Flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density and preparation method thereof

Abstract

The present application relates to a kind of high elasticity, high packing power density flexible aramid-based triboelectric nanoelectrode material and its preparation method, high elasticity, high packing power density flexible aramid-based triboelectric electrode material is structured using electrospinning and rubber in situ infiltration.The meta-aramid solution is infiltrated into the brominated butyl rubber / conductive carbon black solution containing cationic group ionic liquid after electrospinning, and asymmetric flexible aramid-based triboelectric electrode material is formed by in-situ reaction.Further assembled into high packing power density underwater triboelectric nanogenerator.Due to the strong cation contained in the cationic group ionic liquid and the π electron of meta-aramid, brominated butyl rubber / conductive carbon black respectively forms the strong interface interaction of π electron-strong cation, its elasticity and triboelectric output performance are significantly improved.At the same time, based on the strength of aramid matrix itself, the underwater triboelectric nanogenerator constructed does not need external support, and the packing power density is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of triboelectric nanoelectrode materials, in particular to a flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density and a preparation method thereof. BACKGROUND

[0002] In 2012, the academician Wang Zhonglin's team first invented the triboelectric nanogenerator, marking the beginning of a new field of energy harvesting and self-driven sensing. Based on the principles of contact electrification and electrostatic induction, triboelectric nanogenerators can efficiently harvest the widespread and ubiquitous mechanical energy around us, providing a paradigm for self-driven systems, future energy technologies, and high-entropy energy utilization. Among these, underwater triboelectric nanogenerators, as a new energy harvesting technology, utilize the triboelectric effect to convert mechanical energy into electrical energy underwater, with broad application prospects such as underwater sensors, microelectronic devices, and ocean energy harvesting. However, these generators face challenges in practical applications, such as large size and low output performance. Traditional underwater triboelectric nanogenerators require a larger volume to increase the friction surface area, thereby improving energy output, but this also increases system complexity and manufacturing costs, such as Chinese patents CN117937881A and CN117738840A. To overcome these problems, researchers are exploring new design concepts, such as optimizing materials and improving structural design. In addition, the triboelectric effect in underwater environments is affected by water flow and pressure, reducing the power generation capacity. Researchers are trying to improve the performance of triboelectric nanogenerators through nanotechnology and materials science, developing more efficient materials and structural designs to address the issues of large size and low performance.

[0003] Aramid is one of the strongest chemical fibers made by humans. Therefore, choosing aramid as the substrate of the unsupported underwater triboelectric nanogenerator is a good choice. However, aramid material is relatively rigid and difficult to exhibit excellent triboelectric output performance in complex ocean current environments. Electrospun films prepared by electrospinning technology exhibit higher triboelectric output compared to dense films. Among them, constructing an electrode material sensitive to micro-mechanical waves can more easily maintain the simplicity of the triboelectric nanogenerator. Rigid substrate triboelectric electrode materials exhibit stable shape retention and stable output, but their triboelectric output performance is relatively low under micro-mechanical impact. In contrast, soft elastic triboelectric electrodes based on advanced porous materials have been used to collect triboelectric energy from micro-mechanical impact while significantly reducing mechanical performance. Therefore, in the electrode materials of underwater triboelectric nanogenerators, balancing the output stability of rigid substrates and the output performance of soft substrates is a promising research direction.

[0004] Therefore, the aramid-based electrode material with high elasticity and high packing power density has important significance in the practical application of underwater triboelectric nanogenerator. The unique structure endows the material with excellent strength and flexibility, which is suitable for manufacturing lightweight and high-performance materials, and endows it with the potential of underwater high-efficiency energy collection. Such materials not only help to reduce the structural burden and improve the performance, but also can be applied to wearable, engineering and other fields, showing the potential of multi-aspect application. SUMMARY

[0005] In view of the above problems, the purpose of the present application is to provide a flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density and a preparation method thereof.

[0006] The technical solution of the present application to solve the above technical problems is as follows:

[0007] The preparation method of the flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density comprises the following steps:

[0008] Step 1: Dissolve meta-aramid in an organic solvent to obtain a meta-aramid solution, and use the meta-aramid solution for electrospinning to obtain a meta-aramid nanofiber membrane;

[0009] Step 2: Blend the ionic liquid with cationic groups, butyl rubber bromide and conductive carbon black to prepare a conductive rubber emulsion;

[0010] Step 3: Stack multiple layers of meta-aramid together and immerse them in the conductive rubber emulsion obtained in the previous step, then take them out and dry them at high temperature to obtain a flexible aramid-based triboelectric electrode material.

[0011] Further, in step 1, lithium bromide and N,N dimethylacetamide are used to dissolve meta-aramid, and the mass fractions of meta-aramid, lithium bromide and N,N dimethylacetamide are 8%, 10% and 82% respectively, and the dissolution temperature is between 60-90℃.

[0012] Further, during electrospinning, the positive voltage of the electrospinning machine is +18kV, the negative voltage is -6kV, the spinning speed is between 1-1.5mL / h, the spinning temperature is greater than 15℃, the humidity is less than 50%, the spinning solution is not less than 5mL, and the needle type is 23G.

[0013] Further, in step 3, the mass fractions of the ionic liquid with cations, butyl rubber bromide, conductive carbon black and tetrahydrofuran are 0.21%, 20.92%, 0.44% and 78.43% respectively,

[0014] Further, the ionic liquid with cations includes any one of butyl imidazole, 1-decyl-3-methyl imidazole tetrafluoroborate, 1-alkyl-2,3-dimethyl imidazole and 2-alkyl-methyl imidazole.

[0015] Further, in step 3, the number of layers of the meta-aramid film is three, the size is 5 cm x 5 cm, and the content of the conductive rubber emulsion is 5-25 mL, and the oven temperature is between 110-120°C.

[0016] The flexible aramid-based triboelectric nanoelectrode material has high elasticity and high packing power density, and is prepared by the above method.

[0017] The application has the following beneficial effects: on the one hand, the π-electrons in the aromatic benzene ring and the imidazole ring in the meta-aramid molecular chain interact with the imidazole cation of the ionic liquid with a cationic group. This interaction enhances the binding ability between the butyl imidazole and the meta-aramid surface. On the other hand, the aromatic benzene ring in the conductive carbon black in the brominated butyl rubber / conductive carbon black interacts with the imidazole ring of the ionic liquid, forming a stable ionomer. Based on the strong interfacial interaction between the ionic liquid and the meta-aramid and the brominated butyl rubber / conductive carbon black, the interface compatibility of the aramid-based triboelectric electrode material formed by the brominated butyl rubber / conductive carbon black immersed in the meta-aramid electrospun film is improved, resulting in a significant increase in elasticity. In addition, the brominated butyl rubber / conductive carbon black forms an asymmetric gradient structure in the electrospun meta-aramid film (pure meta-aramid on the surface as a triboelectric dielectric layer, and the lower layer of meta-aramid / brominated butyl rubber / conductive carbon black as a conductive layer), resulting in a significant increase in triboelectric output performance. The high breaking strength, high elasticity, and high triboelectric output performance of the aramid-based underwater triboelectric nanogenerator play a crucial role in the underwater triboelectric nanogenerator without external support. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 The figure is a schematic diagram of the method flow of the application;

[0019] Figure 2 The figure is an optical image of the aramid-based triboelectric electrode;

[0020] Figure 3 The figure is an optical image of the aramid-based triboelectric nanogenerator;

[0021] Figure 4 The figure is a tensile curve of the aramid-based triboelectric electrode;

[0022] Figure 5 The figure is an optical image of the aramid-based triboelectric nanogenerator under various compression and rebound;

[0023] Figure 6 The figure is the output voltage of the underwater triboelectric nanogenerator of the aramid-based triboelectric nanogenerator. DETAILED DESCRIPTION

[0024] The principles and characteristics of the present application are described below in conjunction with specific embodiments, and the examples are used to explain the present application and are not intended to limit the scope of the present application.

[0025] As shown in Figure 1 , the flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density is:

[0026] Step one, m-aramid is dissolved with lithium bromide and N,N dimethylacetamide solvent;

[0027] Step two, the obtained m-aramid solution is formed into a film by electrospinning;

[0028] Step three, cationic group-containing ionic liquid, brominated butyl rubber and conductive carbon black are blended to prepare a conductive rubber emulsion;

[0029] Step four, the multilayer m-aramid is immersed in the conductive rubber emulsion and dried at high temperature to obtain a flexible aramid-based triboelectric electrode material;

[0030] Step five, the flexible aramid-based triboelectric electrode material is assembled with polyvinylidene fluoride, polyimide and other materials to form an underwater triboelectric nanogenerator.

[0031] Specifically, in the step one, the mass ratio of m-aramid, lithium bromide and N,N dimethylacetamide is 8%, 10% and 82%, and the dissolution temperature is between 60-90℃.

[0032] Specifically, in the step two, the electrospinning machine has a positive voltage of +18kV and a negative voltage of -6kV, the spinning speed is between 1-1.5mL / h, the spinning temperature is greater than 15℃, the humidity is less than 50%, the spinning solution is not less than 5mL, and the needle type is 23G.

[0033] Specifically, in the step three, the mass ratio of cationic group-containing ionic liquid, brominated butyl rubber, conductive carbon black and tetrahydrofuran is 0.21%, 20.92%, 0.44% and 78.43%, wherein the cationic ionic liquid includes butyl imidazole, 1-decyl-3-methyl imidazole tetrafluoroborate, 1-alkyl-2,3-dimethyl imidazole and 2-alkyl-methyl imidazole, etc.

[0034] Specifically, in the step four, the number of layers of the m-aramid film is fixed at three, the size is 5cm x 5cm, the content of the conductive rubber emulsion is 5-25mL, and the oven temperature is between 110-120℃.

[0035] Specifically, in the fifth step, the materials and actions are polyvinylidene fluoride film (triboelectric negative electrode material), flexible copper adhesive tape (conductive layer), polyimide adhesive tape (encapsulation material), polyethylene film (encapsulation material) and wire, wherein the electrode material and the conductive layer are encapsulated by the polyimide adhesive tape, and then the polyethylene film is encapsulated by a heating plastic encapsulation machine.

[0036] As shown in Figure 1 The method flow of the present application comprises the following aspects: using lithium bromide and N,N dimethylacetamide solvent to dissolve meta-aramid; using electrostatic spinning to form a film from the obtained meta-aramid solution; blending butyl imidazole, butyl rubber and conductive carbon black to prepare a conductive rubber emulsion; immersing the multi-layer meta-aramid in the conductive rubber emulsion and drying at high temperature to obtain a flexible aramid-based triboelectric electrode material; and assembling the flexible aramid-based triboelectric electrode material with polyvinylidene fluoride, polyimide and other materials to form an underwater triboelectric nanogenerator.

[0037] As shown in Figure 2 The aramid-based triboelectric electrode exhibits the result characteristics that the upper surface is meta-aramid and the lower surface is a meta-aramid / butyl rubber bromide / conductive carbon black composite.

[0038] As shown in Figure 3 The aramid-based triboelectric nanogenerator exhibits the characteristic of small overall volume.

[0039] As shown in Figure 4 The aramid-based triboelectric electrode has an elongation at break of more than 100% and a breaking strength of more than 50 mPa, showing superior mechanical strength and tensile resistance.

[0040] As shown in Figure 5 The aramid-based triboelectric nanogenerator shows superior bending resistance and torsion resilience, showing application potential in resisting water flow underwater.

[0041] As shown in Figure 6 The maximum output voltage of the aramid-based triboelectric nanogenerator reaches 200 V, and the higher the frequency of the water wave, the more the triboelectric peak value and the higher the average voltage.

[0042] Example one:

[0043] The preparation method of the aramid-based underwater triboelectric nanogenerator with high elasticity and high packing power density comprises the following steps:

[0044] Step one: using 4 g of lithium bromide and 41 g of N,N dimethylacetamide solvent to dissolve 5 g of meta-aramid at 80℃;

[0045] Step two, 10 mL meta-aramid solution was electrospun into film under the conditions of positive voltage +18 kV, negative voltage -6 kV, 1 mL / h spinning speed, spinning temperature 30℃, humidity 40%, 23G needle;

[0046] Step three, 0.21 g of butyl imidazole, 20.92 g of butyl rubber bromide and 0.44 g of conductive carbon black were blended with 78.43 g of tetrahydrofuran to prepare a conductive rubber emulsion;

[0047] Step four, three layers of meta-aramid (5 cm x 5 cm) were immersed in 5, 10, 15, 20, 25 mL of conductive rubber emulsion and dried at 110℃ to obtain a flexible aramid-based triboelectric electrode material;

[0048] Step five, the flexible aramid-based triboelectric electrode was assembled with a polyvinylidene fluoride film, a flexible copper tape, a polyimide tape, a polyethylene film and a wire to form a triboelectric nanogenerator, and then the polyethylene film was plasticized using a heating plasticizer. A high-elasticity, high-piled power density aramid-based underwater triboelectric nanogenerator was obtained.

[0049] Example two:

[0050] The preparation method of the high-elasticity, high-piled power density aramid-based underwater triboelectric nanogenerator is:

[0051] Step one, 5 g of meta-aramid was dissolved in 4 g of lithium bromide and 41 g of N,N-dimethylacetamide solvent at 80℃;

[0052] Step two, 10 mL meta-aramid solution was electrospun into film under the conditions of positive voltage +18 kV, negative voltage -6 kV, 1 mL / h spinning speed, spinning temperature 30℃, humidity 40%, 23G needle;

[0053] Step three, 0.21 g of 1-decyl-3-methyl imidazole tetrafluoroborate, 20.92 g of butyl rubber bromide and 0.44 g of conductive carbon black were blended with 78.43 g of tetrahydrofuran to prepare a conductive rubber emulsion;

[0054] Step four, three layers of meta-aramid (5 cm x 5 cm) were immersed in 10 mL of conductive rubber emulsion and dried at 110℃ to obtain a flexible aramid-based triboelectric electrode material;

[0055] Step five, the flexible aramid-based triboelectric electrode was assembled with a polyvinylidene fluoride film, a flexible copper tape, a polyimide tape, a polyethylene film and a wire to form a triboelectric nanogenerator, and then the polyethylene film was plasticized using a heating plasticizer. A high-elasticity, high-piled power density aramid-based underwater triboelectric nanogenerator was obtained.

[0056] Example Three:

[0057] A preparation method of the aramid-based underwater triboelectric nanogenerator with high elasticity and high packing power density, the preparation method comprising:

[0058] Step one, 5 g of meta-aramid is dissolved in 4 g of lithium bromide and 41 g of N,N-dimethylacetamide solvent at 80°C;

[0059] Step two, 10 mL of meta-aramid solution is electrospun into a film under the conditions of positive voltage +18 kV, negative voltage -6 kV, spinning speed 1 mL / h, spinning temperature 30°C, humidity 40%, and 23G needle;

[0060] Step three, 0.21 g of 1-decyl-3-methylimidazolium hexafluorophosphate, 20.92 g of brominated butyl rubber, and 0.44 g of conductive carbon black are blended with 78.43 g of tetrahydrofuran to prepare a conductive rubber emulsion;

[0061] Step four, three layers of meta-aramid (5 cm x 5 cm) are immersed in 10 mL of the conductive rubber emulsion and dried at high temperature of 110°C to obtain a flexible aramid-based triboelectric electrode material;

[0062] Step five, the flexible aramid-based triboelectric electrode is assembled with a polyvinylidene fluoride film, a flexible copper tape, a polyimide tape, a polyethylene film, and a wire to form a triboelectric nanogenerator, and then the polyethylene film is plasticized by using a heating plasticizer. Thus, an aramid-based underwater triboelectric nanogenerator with high elasticity and high packing power density is obtained.

[0063] Example Four:

[0064] A preparation method of the aramid-based underwater triboelectric nanogenerator with high elasticity and high packing power density, the preparation method comprising:

[0065] Step one, 5 g of meta-aramid is dissolved in 4 g of lithium bromide and 41 g of N,N-dimethylacetamide solvent at 80°C;

[0066] Step two, 10 mL of meta-aramid solution is electrospun into a film under the conditions of positive voltage +18 kV, negative voltage -6 kV, spinning speed 1 mL / h, spinning temperature 30°C, humidity 40%, and 23G needle;

[0067] Step three, 0.21 g of 1-decyl-3-methylimidazolium hexafluorophosphate, 20.92 g of brominated butyl rubber, and 0.44 g of conductive carbon black are blended with 78.43 g of tetrahydrofuran to prepare a conductive rubber emulsion;

[0068] Step four, three layers of meta-aramid (5 cm x 5 cm) are soaked in 10 mL of conductive rubber emulsion and dried at high temperature of 110°C to obtain a flexible aramid-based triboelectric electrode material;

[0069] Step five, the flexible aramid-based triboelectric electrode is assembled with a polyvinylidene fluoride film, a flexible copper tape, a polyimide tape, a polyethylene film and a wire to form a triboelectric nanogenerator, and then the polyethylene film is plasticized by using a heating plasticizer. Thus, a high-elasticity and high-power-density aramid-based underwater triboelectric nanogenerator is obtained.

[0070] Example four:

[0071] The preparation method of the high-elasticity and high-power-density aramid-based underwater triboelectric nanogenerator is as follows:

[0072] Step one, 5 g of meta-aramid is dissolved in 4 g of lithium bromide and 41 g of N,N-dimethylacetamide solvent at 80°C;

[0073] Step two, 10 mL of meta-aramid solution is electrospun into a film under the conditions of positive voltage +18 kV, negative voltage -6 kV, spinning speed 1 mL / h, spinning temperature 30°C, humidity 40%, and 23G needle;

[0074] Step three, 0.21 g of 2-alkyl-methyl imidazole, 20.92 g of butyl rubber bromide and 0.44 g of conductive carbon black are blended with 78.43 g of tetrahydrofuran to prepare a conductive rubber emulsion;

[0075] Step four, three layers of meta-aramid (5 cm x 5 cm) are soaked in 10 mL of conductive rubber emulsion and dried at high temperature of 110°C to obtain a flexible aramid-based triboelectric electrode material;

[0076] Step five, the flexible aramid-based triboelectric electrode is assembled with a polyvinylidene fluoride film, a flexible copper tape, a polyimide tape, a polyethylene film and a wire to form a triboelectric nanogenerator, and then the polyethylene film is plasticized by using a heating plasticizer. Thus, a high-elasticity and high-power-density aramid-based underwater triboelectric nanogenerator is obtained.

[0077] In the above examples, the butyl imidazole system has the optimal mechanical property, because the cationic amount of butyl imidazole is the largest per unit mass.

[0078] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density, characterized in that, Specifically, the following steps are included: Step 1: Dissolve meta-aramid in an organic solvent to obtain a meta-aramid solution, and then electrospin the meta-aramid solution to obtain a meta-aramid nanofiber membrane. Step 2: Prepare a conductive rubber emulsion by blending an ionic liquid with cationic groups, brominated butyl rubber, and conductive carbon black. Step 3: Stack multiple layers of meta-aramid and immerse them together in the conductive rubber emulsion obtained in the previous step. After removal and drying, a flexible aramid-based triboelectric electrode material is obtained. In the flexible aramid-based triboelectric electrode material, brominated butyl rubber / conductive carbon black forms an asymmetric gradient structure in the electrospun meta-aramid membrane. The pure meta-aramid on the surface serves as the triboelectric dielectric layer, while the lower meta-aramid / bromobutyl rubber / conductive carbon black layer serves as the conductive layer.

2. The method for preparing the highly elastic, high-power-density flexible aramid-based triboelectric nanoelectrode material according to claim 1, characterized in that, In step 1, lithium bromide and N,N-dimethylacetamide are used to dissolve meta-aramid, with the mass fractions of meta-aramid, lithium bromide and N,N-dimethylacetamide being 8%, 10% and 82%, respectively, and the dissolution temperature being between 60 and 90°C.

3. The method for preparing the highly elastic, high-power-density flexible aramid-based triboelectric nanoelectrode material according to claim 1, characterized in that, During electrospinning, the positive voltage of the electrospinning machine is +18kV and the negative voltage is -6kV. The spinning speed is between 1 and 1.5mL / h, the spinning temperature is greater than 15℃, the humidity is less than 50%, the spinning solution is not less than 5mL, and the needle type is 23G.

4. The method for preparing the highly elastic, high-power-density flexible aramid-based triboelectric nanoelectrode material according to claim 1, characterized in that, In step 3, the mass fractions of the cationic liquid, brominated butyl rubber, conductive carbon black, and tetrahydrofuran are 0.21%, 20.92%, 0.44%, and 78.43%, respectively.

5. The method for preparing the highly elastic, high-power-density flexible aramid-based triboelectric nanoelectrode material according to claim 1, characterized in that, The cation-containing ionic liquid includes any one of butylimidazolium, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-alkyl-2,3-dimethylimidazolium, and 2-alkyl-methylimidazolium.

6. The method for preparing the highly elastic, high-power-density flexible aramid-based triboelectric nanoelectrode material according to claim 1, characterized in that, In step 3, the meta-aramid film has three layers, a size of 5cm×5cm, a conductive rubber emulsion content of 5-25mL, and an oven temperature between 110-120℃.

7. A flexible aramid-based triboelectric nanoelectrode material with high elasticity and high packing power density, characterized in that, Prepared by the method described in any one of claims 1-6.

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