A self-healing underwater detection patch based on a biomimetic starfish brachiopod triboelectric nanogenerator, its preparation method, and its application.

Abstract

This invention discloses a self-healing underwater detection patch for a biomimetic starfish tentacle triboelectric nanogenerator, its preparation method, and its application. Belonging to the technical field of underwater detection equipment, the self-healing underwater detection patch for a biomimetic starfish tentacle triboelectric nanogenerator comprises the following structure: a biomimetic topological structure, a gradient dielectric layer, an anti-ion penetration coating, a dynamic self-healing material layer, a biomimetic mucus self-sealing layer, and a silver-carbon nanotube composite electrode. Compared with existing patches, the self-healing underwater detection patch for a biomimetic starfish tentacle triboelectric nanogenerator prepared by this invention achieves significant advantages in charge density (58 μC / m² vs. 1.1 μC / m²), self-healing efficiency (92% vs. 0%), compressive strength (78 MPa vs. 25 MPa), and power density (1.2 W / m² vs. 0.05 W / m²), representing increases of 52.7 times, 3.1 times, and 24 times respectively.

Description

Technical Field

[0001] This invention belongs to the technical field of underwater detection equipment, and in particular relates to a self-healing underwater detection patch with a biomimetic starfish brachial triboelectric nanogenerator, its preparation method, and its application. Background Technology

[0002] With the surge in demand for marine resource development and ecological monitoring, the global underwater detection equipment market is expanding at a CAGR of 18.7%, and is projected to exceed $24 billion by 2030. However, traditional technologies face systemic bottlenecks in energy and materials. The cost of laying cables for deep-sea power supply is as high as $500,000 per kilometer, and maintenance cycles can last for months. Lithium batteries experience a 62% energy density decay under high pressure (>50 MPa) and low temperature (2-4°C) conditions; for example, the lithium polymer battery in Japan's JAMSTEC "Shinkai 6500" manned submersible experienced a sharp drop in capacity to 38% after 6 hours of continuous operation at a depth of 6000 meters. While flexible patch detectors achieve self-powering through triboelectric nanogenerators (TENG), existing commercial products (such as the Teledyne HMS-300 series) show a charge density drop from 5.3 μC / m³ after 300 hours of operation at 12 MPa water pressure. 2 Attenuation to 1.1 μC / m 2 Furthermore, the interface delamination defect rate is as high as 43%. The combined destructive effects of the marine environment on materials are even more significant. For example, salt ion penetration reduces the dielectric constant by 28%, high voltage induces microcrack propagation rates of up to 0.8 μm / h, and biofouling reduces the surface friction coefficient by 37%. Existing technologies are insufficient to meet the dual requirements of energy stability and material durability for deep-sea exploration.

[0003] Triboelectric nanogenerators (TENGs), representing a breakthrough in self-powered technology, have achieved a power output of 3.5 W / m in terrestrial environments. 2 While achieving high power density, its underwater applications face multiple challenges at both the physical and chemical levels. The difference in the medium environment is a core limitation: the dielectric constant of water causes the surface charge dissipation rate to be three orders of magnitude higher than that of air. For example, the charge retention rate of the PDMS-nylon combination in seawater is only 0.8 μC / m³. 2 Compared to air, the concentration decreased by 98.7%. Mechanical damage caused by dynamic water flow is even more fatal: PTFE films containing microcracks (>50μm) completely failed after 48 hours at a flow rate of 2m / s, with a fracture toughness of only 0.6MPa·m. 1 / 2 Furthermore, long-term stability is a significant issue. The liquid metal-TENG developed by KAIST in South Korea exhibited an 89% decrease in conductivity after immersion in seawater for 200 hours. Experiments show that existing TENG material systems experience an exponential decrease in power output under the synergistic effects of salt ion penetration, dynamic stress cycling, and oxidative corrosion (R0). 2=0.97), and its failure mechanism is directly related to the collapse of the interface energy barrier and the blockage of charge migration channels.

[0004] Marine organisms have provided disruptive insights for marine materials design. The tube foot arrays of starfish brachiopods achieve intelligent adhesion of 0.1-2 N / cm² through hydraulic adjustment, and self-assembling proteins (such as asterin-1) in their epidermal mucus can repair 80% of mechanical damage within 30 minutes. The intersection of biomimetic and materials science has spurred two major breakthroughs: first, topological optimization, with the star-shaped fractal structure developed by the Max Planck Institute in Germany increasing the fracture toughness of materials by 3.2 times (fracture energy reaching 12.5 kJ / m²); and second, dynamic self-healing networks based on dynamic disulfide bonds (SS) and metal coordination (Zn). 2+ The dual-network system of α-imidazole achieved a tensile recovery rate of 92% while maintaining a tensile strength of 18 MPa. However, existing research still suffers from functional disconnect: the biomimetic structural design is not integrated with the energy harvesting function, and the conductivity recovery rate of the self-healing material is less than 67%. Summary of the Invention

[0005] To address the aforementioned issues, this invention provides a self-healing underwater detection patch based on a biomimetic starfish brachiopod triboelectric nanogenerator, along with its preparation method and applications.

[0006] One of the technical solutions provided by this invention:

[0007] A self-healing underwater detection patch for a biomimetic starfish brachiopod triboelectric nanogenerator includes the following structure: a biomimetic topological structure, a gradient dielectric layer, an anti-ion penetration coating, a dynamic self-healing material layer, a biomimetic mucus self-sealing layer, and a silver-carbon nanotube composite electrode.

[0008] Furthermore, the biomimetic topology is a biomimetic starfish brachiopod array topology, including a hexagonal close-packed array of tube feet. The diameter of the biomimetic starfish brachiopod tube feet is 50-200μm, the spacing is 100-300μm, and the tilt angle is 30°-60°.

[0009] Furthermore, the dielectric material of the surface layer is fluorinated ethylene propylene with a thickness of 420-500 nm; the dielectric material of the intermediate layer is polyimide with a thickness of 800-1200 nm; and the dielectric material of the base layer is strontium titanate with a thickness of 720-800 nm.

[0010] Furthermore, the gradient dielectric layer comprises a fluorinated ethylene propylene surface layer, a polyimide intermediate layer, and a strontium titanate substrate layer. After deposition, each layer is treated with carboxyl grafting technology to achieve an interfacial -COOH concentration of 1.4 × 10⁻⁶. 15 -1.8×10 15 / cm 2This forms stable chemical bonds, strengthens the interlayer interface bonding, and ultimately enables the interfacial shear strength to reach 14-18.7 MPa, improving the overall structure and durability.

[0011] Furthermore, the preparation method of the dynamic self-healing material layer includes the following steps: dissolving 4,4'-dithiodibenzoic acid, polyethylene glycol diacrylate and a photoinitiator in water to form a prepolymer solution; adding zinc nitrate and polyacrylic acid to the prepolymer solution to adjust the pH of the solution, then injecting the solution into a mold and performing ultraviolet curing to obtain a dual-network material; and embedding nanocellulose and titanium carbide into the dual-network material to prepare the dynamic self-healing material layer.

[0012] Furthermore, the mass ratio of 4,4'-dithiodibenzoic acid, polyethylene glycol diacrylate, and photoinitiator is (2.8-3.2):(96.3-96.7):0.5;

[0013] The concentration of zinc nitrate in the prepolymer solution is 0.07-0.11 mol / L; the concentration of polyacrylic acid in the prepolymer solution is 4.3-4.7 wt.%.

[0014] The pH value is 4.7-5.5;

[0015] The dual-network material comprises a first dynamic disulfide bond network and a second network; the first dynamic disulfide bond network is formed by 4,4'-dithiodibenzoic acid and polyethylene glycol diacrylate during UV curing; Zn 2+ It forms a second network with carboxylate groups.

[0016] Furthermore, the preparation method of the biomimetic mucus self-sealing layer includes the following steps: forming a mucus layer at the encapsulation interface by micro-droplet jetting of a composite solution of sodium alginate and polydopamine, and preparing shark skin-inspired grooves on the mucus layer by nanosecond laser to obtain the biomimetic mucus self-sealing layer; the thickness of the biomimetic mucus self-sealing layer is 16-20 μm.

[0017] Furthermore, the concentrations of sodium alginate and polydopamine in the composite solution are 1.6-2.0 wt.% and 0.3-0.5 wt.%, respectively.

[0018] Furthermore, the silver-carbon nanotube composite electrode has a thickness of 800 nm; its electrode pattern matches the biomimetic starfish brachiopod array on the biomimetic topological structure.

[0019] The second technical solution provided by this invention:

[0020] A method for preparing a self-healing underwater detection patch for a biomimetic starfish tentacle triboelectric nanogenerator includes the following steps: using photocurable polyurethane acrylate as a substrate, a biomimetic topological structure is prepared on a silicon substrate by 3D printing; a gradient dielectric layer is deposited on the biomimetic topological structure by magnetron sputtering to obtain a gradient dielectric layer-biomimetic topological structure; a silver-carbon nanotube composite solution is deposited on the gradient dielectric layer to form a silver-carbon nanotube composite electrode with a pattern matching the array of tube feet of the biomimetic starfish tentacle in the biomimetic structure to obtain a composite electrode-gradient dielectric layer-biomimetic topological structure; an anti-ion permeation coating is uniformly coated on the silver-carbon nanotube composite electrode to obtain an anti-ion permeation coating-composite electrode-gradient dielectric layer-biomimetic topological structure; the anti-ion permeation coating-composite electrode-gradient dielectric layer-biomimetic topological structure, a dynamic self-healing material layer, and a biomimetic mucus self-sealing layer are then stacked sequentially and hot-pressed to prepare the self-healing underwater detection patch for the biomimetic starfish tentacle triboelectric nanogenerator.

[0021] The third technical solution provided by this invention:

[0022] Application of a self-healing underwater detection patch based on the above-mentioned biomimetic starfish brachiopod triboelectric nanogenerator in underwater detection equipment.

[0023] Compared with the prior art, the present invention has the following advantages and technical effects:

[0024] This invention utilizes a 3D-printed starfish brachiopod suction cup topology (feature size 50-200μm) combined with a gradient dielectric layer (dielectric constant 2.3→5.8), achieving a contact charging efficiency of 214% for planar structures (verified by COMSOL simulation). An anti-ion penetration coating is introduced to create a double-layer shielding effect, increasing charge retention to 58μC / m² (6.4 times higher than the uncoated sample). A dynamic disulfide bond and metal coordination dual network achieves a 92% crack closure rate and 83% electrical output recovery within 5 minutes. The biomimetic surface topology reduces barnacle larvae attachment by 89%, and the output fluctuation rate is <3% after being washed by a 2m / s water flow. Real-world data shows that after 2000 hours of continuous operation in a simulated marine environment (80MPa, 2℃, 3.5wt.% NaCl), the patch maintains a stable output of 1.2W / m², with a power density decay rate of <7%, representing an improvement of two orders of magnitude compared to existing technologies. The biomimetic starfish brachiopod triboelectric nanogenerator self-healing underwater detection patch prepared in this invention achieves significant advantages over existing patches, with charge density (58 μC / m² vs. 1.1 μC / m²), self-healing efficiency (92% vs. 0%), compressive strength (78 MPa vs. 25 MPa), and power density (1.2 W / m² vs. 0.05 W / m²) increasing by 52.7 times, 3.1 times, and 24 times respectively. This breakthrough provides a novel solution for lightweight and long-endurance marine exploration equipment, and can be applied to cross-submarine cable IoT and marine organism attachment monitoring. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 Modeling diagram of a biomimetic starfish brachiopod array;

[0027] Figure 2 (a) is a schematic diagram of the three-dimensional morphology of the biomimetic starfish brachiopod; (b) is a test of the interlayer interface bonding state; (c) is the fabrication principle of the biomimetic topological structure. Detailed Implementation

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0031] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0032] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0033] This invention provides a method for fabricating a self-healing underwater detection patch based on a biomimetic starfish brachiopod triboelectric nanogenerator (Bio-TENG), including biomimetic topological structure design, self-healing material synthesis, environmentally adaptive encapsulation, and device integration. This invention also verifies the relevant performance of the fabricated self-healing underwater detection patch.

[0034] The specific fabrication process of a self-healing underwater detection patch based on a biomimetic starfish tentacle triboelectric nanogenerator is as follows:

[0035] Step 1: Digital modeling and parameter optimization of the biomimetic starfish brachiopod array

[0036] Three-dimensional structural data of the arms of starfish (Asterias rubens) were obtained using high-resolution micro-CT scanning (Bruker Skyscan 1272, 0.5 μm resolution). The geometric model of the arm array was reconstructed using reverse engineering software (Materialise Mimics 25.0). Optimized parameters included arm diameter gradient (50-200 μm), spacing (100-300 μm), and tilt angle (30°-60°). Finite element analysis (ANSYS 2025 R1) was used to verify the contact stress distribution, ensuring a hexagonal close-packed topology and maximizing the contact area. Figure 1 Modeling diagram of biomimetic starfish brachiopod array.

[0037] Step 2: 3D printing to form the shape

[0038] A two-photon polymerization 3D printing system (Nanoscribe GT2, laser wavelength 780nm, power 80mW) was used to print biomimetic structures layer by layer on a silicon substrate using photocurable polyurethane acrylate (PUA, Carbon CLIP-3000, elastic modulus 1.2GPa) as the substrate. The printing process parameters were: layer thickness 0.15-0.25μm, single-layer exposure time 100-140ms, curing temperature 55-65℃, and curing time 1.5-2.5h.

[0039] After printing, the surface energy was increased by oxygen plasma treatment (power 50W, time 5min) to enhance the adhesion of the subsequent dielectric layer and prepare a biomimetic topological structure.

[0040] Step 3: Deposit a gradient dielectric layer

[0041] A magnetron sputtering system (Kurt J. Lesker LAB-18, USA) was used to sequentially deposit a substrate layer, an intermediate layer, and a surface layer on a biomimetic topology. The surface layer used fluorinated ethylene propylene (FEP, DuPont, USA, 99.99% purity, dielectric constant ε=2.3) as the dielectric material, with a thickness of 420-500 nm. The intermediate layer used polyimide (PI, Toray U-Varnish-S, Japan, ε=3.5) as the dielectric material, with a thickness of 400 nm-800 nm. The substrate layer used strontium titanate (SrTiO3, Heraeus, Germany, ε=5.8) as the dielectric material, with a thickness of 720-800 nm. The interfacial bonding was strengthened through carboxyl grafting technology, achieving an interfacial shear strength of 14-18.7 MPa.

[0042] Step 4: Deposition of silver-carbon nanotube composite electrode

[0043] Sputtering via mask (vacuum: 5×10⁻⁶) -4On a biomimetic topological structure with a gradient dielectric layer deposited on top, a silver-carbon nanotube composite electrode (thickness 800 nm, silver purity 99.99%, carbon nanotube aspect ratio 1000) was further deposited. The electrode pattern matched the biomimetic starfish brachiopod array. The contact resistance of the silver-carbon nanotube composite electrode was <0.1 Ω·cm (four-probe method, Japanese Hiresta-UP MCP-HT450), and the sheet resistance was 4.2 Ω / sq (ASTM D4496 standard). A composite electrode-gradient dielectric layer-biomimetic topological structure was thus prepared.

[0044] Step 5: Apply an anti-ion penetration coating

[0045] 0.6-1.0 g of polyionic liquid (PIL, IoLiTec, USA) and 0.08-0.10 g of silica nanoparticles (Evonik Aerosil 50, 50 nm diameter, Germany) were ultrasonically mixed in 80-100 mL of ethanol (200 W power, 20 min). The resulting solution was then coated onto the surface of a composite electrode-gradient dielectric layer-biomimetic topology using a spin coater (Laurell WS-650, USA) at 3000 rpm, forming a 120-200 nm anti-ion penetration coating. This coating reduced the charge dissipation rate from 0.28 μC / (m²) 2 The charge retention rate was reduced to 0.03 μC / (m²·h) (uncoated), and the charge retention rate was increased by 9.3 times, thus obtaining an anti-ion penetration coating-composite electrode-gradient dielectric layer-biomimetic topology structure;

[0046] Step 6: Preparation of the dynamic self-healing material layer

[0047] 4,4'-Dithiodibenzoic acid (DTBA, Sigma-Aldrich, USA, 98% purity), polyethylene glycol diacrylate (PEGDA, Mn=700), and photoinitiator Irgacure 2959 (BASF, Germany, 0.5wt%) were mixed in deionized water at a mass ratio of (2.8-3.2):(96.3-96.7):0.5 to form a prepolymer solution. Zinc nitrate (Zn(NO3)2) at a concentration of 0.11-0.15 mol / L and polyacrylic acid (PAA, Mw=250k, 4.3-4.7wt%) were introduced into the prepolymer. NaOH solution (0.1 mol / L) was added to adjust the pH of the solution to 5.1-5.5. The solution was then injected into a mold for UV curing (Omnicure, USA). S1500 (wavelength 365nm, power density 10-15mW / cm², time 30-40min), 4,4'-dithiobenzoic acid and polyethylene glycol diacrylate form a first-layer dynamic disulfide bond network, through Zn 2+Coordination with carboxylate groups forms a second network, resulting in a double-network material. The tensile strength of this double-network material is increased to 18.0 MPa, the elastic modulus reaches 2.3 GPa (ISO 527-2 standard test), and the fracture toughness is 25.3 kJ / m. 2 (ISO 13586 Single-sided notched tensile test); Nanocellulose (CNF, diameter 20nm, aspect ratio 150) and titanium carbide MXene (Ti3C2T) x The nanofibers (1.2 nm interlayer spacing, 320 m² / g specific surface area) were ultrasonically dispersed in an ethanol solution (100 vol%) (Sonics VCX750, 300 W, 30 min), with a mass ratio of nanocellulose, titanium carbide, and ethanol solution of 1:2:100. They were then embedded into a dual-network material to obtain a dynamic self-healing material layer with a thickness of 0.5 mm. The chemical formula for the formation of the second network is as follows:

[0048]

[0049] Furthermore, this embodiment of the invention also separately prepared a first dynamic disulfide bond network: 4,4'-dithiodibenzoic acid, polyethylene glycol diacrylate, and photoinitiator Irgacure 2959 were mixed in deionized water at a mass ratio of 3.2:96.3:0.5 to form a prepolymer solution. The prepolymer solution was then injected into a mold and cured under ultraviolet light. 4,4'-dithiodibenzoic acid and polyethylene glycol diacrylate formed a first dynamic disulfide bond network. The tensile strength of this network was 9.2 MPa, and the elongation at break was 620% (Instron 5967 universal testing machine), demonstrating that the second network can significantly improve the mechanical strength of the dynamic self-healing material layer.

[0050] Step 7: Preparation of the biomimetic self-sealing layer

[0051] A sodium alginate (SA)-polydopamine (PDA) composite solution was prepared, wherein the mass concentrations of SA and PDA were 1.6-2.0 wt.% and 0.3-0.5 wt.%, respectively. A 16-20 μm thick slime layer was formed at the encapsulation interface using a microdroplet jetting system (MicroFab Jetlab 4, USA, droplet diameter 50 μm). A nanosecond laser processing system (Trumpf TruMicro 7050, Germany, wavelength 1064 nm, pulse width 10 ns) was used to fabricate biomimetic grooves (width 50 μm, depth 30 μm, spacing 100 μm) in the slime layer, thus obtaining a biomimetic slime self-sealing layer.

[0052] Step 8: Multi-layer thermoforming and encapsulation

[0053] The self-healing underwater detection patch of the biomimetic starfish brachiopod triboelectric nanogenerator was prepared by stacking an anti-ion penetration coating, a composite electrode, a gradient dielectric layer, a biomimetic topology, a dynamic self-healing material layer, and a biomimetic mucus self-sealing layer in sequence and then bonding them using a hot press (temperature 72-80℃, pressure 0.3-0.5MPa, duration 6-10min). This process is 2.4 times more efficient than traditional bonding processes.

[0054] Figure 2 (a) is a schematic diagram of the three-dimensional morphology of the biomimetic starfish brachiopod; (b) is a test of the interlayer interface bonding state; (c) is the fabrication principle of the biomimetic topological structure.

[0055] The traditional bonding process involves uniformly applying epoxy adhesive to each interface, manually aligning and stacking them, and then allowing them to cure at 25-30℃ for 24 hours. The interface bonding strength is only 6.38 N / cm, which is easily affected by seawater erosion and delamination, resulting in poor long-term stability.

[0056] It should be noted that, unless otherwise specified, all aspects not described in detail in the embodiments of the present invention are implemented using existing conventional technical means.

[0057] Example 1: A method for preparing a self-healing underwater detection patch based on a biomimetic starfish brachiopod triboelectric nanogenerator.

[0058] S1. Fabrication of biomimetic topological structures

[0059] Using photocurable polyurethane acrylate as the substrate, a biomimetic structure was printed layer by layer on a silicon substrate. The printing process parameters were: layer thickness of 0.2 μm, single-layer exposure time of 120 ms, curing temperature of 60℃, and curing time of 2 h. After printing, oxygen plasma treatment (power of 50 W, time of 5 min) was used to prepare a biomimetic topology (bionic starfish brachiopod tube foot diameter gradient of 50 μm and spacing of 100 μm) and tilt angle (60°). In this embodiment, finite element analysis (ANSYS 2025 R1) was used to verify the contact stress distribution. Compared with the traditional planar structure (topology without tube foot array), the hexagonal close-packed topology ensured that the contact area was increased by 2.8 times (from 0.32 mm). 2 / mm 2 Increased to 0.91mm 2 / mm 2 );

[0060] S2. Deposition of gradient dielectric layer

[0061] A gradient dielectric layer-biomimetic topological structure was fabricated sequentially using magnetron sputtering. The surface layer used FEP as the dielectric material with a thickness of 500 nm; the intermediate layer used PI as the dielectric material with a thickness of 600 nm; and the base layer used SrTiO3 as the dielectric material with a thickness of 800 nm. Carboxyl grafting technology was used to strengthen the interfacial bonding between the layers, achieving an interfacial shear strength of 18.7 MPa.

[0062] S3. Deposited silver-carbon nanotube composite electrode

[0063] Sputtering via mask (vacuum: 5×10⁻⁶) -4 A silver-carbon nanotube composite electrode (thickness 800 nm, silver purity 99.99%, carbon nanotube aspect ratio 1000) was prepared by further deposition on the gradient dielectric layer-biomimetic topology. The electrode pattern was matched with the biomimetic tube foot array. The contact resistance of the silver-carbon nanotube composite electrode was <0.1 Ω·cm, and the sheet resistance was 4.2 Ω / sq. The composite electrode-gradient dielectric layer-biomimetic topology was thus prepared.

[0064] S4. Apply an anti-ion penetration coating.

[0065] 0.8 g of PIL and 0.08 g of silica nanoparticles were ultrasonically mixed in 80 mL of ethanol (power 200 W, time 20 min). The resulting solution was then coated onto the surface of the composite electrode-gradient dielectric layer-biomimetic topology using a spin coater (Laurell WS-650, USA) at 3000 rpm to form a 200 nm anti-ion penetration coating. This coating resulted in a charge dissipation rate of 0.03 μC / (m²·h), thus preparing the anti-ion penetration coating-composite electrode-gradient dielectric layer-biomimetic topology.

[0066] S5. Preparation of Dynamic Self-Healing Material Layer

[0067] 4,4'-Dithiodibenzoic acid, polyethylene glycol diacrylate, and photoinitiator Irgacure 2959 were mixed in deionized water at a mass ratio of 3.2:96.3:0.5 to form a prepolymer solution. Zinc nitrate (0.15 mol / L) and polyacrylic acid (Mw=250k, 4.7 wt%) were introduced into the prepolymer. NaOH solution (0.1 mol / L) was added to adjust the pH to 5.5. The solution was then injected into a mold and UV-cured (wavelength 365 nm, power density 10 mW / cm², time 30 min) to form a first-layer dynamic disulfide bond network and a second-layer network, resulting in a dual-network material. The tensile strength was increased to 18.0 MPa, the elastic modulus reached 2.3 GPa (tested according to ISO 527-2 standard), and the fracture toughness was 25.3 kJ / m² (tested according to ISO 13586 single-sided notched tensile test). Nanocellulose and titanium carbide MXene were then mixed in an ethanol solution (100... The nanofibers (cellulose nanoparticles), titanium carbide, and ethanol solution were ultrasonically dispersed in an ethanol solution at a mass ratio of 1:2:100. Subsequently, they were embedded into a dual-network material via an impregnation method (impregnation time 1.5 h, which ensures uniform loading of the nanofibers and titanium carbide MXene). This yielded a dynamic self-healing material layer with a thickness of 0.5 mm and an electrical conductivity of 4.1 × 10⁻⁶. -2 S / m (four-probe method, Loresta-GP MCP-T700, Japan); In order to verify the self-healing performance of the dynamic self-healing material layer, an artificial crack (0.5 mm wide) was also created on the dynamic self-healing material layer in this embodiment. The self-healing was completed after 5 minutes, and the conductivity recovery rate after self-healing was >85%.

[0068] S6. Preparation of a biomimetic self-sealing layer

[0069] A SA-PDA composite solution was prepared, with SA and PDA mass concentrations of 2% and 0.5%, respectively. A 20 μm thick mucus layer was formed at the encapsulation interface using a microdroplet jetting system. Under 80 MPa pressure, the leakage rate was <0.1 mL / h (tested according to GB / T 19624 standard), and the viscoelastic recovery rate after pressure was >95% (dynamic mechanical analyzer TA Q800). A nanosecond laser processing system (wavelength 1064 nm, pulse width 10 ns) was used to prepare sharkskin-inspired grooves (50 μm width, 30 μm depth, and 100 μm spacing) in the mucus layer, thus preparing a biomimetic self-sealing mucus layer. According to ISO 12240-4 standard testing, compared with the mucus layer without sharkskin-inspired grooves, the barnacle larvae adhesion rate decreased from 73% to 8.2%, and the surface fouling residue rate after rinsing with a 2 m / s water flow was <5%.

[0070] S7. Multilayer thermoforming and encapsulation

[0071] The biomimetic starfish tentacle triboelectric nanogenerator self-healing underwater detection patch was prepared by sequentially stacking an anti-ion penetration coating, a composite electrode, a gradient dielectric layer, a biomimetic topology, a dynamic self-healing material layer, and a biomimetic mucus self-sealing layer, and then bonding them using a hot press (temperature 80℃, pressure 0.5MPa, time 10min). The interfacial bonding strength reached 15.3N / cm (passed ASTM D1876 T-type peel test), which is 2.4 times higher than that of traditional bonding processes.

[0072] Examples 2-5

[0073] Same as Example 1, with differences shown in Table 1.

[0074] Table 1

[0075]

[0076] Notes: DTBA (4,4'-dithiodibenzoic acid); PEGDA (polyethylene glycol diacrylate); PAA (polyacrylic acid); SA (sodium alginate); polyPIL (polyionic liquid); NSiO2 (silica nanoparticles, 50nm in diameter).

[0077] Comparative Examples 1-5

[0078] Same as Example 1, with differences shown in Table 2.

[0079] Table 2

[0080]

[0081]

[0082] Notes: DTBA (4,4'-dithiodibenzoic acid); PEGDA (polyethylene glycol diacrylate); PAA (polyacrylic acid); SA (sodium alginate); polyPIL (polyionic liquid); NSiO2 (silica nanoparticles, 50nm in diameter).

[0083] Comparative Example 6

[0084] Existing patch fabrication methods involve using PDMS as the dielectric layer (1 μm thick), sputtering copper electrodes (800 nm thick), manually bonding each planar structural layer with epoxy adhesive, curing at room temperature for 24 hours, and encapsulation. These methods lack biomimetic topology, dynamic self-healing layers, and anti-ion penetration coatings, relying on traditional silicone adhesive for sealing, and do not incorporate a biomimetic self-sealing layer. Compared to existing technologies, the breakthrough of this invention lies in its multi-dimensional performance improvement: charge density (58 μC / m²). 2 vs. 1.1μC / m 2The self-healing efficiency (92% vs. 0%), compressive strength (78MPa vs. 25MPa), and power density (1.2W / m² vs. 0.05W / m²) are improved by 52.7 times, 3.1 times, and 24 times respectively. The "basic improvement" refers to the fact that existing traditional patches completely lack self-healing capabilities (self-healing efficiency is 0%, with no basic self-healing performance), while the detection patch of this invention achieves a 92% self-healing efficiency for the first time. This represents a breakthrough performance improvement "from nothing to something," rather than a multiple-level improvement based on existing non-zero foundations.

[0085] The self-healing underwater detection patches of the biomimetic starfish brachiopod triboelectric nanogenerators prepared in Examples 1-5 and Comparative Examples 1-6 were continuously operated in a simulated marine environment (80 MPa, 2℃, 3.5 wt% NaCl) to conduct tests on charge density, self-healing time, and underwater working life. The charge density was tested by using the open-circuit voltage-charge integration method, recording the total charge of the triboelectric generation cycle using an electrometer, and then dividing it by the effective power generation area. The self-healing time was recorded by artificially creating a 0.5 mm crack and recording the time required for complete repair. The output power density was measured by connecting an external variable resistor to the maximum output power and dividing it by the effective power generation area. The power density decay rate was calculated by measuring the decay ratio after long-term operation in a simulated marine environment.

[0086] The test results are shown in Table 3.

[0087] Table 3

[0088]

[0089] Application Example 1: Marine Organism Attachment Monitoring Patch

[0090] The self-healing underwater detection patch prepared in Example 1 was used, comprising the following core modules: 16×16 interdigitated electrodes (20μm linewidth, 50μm spacing, capacitance detection accuracy of 0.1pF), a micro LED (470nm wavelength) + Sony IMX586 CMOS image sensor (48MP resolution), a YOLOv11 AI recognition module (pre-trained to recognize 12 types of fouling organisms, mAP@0.5=0.93), a Xilinx ZU19EG FPGA data storage module, and a 28kHz / 10W ultrasonic cleaning module. The patch pretreatment involved uniformly spraying a polyethylene glycol (PEG, Mw=2000) anti-protein adsorption layer onto the surface, which, verified by image analysis, reduced non-specific adhesion by 89%. The patch's built-in sharkskin-inspired grooves (50μm width, 30μm depth, 100μm spacing) enhanced self-cleaning performance, with a fouling residue rate of <5% after rinsing with a 2m / s water flow. The integrated patch is mounted on the support frame of the Atlantic research platform. It requires no external power supply and relies on TENG electrical energy converted from bio-attachment vibrations (peak output 0.8W / m).2 Achieve energy self-sufficiency (78% annual self-sufficiency rate); automatically collect impedance data (monitoring capacitance changes caused by biological attachment) and image data every 6 hours, and store them in real time on the FPGA; identify barnacles, tube worms, and other organisms using the YOLOv11 algorithm, combined with capacitance changes (barnacle larva density 10). 3 The growth rate was quantified by ΔC=2.3pF when the number of cells / cm² was 1. When the image analysis showed that the dirt coverage was >30%, the ultrasonic cleaning module was triggered to work for 5 minutes, and the dirt removal rate was >92%. Based on this, the cleaning cycle was optimized. The test results are shown in Table 4.

[0091] Table 4 Performance Verification and Data

[0092]

[0093] Application Example 2: Coral Reef Ecological Restoration Monitoring System

[0094] The self-healing underwater detection patch prepared in Example 1 is used, and its core modules include: an AS7265x six-channel spectral sensor (wavelength 410-940nm), a microfluidic chip (channel width 200μm) + image recognition module, an ISE electrode array (detecting nitrate 0-100mg / L and phosphate 0-50mg / L), a 275nm ultraviolet LED, and an FPGA data storage module. The patch is integrated onto a 3D-printed porous calcium carbonate substrate (porosity 85%, pore size 1-3mm) to simulate the surface of a natural reef. The patch retains its original biomimetic self-sealing layer and anti-ion permeation coating to ensure long-term underwater stability, with a compressive strength of 78MPa suitable for reef environments. The integrated system is fixed to an artificially cultivated tropical coral reef in the Xisha Islands of the South China Sea, relying on the patch's TENG self-powered system (power density 1.2W / m²) to achieve operation without external power supply, with a sampling rate of 1Hz. Real-time data on photosynthetically active radiation (PAR), water quality indicators, and coral larval dynamics were collected and stored on an FPGA. Larval attachment was promoted by applying an electric field of 0.5-1.2 V / cm using patch electrodes, while daily 10-minute UV LED irradiation inhibited excessive algal growth. By combining spectral data with microfluidic image recognition (larval counting accuracy of 98.3%), larval attachment rate and growth status were quantified. Based on the monitoring results, breeding environment parameters were dynamically adjusted to guide the optimization of artificial coral breeding. Test results are shown in Table 5.

[0095] Table 5 Performance Verification and Data

[0096]

[0097] Application Example 3: Ship Corrosion Monitoring and Self-Repair System

[0098] The self-healing underwater detection patch prepared in Example 1 was used, and the core modules were combined as follows: φ0.25mm fluorinated polymer optical fiber (attenuation <0.2dB / km), FBG sensor array (center wavelength 1550nm±0.1nm, strain sensitivity 1με), electrochemical noise sensor (EN, sensitivity 1nA / cm²), pH microelectrode array (accuracy ±0.02), dual microencapsulated repair agent (epoxy resin / polythiol + molybdate corrosion inhibitor), and FPGA data processing module. The patch's anti-ion penetration coating and dynamic self-healing layer were retained and integrated with the ship's gradient coating system—a 120μm zinc-aluminum pseudo-alloy layer (sacrificial anode efficiency 92%) was superimposed as the bottom layer, and a graphene-reinforced epoxy resin (conductivity 10) was added as the intermediate layer. 3 The surface is covered with a fluorosiloxane hydrophobic layer (contact angle 165°); microcapsules (particle size 50-80μm, accounting for 15% of the coating volume) are embedded within the patch and integrated with the FBG sensor, EN sensor, and pH electrode array. On the modified 320,000-ton VLCC "Ocean Star," optical fibers were laid at 1.5-meter intervals along the hull ribs, with a total length of 38km covering 320,000 square meters of surface. Five integrated FBG sensors were implanted per square meter. Relying on the patch's TENG self-powered system (power density 1.2W / m²), strain, temperature, corrosion current, and pH data were collected in real time, stored in an FPGA, and a corrosion rate prediction model was established (error <5%). When the local corrosion rate is detected to be >0.3 mm / year and the acoustic emission reaches 50 dB, the microcapsule is triggered to rupture. The repair agent fills the ≤2 mm crack within 5 minutes and the curing strength reaches 95% of the base material within 24 hours. The docking plan is dynamically adjusted according to the corrosion heat map. It is verified that the coating has a gloss retention rate of >85% after 5 years of exposure in tropical seas. The total life cycle cost is reduced by 63% compared with traditional coatings. The test results are shown in Table 6.

[0099] Table 6 Performance Verification and Data

[0100]

[0101] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A self-healing underwater detection patch based on a biomimetic starfish brachiopod triboelectric nanogenerator, characterized in that, It includes the following structures: biomimetic topology, gradient dielectric layer, anti-ion penetration coating, dynamic self-healing material layer, biomimetic mucus self-sealing layer and silver-carbon nanotube composite electrode; The biomimetic topology is a biomimetic starfish brachiopod array topology, including a hexagonal close-packed array of tube feet. The diameter of the biomimetic starfish brachiopod tube feet is 50-200μm, the spacing is 100-300μm, and the tilt angle is 30°-60°. The gradient dielectric layer includes a surface layer, an intermediate layer, and a base layer, and the interfacial bonding between the layers is strengthened by a carboxyl grafting process. The dielectric material of the surface layer is fluorinated ethylene propylene with a thickness of 420nm-500nm; the dielectric material of the intermediate layer is polyimide with a thickness of 400nm-800nm; and the dielectric material of the base layer is strontium titanate with a thickness of 720nm-800nm. The preparation method of the dynamic self-healing material layer includes the following steps: dissolving 4,4'-dithiodibenzoic acid, polyethylene glycol diacrylate and a photoinitiator in water to form a prepolymer solution; adding zinc nitrate and polyacrylic acid to the prepolymer solution to adjust the pH of the solution, and then injecting the solution into a mold for ultraviolet curing to obtain a dual-network material; and embedding nanocellulose and titanium carbide into the dual-network material to prepare the dynamic self-healing material layer.

2. The self-healing underwater detection patch of the biomimetic starfish brachiopod triboelectric nanogenerator according to claim 1, characterized in that, The mass ratio of 4,4'-dithiodibenzoic acid, polyethylene glycol diacrylate, and photoinitiator is (2.8-3.2):(96.3-96.7):0.

5. The concentration of zinc nitrate in the prepolymer solution is 0.07-0.11 mol / L; the concentration of polyacrylic acid in the prepolymer solution is 4.3-4.7 wt%. The pH value is 4.7-5.5; The dual-network material includes a first dynamic disulfide bond network and a second network. The first dynamic disulfide bond network is formed by the 4,4'-dithiodibenzoic acid and the polyethylene glycol diacrylate during UV curing; The second layer of network consists of Zn 2+ It forms with carboxylate ions.

3. The self-healing underwater detection patch of the biomimetic starfish brachiopod triboelectric nanogenerator according to claim 1, characterized in that, The preparation method of the biomimetic mucus self-sealing layer includes the following steps: using microdroplet jetting to form a mucus layer at the encapsulation interface with a composite solution of sodium alginate and polydopamine, and using a nanosecond laser to prepare shark skin-like biomimetic grooves on the mucus layer to obtain the biomimetic mucus self-sealing layer; the thickness of the biomimetic mucus self-sealing layer is 16-20 μm.

4. The self-healing underwater detection patch of the biomimetic starfish brachiopod triboelectric nanogenerator according to claim 1, characterized in that, The silver-carbon nanotube composite electrode has a thickness of 800 nm; its electrode pattern matches the biomimetic starfish brachiopod array on the biomimetic topological structure.

5. A method for preparing a self-healing underwater detection patch of a biomimetic starfish brachiopod triboelectric nanogenerator as described in any one of claims 1-4, characterized in that, The process includes the following steps: using photocurable polyurethane acrylate as a substrate, a biomimetic topological structure is prepared on a silicon substrate by 3D printing; a gradient dielectric layer is deposited on the biomimetic topological structure by magnetron sputtering to obtain a gradient dielectric layer-biomimetic topological structure; a silver-carbon nanotube composite solution is deposited on the gradient dielectric layer to form a silver-carbon nanotube composite electrode with a pattern matching the biomimetic starfish brachiopod array in the biomimetic topological structure to obtain a composite electrode-gradient dielectric layer-biomimetic topological structure; an anti-ion permeation coating is uniformly coated on the silver-carbon nanotube composite electrode to obtain an anti-ion permeation coating-composite electrode-gradient dielectric layer-biomimetic topological structure; the anti-ion permeation coating-composite electrode-gradient dielectric layer-biomimetic topological structure, a dynamic self-healing material layer, and a biomimetic mucus self-sealing layer are then stacked sequentially and hot-pressed to prepare a self-healing underwater detection patch of the biomimetic starfish brachiopod triboelectric nanogenerator.

6. The application of a self-healing underwater detection patch of the biomimetic starfish brachiopod triboelectric nanogenerator as described in any one of claims 1-4 in an underwater detection device.

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