Space network cross type elastic friction nanometer generator and preparation method and application thereof

Abstract

The invention provides a spatial network cross type elastic friction nano-generator and a preparation method and application thereof, and relates to the technical field of friction nano-generators, and the method comprises the steps: providing a pouring mold of a spatial network cross geometric structure; filling the silica gel mixture serving as a positive electrode filling material into the filling mold from a filling opening until filling is completed, and taking the silica gel mixture as a positive electrode friction material of the friction nano generator after the positive electrode filling material is completely cured; pouring a negative electrode potting material into the pouring mold from the other pouring opening until the pouring is finished, and taking the negative electrode potting material as a negative electrode friction material and an electrode of the friction nano generator after the negative electrode potting material is completely solidified; and placing the solidified pouring mold in a solvent, and dissolving the pouring mold to obtain the spatial network cross type elastic friction nano generator. The spatial network cross type elastic friction nano generator prepared by the method has high flexibility and deformability, and can adapt to various complex and changeable motions.

Description

Technical Field

[0001] The present invention relates to the technical field of friction nanogenerators, and more specifically, to a spatial network cross-type elastic friction nanogenerator and a preparation method and application thereof. Background Art

[0002] Friction nanogenerators are gradually coming into people's view due to their outstanding advantages of small size, light weight, simple structure and diverse material selection. Its working principle is the coupling of triboelectric effect and electrostatic induction effect. When two different materials come into contact with each other under the drive of external force, positive and negative electrostatic charges will be generated on their surfaces; when the two materials are separated, the positive and negative electrostatic charges will also separate to generate an induced potential difference.

[0003] Since most of the current friction nanogenerators are made of inflexible or non-elastic materials and are subject to the limitations of non-elastic materials, most friction nanogenerators have poor applicability in certain application scenarios, especially poor flexibility and deformability, and cannot be used in environments that require deformation, such as limiting their adaptability and applicability in combination with soft biological tissues or human skin; even if the material is replaced with a flexible material according to traditional processes, the preparation process is relatively complicated, and the resulting friction nanogenerator can also be used in wearable devices, biomedical devices and other fields. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a spatial network cross-type elastic friction nanogenerator and a preparation method and application thereof. The spatial network cross-type elastic friction nanogenerator prepared by this method has high flexibility and deformability, can adapt to various complex and changeable movements, and has broad application prospects in wearable devices, biomedical equipment and other fields.

[0005] In order to achieve the above application purpose, the technical solution adopted in this application is as follows: In a first aspect, the present application provides a method for preparing a spatial network cross-type elastic friction nanogenerator, comprising the following steps: Providing a casting mold with a spatial network cross-geometry structure; in the casting mold, the spatial networks cross and communicate with each other to form two casting pipes, each casting pipe having a separate casting port; The silica gel mixture is used as a positive electrode filling material, and is poured into a filling mold from a filling port until the filling is completed, and after the positive electrode filling material is completely solidified, it is used as a positive electrode friction material of the friction nanogenerator; The negative electrode filling material is poured into the filling mold from another filling port until the filling is completed, and the negative electrode filling material is used as the negative electrode friction material and electrode of the friction nanogenerator after it is completely solidified; the preparation method of the negative electrode filling material is as follows: polydimethylsiloxane PDMS prepolymer is added to the multi-walled carbon nanotube mixed solution, and heated and stirred after ultrasonic dispersion to obtain a conductive PDMS prepolymer; PDMS curing agent is added to the conductive PDMS prepolymer as the negative electrode filling material; The solidified infusion mold is placed in a solvent to dissolve the infusion mold to obtain a spatial network cross-type elastic friction nanogenerator.

[0006] As a further improvement of the present invention, the injection mold is composed of a plurality of hollow body-centered cubic monomers, wherein the plurality of body-centered cubic monomers are interconnected vertically and horizontally to form an injection channel for the conductive PDMS, with corresponding injection ports being provided; in addition, a plurality of body-centered cubic monomers are cross-established with the injection channel for the conductive PDMS, and are interconnected vertically and horizontally to form an injection channel for a silicone mixture, with corresponding injection ports being provided.

[0007] As a further improvement of the present invention, the infusion mold providing the spatial network cross-geometry structure comprises: A tubular spatial network cross geometry model is established, a 3D printing control code is input into the 3D printer, printing materials are set, and a casting mold of the spatial network cross geometry structure is obtained.

[0008] As a further improvement of the present invention, the material of the injection mold is one of ABS, PLA, and PVA.

[0009] As a further improvement of the present invention, the preparation method of the silica gel mixture comprises: Mix part A and part B of the silica gel material in proportion and make sure to scrape the bottom and sides of the mixing container several times. After mixing, place in a vacuum box for vacuum degassing to obtain a silica gel mixture.

[0010] As a further improvement of the present invention, the silicone material in the silicone mixture is one of Ecoflex and Dragon Skin.

[0011] As a further improvement of the present invention, the injection mold is injected by connecting a syringe to an air pump and injecting the air pump pressure.

[0012] As a further improvement of the present invention, in the method for preparing the negative electrode filler: The multi-walled carbon nanotube mixed solution is a multi-walled carbon nanotube toluene mixed solution; After ultrasonic dispersion and heating and stirring, the conductive PDMS prepolymer is obtained, which includes: Adding PDMS prepolymer to the mixed solution of multi-walled carbon nanotubes and toluene, after ultrasonic dispersion, placing in a water bath and heating and stirring until the toluene is completely volatilized, thereby obtaining a conductive PDMS prepolymer; The amount of PDMS curing agent added to the conductive PDMS prepolymer satisfies: the PDMS curing agent is added at a mass ratio of PDMS to curing agent of 10:1.

[0013] As a further improvement of the present invention, the solvent is one of dichloromethane and water.

[0014] In a second aspect, the present application provides a spatial network cross-type elastic friction nanogenerator, which is prepared according to the method for preparing a spatial network cross-type elastic friction nanogenerator.

[0015] In a third aspect, the present application provides a spatial network cross-type elastic friction nanogenerator prepared by the preparation method, and its application in the preparation of flexible and wearable electronic products. Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a method for preparing an elastic friction nanogenerator with a spatial network cross structure. The spatial network cross distribution of the positive and negative friction materials is realized through a casting mold with a spatial network cross geometric structure. This structure not only increases the friction area, but also improves the energy conversion efficiency. The positive electrode adopts a silica gel mixture, and the negative electrode adopts a specially treated conductive PDMS. Both materials have good mechanical strength and wear resistance, and can maintain the stability of the structure during long-term friction. The negative electrode material uses MWCNTs with excellent mechanical properties, good conductivity and strong thermal stability as a conductive filler. The MWCNTs are evenly dispersed in PDMS through a simple process to prepare a flexible and stretchable polymer conductive composite material, which further improves the performance of the generator. The preparation method realizes one-time molding through a casting mold, simplifies the preparation process, and reduces the manufacturing cost. At the same time, the solubility of the casting mold also avoids the additional demoulding process in the traditional preparation method, thereby improving production efficiency. Since the generator has the advantages of high-efficiency energy conversion, environmental protection and energy saving, and wide application, it can be used in various scenarios with rich mechanical energy, especially in the fields of Internet of Things, wearable electronic devices, etc. The generator can be used as a self-powered active sensor to collect energy from the environment and implement active sensing, providing new energy solutions for these fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a three-view drawing of a tubular space network intersection geometric model designed in step 1 of the present invention; Figure 2 It is a physical picture of a spatial network cross structure infusion mold 3D printed in step 1 of the present invention; Figure 3 This is a schematic diagram of the preparation process of the silica gel mixture in step 2 of the present invention; Figure 4 It is a schematic diagram of the preparation process of conductive PDMS in step 5 of the present invention; Figure 5 It is a schematic diagram of the process of pouring and dissolving a space network cross structure pouring mold in the present invention; Figure 6 This is a schematic diagram of a five-layer space network cross elastic friction nanogenerator obtained by the present invention; Figure 7 This is a schematic diagram of the open circuit voltage test results of the product prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0017] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0018] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0019] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0020] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0021] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0022] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also indicate the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass in the embodiment description of the present application can be a mass unit known in the chemical industry such as µg, mg, g, kg, etc.

[0023] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0024] The first aspect of the embodiment of the present application provides a method for preparing a spatial network cross-type elastic friction nanogenerator, comprising the following steps: S1, providing a casting mold with a spatial network cross-geometry structure; the spatial networks in the casting mold are cross-connected and connected to form two casting pipes, each of which has a separate casting port; S2, pouring the silica gel mixture as a positive electrode filling material into a filling mold from a filling port until the filling is completed, and after the positive electrode filling material is completely solidified, it is used as a positive electrode friction material of the friction nanogenerator; S3, pouring the negative electrode filling material into the filling mold from another filling port until the filling is completed, and after the negative electrode filling material is completely solidified, it is used as the negative electrode friction material and electrode of the friction nanogenerator; the preparation method of the negative electrode filling material is: adding polydimethylsiloxane PDMS prepolymer to the multi-walled carbon nanotube mixed solution, heating and stirring after ultrasonic dispersion to obtain a conductive PDMS prepolymer; adding PDMS curing agent to the conductive PDMS prepolymer as the negative electrode filling material; S4, placing the solidified infusion mold in a solvent, dissolving the infusion mold, and obtaining a spatial network cross-type elastic friction nanogenerator.

[0025] The first aspect of the present application provides a method for preparing a space network cross-type elastic friction nanogenerator, wherein the injection mold adopts a space network cross-geometry structure, which is designed to form two independent injection pipes, each of which has a separate injection port. This structure allows the positive and negative friction materials to be interlaced in a specific way, thereby increasing the friction area and improving the energy conversion efficiency. The positive electrode material selects a silicone mixture, which has good mechanical properties and chemical stability and is suitable as a positive electrode friction material for a friction nanogenerator. The silicone mixture is injected into the mold through the injection port, and the positive electrode is formed after it is completely cured. The negative electrode material is a specially treated conductive PDMS. This material is a mixture of multi-walled carbon nanotubes and PDMS, and has good conductivity and mechanical properties. Similarly, the negative electrode material is injected into the mold through another injection port, and the negative electrode friction material and electrode are formed after it is completely cured. The cured injection mold is placed in a solvent and dissolved to obtain a prepared space network cross-type elastic friction nanogenerator.

[0026] As an example, the preparation method realizes a special staggered distribution of positive and negative friction materials through the mold design of a spatial network cross geometry. This structure not only increases the friction area, but also optimizes the charge distribution and transmission path, thereby improving the energy conversion efficiency. The selection of silicone mixture and conductive PDMS makes the prepared friction nanogenerator have good mechanical properties and chemical stability. At the same time, the multi-walled carbon nanotubes in the negative electrode material make PDMS conductive, and no external electrodes are required for electrical connection. The preparation method realizes one-time molding through the infusion mold, avoiding the complicated processing and assembly steps in the traditional preparation method. This not only reduces the manufacturing cost, but also improves the production efficiency.

[0027] Furthermore, the elastic friction nanogenerator formed by the spatial network cross-geometry structure adopts a special staggered distribution of positive and negative friction materials. This design not only increases the friction area, but also makes the charge distribution more uniform, thereby improving the energy conversion efficiency. Through complex geometric design, the structure optimizes the charge transmission path, reduces the charge loss during the transmission process, and further improves the energy conversion efficiency. The selection of silicone mixture and conductive polydimethylsiloxane (PDMS) makes the prepared friction nanogenerator have good mechanical properties and chemical stability. These two materials not only have excellent wear resistance and corrosion resistance, but also maintain stable performance during long-term use. The multi-walled carbon nanotubes in the negative electrode material give PDMS conductivity, so that the generator does not need external electrodes for electrical connection. This innovation not only simplifies the structure of the generator, but also reduces the manufacturing cost.

[0028] As an example, the preparation method achieves one-time molding through an infusion mold, avoiding the complex processing and assembly steps in the traditional preparation method. This innovation not only improves production efficiency, but also reduces manufacturing costs. Compared with the preparation process of traditional generators, the preparation process of elastic friction nanogenerators is simpler and more efficient. This helps to achieve large-scale production and meet market demand. Due to the special staggered distribution and optimized charge transfer path, the elastic friction nanogenerator has a higher energy conversion efficiency. This gives it a significant advantage in collecting and utilizing tiny mechanical energy.

[0029] In a specific embodiment, in combination Figures 1 to 6 The present invention provides a method for preparing a spatial network cross-type elastic friction nanogenerator, and the specific technical solution is: Step 1: Use SOLIDWORKS software to design and establish a tubular spatial network cross geometry model in a computer, input the 3D printing control code into the 3D printer, set the printing material, and obtain a casting mold of the spatial network cross geometry structure.

[0030] More preferably, the printing material is one of ABS (Acrylonitrile Butadiene Styrene), PLA (polylactic acid), and PVA (Polyvinyl Alcohol).

[0031] By manufacturing the injection mold through 3D printing technology, various complex and diverse spatial network cross structures can be produced. Importantly, even if the spatial network cross structure is more complex, its manufacturing cost will not increase significantly. This is because 3D printing is a one-time molding additive manufacturing technology with no seams and welds, which ensures the dimensional accuracy and surface quality of the friction nanogenerator.

[0032] Specifically, Figure 1 and Figure 2 As shown in the figure, as a tubular space network cross geometry model of a small design unit, the model is composed of 6 hollow body-centered cubic monomers, of which 6 body-centered cubic monomers are interconnected up and down, left and right, forming an upper and lower layer, with three structures on each layer, leaving three perfusion ports 1, 2, and 3. The other 4 body-centered cubic monomers are cross-established with the perfusion pipeline of the conductive PDMS, and are also interconnected up and down, left and right, forming a silicone mixture perfusion pipeline, and leaving three perfusion ports 4, 5, and 6. Generate a 3D printing control code and input it into the 3D printer, set the printing material to PLA, and get Figure 2 The final product can be made as shown in the infusion mold of the spatial network cross geometry. Figure 6 The structure shown can be spliced ​​and expanded as needed.

[0033] The elastic triboelectric nanogenerator formed by this spatial network cross-geometry realizes a special staggered distribution of positive and negative friction materials. This structure not only increases the friction area, but also optimizes the charge distribution and transmission path, thereby improving the energy conversion efficiency.

[0034] Step 2, mix and stir the silica gel part A and part B in a ratio of 1:1 by volume or weight, ensure that the bottom and sides of the mixing container are scraped several times, and after the mixing is completed, place in a vacuum box for vacuum degassing. Preferably, the silica gel material is one of Ecoflex and Dragon Skin.

[0035] Step 3, inject the silicone mixture with bubbles removed in step 2 into the syringe, connect the air pump, and pour it into the injection port at one end of the injection pipe of the silicone mixture printed in the injection mold in step 1. The injection is completed when the mixture flows out from the injection port at the other end.

[0036] Step 4: Place the casting mold filled with the silicone mixture in a drying oven at room temperature or 100°C to completely solidify the silicone mixture as the positive electrode friction material of TENG.

[0037] Step 5, weigh multi-walled carbon nanotubes (MWCNTs) and add them to excess toluene (TL), stir and then perform ultrasonic dispersion to uniformly disperse the MWCNTs in the TL to obtain a MWCNTs / TL mixed solution; add PDMS (polydimethylsiloxane) prepolymer to the MWCNTs / TL mixed solution, and after ultrasonic dispersion, obtain a MWCNTs / PDMS prepolymer / TL mixed solution, place the mixed solution in a water bath and heat and stir until TL is completely volatilized to obtain a conductive PDMS prepolymer; after the conductive PDMS prepolymer is cooled, add PDMS curing agent at a mass ratio of PDMS to curing agent of 10:1, and stir thoroughly.

[0038] Step 6, inject the conductive PDMS stirred in step 5 into the syringe, connect the air pump, and pour it into the conductive PDMS pipe at one end of the perfusion mold printed in step 1. The perfusion is completed when the conductive PDMS flows out from the other end.

[0039] Step 7, placing the casting mold filled with conductive PDMS in a drying oven at room temperature or 100°C to completely solidify the conductive PDMS as the negative friction material and electrode of TENG. Preferably, the solvent is one of dichloromethane (dissolving ABS, PLA) or water (dissolving PVA).

[0040] Step 8, placing the cast mold solidified in step 7 in a solvent, dissolving the cast mold, and obtaining a spatial network cross-type elastic friction nanogenerator.

[0041] Therefore, the present invention provides an elastic friction nanogenerator with a spatial network cross structure and a manufacturing method thereof, selects MWCNTs with excellent mechanical properties, good electrical conductivity and strong thermal stability as conductive fillers, and uniformly disperses MWCNTs in PDMS through a simple process to prepare a flexible and stretchable polymer conductive composite material as a negative electrode friction material.

[0042] In the present application, the preparation steps of the above-mentioned space network cross-type elastic friction nanogenerator, each step has important advantages in the preparation of the space network cross-type elastic friction nanogenerator, and together ensures the performance and quality of the generator. The present invention provides a method for manufacturing and dissolving a space network cross-structure casting mold. The method can manufacture various complex and diverse space network cross-structure casting molds through 3D printing technology. Even if the structure is more complex, the manufacturing cost will not increase significantly. The manufactured casting mold has no seams and welding points, which ensures the dimensional accuracy and surface quality of the friction nanogenerator.

[0043] In some embodiments, in step 1: various complex and diverse spatial network cross-geometry models can be designed using SOLIDWORKS software to meet different application requirements. 3D printing technology, as a one-time additive manufacturing technology, can ensure the dimensional accuracy and surface quality of the mold, thereby improving the performance of the generator. Even if the spatial network cross-structure is more complex, the manufacturing cost of 3D printing will not increase significantly, which has high cost-effectiveness.

[0044] For example, in terms of material selection: printing materials such as ABS, PLA, PVA, etc. have good mechanical properties and chemical stability, and are suitable as materials for infusion molds.

[0045] In some embodiments, in step 2: preparation and degassing of silicone mixture, silicone materials such as Ecoflex and Dragon Skin have good elasticity, wear resistance and chemical stability, and are suitable as positive friction materials. Mix and stir in a ratio of 1:1 by volume or weight to ensure that silicone part A and part B are fully mixed to improve the performance of the material. Through vacuum degassing in a vacuum box, bubbles in the silicone mixture can be removed to avoid defects during the curing process and affect the performance of the generator.

[0046] In some embodiments, in step 3: pouring the silicone mixture; pouring using a syringe connected to an air pump can ensure that the silicone mixture is evenly distributed in the mold to avoid the formation of voids or bubbles. Pour from one end of the pouring port, and when the mixture flows out from the other end of the pouring port, the pouring is completed, which can ensure that every corner of the mold is fully filled.

[0047] In some embodiments, in step 4: the silica gel mixture is cured; cured in a drying oven at room temperature or 100°C, and appropriate curing conditions can be selected according to actual needs to improve the curing efficiency. The fully cured silica gel mixture has good mechanical properties and chemical stability, and can be used as the positive electrode friction material of TENG.

[0048] In some embodiments, in step 5: preparation of conductive PDMS prepolymer, the combination of multi-walled carbon nanotubes (MWCNTs) and PDMS prepolymer can prepare a conductive PDMS prepolymer with good conductivity and mechanical properties. By stirring and ultrasonic dispersion, it can be ensured that MWCNTs are evenly dispersed in the PDMS prepolymer to improve the conductive properties. Heating and stirring in a water bath until toluene (TL) is completely volatilized can avoid the influence of solvent residue on the conductive properties.

[0049] In some embodiments, in step 6: conductive PDMS is poured; similar to the silicone mixture pouring, a syringe connected to an air pump is used for pouring, which can ensure that the conductive PDMS is evenly distributed in the mold. Pour in from one end of the pouring port, and the pouring is completed when the conductive PDMS flows out from the other end of the pouring port, which can ensure that every corner of the mold is fully filled.

[0050] In some embodiments, in step 7: the conductive PDMS is cured; similar to the curing of the silica gel mixture, it is cured at room temperature or in a drying oven at 100°C, and appropriate curing conditions can be selected according to actual needs. The fully cured conductive PDMS has good conductivity and mechanical properties and can be used as the negative friction material and electrode of TENG.

[0051] In some embodiments, in step 8: mold dissolution and generator acquisition; selecting a suitable solvent (such as dichloromethane or water) can efficiently dissolve the injection mold to avoid affecting the performance of the generator. After dissolving the mold, a complete and clearly structured spatial network cross-type elastic friction nanogenerator can be obtained, which provides convenience for subsequent testing and application.

[0052] The second purpose of the present application is to provide a spatial network cross-type elastic friction nanogenerator, which is prepared according to the method for preparing a spatial network cross-type elastic friction nanogenerator.

[0053] As an example, the spatial network cross-type elastic friction nanogenerator of the present application works based on the principles of friction electrification and electrostatic induction. When the positive and negative friction materials in its structure rub against each other, due to the difference in electron affinity between different materials, the electrons will be redistributed on the surfaces of the two materials, so that one material is positively charged and the other material is negatively charged. Subsequently, electrostatic induction causes the charge to accumulate on the substrate and the electrode, generating a potential difference. When the friction layer separates, the potential difference causes the current to flow in the circuit, thereby converting mechanical energy into electrical energy.

[0054] The third purpose of the present application is to provide a spatial network cross-type elastic friction nanogenerator prepared by the preparation method, and its application in the preparation of flexible and wearable electronic products.

[0055] This application selects materials with high triboelectric effect and good elasticity, such as stretchable composite materials, which can ensure sufficient charge separation when subjected to external forces. A spatial network cross-type structure design is adopted, which can increase the contact area and friction frequency between materials, thereby improving the efficiency of charge generation. At the same time, the elastic design enables the generator to quickly restore its shape when subjected to external forces and maintain long-term stability. The negative electrode material itself is conductive, so that the generator can be connected to an external circuit without adding electrodes to output the generated electrical energy.

[0056] Furthermore, the space network cross-type elastic friction nanogenerator can collect energy from tiny mechanical energy such as human body movement and environmental vibration, and convert it into electrical energy. This self-powered method can solve the problem of frequent battery replacement or charging of wearable electronic products during long-term use, and achieve continuous and stable energy supply. Because the generator is flexible and elastic, it can be easily integrated into various flexible and wearable electronic products, such as smart bracelets and smart shoes. This integration method does not limit the flexibility of the device or affect the user's wearing experience. Through the collected energy, wearable electronic products can realize more functions, such as health monitoring, sports tracking, communication, etc. The realization of these functions not only improves the use value of the device, but also brings a better user experience to the user. The space network cross-type elastic friction nanogenerator has broad application prospects in the preparation of flexible and wearable electronic products.

[0057] The following describes the invention in conjunction with specific embodiments.

[0058] Example 1 Step 1, such as Figure 1As shown in the figure, a tubular space network cross geometry model was designed by using SOLIDWORKS software in a computer. The model consists of multiple hollow body-centered cubic monomers, of which 6 body-centered cubic monomers are interconnected up and down, left and right to form a perfusion channel for conductive PDMS, leaving three perfusion ports 1, 2, and 3. The other 4 body-centered cubic monomers are cross-established with the perfusion channel of conductive PDMS, and are also interconnected up and down, left and right to form a perfusion channel for silicone mixture, leaving three perfusion ports 4, 5, and 6. A 3D printing control code is generated and input into the 3D printer, and the printing material is set to PLA, and the result is Figure 2 Infusion mold with spatial network cross-section geometry shown.

[0059] Step 2, such as Figure 3 As shown, take 10g of dragon skin 10 part A and 10g of part B in a beaker and mix and stir. Make sure to scrape the bottom and sides of the beaker several times. After mixing, put it into a vacuum box for vacuum degassing for 5 minutes.

[0060] Step 3, inject the dragon skin 10 mixture with bubbles removed in step 2 into the syringe, connect the air pump, and pour it into the injection port 4 of the injection pipe of the silicone mixture printed in the injection mold in step 1. The injection is completed when the mixture flows out from the injection port 6.

[0061] Step 4: Place the casting mold filled with the dragon skin 10 mixture in a drying oven at 100°C for 1 hour to completely solidify the dragon skin 10 mixture as the positive electrode friction material of TENG.

[0062] Step 5, such as Figure 4 As shown, 0.2 g MWCNTs was weighed and added to 40 mL of TL. After stirring for 10 min, ultrasonic dispersion was performed for 1 h to uniformly disperse the MWCNTs in TL to obtain a MWCNTs / TL mixed solution. 5 g PDMS prepolymer was added to the MWCNTs / TL mixed solution. After ultrasonic dispersion for 1 h, a MWCNTs / PDMS prepolymer / TL mixed solution was obtained. The mixed solution was placed in a 80°C water bath and heated and stirred until TL was completely volatilized to obtain a conductive PDMS prepolymer. After the conductive PDMS prepolymer was cooled, 0.5 g PDMS curing agent was added and stirred thoroughly.

[0063] Step 6, inject the conductive PDMS stirred in step 5 into the syringe, connect the air pump, and pour it into the conductive PDMS pipe of the perfusion mold printed in step 1 from the No. 1 perfusion port. The perfusion is completed when the conductive PDMS flows out from the No. 3 perfusion port.

[0064] Step 7: Place the casting mold filled with conductive PDMS in a drying oven at 100°C for 5 h to completely solidify the conductive PDMS as the negative friction material and electrode of TENG.

[0065] Step 8, placing the cast mold cured in step 7 in solvent dichloromethane to dissolve the cast mold to obtain a spatial network cross-elastic friction nanogenerator.

[0066] Example 2 Step 1, such as Figure 1 As shown in the figure, a tubular space network cross geometry model was designed using SOLIDWORKS software in the computer, a 3D printing control code was generated and input into the 3D printer, and the printing material was set to ABS. Figure 2 The infusion mold of the spatial network cross geometric structure shown has the same specific structure as that of embodiment 1.

[0067] Step 2, such as Figure 3 As shown, take 10g of Ecoflex Part A and 10g of Part B in a beaker and mix and stir, making sure to scrape the bottom and sides of the beaker several times. After mixing, put it in a vacuum box for vacuum degassing for 6 minutes.

[0068] Step 3, inject the Ecoflex mixture with bubbles removed in step 2 into the syringe, connect the air pump, and pour it into the injection port 4 of the injection pipe of the silicone mixture printed in the injection mold in step 1. The injection is completed when the mixture flows out from the injection port 6.

[0069] Step 4: Place the casting mold filled with the Ecoflex mixture in a drying oven at 90°C for 1.5 h to completely solidify the Ecoflex mixture as the positive electrode friction material of TENG.

[0070] Step 5, such as Figure 4 As shown, 0.2 g MWCNTs was weighed and added to 50 mL of TL. After stirring for 15 min, ultrasonic dispersion was performed for 1.5 h to uniformly disperse the MWCNTs in TL to obtain a MWCNTs / TL mixed solution. 5 g PDMS prepolymer was added to the MWCNTs / TL mixed solution. After ultrasonic dispersion for 1 h, a MWCNTs / PDMS prepolymer / TL mixed solution was obtained. The mixed solution was placed in a 85°C water bath and heated and stirred until TL was completely volatilized to obtain a conductive PDMS prepolymer. After the conductive PDMS prepolymer was cooled, 0.5 g PDMS curing agent was added and stirred thoroughly.

[0071] Step 6, inject the conductive PDMS stirred in step 5 into the syringe, connect the air pump, and pour it into the conductive PDMS pipe of the perfusion mold printed in step 1 from the No. 1 perfusion port. The perfusion is completed when the conductive PDMS flows out from the No. 3 perfusion port.

[0072] Step 7: Place the casting mold filled with conductive PDMS in a drying oven at 100°C for 5 h to completely solidify the conductive PDMS as the negative friction material and electrode of TENG.

[0073] Step 8, placing the cast mold cured in step 7 in solvent dichloromethane to dissolve the cast mold to obtain a spatial network cross-elastic friction nanogenerator.

[0074] Example 3 Step 1, such as Figure 1 As shown in the figure, a tubular space network cross geometry model was designed using SOLIDWORKS software in the computer, and the printing material was set to PLA. Figure 2 The infusion mold of the spatial network cross geometric structure shown has the same specific structure as that of embodiment 1.

[0075] Step 2, such as Figure 3 As shown, take 10g of Ecoflex Part A and 10g of Part B in a beaker and mix and stir, making sure to scrape the bottom and sides of the beaker several times. After mixing, put it in a vacuum box for vacuum degassing for 5 minutes.

[0076] Step 3, inject the Ecoflex mixture with bubbles removed in step 2 into the syringe, connect the air pump, and pour it into the injection port 4 of the injection pipe of the silicone mixture printed in the injection mold in step 1. The injection is completed when the mixture flows out from the injection port 6.

[0077] Step 4: Place the casting mold filled with the Ecoflex mixture in a drying oven at 95°C for 1 h to completely solidify the Ecoflex mixture as the positive electrode friction material of TENG.

[0078] Step 5, such as Figure 4 As shown, 0.2 g MWCNTs was weighed and added to 55 mL of TL. After stirring for 10 min, ultrasonic dispersion was performed for 0.9 h to uniformly disperse the MWCNTs in TL to obtain a MWCNTs / TL mixed solution. 5 g PDMS prepolymer was added to the MWCNTs / TL mixed solution. After ultrasonic dispersion for 1 h, a MWCNTs / PDMS prepolymer / TL mixed solution was obtained. The mixed solution was placed in a 83°C water bath and heated and stirred until TL was completely volatilized to obtain a conductive PDMS prepolymer. After the conductive PDMS prepolymer was cooled, 0.5 g PDMS curing agent was added and stirred thoroughly.

[0079] Step 6, inject the conductive PDMS stirred in step 5 into the syringe, connect the air pump, and pour it into the conductive PDMS pipe of the perfusion mold printed in step 1 from the No. 1 perfusion port. The perfusion is completed when the conductive PDMS flows out from the No. 3 perfusion port.

[0080] Step 7: Place the casting mold filled with conductive PDMS in a drying oven at 105°C for 4.5 h to completely solidify the conductive PDMS, which serves as the negative friction material and electrode of TENG.

[0081] Step 8, placing the cast mold cured in step 7 in solvent dichloromethane to dissolve the cast mold to obtain a spatial network cross-elastic friction nanogenerator.

[0082] Example 4 Step 1, such as Figure 1 As shown in the figure, a tubular space network cross geometry model was designed using SOLIDWORKS software in the computer, a 3D printing control code was generated and input into the 3D printer, and the printing material was set to PVA. Figure 2 The infusion mold of the spatial network cross geometric structure shown has the same specific structure as that of embodiment 1.

[0083] Step 2, such as Figure 3 As shown, take 10g of dragon skin 10 part A and 10g of part B in a beaker and mix and stir. Make sure to scrape the bottom and sides of the beaker several times. After mixing, put it into a vacuum box for vacuum degassing for 5 minutes.

[0084] Step 3, inject the dragon skin 10 mixture with bubbles removed in step 2 into the syringe, connect the air pump, and pour it into the injection port 4 of the injection pipe of the silicone mixture printed in the injection mold in step 1. The injection is completed when the mixture flows out from the injection port 6.

[0085] Step 4: Place the casting mold filled with the dragon skin 10 mixture in a drying oven at 100°C for 1 hour to completely solidify the dragon skin 10 mixture as the positive electrode friction material of TENG.

[0086] Step 5, such as Figure 4 As shown, 0.2 g MWCNTs was weighed and added to 40 mL of TL. The mixture was stirred for 10 min and then ultrasonically dispersed for 1 h to uniformly disperse the MWCNTs in TL to obtain a MWCNTs / TL mixed solution. 5 g PDMS prepolymer was added to the MWCNTs / TL mixed solution and ultrasonically dispersed for 1 h to obtain a MWCNTs / PDMS prepolymer / TL mixed solution. The mixed solution was placed in a 85°C water bath and heated and stirred until TL was completely volatilized to obtain a conductive PDMS prepolymer. After the conductive PDMS prepolymer was cooled, 0.5 g PDMS curing agent was added and stirred thoroughly.

[0087] Step 6, inject the conductive PDMS stirred in step 5 into the syringe, connect the air pump, and pour it into the conductive PDMS pipe of the perfusion mold printed in step 1 from the No. 1 perfusion port. The perfusion is completed when the conductive PDMS flows out from the No. 3 perfusion port.

[0088] Step 7: Place the casting mold filled with conductive PDMS in a drying oven at 90°C for 6 h to completely solidify the conductive PDMS as the negative friction material and electrode of TENG.

[0089] Step 8, placing the cast mold solidified in step 7 into solvent water, dissolving the cast mold, and obtaining a spatial network cross-elastic friction nanogenerator.

[0090] Example 5 Step 1, such as Figure 1 As shown in the figure, a tubular space network cross geometry model was designed using SOLIDWORKS software in the computer, a 3D printing control code was generated and input into the 3D printer, and the printing material was set to ABS. Figure 2 The infusion mold of the spatial network cross geometric structure shown has the same specific structure as that of embodiment 1.

[0091] Step 2, such as Figure 3 As shown, take 10g of Ecoflex Part A and 10g of Part B in a beaker and mix and stir, making sure to scrape the bottom and sides of the beaker several times. After mixing, put it in a vacuum box for vacuum degassing for 5 minutes.

[0092] Step 3, inject the Ecoflex mixture with bubbles removed in step 2 into the syringe, connect the air pump, and pour it into the injection port 4 of the injection pipe of the silicone mixture printed in the injection mold in step 1. The injection is completed when the mixture flows out from the injection port 6.

[0093] Step 4: Place the casting mold filled with the Ecoflex mixture in a drying oven at 105°C for 1.2 h to completely solidify the Ecoflex mixture as the positive electrode friction material of TENG.

[0094] Step 5, such as Figure 4 As shown, 0.2 g MWCNTs was weighed and added to 40 mL of TL. After stirring for 10 min, ultrasonic dispersion was performed for 1 h to uniformly disperse the MWCNTs in TL to obtain a MWCNTs / TL mixed solution. 5 g PDMS prepolymer was added to the MWCNTs / TL mixed solution. After ultrasonic dispersion for 1 h, a MWCNTs / PDMS prepolymer / TL mixed solution was obtained. The mixed solution was placed in a 80°C water bath and heated and stirred until TL was completely volatilized to obtain a conductive PDMS prepolymer. After the conductive PDMS prepolymer was cooled, 0.5 g PDMS curing agent was added and stirred thoroughly.

[0095] Step 6, inject the conductive PDMS stirred in step 5 into the syringe, connect the air pump, and pour it into the conductive PDMS pipe of the perfusion mold printed in step 1 from the No. 1 perfusion port. The perfusion is completed when the conductive PDMS flows out from the No. 3 perfusion port.

[0096] Step 7: Place the casting mold filled with conductive PDMS in a drying oven at 108°C for 5.1 h to completely solidify the conductive PDMS, which serves as the negative friction material and electrode of TENG.

[0097] Step 8, placing the cast mold cured in step 7 in solvent dichloromethane to dissolve the cast mold to obtain a spatial network cross-elastic friction nanogenerator.

[0098] During the experiment, an electrometer was used to measure the open circuit voltage of the triboelectric nanogenerator. The exciter frequency and displacement were controlled to test the extrusion output of the triboelectric nanogenerator. Example 3 was used as a specific example. The ambient temperature was 23°C, the humidity was 33%, the exciter frequency was set to 1-5 Hz, and the extrusion contact force was fixed to 2N. The experimental results are shown in Figure 3. Figure 7 As shown: the open circuit voltage is 15.31V at 1Hz, rises to 18.54V at 2Hz, reaches 19.41V at 3Hz, further increases to 20.73V at 4Hz, and finally reaches 21.21V at 5Hz. As the extrusion frequency increases, the open circuit voltage shows an upward trend.

[0099] The open circuit voltage of TENG was measured using an electrometer. The extrusion output test of TENG was performed by controlling the frequency and displacement of the exciter. The exciter frequency was set to 1~5Hz, and the fixed extrusion contact force was 2N. Open circuit voltage change: As the exciter frequency increased from 1Hz to 5Hz, the open circuit voltage of TENG gradually increased from 15.31V to 21.21V. This shows that under a fixed contact force, increasing the exciter frequency can effectively increase the open circuit voltage of TENG.

[0100] The experimental results clearly show that the open circuit voltage of TENG increases with the increase of the exciter frequency. This is because the increase in frequency reduces the time for transferring charges and accelerates charge accumulation, thereby improving the energy conversion efficiency.

[0101] Therefore, it can be concluded that the embodiment of the present invention successfully prepared an elastic friction nanogenerator with a spatial network cross structure, and its performance was tested by controlling the exciter frequency. The experimental results show that increasing the exciter frequency can significantly increase the open circuit voltage of TENG, which provides a useful reference for the further optimization and practical application of TENG.

[0102] The preferred embodiments in this specification are only to further explain the present invention, and the above content cannot be considered that the present invention is limited to these descriptions. For ordinary technicians in this technical field, several changes and substitutions made without departing from the principle of the present invention should be regarded as belonging to the protection scope of the present invention.

Claims

1. A method for preparing a spatial network cross-type elastic friction nanogenerator, characterized in that: The steps include: Providing a casting mold with a spatial network cross-geometry structure; in the casting mold, the spatial networks cross and communicate with each other to form two casting pipes, each casting pipe having a separate casting port; The silica gel mixture is used as a positive electrode filling material, and is poured into a filling mold from a filling port until the filling is completed, and after the positive electrode filling material is completely solidified, it is used as a positive electrode friction material of the friction nanogenerator; The negative electrode filling material is poured into the filling mold from another filling port until the filling is completed, and the negative electrode filling material is used as the negative electrode friction material and electrode of the friction nanogenerator after it is completely solidified; the preparation method of the negative electrode filling material is as follows: polydimethylsiloxane PDMS prepolymer is added to the multi-walled carbon nanotube mixed solution, and heated and stirred after ultrasonic dispersion to obtain a conductive PDMS prepolymer; PDMS curing agent is added to the conductive PDMS prepolymer as the negative electrode filling material; The solidified infusion mold is placed in a solvent to dissolve the infusion mold to obtain a spatial network cross-type elastic friction nanogenerator.

2. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The injection mold is composed of a plurality of hollow body-centered cubic monomers, wherein the plurality of body-centered cubic monomers are interconnected vertically and horizontally to form an injection channel for conductive PDMS, with corresponding injection ports being left; in addition, a plurality of body-centered cubic monomers are cross-established with the injection channels for conductive PDMS, and are interconnected vertically and horizontally to form an injection channel for a silicone mixture, with corresponding injection ports being left.

3. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The infusion mold providing a spatial network cross-geometry structure comprises: A tubular spatial network cross geometry model is established, a 3D printing control code is input into the 3D printer, printing materials are set, and a casting mold of the spatial network cross geometry structure is obtained.

4. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The material of the injection mold is one of ABS, PLA and PVA.

5. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The preparation method of the silica gel mixture comprises: Mix part A and part B of the silica gel material in proportion and make sure to scrape the bottom and sides of the mixing container several times. After mixing, place in a vacuum box for vacuum degassing to obtain a silica gel mixture.

6. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The silicone material in the silicone mixture is one of Ecoflex and Dragon Skin.

7. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The injection mold is injected by connecting a syringe to an air pump and injecting the air through the pressure of the air pump.

8. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: In the preparation method of the negative electrode filling material: The multi-walled carbon nanotube mixed solution is a multi-walled carbon nanotube toluene mixed solution; After ultrasonic dispersion and heating and stirring, the conductive PDMS prepolymer is obtained, which includes: Adding PDMS prepolymer to the mixed solution of multi-walled carbon nanotubes and toluene, after ultrasonic dispersion, placing in a water bath and heating and stirring until the toluene is completely volatilized, thereby obtaining a conductive PDMS prepolymer; The amount of PDMS curing agent added to the conductive PDMS prepolymer satisfies: the PDMS curing agent is added at a mass ratio of PDMS to curing agent of 10:

1.

9. The method for preparing a spatial network cross-type elastic friction nanogenerator according to claim 1, characterized in that: The solvent is one of dichloromethane or water.

10. A spatial network cross-type elastic friction nanogenerator, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.

11. A spatial network cross-type elastic friction nanogenerator prepared by the preparation method according to any one of claims 1 to 9, characterized in that: Application in the preparation of flexible and wearable electronic products.

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