great potential for wearable applications. Although it achieves arbitrarily designed micro / nano patterns across the entire fiber surface, the output performance reaches 4.8V and 2.9mA / m 2 It exhibits good solvent resistance, but this method is inefficient and requires expensive equipment. More importantly, it has limited post-treatment capabilities for commercial textiles.

[0004] Zhi-Qiang Bai et al. reported a conductive fabric-based TENG with a nanocomposite layer at Nano Energy 2019 [Zhi-Qiang Bai, et al. Nano Energy 2019, 65], achieving high output performance (490V, 43μA, 32mA / m). 2 60W / m 2 This method also shows great potential in portable electronic products and electronic textiles. However, the top-down sandwich structure of this method results in a loss of the fabric's texture and breathability, and its wearability needs to be improved.

[0005] Furthermore, patent application [CN110138259A] discloses "a high-humidity resistant flexible wearable triboelectric nanogenerator and its preparation method and application." This triboelectric nanogenerator uses a hydroxyl-rich polyhydroxy polymer as the friction layer, and the outer surface of the friction layer has raised micro-nano patterns. Hydroxyl groups readily form hydrogen bonds with water molecules, fixing water molecules from the environment to the material surface. The water molecules participate in triboelectric charging as a whole, increasing the total electrical output of the friction layer (17V, 2.7μA, 1.7mA / m). 2 0.028W / m 2 This allows it to be used in high-humidity environments. However, due to the use of polymer films as the substrate and friction layer, they lack breathability, thus limiting their wearability. The surface micro-nano patterns are fabricated via laser etching, requiring sophisticated equipment. Furthermore, the output performance of the TENG needs improvement.

[0006] Patent application [CN109104117A] discloses a wearable fabric nanogenerator and its preparation method. The method involves chemically electroplating pure cotton yarn to create conductive yarn. Then, the resulting core yarn is spun using conjugate electrospinning technology to prepare a yarn coated with nanofibers. The two core-spun yarns are then woven separately to form a single-layer nanofiber fabric. Finally, ultrafine transparent nylon is used to connect the two fabric layers, leaving corresponding air layers between them, ultimately obtaining the wearable fabric nanogenerator. This method is highly innovative and offers good wearability. However, due to the numerous preparation steps and relatively complex process, it requires sophisticated equipment. Fabrics prepared using classical spinning exhibit poor solvent resistance.

[0007] In summary, the existing technology has the following main shortcomings:

[0008] 1. The preparation process is complex, costly, technologically limited, and difficult to scale up;

[0009] 2. The sandwich structure of the device from top to bottom loses the texture and breathability of the fabric itself, resulting in poor wearability.

[0010] 3. The surface micro-nano structure has poor solvent resistance and is easily destroyed in solvents, which directly affects the electrical output performance of TENG;

[0011] 4. TENG has low output performance. Summary of the Invention

[0012] To overcome the shortcomings of the prior art, the present invention aims to provide a fabric-based triboelectric nanogenerator and its preparation method. The method uses fabric as a substrate, prepares micro-nano structures on the fabric surface to improve electrical output, and treats the friction part with plasma treatment technology to improve solvent resistance through cross-linking. Polyaniline is polymerized in situ on the fabric surface as an electrode. The method has the characteristics of simple preparation process, low cost, good air permeability, strong wearability, high electrical output performance and solvent resistance.

[0013] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0014] A fabric-based triboelectric nanogenerator includes a positive electrode friction portion and a negative electrode friction portion that is in cyclic contact with and separates from the positive electrode friction portion. The positive electrode friction portion includes a positive electrode substrate, a positive electrode layer and a positive electrode friction layer stacked together. The negative electrode friction portion includes a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer stacked together.

[0015] The positive electrode substrate of the positive electrode friction part is made of fabric, the positive electrode layer is made of polyaniline, and the positive electrode friction layer is made of polymer.

[0016] The negative electrode base material of the negative electrode friction part is fabric, the negative electrode structural layer material is polymer, the negative electrode electrode layer material is polyaniline, and the negative electrode friction layer material is polymer.

[0017] The positive electrode friction layer and the negative electrode friction layer are the same or different polymers with micro-nano structures and solvent resistance.

[0018] The effect is the same if the materials of the positive electrode layer and the positive electrode friction layer are interchanged.

[0019] A method for preparing a fabric-based triboelectric nanogenerator includes the following steps:

[0020] Step 1: Prepare the positive electrode layer on the surface of the positive electrode substrate using in-situ polymerization: Place the positive electrode substrate in a reaction vessel, then add deionized water, aniline, perchloric acid, and ammonium persulfate sequentially, and react at a temperature of 0-5℃ for 24-36 hours. After the reaction is complete, wash the reacted positive electrode substrate with deionized water. Specifically, wash every 16 cm... 2 -25cm 2 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 to the positive electrode substrate to obtain a positive electrode layer with polyaniline surface modification.

[0021] Step 2: Prepare a positive electrode friction layer on the surface of the positive electrode layer modified with polyaniline: Immerse the positive electrode layer modified with polyaniline prepared in Step 1 in a chloroform solution with a polymer concentration of 10-100 mg / mL for 10-30 min, then remove and dry for 1-2 hours to obtain a positive electrode layer with a polymer micro-nano structure on the surface. Then treat the positive electrode layer with a polymer micro-nano structure on the surface with plasma technology for 1-3 min to obtain a positive electrode friction layer with a polymer micro-nano structure on the surface and solvent resistance.

[0022] Step 3: Prepare a negative electrode structure layer on the surface of the negative electrode substrate: Immerse the negative electrode substrate in a chloroform solution with a polymer concentration of 10-100 mg / mL for 10-30 min, then remove and dry for 1-2 hours to obtain a negative electrode structure layer with a polymer micro-nano structure on the surface.

[0023] Step 4: Prepare the negative electrode layer on the surface of the negative electrode structure layer with micro / nano-structured polymer using in-situ polymerization: Place the negative electrode structure layer with micro / nano-structured polymer prepared in Step 3 into a reaction vessel, then add deionized water, aniline, perchloric acid, and ammonium persulfate sequentially, and react at a temperature of 0-5℃ for 24-36 hours. After the reaction, wash the negative electrode structure layer with micro / nano-structured polymer with deionized water. The washing process involves washing the surface of the negative electrode structure layer with micro / nano-structured polymer every 16 cm³. 2 -25cm 2 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 to the negative electrode structure layer with micro-nano structure polymer on the surface after the reaction to obtain a negative electrode layer with micro-nano structure polymer on the surface and modified with polyaniline.

[0024] Step 5: Prepare a negative electrode friction layer on the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline: Spray 0.012-0.032 mL / cm onto the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline prepared in Step 4. 2 Prepare a dimethylformamide solution with a polymer concentration of 10-30 mg / mL, and then treat it with plasma technology for 1-3 min to obtain a negative electrode friction layer with a polymer micro-nano structure on the surface and solvent resistance.

[0025] Step 6: The stacked positive electrode substrate, the positive electrode layer prepared in Step 1, and the positive electrode friction layer prepared in Step 2 are used as the positive electrode friction part. The stacked negative electrode substrate, the negative electrode structure layer prepared in Step 3, the negative electrode layer prepared in Step 4, and the negative electrode friction layer prepared in Step 5 are used as the negative electrode friction part. The positive electrode friction part and the negative electrode friction part are allowed to reciprocate to achieve contact and separation between the positive electrode friction layer and the negative electrode friction layer. When they contact, triboelectric power generation occurs, thereby realizing the preparation of the triboelectric nanogenerator.

[0026] The positive or negative electrode substrate comprises a single-layer woven fabric, preferably nylon fabric with a pore size of 250-800 mesh.

[0027] The polymers include: polystyrene, polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS), polyvinylidene fluoride or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDFHFP).

[0028] The steps of modifying polyaniline in step 1 and preparing micro / nano-structured polymers in step 2 are interchangeable and achieve the same effect.

[0029] The resistance of the polyaniline electrode is 0.1-10kΩ.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] 1. Compared with the prior art, the present invention coats the fabric surface with polymer to construct a micro-nano structure. The micro-nano structure can improve the surface roughness of the friction layer, increase the effective friction area and charge density, and significantly improve the electrical output performance.

[0032] 2. Compared with the prior art, the present invention adopts plasma treatment technology. After plasma treatment, the polymer molecular chains on the surface of the friction layer are cross-linked together to form a three-dimensional network cross-linked structure. This cross-linked layer has good solvent resistance and protects the structure and internal materials from the influence of solvents and moisture.

[0033] 3. Compared to existing technologies, this invention uses fabric as a substrate, in-situ polymerized polyaniline as an electrode, and a polymer as a friction layer. The resulting triboelectric nanogenerator has an all-organic structure and excellent flexibility. Simultaneously, the texture characteristics of the fabric are preserved, providing good breathability. Therefore, the triboelectric nanogenerator prepared by this invention offers excellent wearability and comfort.

[0034] In summary, this invention uses fabric as a substrate, coats the fabric surface with polymer to construct micro-nano structures, and uses plasma treatment technology and in-situ polymerization of polyaniline to prepare triboelectric nanogenerators. The preparation process is simple and efficient, with excellent wearability, comfort, versatility, and wide application range. It improves the electrical output performance of triboelectric nanogenerators and is unaffected by solvents and moisture. It can achieve large-size and large-scale production and is easy to industrialize. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the structure of the triboelectric nanogenerator of the present invention.

[0036] Figure 2This is a scanning electron microscope image of the 500-mesh nylon fabric used in the embodiments of the present invention.

[0037] Figure 3 This is a scanning electron microscope image of nylon-polyaniline-SEBS-solvent resistant material in Example 1 of the present invention.

[0038] Figure 4 The electrical output performance of the triboelectric nanogenerator with micro-nano structure in Embodiment 1 of the present invention is shown.

[0039] Figure 5 This is a scanning electron microscope image of nylon-SEBS-polyaniline in Example 3 of the present invention.

[0040] Figure 6 This is a graph showing the air permeability test of a triboelectric nanogenerator. Detailed Implementation

[0041] The present invention will now be described in detail with reference to the accompanying drawings.

[0042] Example 1

[0043] See Figure 1 A fabric-based triboelectric nanogenerator includes a positive electrode friction portion and a negative electrode friction portion that is in cyclic contact with and separates from the positive electrode friction portion. The positive electrode friction portion includes a positive electrode substrate, a positive electrode layer and a positive electrode friction layer stacked together. The negative electrode friction portion includes a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer stacked together.

[0044] The positive electrode substrate of the positive electrode friction part is made of nylon fabric, the positive electrode layer is made of polyaniline, and the positive electrode friction layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS).

[0045] The negative electrode substrate of the negative electrode friction part is made of nylon fabric, the negative electrode structural layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS), the negative electrode layer is made of polyaniline, and the negative electrode friction layer is made of polyvinylidene fluoride.

[0046] The positive electrode friction layer is a polymer with micro / nano structure and solvent resistance, namely polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS); the negative electrode friction layer is a polymer with micro / nano structure and solvent resistance, namely polyvinylidene fluoride.

[0047] The effect is the same if the materials of the positive electrode layer and the positive electrode friction layer are interchanged.

[0048] A method for preparing a fabric-based triboelectric nanogenerator includes the following steps:

[0049] See Figure 2 Step 1: Prepare a positive electrode layer on the surface of nylon fabric by in-situ polymerization: Place a 4×4cm single-layer nylon fabric with a pore size of 500 mesh in a reaction vessel, then add 30mL of deionized water, 25μL of aniline, 2mL of perchloric acid and 40mg of ammonium persulfate in sequence, and react at 0℃ for 24 hours. After the reaction is completed, wash the nylon fabric with deionized water to obtain a positive electrode layer with a surface modified with polyaniline and a resistance of 5kΩ.

[0050] Step 2: Prepare a positive electrode friction layer on the surface of the positive electrode layer modified with polyaniline: Immerse the positive electrode layer modified with polyaniline prepared in Step 1 in a chloroform solution of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) with a concentration of 100 mg / mL for 10 min, then remove and dry for 1 hour to obtain a positive electrode layer with a polymer with micro-nano structure on the surface. Then treat the positive electrode layer with the polymer with micro-nano structure on the surface with plasma technology for 3 min to obtain a positive electrode friction layer with a polymer with micro-nano structure on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the positive electrode friction layer. This cross-linked network layer has a good solvent resistance effect.

[0051] Step 3: Prepare a negative electrode structure layer on the surface of nylon fabric: Immerse a 4×4cm single-layer nylon fabric with a pore size of 500 mesh in a chloroform solution containing 100mg / mL polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) for 10min, then remove and dry for 1 hour to obtain a negative electrode structure layer with a micro-nano structure polymer on the surface. This negative electrode structure layer serves as a template for the next patterned layer.

[0052] Step 4: Prepare a negative electrode layer on the surface of the negative electrode structure layer with micro-nano structure polymer by in-situ polymerization: Place the negative electrode structure layer with micro-nano structure polymer prepared in step 3 into a reaction vessel, and then add 30 mL of deionized water, 25 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 negative electrode structure layer with micro-nano structure polymer with micro-nano structure polymer with deionized water to obtain a negative electrode layer with micro-nano structure polymer and modified with polyaniline, with a resistance of 8 kΩ.

[0053] Step 5: Prepare a negative electrode friction layer on the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline: Apply a layer of the negative electrode friction layer with a micro / nano-structured polymer and modified with polyaniline to the surface of the negative electrode layer prepared in Step 4, per 1 cm... 2Spray 0.012 mL of a dimethylformamide solution containing 20 mg / mL polyvinylidene fluoride, and then treat with plasma technology for 3 min to obtain a negative electrode friction layer with a micro-nano structure polymer on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the negative electrode friction layer, and this cross-linked network layer has a good solvent resistance effect.

[0054] Step 6: The stacked positive electrode substrate, the positive electrode layer prepared in step 1, and the positive electrode friction layer prepared in step 2 are used as the positive electrode friction part. The stacked negative electrode substrate, the negative electrode structure layer prepared in step 3, the negative electrode layer prepared in step 4, and the negative electrode friction layer prepared in step 5 are used as the negative electrode friction part. The positive electrode friction part and the negative electrode friction part are allowed to reciprocate to achieve contact and separation between the positive electrode friction layer and the negative electrode friction layer. When they contact, triboelectric power generation occurs, thereby realizing the preparation of the triboelectric nanogenerator.

[0055] See Figure 4 The following conclusions were drawn from testing the electrical output performance of a vertically separated triboelectric nanogenerator during a periodic vertical pressure-release process:

[0056] In this embodiment, the triboelectric nanogenerator with surface micro / nano structures has an open-circuit voltage of 208.9V, a short-circuit current of 4.6μA, and an energy density of 0.6W / m³. 2 Compared with existing triboelectric nanogenerators without surface micro / nano structures, the open-circuit voltage is increased by 2.7 times, the short-circuit current by 3.1 times, and the energy density by 29 times.

[0057] Example 2

[0058] See Figure 1 A fabric-based triboelectric nanogenerator includes a positive electrode friction portion and a negative electrode friction portion that is in cyclic contact with and separates from the positive electrode friction portion. The positive electrode friction portion includes a positive electrode substrate, a positive electrode layer and a positive electrode friction layer stacked together. The negative electrode friction portion includes a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer stacked together.

[0059] The positive electrode base of the positive electrode friction part is made of nylon fabric, the positive electrode layer is made of polyaniline, and the positive electrode friction layer is made of polystyrene.

[0060] The negative electrode substrate of the negative electrode friction part is made of nylon fabric, the negative electrode structural layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS), the negative electrode layer is made of polyaniline, and the negative electrode friction layer is made of polyvinylidene fluoride.

[0061] The positive electrode friction layer is a polymer polystyrene with micro / nano structure and solvent resistance; the negative electrode friction layer is a polymer polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) with micro / nano structure and solvent resistance.

[0062] The effect is the same if the materials of the positive electrode layer and the positive electrode friction layer are interchanged.

[0063] A method for preparing a fabric-based triboelectric nanogenerator includes the following steps:

[0064] Step 1: Prepare a positive electrode layer on the surface of nylon fabric by in-situ polymerization: Place a 4×4cm single-layer nylon fabric with a pore size of 800 mesh in a reaction vessel, then add 30mL of deionized water, 30μL of aniline, 2.5mL of perchloric acid and 45mg of ammonium persulfate in sequence, and react at 0℃ for 36 hours. After the reaction is completed, wash the nylon fabric with deionized water to obtain a positive electrode layer with a surface modified with polyaniline and a resistance of 8kΩ.

[0065] Step 2: Prepare a positive electrode friction layer on the surface of the positive electrode layer modified with polyaniline: Immerse the positive electrode layer modified with polyaniline prepared in Step 1 in a chloroform solution with a concentration of 100 mg / mL polystyrene for 30 min, then remove and dry for 1 hour to obtain a positive electrode layer with a polymer with micro-nano structure on the surface. Then treat the positive electrode layer with the polymer with micro-nano structure on the surface with plasma technology for 2 min to obtain a positive electrode friction layer with a polymer with micro-nano structure on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the positive electrode friction layer. This cross-linked network layer has a good solvent resistance effect.

[0066] Step 3: Prepare a negative electrode structure layer on the surface of nylon fabric: Immerse a 4×4cm single-layer nylon fabric with a pore size of 800 mesh in a chloroform solution containing 100mg / mL polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) for 30min, then remove and dry for 1 hour to obtain a negative electrode structure layer with a micro-nano structure polymer on the surface. This negative electrode structure layer serves as a template for the next patterned layer.

[0067] Step 4: Prepare a negative electrode layer on the surface of the negative electrode structure layer with micro-nano structure polymer by in-situ polymerization: Place the negative electrode structure layer with micro-nano structure polymer prepared in step 3 into a reaction vessel, and then add 30 mL of deionized water, 30 μL of aniline, 2.5 mL of perchloric acid and 45 mg of ammonium persulfate in sequence. React at 0℃ for 36 hours. After the reaction is completed, wash the negative electrode structure layer with micro-nano structure polymer with the reaction with deionized water to obtain a negative electrode layer with micro-nano structure polymer and modified with polyaniline, with a resistance of 8 kΩ.

[0068] Step 5: Prepare a negative electrode friction layer on the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline: Apply a friction layer to the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline prepared in Step 4, per 1 cm... 2 Spray 0.021 mL of a dimethylformamide solution containing polyvinylidene fluoride at a concentration of 20 mg / mL, and then treat with plasma technology for 2 min to obtain a negative electrode friction layer with a micro-nano structure polymer on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the negative electrode friction layer, and this cross-linked network layer has a good solvent resistance effect.

[0069] Step 6: The stacked positive electrode substrate, the positive electrode layer prepared in step 1, and the positive electrode friction layer prepared in step 2 are used as the positive electrode friction part. The stacked negative electrode substrate, the negative electrode structure layer prepared in step 3, the negative electrode layer prepared in step 4, and the negative electrode friction layer prepared in step 5 are used as the negative electrode friction part. The positive electrode friction part and the negative electrode friction part are allowed to reciprocate to achieve contact and separation between the positive electrode friction layer and the negative electrode friction layer. When they contact, triboelectric power generation occurs, thereby realizing the preparation of the triboelectric nanogenerator.

[0070] The following conclusions were drawn from testing the electrical output performance of a vertically split triboelectric nanogenerator during a periodic vertical pressure-release process:

[0071] In this embodiment, the triboelectric nanogenerator with surface micro / nano structures has an open-circuit voltage of 51.3V, a short-circuit current of 1.64μA, and an energy density of 0.05W / m³. 2 Compared with existing triboelectric nanogenerators without surface micro / nano structures, the open-circuit voltage is increased by 0.6 times, the short-circuit current by 2.8 times, and the energy density by 4.6 times.

[0072] Example 3

[0073] See Figure 1A fabric-based triboelectric nanogenerator includes a positive electrode friction portion and a negative electrode friction portion that is in cyclic contact with and separates from the positive electrode friction portion. The positive electrode friction portion includes a positive electrode substrate, a positive electrode layer and a positive electrode friction layer stacked together. The negative electrode friction portion includes a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer stacked together.

[0074] The positive electrode substrate of the positive electrode friction part is made of nylon fabric, the positive electrode layer is made of polyaniline, and the positive electrode friction layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS).

[0075] The negative electrode substrate of the negative electrode friction part is made of nylon fabric, the negative electrode structural layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS), the negative electrode layer is made of polyaniline, and the negative electrode friction layer is made of polyvinylidene fluoride.

[0076] The positive electrode friction layer is a polymer with micro / nano structure and solvent resistance, namely polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS); the negative electrode friction layer is a polymer with micro / nano structure and solvent resistance, namely polyvinylidene fluoride.

[0077] The effect is the same if the materials of the positive electrode layer and the positive electrode friction layer are interchanged.

[0078] A method for preparing a fabric-based triboelectric nanogenerator includes the following steps:

[0079] Step 1: Prepare a positive electrode layer on the surface of nylon fabric: Immerse a 4×4cm single-layer nylon fabric with a pore size of 250 mesh in a chloroform solution containing 10mg / mL polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) for 20min, then remove and dry for 1.5 hours to obtain a positive electrode layer with a polymer with micro-nano structure on the surface.

[0080] See Figure 5Step 2: Prepare a positive electrode friction layer on the surface of the positive electrode layer with micro-nano structured polymer: Place the positive electrode layer with micro-nano structured polymer prepared in step 1 into a reaction vessel using in-situ polymerization, then add 20 mL of deionized water, 20 μL of aniline, 2 mL of perchloric acid and 40 mg of ammonium persulfate in sequence, and react at 5 °C for 30 hours. After the reaction is completed, wash the positive electrode layer with micro-nano structured polymer with deionized water to obtain a positive electrode layer with surface-modified polyaniline. Then treat the positive electrode layer with plasma technology for 2 min to obtain a positive electrode friction layer with micro-nano structured polymer and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the positive electrode friction layer. This cross-linked network layer has a good solvent resistance effect.

[0081] Step 3: Prepare a negative electrode structure layer on the surface of nylon fabric: Immerse a 4×4cm single-layer nylon fabric with a pore size of 250 mesh in a chloroform solution containing 10mg / mL polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) for 20min, then remove and dry for 1.5 hours to obtain a negative electrode structure layer with a micro-nano structure polymer on the surface. This negative electrode structure layer serves as a template for the next patterned layer.

[0082] Step 4: Prepare a negative electrode layer on the surface of the negative electrode structure layer with micro-nano structure polymer by in-situ polymerization: Place the negative electrode structure layer with micro-nano structure polymer prepared in step 3 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 5 °C for 30 hours. After the reaction is completed, wash the negative electrode structure layer with micro-nano structure polymer with the reaction with deionized water to obtain a negative electrode layer with micro-nano structure polymer and modified with polyaniline, with a resistance of 10 kΩ.

[0083] Step 5: Prepare a negative electrode friction layer on the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline: Apply a layer of the negative electrode friction layer with a micro / nano-structured polymer and modified with polyaniline to the surface of the negative electrode layer prepared in Step 4, per 1 cm... 2 Spray 0.029 mL of a dimethylformamide solution containing polyvinylidene fluoride at a concentration of 10 mg / mL, and then treat with plasma technology for 1 min to obtain a negative electrode friction layer with a micro-nano structure polymer on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the negative electrode friction layer, and this cross-linked network layer has a good solvent resistance effect.

[0084] Step 6: The stacked positive electrode substrate, the positive electrode layer prepared in step 1, and the positive electrode friction layer prepared in step 2 are used as the positive electrode friction part. The stacked negative electrode substrate, the negative electrode structure layer prepared in step 3, the negative electrode layer prepared in step 4, and the negative electrode friction layer prepared in step 5 are used as the negative electrode friction part. The positive electrode friction part and the negative electrode friction part are allowed to reciprocate to achieve contact and separation between the positive electrode friction layer and the negative electrode friction layer. When they contact, triboelectric power generation occurs, thereby realizing the preparation of the triboelectric nanogenerator.

[0085] The following conclusions were drawn from testing the electrical output performance of a vertically split triboelectric nanogenerator during a periodic vertical pressure-release process:

[0086] In this embodiment, the triboelectric nanogenerator with surface micro / nano structures has an open-circuit voltage of 31.7V, a short-circuit current of 0.94μA, and an energy density of 0.019W / m³. 2 Compared with existing triboelectric nanogenerators without surface micro / nano structures, the open-circuit voltage is increased by 0.1 times, the short-circuit current by 1.6 times, and the energy density by 2.2 times.

[0087] Example 4

[0088] See Figure 1 A fabric-based triboelectric nanogenerator includes a positive electrode friction portion and a negative electrode friction portion that is in cyclic contact with and separates from the positive electrode friction portion. The positive electrode friction portion includes a positive electrode substrate, a positive electrode layer and a positive electrode friction layer stacked together. The negative electrode friction portion includes a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer stacked together.

[0089] The positive electrode substrate of the positive electrode friction part is made of nylon fabric, the positive electrode layer is made of polyaniline, and the positive electrode friction layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS).

[0090] The negative electrode substrate of the negative electrode friction part is made of nylon fabric, the negative electrode structural layer is made of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS), the negative electrode layer is made of polyaniline, and the negative electrode friction layer is made of polyvinylidene fluoride.

[0091] The positive electrode friction layer is a polymer with micro / nano structure and solvent resistance, namely polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS); the negative electrode friction layer is a polymer with micro / nano structure and solvent resistance, namely polyvinylidene fluoride.

[0092] The effect is the same if the materials of the positive electrode layer and the positive electrode friction layer are interchanged.

[0093] A method for preparing a fabric-based triboelectric nanogenerator includes the following steps:

[0094] See Figure 2 Step 1: Prepare a positive electrode layer on the surface of nylon fabric by in-situ polymerization: Place a 5×5cm single-layer nylon fabric with a pore size of 500 mesh in a reaction vessel, then add 25mL of deionized water, 28μL of aniline, 2.5mL of perchloric acid and 50mg of ammonium persulfate in sequence, and react at 2℃ for 36 hours. After the reaction is completed, wash the nylon fabric with deionized water to obtain a positive electrode layer with a surface modified with polyaniline and a resistance of 0.1kΩ.

[0095] Step 2: Prepare a positive electrode friction layer on the surface of the positive electrode layer modified with polyaniline: Immerse the positive electrode layer modified with polyaniline prepared in Step 1 in a chloroform solution of polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) with a concentration of 80 mg / mL for 30 min, then remove and dry for 1 hour to obtain a positive electrode layer with a polymer with micro-nano structure on the surface. Then treat the positive electrode layer with the polymer with micro-nano structure on the surface with plasma technology for 3 min to obtain a positive electrode friction layer with a polymer with micro-nano structure on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the positive electrode friction layer. This cross-linked network layer has a good solvent resistance effect.

[0096] See Figure 2 Step 3: Prepare a negative electrode structure layer on the surface of nylon fabric: Immerse a 4×4cm single-layer nylon fabric with a pore size of 500 mesh in a chloroform solution containing 80mg / mL polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS) for 30min, then remove and dry for 1 hour to obtain a negative electrode structure layer with a micro-nano structure polymer on the surface. This negative electrode structure layer serves as a template for the next patterned layer.

[0097] Step 4: Prepare a negative electrode layer on the surface of the negative electrode structure layer with micro-nano structure polymer by in-situ polymerization: Place the negative electrode structure layer with micro-nano structure polymer prepared in step 3 into a reaction vessel, and then add 25 mL of deionized water, 28 μL of aniline, 2.5 mL of perchloric acid and 50 mg of ammonium persulfate in sequence. React at 2 °C for 36 hours. After the reaction is completed, wash the negative electrode structure layer with micro-nano structure polymer with micro-nano structure polymer with deionized water to obtain a negative electrode layer with micro-nano structure polymer with polyaniline modified on the surface, with a resistance of 0.1 kΩ.

[0098] Step 5: Prepare a negative electrode friction layer on the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline: Apply a layer of the negative electrode friction layer with a micro / nano-structured polymer and modified with polyaniline to the surface of the negative electrode layer prepared in Step 4, per 1 cm...2 Spray 0.032 mL of a dimethylformamide solution containing 30 mg / mL poly(vinylidene fluoride-co-hexafluoropropylene) (PVDFHFP), and then treat with plasma technology for 3 min to obtain a negative electrode friction layer with a micro-nano structured polymer on the surface and solvent resistance. The polymer molecules form a cross-linked network layer on the surface of the negative electrode friction layer, which has a good solvent resistance effect.

[0099] Step 6: The stacked positive electrode substrate, the positive electrode layer prepared in step 1, and the positive electrode friction layer prepared in step 2 are used as the positive electrode friction part. The stacked negative electrode substrate, the negative electrode structure layer prepared in step 3, the negative electrode layer prepared in step 4, and the negative electrode friction layer prepared in step 5 are used as the negative electrode friction part. The positive electrode friction part and the negative electrode friction part are allowed to reciprocate to achieve contact and separation between the positive electrode friction layer and the negative electrode friction layer. When they contact, triboelectric power generation occurs, thereby realizing the preparation of the triboelectric nanogenerator.

[0100] The following conclusions were drawn from testing the electrical output performance of a vertically split triboelectric nanogenerator during a periodic vertical pressure-release process:

[0101] In this embodiment, the triboelectric nanogenerator with surface micro / nano structures has an open-circuit voltage of 56.3V, a short-circuit current of 2.74μA, and an energy density of 0.1W / m³. 2 Compared with existing triboelectric nanogenerators without surface micro / nano structures, the open-circuit voltage is increased by 0.1 times, the short-circuit current by 11.2 times, and the energy density by 1.8 times.

[0102] Breathability test:

[0103] A certain mass of ethanol was placed in a bottle, and the bottle opening was left open and tightly wrapped with different polymer films to test the diffusion rate of ethanol vapor.

[0104] See Figure 6 The amount of ethanol vapor per 100 hours is as follows: 1.77 g / cm³ with the lid open (None). -2 The nylon fabric (NY) weighs 1.78 g / cm³. -2 The nylon-polyaniline (NY-PANi) content is 1.71 g cm⁻¹. -2 The nylon-polyaniline-SEBS (NY-PANI-SEBS) content is 0.63 g / cm³. -2 Pure SEBS film has a content of 0.08 g / cm³. -2 This indicates that the triboelectric nanogenerator has excellent air permeability.

[0105] In summary, the triboelectric nanogenerator prepared in this invention has better solvent resistance, electrical output, and air permeability compared to existing triboelectric nanogenerators.

Claims

1. A fabric-based triboelectric nanogenerator, 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 positive electrode substrate, a positive electrode layer and a positive electrode friction layer stacked together; the negative electrode friction portion includes a negative electrode substrate, a negative electrode structure layer, a negative electrode layer and a negative electrode friction layer stacked together. The fabric-based triboelectric nanogenerator was prepared using a method for fabric-based triboelectric nanogenerators, the method comprising the following steps: Step 1: Prepare the positive electrode layer on the surface of the positive electrode substrate using in-situ polymerization: Place the positive electrode substrate in a reaction vessel, then add deionized water, aniline, perchloric acid, and ammonium persulfate sequentially, and react at a temperature of 0-5℃ for 24-36 hours. After the reaction is complete, wash the reacted positive electrode substrate with deionized water. Specifically, wash every 16 cm... 2 -25cm 2 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 to the positive electrode substrate to obtain a positive electrode layer with polyaniline surface modification. Step 2: Prepare a positive electrode friction layer on the surface of the positive electrode layer modified with polyaniline: Immerse the positive electrode layer modified with polyaniline prepared in Step 1 in a chloroform solution with a polymer concentration of 10-100 mg / mL for 10-30 min, then remove and dry for 1-2 hours to obtain a positive electrode layer with a polymer micro-nano structure on the surface. Then treat the positive electrode layer with a polymer micro-nano structure on the surface with plasma technology for 1-3 min to obtain a positive electrode friction layer with a polymer micro-nano structure on the surface and solvent resistance. Step 3: Prepare a negative electrode structure layer on the surface of the negative electrode substrate: Immerse the negative electrode substrate in a chloroform solution with a polymer concentration of 10-100 mg / mL for 10-30 min, then remove and dry for 1-2 hours to obtain a negative electrode structure layer with a polymer micro-nano structure on the surface. Step 4: Prepare the negative electrode layer on the surface of the negative electrode structure layer with micro / nano-structured polymer using in-situ polymerization: Place the negative electrode structure layer with micro / nano-structured polymer prepared in Step 3 into a reaction vessel, then add deionized water, aniline, perchloric acid, and ammonium persulfate sequentially, and react at a temperature of 0-5℃ for 24-36 hours. After the reaction, wash the negative electrode structure layer with micro / nano-structured polymer with deionized water. The washing process involves washing the surface of the negative electrode structure layer with micro / nano-structured polymer every 16 cm³. 2 -25cm 2 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 to the negative electrode structure layer with micro-nano structure polymer on the surface after the reaction to obtain a negative electrode layer with micro-nano structure polymer on the surface and modified with polyaniline. Step 5: Prepare a negative electrode friction layer on the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline: Spray 0.012-0.032 mL / cm onto the surface of the negative electrode layer with a micro / nano-structured polymer and modified with polyaniline prepared in Step 4. 2 Prepare a dimethylformamide solution with a polymer concentration of 10-30 mg / mL, and then treat it with plasma technology for 1-3 min to obtain a negative electrode friction layer with a polymer micro-nano structure on the surface and solvent resistance. Step 6: The stacked positive electrode substrate, the positive electrode layer prepared in Step 1, and the positive electrode friction layer prepared in Step 2 are used as the positive electrode friction part. The stacked negative electrode substrate, the negative electrode structure layer prepared in Step 3, the negative electrode layer prepared in Step 4, and the negative electrode friction layer prepared in Step 5 are used as the negative electrode friction part. The positive electrode friction part and the negative electrode friction part are allowed to reciprocate to achieve contact and separation between the positive electrode friction layer and the negative electrode friction layer. When they contact, triboelectric power generation occurs, thereby realizing the preparation of the triboelectric nanogenerator.

2. The fabric-based triboelectric nanogenerator according to claim 1, characterized in that, The positive electrode substrate of the positive electrode friction part is made of fabric, the positive electrode layer is made of polyaniline, and the positive electrode friction layer is made of polymer.

3. The fabric-based triboelectric nanogenerator according to claim 1, characterized in that, The negative electrode base material of the negative electrode friction part is fabric, the negative electrode structural layer material is polymer, the negative electrode electrode layer material is polyaniline, and the negative electrode friction layer material is polymer.

4. A fabric-based triboelectric nanogenerator according to claim 1, 2, or 3, characterized in that, The positive electrode friction layer and the negative electrode friction layer are the same or different polymers with micro-nano structures and solvent resistance.

5. A fabric-based triboelectric nanogenerator according to claim 2, characterized in that, The effect is the same if the materials of the positive electrode layer and the positive electrode friction layer are interchanged.

6. The method for preparing a fabric-based triboelectric nanogenerator according to claim 1, characterized in that, The positive or negative electrode substrate comprises a single-layer woven fabric, which is nylon fabric with a pore size of 250-800 mesh.

7. The method for preparing a fabric-based triboelectric nanogenerator according to claim 1, characterized in that, The polymers include: polystyrene, polystyrene-poly(ethylene-butene)-polystyrene block copolymer (SEBS), polyvinylidene fluoride or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDFHFP).

8. The method for preparing a fabric-based triboelectric nanogenerator according to claim 1, characterized in that, The steps of modifying polyaniline in step 1 and preparing micro / nano-structured polymers in step 2 are interchangeable and achieve the same effect.

9. The method for preparing a fabric-based triboelectric nanogenerator according to claim 5, characterized in that, The resistance of the polyaniline electrode is 0.1-10kΩ.

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