Super-tough flexible water-repellent functional layer and its manufacturing method and application

Abstract

The application discloses a super-tough flexible water-volte function layer and a preparation method and application thereof. The flexible water-volte function layer comprises a porous network framework and a polymer material, the porous network framework comprises a plurality of polar nanoparticles gathered, the polymer material is used at least for connecting adjacent polar nanoparticles, and a plurality of nanochannels are distributed in the porous network framework. The flexible water-volte function layer has good flexibility and super-toughness, can produce energy and detect ions based on the water-volte effect, has low cost, is easy to integrate, has good reliability, has long service life, is suitable for being applied to wearable devices as a water-volte power generation device, an ion sensor and the like, can adapt to various motion scenes, and has wide application prospect.

Description

Technical Field

[0001] This invention specifically relates to an ultra-tough flexible hydrothermal functional layer and its application, belonging to the field of hydrothermal technology. Background Technology

[0002] In recent years, flexible electronics technology has demonstrated advantages such as flexibility, stretchability, high sensitivity, and fast response. Driven by continuous advancements in materials science and computer science, it is rapidly developing towards extensibility, integration, multifunctionality, and intelligence, showing broad application prospects in wearable healthcare, intelligent sensing, and human-computer interaction. However, most existing flexible electronic devices rely on external power sources, such as rigid batteries, electrochemical capacitors, and lithium-ion batteries. Furthermore, existing flexible electronic devices generally suffer from high stiffness, large size, and difficulty in achieving lightweight and flexible designs. This reduces the fit between the flexible device and the object under test, significantly decreasing testing accuracy and failing to meet the complex and ever-changing power supply requirements of flexible devices. Therefore, exploring power generation devices that can supply power to flexible electronic devices is particularly important.

[0003] Evaporation-driven hydrovoltaic generators can produce continuous electricity and represent a clean and renewable energy capture technology. However, on the one hand, existing hydrovoltaic power generation devices have low structural stability, making it difficult to maintain a stable and continuous power output. On the other hand, existing hydrovoltaic power generation devices require extremely low ion concentrations in the water source, while clean water sources that meet these requirements are scarce in nature. Summary of the Invention

[0004] The main objective of this invention is to provide an ultra-tough flexible water-based functional layer, its preparation method, and its application, thereby overcoming the shortcomings of the prior art.

[0005] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0006] One aspect of the present invention provides an ultra-tough flexible hydrophobic functional layer comprising a porous network framework and a polymer material, wherein the porous network framework comprises an aggregated plurality of polar nanoparticles, the polymer material is used to connect at least adjacent polar nanoparticles, and a plurality of nanochannels are distributed within the porous network framework.

[0007] In one embodiment, the mass ratio of polymer material to polar nanoparticles in the flexible hydrophobic functional layer is greater than 0 but less than or equal to 5 / 100, preferably greater than 0 but less than or equal to 3 / 100, and more preferably greater than 1 but less than or equal to 3 / 100. If the proportion of polymer material is too high, it will block the nanochannels; if the proportion of polymer material is too low, the structural stability (e.g., flexibility) of the flexible hydrophobic functional layer will be poor.

[0008] In one embodiment, the polymer material in the flexible hydrophobic functional layer exhibits morphology such as adhesion, binding, and encapsulation of polar nanoparticles.

[0009] In some cases, the polymer material is distributed on the surface of the porous network framework.

[0010] In some cases, the polymer material in the flexible hydrophobic functional layer partially or completely encapsulates polar nanoparticles, which helps to effectively improve the structural stability of the porous network framework formed by multiple polar nanoparticles.

[0011] The polymer material may or may not have polar functional groups. Its main function is to bind polar nanoparticles, stabilizing the porous network framework structure without blocking the nanochannels formed by the nanoparticles. Especially for non-polar polymer materials, they cannot completely encapsulate polar nanoparticles; otherwise, the surface of the nanochannels would be non-polar, causing the flexible hydrophobic functional layer to lose its hydrophobic properties. Preferably, the polymer material layer is made of, but is not limited to, one or a combination of two or more of polyacrylonitrile, polyurethane, and polyvinyl alcohol.

[0012] In one embodiment, the polar nanoparticles are made of, but are not limited to, one or a combination of two or more of the following: metal oxides, non-metal oxides, metal-organic frameworks, bimetallic hydroxides, polymers, and carbon functional materials.

[0013] In one embodiment, the polar nanoparticles have a particle size of 10–2000 nm. For example, the particle size of the polar nanoparticles can be 10 nm, 20 nm, 30 nm, 45 nm, 58 nm, 100 nm, 130 nm, 145 nm, 180 nm, 200 nm, 230 nm, 300 nm, 500 nm, 600 nm, 730 nm, 820 nm, 1000 nm, 1200 nm, 1300 nm, 1500 nm, 1600 nm, 2000 nm, etc., but preferably 100–500 nm, more preferably 100–300 nm. If the particle size of the polar nanoparticles is too large, it will not only affect the structural stability of the flexible water-repellent functional layer, but also lead to a deterioration in its water-repellent performance. Conversely, if the particle size of the polar nanoparticles is too small, the pore size of the nanochannels will be unsatisfactory, which will also lead to a deterioration in its water-repellent performance.

[0014] In one embodiment, the polar nanoparticles may be at least one of regular or irregular spherical, flower-like, polyhedral, or sheet-like shapes, and are not limited thereto.

[0015] In one embodiment, the pore size of the nanochannel is 1–1800 nm. For example, the pore size of the nanochannel inside the porous network framework can be 10 nm, 20 nm, 30 nm, 45 nm, 58 nm, 100 nm, 130 nm, 145 nm, 180 nm, 200 nm, 230 nm, 300 nm, 500 nm, 600 nm, 730 nm, 820 nm, 1000 nm, 1200 nm, 1300 nm, 1500 nm, 1600 nm, 1800 nm, etc., preferably 10–200 nm.

[0016] In one embodiment, the porosity of the flexible hydroelectric functional layer is 5% to 95%, preferably 20% to 95%. Within this porosity range, the comprehensive mechanical properties of the flexible hydroelectric functional layer, such as compressive strength and flexibility, are quite ideal. Moreover, it has abundant nanochannels with suitable pore sizes, thus enabling the flexible hydroelectric functional layer to exhibit good hydroelectric power generation performance.

[0017] In one embodiment, the polar nanoparticles are preferably made of metal oxides, such as aluminum oxide, and the polymeric material is preferably a polymeric material with polar functional groups, such as polyacrylonitrile. In the flexible water-based functional layer formed therefrom, the nanochannels allow anions to pass through while repelling cations.

[0018] In one embodiment, the thickness of the flexible water-based functional layer is 0.1 to 100 μm, for example, the thickness of the flexible water-based functional layer is 0.1 μm, 0.2 μm, 1 μm, 3 μm, 10 μm, 15 μm, 25 μm, 40 μm, 50 μm, 60 μm, 90 μm, 100 μm, etc.

[0019] The flexible water-voltaic functional layer of the present invention has high mechanical stability and good flexibility due to the above-mentioned structural design. After absorbing water, based on the water-voltaic effect, water can flow smoothly in the nanochannels and form a flowing potential under the drive of evaporation, thereby generating electricity quickly, efficiently and continuously, and with relatively low requirements for the purity of the water source.

[0020] Another aspect of the present invention provides a method for preparing the ultra-tough flexible hydrophobic functional layer, comprising:

[0021] A fluid precursor composition is provided, the precursor composition comprising a solvent, a polymeric material dissolved in the solvent, and uniformly dispersed polar nanoparticles;

[0022] The precursor composition is applied to the substrate surface to form a coating, and then at least part of the solvent in the coating is removed to form the flexible water-based functional layer.

[0023] In one embodiment, the preparation method includes: applying the precursor composition to the substrate surface by at least spraying to form the flexible water-based functional layer.

[0024] In one embodiment, the spraying method preferably uses a pressure of 2 to 6 MPa, and the substrate temperature is preferably 80 to 120°C.

[0025] In one embodiment, the precursor composition is a liquid or a slurry. Furthermore, the precursor composition can be obtained by dissolving a polymer material in a solvent to form a solution, and then uniformly dispersing polar nanoparticles in the solution.

[0026] In one embodiment, the substrate is a flexible substrate.

[0027] In one embodiment, the solvent may be DMF or the like, but is not limited thereto.

[0028] In one embodiment, the substrate has a plurality of through holes extending through the substrate along its thickness direction, and the diameter of the through holes is 100–400 μm. Further, the substrate is formed of materials such as polyethylene phthalate, polyethylene, polystyrene, natural rubber, thermoplastic elastomer, polyimide, polyurethane, nylon, polyvinyl chloride, and natural fibers, preferably a water-blocking material.

[0029] In one embodiment, the substrate has multiple pores distributed on its surface and interior, and these pores are interconnected. Preferably, the pores are submicron or nanometer-sized. When the precursor composition is applied to such a substrate surface to form a coating, a portion of the precursor composition penetrates into the surface layer of the substrate, causing the bottom region of the formed flexible hydrophobic functional layer to bond integrally with the substrate. This results in a stronger bond between the flexible hydrophobic functional layer and the substrate, and allows the nanochannels to directly communicate with the porous structure in the substrate, effectively shortening the path length for water or aqueous solutions to be transported from the substrate to the flexible hydrophobic functional layer, thereby improving the response speed of the flexible hydrophobic functional layer to water. More preferably, if a local area on the substrate surface is defined as a first region and the remaining area as a second region, then the first region is hydrophilic, the second region is hydrophobic or covered with a water-resistant encapsulation layer, and the flexible hydrophobic functional layer at least continuously covers a portion of the first region and a portion of the second region. For example, the second region can be hydrophobically modified using fluorinated silanes (such as 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, tridecafluorooctyltriethoxysilane, etc.), or the second region can be coated and encapsulated using ecoflex, PDMS, etc.

[0030] The method for preparing the flexible water-based functional layer provided by this invention is simple to operate, low in cost, and highly controllable.

[0031] Another aspect of the present invention provides a flexible functional device comprising the aforementioned ultra-tough flexible hydrophobic functional layer.

[0032] In one embodiment, the flexible functional device further includes:

[0033] A water collection layer is stacked with the flexible water-floating functional layer, the water collection layer being used to collect water or aqueous solution and transport it to the flexible water-floating functional layer;

[0034] In addition, a first electrode and a second electrode are electrically connected to the flexible water-voltaic functional layer, with the first electrode and the second electrode spaced apart.

[0035] In one embodiment, the flexible functional device further includes a flexible insulating substrate disposed between the flexible water-cooled functional layer and the water collection layer, and the flexible insulating substrate has a plurality of through holes distributed thereon, which are used to form a water or aqueous solution transport channel between the flexible water-cooled functional layer and the water collection layer.

[0036] In one embodiment, both the first electrode and the second electrode are disposed on the flexible insulating substrate, and the flexible water-voltaic functional layer is stacked on the first electrode and the second electrode and is in electrical contact with the first electrode and the second electrode.

[0037] In one embodiment, a plurality of through holes are distributed in the area covered by the first electrode or the second electrode on the surface of the flexible insulating substrate, and the through holes also continuously penetrate the first electrode or the second electrode along the thickness direction.

[0038] In one embodiment, the water collecting layer is hydrophilic and can collect water through capillary action. The through-holes inside the flexible insulating substrate are mainly used to allow the collected water and other fluids to pass through. It should be noted that the flexible insulating substrate and the water collecting layer are conformally attached.

[0039] In one embodiment, the water collection layer has a capillary structure, which may be selected from one or more of the following materials: dust-free paper, cellulose membrane, sponge, pure cotton cloth, etc., but is not limited thereto.

[0040] In one embodiment, the aperture of the through hole is 100-500 μm, such as 100 μm, 110 μm, 130 μm, 200 μm, 220 μm, 240 μm, 270 μm, 300 μm, 330 μm, 360 μm, 390 μm, 400 μm, etc., but preferably 200-300 μm.

[0041] In one embodiment, the distribution density of the vias on the flexible insulating substrate is 1 to 5 per mm. 2 For example, 1 per mm 2 2 pieces / mm 2 3 / mm 2 4 pieces / mm 2 5 pieces / mm 2 .

[0042] In one embodiment, the flexible insulating substrate is made of one or more of the following materials: polyethylene phthalate, polyethylene, polystyrene, natural rubber, thermoplastic elastomer, polyimide, polyurethane, nylon, polyvinyl chloride, and natural fibers, but is not limited thereto.

[0043] In one embodiment, the first electrode and the second electrode can be formed by conductive paste, conductive slurry, conductive adhesive, etc., or by printing, coating, etc. using nano silver ink, etc., or by conductive carbon film, conductive tape, etc.

[0044] In one embodiment, the flexible functional device includes a hydroelectric power generation device or an ion sensor device.

[0045] Another aspect of the present invention provides a method for fabricating the flexible functional device, comprising:

[0046] Provide a flexible insulating substrate as a base;

[0047] An ultra-tough flexible water-voltaic functional layer is fabricated on the first surface of the flexible insulating substrate using the aforementioned method;

[0048] A water collection layer is bonded to the second side of the flexible insulating substrate, and the second side is disposed opposite to the first side;

[0049] Furthermore, the first electrode and the second electrode, which are spaced apart from each other, are electrically connected to the flexible water-voltaic functional layer, respectively.

[0050] In one embodiment, the method for fabricating the flexible functional device includes: first forming a first electrode and a second electrode on a first surface of a flexible insulating substrate; then processing a plurality of through holes on the first electrode or the second electrode and making the through holes continuously penetrate the first electrode or the second electrode and the flexible insulating substrate along the thickness direction; then fabricating the flexible water-voltaic functional layer on the first surface of the flexible insulating substrate and stacking the flexible water-voltaic functional layer on the first electrode and the second electrode.

[0051] In one embodiment, if the flexible insulating substrate is a porous material such as dust-free paper, the fabrication method of the flexible functional device includes: firstly, hydrophobic treatment of the first surface of the flexible insulating substrate with a low surface energy material such as fluorosilane, or coating and encapsulation treatment of the first surface with ecoflex, PDMS, etc.; then, forming a first electrode and a second electrode on the first surface; then, processing multiple through holes on the first electrode or the second electrode, and making the through holes continuously penetrate the first electrode or the second electrode and the flexible insulating substrate along the thickness direction; then, fabricating the flexible hydrophobic functional layer on the first surface of the flexible insulating substrate, and stacking the flexible hydrophobic functional layer on the first electrode and the second electrode. Compared with the coating and encapsulation method, the hydrophobic treatment method is more preferred, as it is not only lower in cost but also, to a certain extent, helps to eliminate or blur the interface between the flexible hydrophobic functional layer and the substrate, improving the bonding strength between the two and making the device structure thinner and lighter. Preferably, a local area of ​​the flexible hydrophobic functional layer completely fills the through holes, allowing the nanochannels in the flexible hydrophobic functional layer to directly communicate with the porous structure in the substrate, which also helps to significantly improve the device's response speed to water.

[0052] Another aspect of the present invention provides a method for generating hydroelectric power, comprising:

[0053] Provide the aforementioned flexible functional device;

[0054] The flexible functional device generates electricity by bringing its water collection layer into contact with water, an aqueous solution, or water vapor.

[0055] Another aspect of the present invention provides an ion detection method, characterized in that it comprises:

[0056] Provide the aforementioned flexible functional device;

[0057] By bringing the aqueous phase system containing ions into contact with the water collection layer of the flexible functional device, at least the type and / or concentration of ions in the aqueous phase system can be detected.

[0058] Another aspect of the present invention provides a wearable device including the aforementioned flexible functional device.

[0059] Compared with the prior art, the advantages of the present invention include:

[0060] (1) The ultra-tough flexible water vapor functional layer provided by the present invention adopts nanoparticle materials and polymer materials that are simple to prepare and have good stability. It has low requirements for flexible insulating substrate and water collection layer, breaks through the limitation of low mechanical strength of water vapor devices, can be used in complex motion environment, and achieves a significant improvement in the performance of water vapor functional layer. It can provide power for wearable electronic devices and overcomes the shortcomings of existing water vapor functional layers such as insufficient stability, large environmental impact and short service life.

[0061] (2) The construction of the ultra-tough flexible water vapor functional layer provided by the present invention has the advantages of low cost, easy integration and adaptability to various sports scenarios. It can directly collect and utilize various steam, such as water vapor brought by sweat evaporation during exercise, to reliably generate electricity. In addition, the water vapor functional layer provided by the present invention has different responses to different ion concentrations and can be used as an ion concentration sensor. Its application scenarios are more extensive and the environmental requirements are lower.

[0062] (3) The ultra-tough flexible water-voltaic functional layer provided by the present invention can also realize the construction of a power supply system through circuit design such as series and parallel connection, so as to provide continuous power to wearable electronic devices in different environments. Attached Figure Description

[0063] Figure 1 This is a schematic cross-sectional view of a flexible functional device based on an ultra-tough flexible hydrophobic functional layer in Example 1.

[0064] Figure 2 yes Figure 1 Top view of the flexible functional device shown;

[0065] Figure 3 This is a SEM image of a flexible insulating substrate and the surface of the lower electrode in Example 1;

[0066] Figure 4 This is a surface SEM image of a flexible hydrophobic functional layer in Example 1;

[0067] Figure 5 This is a TEM image of the surface of a flexible water-based functional layer in Example 1;

[0068] Figure 6 This is a test graph showing the change of the open-circuit voltage of the water-voltaic functional layer over time when a hot plate at 37°C simulates the evaporation of human sweat.

[0069] Figure 7 This is a test diagram showing the open-circuit voltage response of the water-based functional layer in Example 1 to sodium chloride solutions of different concentrations. Detailed Implementation

[0070] In view of the shortcomings of existing technologies, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention, which mainly relates to an ultra-tough flexible hydrophobic functional layer, its preparation method, and its application. This invention increases the mechanical strength of the hydrophobic functional layer while simultaneously making it flexible by employing polymer adhesion and / or binding and / or encapsulation of a porous network framework of polar nanoparticles, thereby constructing an ultra-tough flexible hydrophobic functional layer that can meet its stable performance under different environmental conditions. This hydrophobic functional layer can be used in power / energy generation devices, ion concentration sensors, and wearable electronic devices, providing an innovative strategy for overcoming water source limitations and meeting usage requirements under different environmental conditions and states.

[0071] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of the embodiments of this invention will be described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0072] Example 1

[0073] See Figure 1 and Figure 2 This embodiment provides a flexible functional device based on an ultra-tough flexible water-voltaic functional layer, which includes a water collection layer 3, a flexible insulating substrate 2, and a flexible water-voltaic functional layer 1 stacked together. The flexible insulating substrate 2 has an upper electrode 5 (also known as the first electrode) and a lower electrode 6 (also known as the second electrode) that do not intersect on its front side. The water-voltaic functional layer 1 is stacked on the upper electrode 5 and the lower electrode 6 and is electrically connected to the upper electrode 5 and the lower electrode 6 respectively.

[0074] The flexible insulating substrate 2 is a PET film with a thickness of approximately 150 μm. The water collecting layer 3 is made of hydrophilic dust-free paper and is conformally attached to the back side of the flexible insulating substrate 2. The upper electrode 5 and the lower electrode 6 are L-shaped carbon electrodes formed by printing chemically inert conductive carbon paste on the front side of the flexible insulating substrate 2. The lower electrode 6 has an array of multiple through-holes 4, which can be formed by laser drilling and continuously penetrate the lower electrode 6 and the flexible insulating substrate 2 along the thickness direction. The diameter of the through-holes 4 is approximately 300 μm, and the distribution density can be 4 holes / mm. 2 The flexible water-based functional layer 1 partially enters these through-holes 4 and completely fills them.

[0075] This flexible functional device can be fabricated by the following method, which includes the following steps:

[0076] S1. The PET film 2 is ultrasonically cleaned in ethanol, then dried in an oven at 80°C. A chemically inert conductive carbon paste is then screen-printed onto the front side of the PET film 2 to form the upper electrode 5 and the lower electrode 6, with a spacing of approximately 1.6 cm between them. Subsequently, an array of through-holes 4 is fabricated on the lower electrode 6 and the PET film using laser drilling, as described above. Figure 3 As shown.

[0077] S2. Dissolve approximately 0.18g of PAN (Mw approximately 85000) in approximately 80mL of LDMF, then disperse approximately 6g of α-alumina nanoparticles (irregular spherical shape, particle size approximately 200nm) into the PAN solution and sonicate (approximately 300W) for approximately 120min to obtain a precursor composition. Then, place the PET film 2 with electrodes treated in step S1 on a hot plate at approximately 100°C, and under a pressure of approximately 4MPa, spray the precursor composition onto an area of ​​approximately 1.5cm in width on the PET film 2, the upper electrode 5, and the lower electrode 6 to form a continuous flexible hydrophobic functional layer.

[0078] S3. Conformally attach the hydrophilic dust-free paper 3 to the back of the PET film 2.

[0079] Figure 4 This is a surface SEM image of the flexible hydrophobic functional layer in this embodiment. It can be seen that the flexible hydrophobic functional layer has abundant regular and irregular pores and channels. Figure 5 This is a TEM image of the flexible water-based functional layer in this embodiment. As can be seen, the addition of polyacrylonitrile plays a good adhesive role, which can connect the alumina nanoparticles to form a "beaded" structure. This makes the flexible water-based functional layer strong and tough, and it can be bent more than 180°. The critical bonding force in the scratch test is greater than 4N.

[0080] In this embodiment, the aforementioned flexible functional device is placed on an open culture dish with the water collection layer facing downwards. Deionized water is filled into the culture dish, which is then placed on a 37°C hot plate to simulate human body temperature. The evaporated water is collected through the water collection layer, and the collected water flows through a flexible insulating substrate to drive the flexible water-voltaic functional layer. Driven by evaporation, the water flows within the nanochannels, forming a flowing potential. The corresponding water-voltaic output open-circuit voltage changes over time as follows: Figure 6 As shown, it is feasible to drive this flexible functional device by collecting water through evaporation.

[0081] In this embodiment, sodium chloride solutions of different concentrations can be used to simulate human sweat to test the ion sensing performance of the aforementioned flexible functional device. Specifically, sodium chloride solutions of different concentrations can be dropped onto the water collection layer, and then the open-circuit voltage of the flexible water-voltaic functional layer in response to sodium chloride solutions of different concentrations can be tested. The test results are as follows: Figure 7As shown, the flexible functional device in this embodiment exhibits significant differences in open-circuit voltage for sodium chloride solutions of different concentrations. This demonstrates that the flexible functional device can function as an ion concentration sensor to detect changes in sweat concentration during human exercise, thereby assessing health status. Furthermore, similar experimental results can be obtained by performing the same experiment with calcium chloride and aluminum chloride solutions of different concentrations. It is noteworthy that the open-circuit voltage of the flexible functional device also shows significant differences for sodium chloride, calcium chloride, and aluminum chloride solutions of the same concentration; therefore, it can also be used to identify the types of ions.

[0082] A water flow impact test was conducted on the water-voltaic functional layer of this flexible functional device (approximately 9.92 ms). -1 It was found that the flexible hydrovoltaic functional layer showed no damage or powdering, and its hydrovoltaic power generation and ion sensing performance remained essentially unchanged. Bending the hydrovoltaic functional layer in the flexible functional device by more than 150° did not alter its morphology, and its hydrovoltaic power generation and ion sensing performance remained essentially unchanged. After immersing the flexible hydrovoltaic functional layer in water for two consecutive months and then allowing it to air dry, its microstructure remained unchanged, and its hydrovoltaic power generation and ion sensing performance remained essentially unchanged.

[0083] The flexible functional device of this embodiment can be used to fabricate wearable devices. For example, the flexible functional device can be placed on a ring-shaped silicone pad. During use, the pad comes into contact with the human skin, and the annular space within the pad forms a sweat collection chamber between the water collection layer and the skin. This wearable device is both a power source and an ion sensor, requiring no additional power supply. It is also lightweight, thin, and flexible, providing a good user experience.

[0084] Example 2

[0085] The flexible functional device in this embodiment is basically the same as that in Embodiment 1, except that the mass ratio of PAN to α-alumina nanoparticles in the precursor composition is 1:100 when fabricating the flexible hydrovoltaic functional layer. The hydrovoltaic power generation and ion sensing performance of this flexible functional device are similar to those of the flexible functional device in Embodiment 1. However, the flexible hydrovoltaic functional layer will break when bent at approximately 90°.

[0086] Example 3

[0087] The flexible functional device in this embodiment is basically the same as that in Example 1, except that the mass ratio of PAN to α-alumina nanoparticles in the precursor composition is 5:100 when fabricating the flexible hydrovoltaic functional layer. The hydrovoltaic power generation performance and ion sensing performance of this flexible functional device are significantly worse than those of the flexible functional device in Example 1, possibly because excessive PAN can lead to blockage of the nanochannels. The flexibility and other properties of this flexible functional device are similar to those of the flexible functional device in Example 1.

[0088] Example 4

[0089] The flexible functional device in this embodiment is basically the same as that in Embodiment 1, except that the aperture of the through-hole that continuously penetrates the lower electrode and the flexible insulating substrate along the thickness direction is about 100 μm. The hydrovoltaic power generation performance and ion sensing performance of this flexible functional device are significantly worse than those of the flexible functional device in Embodiment 1. This may be due to the small aperture of the through-hole, which restricts the flow of water or aqueous solution.

[0090] Example 5

[0091] The flexible functional device in this embodiment is basically the same as that in Embodiment 1, except that the aperture of the through-hole that continuously penetrates the lower electrode and the flexible insulating substrate along the thickness direction is about 500 μm. The hydrovoltaic power generation performance and ion sensing performance of this flexible functional device are also significantly worse than those of the flexible functional device in Embodiment 1. This may be due to the excessively large aperture of the through-hole, resulting in insufficient filling of the through-hole in some areas of the flexible hydrovoltaic functional layer.

[0092] Example 6

[0093] The fabrication method of the flexible functional device in this embodiment is basically the same as that in Embodiment 1, except that the PET film is omitted. Instead, the front side of the hydrophilic cleanroom paper is first treated with tridecafluorooctyltriethoxysilane for hydrophobicity. Then, referring to steps S1 and S2 in the embodiment, upper and lower electrodes, through holes, and a flexible hydrovoltaic functional layer are formed on the front side of the hydrophilic cleanroom paper. The hydrovoltaic power generation performance and ion sensing performance of this flexible functional device are similar to those of the flexible functional device in Embodiment 1.

[0094] Example 7

[0095] The fabrication method of the flexible functional device in this embodiment is basically the same as that in Example 6, except that the mass ratio of PAN to α-alumina nanoparticles in the precursor composition is 1:100 when fabricating the flexible hydrophobic functional layer. The various properties of the flexible hydrophobic functional layer in this flexible functional device were tested using the water flow impact method, bending method, and immersion method described in Example 1. The mechanical property test results were similar to those of Example 1. Surprisingly, the hydrophobic power generation performance and ion sensing performance of this flexible functional device are significantly better than those of the flexible functional device in Example 1. This may be because the bottom of the flexible hydrophobic functional layer partially penetrates the surface layer of the cleanroom paper, integrating the two and allowing the nanochannels within the flexible hydrophobic functional layer to directly communicate with the porous structure within the cleanroom paper, thus shortening the path for water or aqueous solution to be transported from the substrate to the flexible hydrophobic functional layer.

[0096] The ultra-tough flexible water-based functional layer provided by this invention uses nanoparticle materials and polymer materials that are simple to prepare and have good stability. It also has low requirements for flexible insulating substrates and water collection layers, breaking through the limitation of low mechanical strength of water-based devices. It can be used in complex motion environments and achieves a significant improvement in the performance of water-based functional layers. It can power wearable electronic devices and overcome the shortcomings of traditional water-based functional layers, such as insufficient stability, large environmental impact, and short service life.

[0097] The ultra-tough and flexible hydrophobic functional layer provided by this invention has the advantages of low cost, easy integration, and adaptability to various sports scenarios. It can directly collect and utilize various vapors, such as water vapor generated by sweat evaporation during exercise, for reliable power generation. Furthermore, the hydrophobic functional layer provided by this invention has different responses to different ion concentrations and can be used as an ion concentration sensor, thus expanding its application scenarios and reducing environmental requirements.

[0098] The ultra-tough flexible hydrothermal functional layer provided by this invention can also be used to construct a power supply system through circuit design such as series and parallel connections, providing continuous power to wearable electronic devices in different environments.

[0099] The ultra-tough flexible water-voltaic functional layer provided by this invention has the characteristics of simple process, easy implementation, low substrate requirements, cleanliness, low cost, and wide application. It adopts a conductive material with micro-nano structure that is simple to prepare, has a wide range of applications, good stability, and is easy to prepare on a large scale. It can obtain good power generation performance, realize the direct acquisition of energy from ambient water without any water requirements or special external conditions, and can be used as a power source to power various electronic / electrical devices. It also has the characteristics of being more stable, clean, less affected by environmental limitations, and can be used for a long time.

[0100] It should be understood that the above embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A flexible functional device, characterized in that, include: The hydrophilic cleanroom paper has a front and a back side facing away from each other, wherein the front side is hydrophobically treated with tridecylfluorooctyltriethoxysilane; A first electrode and a second electrode are spaced apart on the front side of the cleanroom paper, and a plurality of through holes are distributed in the area on the front side of the cleanroom paper covered by the first electrode or the second electrode, and the through holes continuously penetrate the first electrode or the second electrode and the cleanroom paper along the thickness direction. An ultra-tough and flexible water-based functional layer is stacked on the first electrode and the second electrode and is in electrical contact with the first electrode and the second electrode. The flexible water-based functional layer includes a porous network framework and a polymer material. The porous network framework includes multiple aggregated polar nanoparticles and multiple nanochannels distributed within the porous network framework. The polymer material is used to connect at least adjacent polar nanoparticles. The polymer material is polyacrylonitrile, and the polar particles are α-alumina nanoparticles. The mass ratio of the polymer material to the polar nanoparticles is 1 / 100. Furthermore, the bottom of the flexible water-based functional layer partially penetrates into the surface layer of the dust-free paper, integrating the two into one, and allowing the nanochannels within the flexible water-based functional layer to directly communicate with the porous structure within the dust-free paper.

2. The flexible functional device according to claim 1, characterized in that: The polar nanoparticles have a particle size of 100~300 nm.

3. The flexible functional device according to claim 1, characterized in that: The polar nanoparticles can be shaped into regular or irregular spheres, flowers, polyhedra, or sheets.

4. The flexible functional device according to claim 1, characterized in that: The pore size of the nanochannel is 10~200nm.

5. The flexible functional device according to claim 1, characterized in that: The polymer material is distributed on the surface of the porous network framework.

6. The flexible functional device according to claim 1, characterized in that: The thickness of the flexible hydrophobic functional layer is 10-70 μm.

7. The flexible functional device according to claim 1, characterized in that: The porosity of the flexible hydrophobic functional layer is 20%-95%.

8. The flexible functional device according to claim 1, characterized in that: The diameter of the through hole is 100~400μm.

9. The flexible functional device according to claim 1, characterized in that: The distribution density of the through-holes on the lint-free paper is 1~5 per mm. 2 .

10. The flexible functional device according to claim 1, characterized in that: The flexible functional devices include hydroelectric power generation devices or ion sensor devices.

11. A method for fabricating the flexible functional device according to any one of claims 1-10, characterized in that, Includes the following steps: S1. The front side of the hydrophilic cleanroom paper is hydrophobically treated with tridecafluorooctyltriethoxysilane; S2. A first electrode and a second electrode are formed on the front side of the cleanroom paper. Then, multiple through holes are processed on the first electrode or the second electrode, and the through holes are made to continuously penetrate the first electrode or the second electrode and the cleanroom paper along the thickness direction. S3. A fluid precursor composition is applied to the front side of the dust-free paper to form a coating, and at least part of the solvent in the coating is removed to form an ultra-tough flexible water-based functional layer. The flexible water-based functional layer is then directly stacked on the first electrode and the second electrode. The precursor composition contains a solvent, a polymer material dissolved in the solvent, and uniformly dispersed polar nanoparticles.

12. The preparation method according to claim 11, characterized in that, Step S3 includes: applying the precursor composition to the front side of the cleanroom paper by at least spraying, thereby forming the flexible water-soluble functional layer, wherein the spraying pressure is 2~6MPa and the temperature of the cleanroom paper is 80~120℃.

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