Ocean concrete structure self-energy-supply protection system

Abstract

The invention provides a self-energy-supply protection system for an ocean concrete structure. The self-energy-supply protection system comprises an energy management unit, a bonding functional layer, an energy collection layer and a protection power generation layer, wherein the energy collection layer and the protection power generation layer are sequentially arranged on the bonding functional layer; the bonding functional layer is used for being adhered to a concrete matrix, and the bonding functional layer comprises a viscoelastic matrix and zinc powder sacrificial anode particles; the energy collecting layer comprises an elastic supporting structure, a lower electrode layer and an electronegative friction material layer, wherein the lower electrode layer and the electronegative friction material layer are sequentially arranged on the bonding function layer. The lower electrode layer adheres to the bonding function layer through insulating glue. The protective power generation layer comprises a protective steel plate and a sealing structure; the energy management unit is used for converting alternating current pulses generated by friction power generation of the energy collection layer and the protective power generation layer into direct current, storing the direct current in the energy storage module and supplying power to the bonding function layer according to needs. According to the invention, continuous and stable cathode protection current can be provided for the concrete structure, and energy self-sufficiency and long-acting protection are realized.

Description

Technical Field

[0001] This application relates to the field of marine engineering protection technology, and in particular to a self-powered protection system for marine concrete structures. Background Technology

[0002] Marine environments are characterized by high salinity, high humidity, and strong corrosivity. Marine concrete structures are subjected to multiple deterioration effects over a long period of time, including seawater erosion, chloride ion penetration, carbonization, freeze-thaw cycles, and microbial erosion. As their service life extends, these numerous marine concrete structures suffer varying degrees of damage. If effective protective measures are not taken in a timely manner, it will not only affect the service life of the structure but may also lead to major safety accidents, causing huge economic losses and social impacts.

[0003] Currently, protective technologies for marine concrete structures mainly include surface coatings, sacrificial anodes, and impressed current cathodic protection. Surface coating protection involves applying materials such as epoxy resin, polyurethane, or inorganic coatings to the concrete surface to form a physical barrier against corrosive media. However, mechanical shocks, UV aging, and temperature changes in the marine environment can cause the coating to crack, blister, and peel off, exposing the substrate to a corrosive environment. Furthermore, coating repair is difficult and maintenance costs are high.

[0004] The sacrificial anode method uses a more negatively charged metal (such as zinc, magnesium, or aluminum) as the anode, and provides a protective current to the protected structure through galvanic corrosion. This method does not require an external power supply, but the anode material is consumed quickly. In highly conductive seawater environments, its service life is usually only 3-8 years, requiring frequent replacement, which increases operation and maintenance costs and construction difficulty, especially in underwater or semi-underwater environments where replacement operations are extremely difficult.

[0005] Impressed current cathodic protection technology applies a cathodic polarization current to the protected structure via an external DC power supply, shifting its potential negative to the protection range, thus achieving precise and controllable protection. However, the core bottleneck of this technology lies in a continuous and stable power supply. In nearshore areas, submarine cables can be laid to connect to shore-based power sources, but cable laying is costly and susceptible to damage from external forces such as ship anchor chains and fishing nets. In offshore and deep-sea environments, power supply is even more difficult. While solar power systems are clean and environmentally friendly, they are greatly affected by climate and seasons, with low power generation efficiency in high-latitude regions during winter or prolonged cloudy and rainy weather, making it difficult to guarantee all-weather power supply. Wind power generation is suitable for marine environments, but the equipment is large, the initial investment is high, and maintenance is complex. Diesel generators are reliable, but they require regular refueling, resulting in high operating and maintenance costs, and they pollute the environment, which is inconsistent with the concept of green development. These factors severely restrict the widespread application of impressed current cathodic protection technology in marine environments.

[0006] In recent years, triboelectric nanogenerators have attracted widespread attention as an emerging energy harvesting technology. Based on triboelectricity and electrostatic induction coupling effects, this technology can efficiently convert mechanical energy in the environment into electrical energy, offering significant advantages such as simple structure, inexpensive materials, strong adaptability, and environmental friendliness. The marine environment contains abundant mechanical energy resources, and wave energy and tidal energy have high energy density and strong sustainability, providing ideal scenarios for the application of triboelectric nanogenerators. However, existing triboelectric nanogenerators are mainly used for powering low-power sensors or charging portable electronic devices, with output power typically in the milliwatt range, which is insufficient to meet the power requirements of cathodic protection for marine structures (usually requiring several to tens of watts). Simultaneously, the high salinity of the marine environment accelerates electrode corrosion, high humidity leads to electrical insulation failure, and strong wave impacts cause structural damage. These harsh conditions place extremely high demands on the sealing, durability, and reliability of the power generation device, and existing technologies have significant shortcomings in these aspects. Furthermore, traditional protection technologies often employ a single protection mechanism, and its failure leads to the loss of overall protection effectiveness.

[0007] In summary, long-term protection of marine concrete structures faces numerous technical challenges: surface coatings are prone to failure, sacrificial anodes have short lifespans, power supply for impressed current cathodic protection is difficult, and single protection mechanisms have low reliability. Designing an innovative protection system that can utilize the abundant wave energy in the marine environment to achieve self-powered cathodic protection, integrate multiple protection mechanisms, possess intelligent monitoring and control capabilities, and adapt to long-term stable operation in harsh marine environments is of significant theoretical and engineering application value for extending the service life of marine concrete structures, reducing maintenance costs, and ensuring the safety of marine engineering projects. Summary of the Invention

[0008] The purpose of this application is to provide a self-powered protection system for marine concrete structures to solve or alleviate the problems existing in the prior art.

[0009] To achieve the above objectives, this application provides the following technical solution: A self-powered protection system for marine concrete structures includes an energy management unit, a bonding functional layer, and an energy harvesting layer and a protective power generation layer sequentially disposed on the bonding functional layer. The adhesive functional layer is used to adhere to the concrete matrix. The adhesive functional layer includes a viscoelastic matrix and functional components distributed therein. The functional components include at least a hydrophobic agent, aerogel slow-release particles, cement-based filler, magnesium oxide, and zinc powder sacrificial anode particles. The energy harvesting layer includes an elastic support structure and a lower electrode layer and a negatively charged triboelectric material layer sequentially disposed on the adhesive functional layer. The lower electrode layer is adhered to the adhesive functional layer by insulating adhesive, and the elastic support structure is connected between the adhesive functional layer and the protective power generation layer. Specifically, the energy harvesting layer is adhered to the adhesive functional layer by conductive adhesive. The protective power generation layer includes a protective steel plate with a textured outer surface and superhydrophobic properties, and a sealing structure that is sealed between the steel edge and the adhesive functional layer. The energy management unit includes a rectifier module, an energy storage module, and a control module. The energy management unit is used to convert the AC pulses generated by the friction between the energy harvesting layer and the protective power generation layer into DC power and store it in the energy storage module, and to supply power to the bonding functional layer as needed.

[0010] Furthermore, the adhesive functional layer comprises the following raw materials in parts by weight: 100 parts butyl rubber, 5-15 parts hydrophobic agent, 3-5 parts aerogel slow-release particles, 5-10 parts cement-based filler, 2-4 parts magnesium oxide, 5-15 parts zinc powder sacrificial anode particles, 3-5 parts plasticizer.

[0011] Furthermore, the butyl rubber has a molecular weight of 300,000-500,000 and an unsaturation degree of less than 2%; the hydrophobic agent is one or a mixture of several of nano-silica hydrophobic agents, fluorosilanes, or organosilicon hydrophobic agents; the aerogel slow-release particles are silica aerogel particles with a particle size of 0.5-5 mm; the cement-based filler is one or a mixture of several of calcium silicate, silica fume, or metakaolin; the zinc powder sacrificial anode particles have a particle size of 10-100 μm and a purity greater than 99%; and the plasticizer is one or a mixture of several of dioctyl phthalate, dioctyl sebacate, or epoxidized soybean oil.

[0012] Furthermore, the method for preparing the adhesive functional layer includes the following steps: Step 1: Add butyl rubber to the planetary mixer, keep the temperature between 15-25℃, and start low-speed stirring. Step 2: Add the hydrophobic agent, aerogel slow-release particles, cement-based filler, and magnesium oxide in batches; each batch should be 20-30% of the total amount added, and stir for 5-10 minutes after each addition. Step 3: Add zinc powder sacrificial anode particles and continue stirring for 20-30 minutes; Step 4: Add plasticizer and stir for 10-20 minutes; Step 5: Vacuum degassing for 15-25 minutes, with a vacuum degree of 0.1-1 kPa, to obtain the adhesive functional layer material.

[0013] Furthermore, the thickness of the bonding functional layer is 3-8 mm; the content of zinc powder sacrificial anode particles in the bonding functional layer is 5%-12% of the total mass, and they are uniformly dispersed to form a distributed primary electrochemical protection network.

[0014] Furthermore, the bonding functional layer is also fixed to the concrete substrate surface with the assistance of anchor bolts. The anchor bolt spacing is 20-50cm, the anchor bolt material is stainless steel or corrosion-resistant carbon steel, the diameter is 8-16mm, and the anchoring depth is 80-150mm.

[0015] Furthermore, the lower electrode layer is made of a flexible conductive material, such as a graphene composite conductive film, a carbon nanotube film, or a metallized polymer film, with a thickness of 0.05-0.3 mm and a conductivity greater than 1000 S / m; the lower electrode layer and the negatively charged triboelectric material layer are bonded face-to-face by conductive silver paste. The thickness of the negatively charged triboelectric material layer is 0.1-1 mm, and the material is selected from polytetrafluoroethylene, fluorinated ethylene propylene copolymer or polyvinylidene fluoride, with a thickness of 0.1-1 mm; the surface of the negatively charged triboelectric material layer is subjected to micro-nano structuring treatment, and multi-level composite morphology is prepared by reactive ion etching, nanoimprinting or template method. The elastic support structure is made of silicone rubber, polyurethane, or shape memory polymer, and is formed into a micro-spring array or porous elastomer through injection molding or 3D printing. The elastic support structure has a compressive modulus of 5-20 MPa and a resilience greater than 80%. Too low a compressive modulus will cause excessive deformation of the elastic support structure under wave action, resulting in insufficient contact pressure between the friction layer and the protective layer, inadequate contact, and low triboelectric power generation efficiency. A low resilience rate results in slow separation and recovery speed, making it unable to follow high-frequency waves (>3Hz), thus limiting the power generation frequency. Too high a compressive modulus makes the elastic support structure too rigid, resulting in insufficient deformation under low-wave conditions (wave height <1m), with a relative displacement between the friction layer and the protective layer of only 0.3-0.8 mm, insufficient contact and separation movement, and low power generation efficiency. When the elastic support structure is a distributed micro-spring array, the diameter of a single spring is 1-10mm, the height is 3-20mm, and the distribution spacing is 5-50mm; when the elastic support structure is a continuous porous elastomer, the porosity is 40%-70% and the pore diameter is 0.5-5mm.

[0016] Preferably, a multi-level composite morphology is prepared on the surface of the negatively charged triboelectric material layer by micro-nano structuring treatment. The process parameters for micro-nano structuring treatment are: radio frequency power of 50-150W, chamber pressure of 5-15Pa, and etching time of 5-15min during reactive ion etching; or pressure of 5-20MPa, temperature of 150-200℃, and holding time of 30-120s during nanoimprinting.

[0017] Furthermore, the energy harvesting layer includes several distributed array-designed power generation units, each comprising a unit electrode layer and a unit friction layer sequentially disposed on the bonding functional layer; the effective area of ​​a single power generation unit is 0.01-0.25m². 2 Multiple power generation units are connected in parallel.

[0018] Furthermore, the protective steel plate is made of 316L or 2205 duplex stainless steel with a thickness of 1-3mm; the protective steel plate is processed into a Miura folded texture structure; the outer surface of the protective steel plate is formed into a micro-nano composite rough structure by laser texturing or chemical etching, and coated with a low surface energy material layer; the low surface energy material is perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane.

[0019] The superhydrophobic properties of the outer surface of the protective power generation layer are achieved through a micro / nano-scale composite rough structure combined with a low surface energy material layer. The micro / nano-scale composite rough structure comprises a micron-scale array structure (characteristic size 10-50 μm) first formed on the surface of a stainless steel plate, and a nano-scale rough structure (characteristic size 50-500 nm) formed on the surface of the micron-scale structure; finally, a low surface energy material is added. The combined effect of these three elements results in a water contact angle greater than 150° and a roll-off angle less than 10°. Preferably, the micron-scale array structure is laser-textured, specifically using a nanosecond laser or femtosecond laser with a laser power of 10-100 W and a scanning speed of 100-1000 mm / s, forming micron-scale pits with a diameter of 10-50 μm and a depth of 5-20 μm; the nano-scale rough structure is chemically etched, specifically using a mixed solution of hydrofluoric acid and nitric acid in a volume ratio of 1:3-3:1 for an etching time of 10-30 min.

[0020] Furthermore, the apex angle of the folding unit of the protective steel plate with the Miura folded texture structure is 60-120°, the crease depth is 1-2mm, and the root is provided with a rounded transition to form a rhombus or hexagonal unit array with a unit side length of 5-15cm. The Miura folded texture structure can generate controllable deformation under the action of waves, with a deformation of 50%-200% of the crease depth, driving relative displacement between the protective layer and the energy harvesting layer, with a displacement amplitude of 1-20mm and a motion frequency of 0.3-5Hz.

[0021] Furthermore, the self-powered protection system for marine concrete structures adopts a modular design, with each module measuring 1-3m in size. 2 The modules are connected by flexible connectors made of EPDM rubber or polyurethane, which are V-shaped or accordion-shaped (W-shaped) expansion joint rubber strips with a width of 3-8cm. The sealing structure is set at the edge of the module, and the sealing material of the sealing structure is fluororubber or silicone rubber with a compression rate of 20%-30%.

[0022] Furthermore, the self-powered protection system for marine concrete structures also includes a reference electrode network uniformly arranged on the surface of the bonding functional layer. The reference electrode network is used to collect the potential of the concrete matrix in real time, with a sampling frequency of 0.1-10Hz. The control module monitors the triboelectric power generation, energy storage status of the energy storage module, surface potential of the concrete matrix, and corrosion rate in real time, and controls the protective current density output to the bonding function to maintain the concrete surface potential within the range of -800 to -950mV. When the energy storage status is above 80% and the power generation is sufficient, the output protection current density is 50-100 mA / m. 2 ; When the energy storage state is 30%-80%, the output protection current density is 20-50 mA / m. 2 ; When the energy storage state is below 30%, the output protection current density is 10-20 mA / m. 2 .

[0023] Furthermore, the reference electrode is a silver / silver chloride electrode or a zinc electrode, which is uniformly arranged on the surface of the protection system with a spacing of 1-3m. The electrode size is 10-20mm in diameter and 50-120mm in length. The reference electrode is communicatively connected to the energy management unit through the data acquisition and transmission unit. The data acquisition and transmission unit includes an analog-to-digital converter, a data processor, and a wireless communication module. The analog-to-digital converter has a resolution of no less than 12 bits. The wireless communication module supports at least one of the following communication protocols: NB-IoT, LoRa, 4G, 5G, or BeiDou satellite communication.

[0024] Furthermore, the energy management unit includes a rectifier module, a voltage regulator module, an energy storage module, and a control module; The rectifier module employs a full-wave bridge rectifier or a multi-stage voltage multiplier rectifier circuit, with a forward voltage drop of less than 0.5V. The voltage regulation module uses a Buck converter, with an input voltage range of 5-100V and an output voltage stable at 5-20V. The voltage regulation module uses pulse width modulation control with a switching frequency of 50-500kHz. The energy storage module uses a supercapacitor bank and a lithium battery bank. The total energy storage capacity of the supercapacitors is 50-1000Wh, and the capacity of a single supercapacitor cell is 10-500F, with multiple capacitors connected in series and parallel. The lithium battery bank has a capacity of 10-100Ah and an operating voltage of 12-48V. The control module is a control board including a microcontroller, integrating a current sensor, a voltage sensor, a reference electrode signal acquisition circuit, and a PWM drive circuit. The microcontroller uses an ARM Cortex-M series or an STM32 series. The energy management unit is encapsulated and fixed in a protective housing (such as one made of engineering plastics or stainless steel). The protection level is required to be above IP6. It is generally fixed to the concrete substrate by a bracket or the mounting structure on the protective housing. During installation, try to avoid the splash zone or add a protective cover.

[0025] Furthermore, an LC filter composed of inductors and capacitors is set at the front end of the rectifier circuit as an impedance matching network, and its resonant frequency matches the wave drive frequency. The wave drive frequency is the frequency of wave motion, which is the reciprocal of the wave period. When the wave period is 0.5-6s, the corresponding wave drive frequency is 0.167-2Hz. Therefore, the resonant frequency range of the LC filter is 0.3-5Hz, which can cover the wave frequency range under typical sea conditions and extend to higher frequencies to adapt to high-frequency excitations such as gusts and broken waves.

[0026] The self-powered protection system for marine concrete structures can be applied to the long-term protection of marine concrete structures such as offshore platforms, cross-sea bridges, wharves, and offshore wind power foundations. The environmental conditions for application are: seawater environment, temperature -20℃ to 45℃, salinity 25‰-40‰, wave height 0.3m-8m, and wave period 0.5s-6s.

[0027] The technical solution of this application has the following beneficial effects: The adhesive functional layer of this application achieves a synergistic effect of multiple protective mechanisms through a composite design of butyl rubber matrix and functional components. Specifically, butyl rubber provides rapid initial adhesion, aerogel slow-release particles impart hydrophobic properties to the system, and distributed zinc powder sacrificial anodes provide primary electrochemical protection. The addition of cement-based fillers and magnesium oxide enhances the chemical compatibility and mechanical anchoring force with the concrete matrix, preventing debonding at the concrete-matrix interface and laying the foundation for the stable service of the subsequent protective layer.

[0028] This application significantly improves triboelectric power generation performance by forming a multi-level composite structure through micro-nano structuring of the surface of the negatively charged triboelectric material layer. The elastic support structure ensures that the triboelectric layer provides a continuous and stable cathodic protection current to the concrete structure under typical sea conditions. The protective power generation layer with a Miura folded texture structure achieves the dual functions of mechanical buffering and energy harvesting. It can generate controllable deformation under wave impact (frontal impact), effectively buffering stress. Simultaneously, it transforms disordered wave motion into regular plate deformation, driving a relative displacement of 1-20 mm between the protective layer and the energy harvesting layer, improving energy conversion efficiency. The superhydrophobic surface treatment of the outer surface of the protective steel plate effectively blocks the influence of seawater on the friction interface, ensuring long-term stability of power generation performance.

[0029] The self-powered protection system for marine concrete structures presented in this application exhibits superior performance, providing a continuous and stable cathodic protection current to the concrete structure, achieving true energy self-sufficiency and long-term protection. The system has a design life of 20-30 years, saving 60%-80% on cable laying and power equipment investment compared to traditional impressed current cathodic protection schemes, and reducing annual operation and maintenance costs by over 70%. Traditional sacrificial anodes have a lifespan of only 3-8 years; compared to the sacrificial anode method, this application eliminates the need for frequent anode material replacement, reducing total life-cycle costs by over 40%. Attached Figure Description

[0030] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. Wherein: Figure 1 This is a schematic diagram of the structure of an embodiment of the present invention.

[0031] Figure 2 This is a schematic diagram of the layout of the power generation unit and the elastic support structure according to an embodiment of the present invention.

[0032] In the figure, 1-adhesive functional layer, 2-unit electrode layer, 3-unit friction layer, 4-elastic support structure, 5-sealing structure, 6-protective steel plate, 7-flexible connector, 8-edge bolt, 9-sealing gasket, 100-concrete substrate. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention are within the scope of protection of the present invention.

[0034] In the description of this application, the terms "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this application and do not require this application to be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0035] This invention addresses at least one of the problems existing in current marine concrete protection technologies, such as power supply difficulties, low reliability of single protection mechanisms, high maintenance costs, and lack of intelligent management, by providing a self-powered protection system for marine concrete structures.

[0036] The marine environment contains abundant wave and tidal energy, which are characterized by their persistence and wide distribution. Meanwhile, the development of triboelectric nanogenerator technology provides a new pathway for converting mechanical energy into electrical energy. The inventors envisioned combining wave energy harvesting with cathodic protection to construct a self-powered protection system, fundamentally solving the power supply problem for marine engineering structure protection. Furthermore, origami structures, such as the Miura fold, have proven in aerospace engineering to possess excellent mechanical cushioning performance and controllable deformation characteristics. Applying these principles to research on marine protective materials would help solve or improve the aforementioned problems existing in current marine concrete protection technology.

[0037] like Figures 1 to 2 As shown, this application proposes a self-powered protection system for marine concrete structures, including an energy management unit, a bonding functional layer 1, and an energy collection layer and a protective power generation layer sequentially disposed on the bonding functional layer 1. The adhesive functional layer 1 is used to adhere to the concrete substrate 100. The adhesive functional layer 1 includes a viscoelastic matrix and functional components distributed therein. The functional components include at least a hydrophobic agent, aerogel slow-release particles, cement-based filler, magnesium oxide and zinc powder sacrificial anode particles. The energy harvesting layer includes an elastic support structure 4 and a lower electrode layer and a negatively charged friction material layer sequentially disposed on the adhesive functional layer 1. The elastic support structure 4 connects the adhesive functional layer 1 and the protective power generation layer. Specifically, the energy harvesting layer is bonded to the adhesive functional layer 1 with conductive adhesive. The protective power generation layer includes a protective steel plate 6 with a textured outer surface and superhydrophobic properties, and a sealing structure 5 that is sealed between the steel edge and the adhesive functional layer 1. The energy management unit includes a rectifier module, an energy storage module, and a control module. The energy management unit is used to convert the AC pulses generated by the friction between the energy harvesting layer and the protective power generation layer into DC power and store it in the energy storage module, and to supply power to the bonding functional layer 1 as needed.

[0038] The adhesive functional layer 1 has a thickness of 3-8mm (e.g., 3mm, 4mm, 5mm, 6mm, 7mm, 8mm), the total thickness of the energy harvesting layer is 3-20mm (e.g., 3mm, 5mm, 8mm, 10mm, 15mm, 20mm), and the thickness of the protective power generation layer is 1-3mm (e.g., 1mm, 1.5mm, 2mm, 2.5mm, 3mm).

[0039] In the bonding functional layer 1 of this application, the butyl rubber matrix provides rapid initial bonding force and good airtightness and watertightness. The hydrophobic agent in the functional components imparts hydrophobic properties to the surface of the bonding layer, reducing water intrusion. The aerogel slow-release particles have ultra-low density and high porosity, enabling slow release and providing long-term protection. The cement-based filler enhances the chemical compatibility with the concrete matrix 100. Magnesium oxide acts as an alkaline regulator, optimizing the interfacial pH environment. Zinc powder sacrificial anode particles are uniformly dispersed in the matrix, forming a distributed primary electrochemical protection network, which shifts the self-corrosion potential of the steel reinforcement negatively by 150-200mV, providing a basic guarantee for subsequent impressed current cathodic protection.

[0040] In a preferred embodiment of the self-powered protection system for marine concrete structures of the present invention, the energy harvesting layer is constructed based on the principle of electret triboelectric nanogenerator (TENG) and includes a lower electrode layer, a negatively charged triboelectric material layer, and an elastic support structure 4. The lower electrode layer is made of a flexible conductive material with a thickness of 0.05-0.3 mm and a conductivity greater than 1000 S / m, serving to collect and conduct charge. The negatively charged triboelectric material layer is made of a polymer at the negative end of the triboelectric series, such as polytetrafluoroethylene, fluorinated ethylene propylene copolymer, or polyvinylidene fluoride, with a thickness of 0.1-1 mm. The surface of the negatively charged triboelectric material layer is treated with micro- and nano-structures to form a multi-level composite structure with micron-level feature sizes of 5-50 μm and nano-level feature sizes of 50-500 nm, resulting in a surface charge density of 100-200 μC / m. 2 Compared to smooth surfaces, this improves performance by 200%-300%. The elastic support structure 4 is made of silicone rubber, polyurethane, or shape memory polymer, with a compression modulus of 5-20 MPa and a resilience greater than 80%, ensuring effective contact-separation movement of the friction layer under wave-driven conditions. Under wave action, the inner surface of the protective power generation layer contacts and separates from the negatively charged friction material layer of the energy harvesting layer, or slides relative to it. Due to the positional difference of the two materials in the triboelectric sequence, charge transfer occurs upon contact, and a potential difference is generated between the two electrodes upon separation, forming an alternating current output.

[0041] The protective steel plate 6 of the protective power generation layer in this application is made of stainless steel, specifically 316L or 2205 duplex stainless steel, with a thickness of 1-3 mm. The outer surface of the protective steel plate 6 is formed with a micro-nano composite rough structure by laser texturing or chemical etching, and coated with a low surface energy material layer. The micro-nano composite rough structure includes a micron-level array structure with a characteristic size of 10-50 μm first formed on the stainless steel surface, and a nano-level rough structure with a characteristic size of 50-500 nm formed on the micron-level structure surface. The stainless steel plate is formed with a folded texture structure by precision embossing or CNC bending, with the apex angle of the folded unit being 60-120° (e.g., 60°, 75°, 90°, 105°, 120°), the crease depth being 1-2 mm (e.g., 0.5 mm, 1 mm, 1.5 mm, 2 mm), and a rounded corner transition at the root, forming a rhomboid or hexagonal unit array.

[0042] This application designs the protective steel plate 6 as a Miura folded structure to achieve the dual functions of mechanical buffering and energy harvesting. The Miura folded structure can generate controllable deformation under wave impact, with a deformation of 50%-200% of the crease depth, effectively buffering stress and preventing the protective layer from cracking due to fatigue. At the same time, this topology transforms disordered wave motion into regular plate deformation, driving a relative displacement of 0.25-4mm between the protective layer and the energy harvesting layer. After the wave pressure subsides, the elastic restoring force of the stainless steel plate, together with the elastic support structure 4, restores the folded structure to its initial state, with a motion frequency of 0.3-5Hz matching the ocean wave cycle.

[0043] The energy management unit of this application, including a rectifier module, an energy storage module, and an intelligent control module, utilizes conventional technology and can be designed and manufactured by a professional company according to the following requirements. The rectifier module employs a full-wave bridge rectifier or a multi-stage voltage multiplier rectifier circuit. Schottky diodes or silicon carbide diodes are used as rectifier diodes to convert AC pulses generated by triboelectric power generation into DC current. An impedance matching network, including an LC filter composed of inductors and capacitors, is installed at the front end of the rectifier circuit. The resonant frequency matches the wave drive frequency (0.3-5Hz) to maximize energy transfer efficiency. The voltage regulation module uses a Buck converter with an input voltage range of 5-100V and an output voltage stable at 5-20V. The voltage regulation accuracy is 2%, and the conversion efficiency is greater than 85%.

[0044] The energy storage module can employ supercapacitor banks or lithium battery banks. The supercapacitors have individual capacities of 10-500F and an operating voltage of 2.7V. Multiple supercapacitors are connected in series and parallel to achieve a total energy storage capacity of 50-1000Wh. Supercapacitors can effectively balance the intermittency and randomness of wave energy. The lithium battery bank serves as a long-term energy storage backup, providing basic protection current during periods of continuous low wave activity. The lithium battery bank has a capacity of 10-100Ah and an operating voltage of 12-48V. The energy management system employs an intelligent charge and discharge control strategy, dynamically allocating energy according to the energy storage status and load demand.

[0045] The intelligent control module is implemented based on a microcontroller, which uses an ARM Cortex-M series or STM32 series microcontroller with a main frequency of no less than 48MHz. The intelligent control module integrates a current sensor (Hall effect sensor, range 0-10A, accuracy 1%), a voltage sensor (voltage divider resistor network, range 0-100V, accuracy 0.5%), a reference electrode signal acquisition circuit, and a PWM drive circuit (switching frequency 50-500kHz). The control strategy is to monitor triboelectric power generation, energy storage status, concrete surface potential, and corrosion rate in real time, with a sampling frequency of 0.1-10Hz. Control strategy: When the energy storage state is above 80% and the power generation is sufficient, the output protection current density is 50-100mA / m 2 When the energy storage state is 30%-80%, the output protection current density is 20-50 mA / m. 2 When the energy storage state is below 30%, the output protection current density is 10-20 mA / m. 2 The protective current is dynamically adjusted using PID control or fuzzy control algorithms to maintain the concrete surface potential within the range of -800 to -950 mV (relative to a saturated calomel electrode), meeting the requirements of GB / T21447-2018 standard.

[0046] Furthermore, the reference electrodes are Ag / AgCl electrodes (KCl saturated solution, +199mV vs SHE) or zinc electrodes (purity >99.99%, -763mV vs SHE), uniformly arranged on the surface of the protection system at intervals of 1-3m, with dimensions of 10-20mm in diameter and 50-120mm in length. The electrodes are connected to the data acquisition and transmission unit via seawater-resistant copper-core polyurethane-sheathed shielded cables.

[0047] The data acquisition and transmission unit includes an analog-to-digital converter (ADC), a data processor, and a wireless communication module. The ADC has a sampling rate of 1-100 kSPS. The data processor is capable of data preprocessing, anomaly detection, and fault diagnosis. The wireless communication module supports multiple protocols. Monitoring data is uploaded to the cloud platform every 5 minutes to 1 hour. The cloud platform provides data storage, visualization, anomaly alarms, and remote control functions.

[0048] like Figures 1 to 2 As shown ( Figure 2 (The protective steel plate and sealing structure are not shown in the original drawing). The self-powered protection system for marine concrete structures in this application adopts a modular design, with each module measuring 1-3m in size. 2 (For example, 1m) 2 1.5m 2 2m 2 2.5m 2 3m 2 Weighing 20-80kg, each module can be handled and installed by 2-3 workers. A single module consists of a protective steel plate and multiple power generation units that can be covered by the protective steel plate. The modules are connected by flexible connectors made of EPDM rubber or polyurethane, which are V-shaped or accordion-shaped (W-shaped) expansion joint rubber strips with a width of at least 3-8cm (e.g., 3cm, 4cm, 5cm, 6cm, 7cm or 8cm).

[0049] The processing of the Miura folded stainless steel sheet for the protective power generation layer can be outsourced to a specialized company. For example... Figure 1 As shown, the protective steel plate 6 of the protective power generation layer has a smooth edge without creases and is folded to facilitate the installation of the sealing structure 5. The sealing structure 5 uses a square-shaped sealing strip made of fluororubber or silicone rubber with a compression rate of 20%-30%. Mounting holes are opened on the folded edge. One end of the mounting bolt 8 passes through the mounting hole and the bonding functional layer 1 and is fixed in the concrete substrate 100. The fluororubber sealing strip and the protective steel plate 6 are installed on the concrete substrate 100. The compression rate of the fluororubber sealing strip is adjusted by adjusting the tightness of the mounting bolt 8. The mounting bolt 8 is set inside the fluororubber sealing strip to avoid contact with seawater as much as possible. The mounting bolt 8 is made of stainless steel or marine engineering special bolts. A butyl sealing gasket 9 is placed between the bolt and the folded edge. Marine-grade silicone sealant is applied to the inside of the bolt hole to prevent seawater from seeping in through the hole and causing a short circuit in the lower electrode layer or failure of the bonding functional layer 1.

[0050] Several embodiments and comparative examples are given below. The main raw materials used in the following embodiments and comparative examples are: Butyl rubber: from ExxonMobil Chemical Company, model Butyl 268; Nano silica hydrophobic agent: hydrophobic fumed silica, from Cabot Corporation, model TS-720, particle size 7-30nm; Silica aerogel particles (nano silica hydrophobic agent): Aspen Aerogels (USA), model Spaceloft; Organosilicon hydrophobic agent: Dow Corning, model Xiameter PMX-200, the main component is polydimethylsiloxane (PDMS).

[0051] Calcium silicate: Wollaston Mining Company, particle size 1-10μm, purity >95%; Magnesium oxide: Sinopharm Chemical Reagent Co., Ltd., analytical grade, particle size <5μm; Zinc powder: Zhongjin Lingnan Nonferrous Metals Co., Ltd., purity 99.9%, particle size 10-100μm; Polytetrafluoroethylene film: DuPont, model Teflon FEP, thickness 0.1-0.5mm; Fluorinated ethylene propylene copolymer: Daikin Industries, Ltd., model Neoflon FEP, thickness 0.2-0.5mm; Silicone rubber: Dow Corning, model Sylgard 184, Shore A 40; Polyurethane: BASF, model Elastollan, Shore A 80. 316L stainless steel sheet: Baosteel Stainless Steel Co., Ltd., thickness 1-3mm, composition conforms to ASTM A240 standard; 2205 duplex stainless steel sheet: Taiyuan Iron & Steel Co., Ltd., thickness 1-3mm, composition conforms to ASTM A240 standard; Perfluorooctyltriethoxysilane: Shin-Etsu Chemical Co., Ltd., purity >97%; Silver / silver chloride electrode: Commercially available marine silver / silver chloride electrode, size φ12mm×120mm; Zinc electrode: Self-made, purity 99.99%, size φ15mm×80mm.

[0052] Example 1 A self-powered protection system for marine concrete structures, characterized in that it includes an energy management unit, a bonding functional layer, and an energy collection layer and a protective power generation layer sequentially disposed on the bonding functional layer; The adhesive functional layer comprises 100 parts butyl rubber (molecular weight 400,000, unsaturation 1.8%), 5 parts nano silica hydrophobic agent, 3 parts aerogel slow-release particles (particle size 1 mm), 5 parts calcium silicate (cement-based filler), 2 parts magnesium oxide, 5 parts zinc powder sacrificial anode particles (particle size 50 μm), and 3 parts dioctyl phthalate (plasticizer). The energy harvesting layer includes an elastic support structure and a lower electrode layer and a negatively charged friction material layer sequentially disposed on the adhesive functional layer. The lower electrode layer is made of graphene composite conductive film with a thickness of 0.15 mm and a conductivity of 1500 S / m. The negatively charged friction material layer is made of polytetrafluoroethylene film with a thickness of 0.3 mm. The elastic support structure is made of silicone rubber, which is 3D printed to form a micro-spring array. Each spring has a diameter of 3 mm, a height of 8 mm, a distribution spacing of 15 mm, an elastic modulus of 10 MPa, and a resilience of 85%. The protective steel plate in the protective power generation layer is made of 316L stainless steel with a thickness of 2mm; the edge of the protective steel plate and the bonding functional layer are sealed by a sealing structure. The energy management unit includes a rectifier module, an energy storage module, and a control module. The rectifier module uses a full-wave bridge rectifier circuit with Schottky diodes (Infineon 1N5819) and an LC filter (10mH inductor, 100μF capacitor, resonant frequency 1.6Hz) at the front end of the rectifier circuit. The voltage regulation module uses a Buck converter (Texas Instruments LM2596, switching frequency 150kHz), with an input voltage range of 5-100V, an output voltage of 12V, and a conversion efficiency of 88%. The total energy storage capacity of the storage module is approximately 700Wh, with the supercapacitor bank having a storage capacity of approximately 100Wh and the lithium battery bank having a storage capacity of 600Wh. The intelligent control module is based on an STM32F407 microcontroller and integrates a Hall current sensor and a voltage sensor. The reference electrode network uses silver / silver chloride reference electrodes, evenly distributed on the surface of the protection system at 1.5m intervals, and connected to the data acquisition and transmission unit via shielded cables. The data acquisition and transmission unit uploads monitoring data every 30 minutes.

[0053] The preparation steps of the adhesive functional layer are as follows: Step 1: Add 100 parts of butyl rubber to a planetary mixer equipped with a temperature control system, keep the temperature at 20°C, and stir at a low speed of 50 rpm. Step 2: Add functional components in batches: First batch: add 2 parts of nano-silica hydrophobic agent and stir for 5 minutes; Second batch: add 2 parts of hydrophobic agent and 1 part of aerogel sustained-release particles and stir for 5 minutes; Third batch: add 1 part of hydrophobic agent, 1 part of aerogel sustained-release particles, 2 parts of calcium silicate and 1 part of magnesium oxide and stir for 10 minutes; Fourth batch: add 1 part of aerogel sustained-release particles, 3 parts of calcium silicate and 1 part of magnesium oxide and stir for 10 minutes. Step 3: Add 5 parts of zinc powder sacrificial anode particles with a particle size of 50μm, and continue stirring for 25 minutes; Step 4: Add 3 parts of dioctyl phthalate (plasticizer) and stir for 15 minutes; Step 5: Degas under a vacuum of 0.5 kPa for 20 minutes to obtain the adhesive functional layer material.

[0054] The bonding functional layer material is applied to the concrete substrate surface with a thickness of 5mm. After the bonding functional layer material is cured, it is fixed with stainless steel 316L anchors with a diameter of 10mm, an anchoring depth of 100mm, and an anchor spacing of 30cm.

[0055] The steps for preparing the energy harvesting layer are as follows: Step 1: Prepare the lower electrode layer (graphene composite conductive film) and the negatively charged triboelectric material film (polytetrafluoroethylene film). Step 2: The surface of the negatively charged triboelectric material film is subjected to micro- and nano-structural treatment by reactive ion etching: RF power 80W, chamber pressure 8Pa, atmosphere is a mixture of oxygen and carbon tetrafluoride in a volume ratio of 1:3, etching time 8 minutes, forming a multi-level composite structure with a micron-level feature size of 15μm and a nano-level feature size of 100nm. Step 3: Prepare the elastic support structure by 3D printing a micro-spring array using silicone rubber as the raw material. Each spring has a diameter of 3mm, a height of 8mm, a distribution spacing of 15mm, an elastic modulus of 10MPa, and a resilience of 85%. The processing of graphene composite conductive film, polytetrafluoroethylene film, and elastic support structure in steps 1, 2, and 3 can be outsourced to specialized companies. Step 4: Bond the lower electrode layer and the negatively charged tribological material layer together with conductive silver paste to form an energy harvesting layer; the lower electrode layer is adhered to the bonding functional layer with an insulating adhesive, such as marine-grade silicone insulating adhesive; the energy harvesting layer includes 16 distributed array-designed power generation units, each power generation unit comprising a unit electrode layer and a unit tribological layer sequentially arranged on the bonding functional layer, with an effective area of ​​0.09 m² for each power generation unit. 2 (300mm×300mm), total effective area 1.44m² 2 The elastic support structure is arranged in a frame-like manner on the outer ring of the power generation unit; the bottom of the elastic support structure is fixed to the surface of the bonding functional layer by silicone rubber adhesive (Dow Corning 734), and the silicone rubber adhesive cures in 24 hours.

[0056] The preparation steps of the protective power generation layer are as follows: Step 1: The outer surface of a 2mm thick 316L stainless steel plate (wavelength 1064nm, power 50W, scanning speed 500mm / s) was textured using a nanosecond laser to form micron-sized pits (diameter 25μm, depth 10μm). Then, it was immersed in an anhydrous ethanol solution of 1% perfluorooctyltriethoxysilane for 30 minutes and cured at 120℃ for 1 hour to form a superhydrophobic surface. The surface was tested and found to have a water contact angle of 156° and a roll-off angle of 8°. Step 2: The protective steel plate of the protective power generation layer has a pre-reserved smooth edge. The middle area of ​​the protective steel plate is formed with a Miura folded texture structure through a precision embossing process. The folded unit has a 90° apex angle and a fold depth of 1mm, forming a diamond unit array with a unit side length of 8cm. After embossing, the edge of the protective steel plate of the protective power generation layer is folded to facilitate the installation of the sealing structure, and mounting holes are made on the folded edge. Figure 1 The diagram schematically illustrates the protective steel plate structure of the protective power generation layer; The processing of the stainless steel plate of the Miura folding protective power generation layer in steps 1 and 2 can be outsourced to a specialized company. Step 3: Assemble the treated stainless steel plate with the energy harvesting layer. For example... Figure 1 As shown, the sealing structure uses a square-shaped fluororubber sealing strip. One end of the edge bolt passes through the mounting hole and the bonding functional layer and is fixed in the concrete substrate. The fluororubber sealing strip and the protective steel plate are installed on the concrete substrate. The edge bolt is placed inside the fluororubber sealing strip to avoid contact with seawater as much as possible. The edge bolt is made of stainless steel or marine engineering special bolts. The elastic support structure is pre-compressed by compressing the fluororubber sealing strip by turning the bolt. The compression rate of the fluororubber sealing strip is about 25%. The original length of the elastic support structure is 8mm, the pre-compression rate is 9%, and the target length is 7.25mm.

[0057] The self-powered protection system in this embodiment adopts a modular design. Each module includes 16 power generation units and a Miura folded stainless steel plate (protective power generation layer). The area of ​​the protective power generation layer completely covers all 16 power generation units of this module, and the protective steel plate has a size of 2.25m. 2 (1.5m × 1.5m). Adjacent modules are connected by EPDM rubber flexible connectors, with appropriate V-shaped / accordion-shaped expansion joint strips selected.

[0058] Example 2 The main difference between this embodiment and Example 1 lies in the component dosage and some process parameters. Only the differences will be explained here: The bonding functional layer consists of 100 parts butyl rubber, 10 parts hydrophobic agent (6 parts nano-silica hydrophobic agent + 4 parts organosilicon hydrophobic agent), 4 parts aerogel slow-release particles (particle size 2 mm), 8 parts cement-based filler (5 parts calcium silicate + 3 parts silica fume), 3 parts magnesium oxide, 10 parts zinc powder sacrificial anode particles (particle size 30 μm), and 4 parts plasticizer (dioctyl sebacate). The preparation process is the same as in Example 1. The coating thickness of the bonding functional layer on the concrete substrate is 6 mm.

[0059] Energy harvesting layer: The lower electrode layer uses a carbon nanotube film (0.2 mm thick, 2000 S / m conductivity); the negatively charged triboelectric material layer uses fluorinated ethylene propylene copolymer (Daikin Neoflon FEP, 0.5 mm thick); the micro-nano structuring process uses nanoimprinting (pressure 10 MPa, temperature 180 °C, holding time 60 s) to form a structure with a micron-level feature size of 30 μm and a nano-level feature size of 200 nm. The elastic support structure uses a porous polyurethane elastomer with a porosity of 55%, a pore size of 2 mm, a compressive modulus of 12 MPa, and a resilience of 88%.

[0060] Protective power generation layer: Made of 2205 duplex stainless steel plate (2.5mm thick); chemically etched for 20 minutes with hydrofluoric acid:nitric acid in a volume ratio of 1:3 to form a micro-nano composite structure; the outer surface of the stainless steel plate is coated with perfluorodecyltrimethoxysilane, resulting in a water contact angle of 162° and a roll-off angle of 6°; the protective steel plate has a 75° apex angle, a crease depth of 1.5mm, and a unit side length of 10cm.

[0061] The self-powered protection system in this embodiment adopts a modular design. The effective area, number of connections, connection method, and size of a single module of a single power generation unit are the same as those in Embodiment 1.

[0062] Example 3 This embodiment uses the upper limit of the formulation or numerical range in the claims for preparation: Adhesive functional layer: 100 parts butyl rubber, 15 parts hydrophobic agent (8 parts fluorosilane + 7 parts organosilicon hydrophobic agent), 5 parts aerogel slow-release particles (particle size 4mm), 10 parts cement-based filler (4 parts calcium silicate + 3 parts silica fume + 3 parts metakaolin), 4 parts magnesium oxide, 15 parts zinc powder sacrificial anode particles (particle size 80μm), 5 parts plasticizer (epoxidized soybean oil), temperature 18℃, stirring speed 60rpm; adhesive functional layer coating thickness 8mm.

[0063] Energy harvesting layer: The lower electrode layer uses a metallized polymer film (thickness 0.3 mm, conductivity 1200 S / m); the negatively charged triboelectric material layer uses polyvinylidene fluoride (thickness 1 mm); reactive ion etching (power 150 W, pressure 15 Pa, time 15 minutes), micron-level features 50 μm, nano-level features 500 nm; silicone rubber micro-spring array (spring diameter 10 mm, height 20 mm, spacing 50 mm, compression modulus 20 MPa, resilience 82%).

[0064] Protective power generation layer: The protective steel plate is made of 316L stainless steel plate with a thickness of 3mm; the outer surface of the protective steel plate is treated with femtosecond laser (power 100W, scanning speed 1000mm / s), with a micron-sized pit diameter of 50μm and a depth of 20μm; after superhydrophobic treatment, the water contact angle is 168° and the roll-off angle is 4°; the Miura folding unit has a top angle of 120°, a crease depth of 2mm, and a unit side length of 15cm.

[0065] The self-powered protection system in this embodiment adopts a modular design. The effective area, number of connections, connection method, and size of a single module of a single power generation unit are the same as those in Embodiment 1.

[0066] Example 4 This embodiment uses the lower limit formulation as described in the claims: Adhesive functional layer: 100 parts butyl rubber, 5 parts hydrophobic agent (nano silica hydrophobic agent), 3 parts aerogel slow-release particles (particle size 0.5 mm), 5 parts cement-based filler (calcium silicate), 2 parts magnesium oxide, 5 parts zinc powder sacrificial anode particles (particle size 10 μm), 3 parts plasticizer (dioctyl phthalate), temperature 25℃, stirring speed 30 rpm; coating thickness 3 mm, anchor bolt diameter 8 mm, spacing 20 cm, anchoring depth 80 mm.

[0067] Energy harvesting layer: lower electrode layer graphene composite conductive film (thickness 0.05 mm, conductivity 1000 S / m); polytetrafluoroethylene film thickness 0.1 mm; nanoimprinting (pressure 5 MPa, temperature 150 ℃, time 30 s), micron-level features 5 μm, nano-level features 50 nm; polyurethane porous elastomer (porosity 40%, pore size 0.5 mm, compression modulus 5 MPa, resilience 80%).

[0068] Protective power generation layer: 1mm thick 316L stainless steel plate; laser texturing (power 10W, speed 100mm / s), micron-sized pits with a diameter of 10μm and a depth of 5μm; water contact angle of 151°, roll-off angle of 9.5°; Miura folded unit with a 60° apex angle, crease depth of 0.5mm, and unit side length of 5cm.

[0069] The self-powered protection system in this embodiment adopts a modular design. The effective area, number of connections, connection method, and size of a single module of a single power generation unit are the same as those in Embodiment 1.

[0070] Example 5 This embodiment represents an optimized combination of intermediate value formulations: Adhesive functional layer: 100 parts butyl rubber, 8 parts hydrophobic agent (4 parts nano silica + 4 parts fluorosilane), 3.5 parts aerogel slow-release particles (particle size 1.5 mm), 7 parts cement-based filler (4 parts calcium silicate + 3 parts metakaolin), 2.5 parts magnesium oxide, 8 parts zinc powder sacrificial anode particles (particle size 40 μm), 3.5 parts plasticizer (2 parts dioctyl sebacate + 1.5 parts epoxidized soybean oil), temperature 22℃, stirring speed 45 rpm; coating thickness 5.5 mm, anchor bolt diameter 12 mm, spacing 35 cm, anchoring depth 110 mm.

[0071] Energy harvesting layer: lower electrode layer carbon nanotube film (thickness 0.18 mm, conductivity 1800 S / m); FEP film thickness 0.4 mm; reactive ion etching (power 100 W, pressure 10 Pa, time 10 min), micron-level features 25 μm, nano-level features 250 nm; silicone rubber microspring array (spring diameter 5 mm, height 12 mm, spacing 25 mm, compression modulus 13 MPa, resilience 85%).

[0072] Protective power generation layer: The protective steel plate is made of 2205 duplex stainless steel with a thickness of 2mm; nanosecond laser + chemical etching composite treatment, micron pit diameter of 30μm and depth of 12μm; water contact angle of 159° and roll-off angle of 7°; Miura folded unit apex angle of 90°, crease depth of 1.2mm and unit side length of 9cm.

[0073] The self-powered protection system in this embodiment adopts a modular design. The effective area, number of connections, connection method, and size of a single module of a single power generation unit are the same as those in Embodiment 1.

[0074] Example 6 This embodiment represents the boundary combination of hydrophobic agent and aerogel sustained-release particles in the adhesive functional layer: Adhesive functional layer: 100 parts butyl rubber, 15 parts hydrophobic agent (organosilicon hydrophobic agent), 3 parts aerogel slow-release particles (particle size 5mm), 6 parts cement-based filler (silica fume), 3 parts magnesium oxide, 12 parts zinc powder sacrificial anode particles (particle size 60μm), 4 parts plasticizer, and other components are the same as in Example 2.

[0075] Energy harvesting layer, protective power generation layer, and energy management unit: Same as in Example 2.

[0076] Example 7 This embodiment represents a boundary combination of the Miura folding structure and motion parameters: Energy harvesting layer: The raw materials and preparation process are the same as in Example 2, but the pre-compression of the elastic support structure is adjusted to 15%, so that the relative displacement amplitude reaches 18mm.

[0077] Protective power generation layer: 316L stainless steel plate, 1.5mm thick; Miura folding unit, apex angle 105°, crease depth 1.8mm, unit side length 12cm; other features are the same as in Example 2.

[0078] The bonding functional layer and energy management unit are the same as in Example 2.

[0079] Comparative Example 1 The only difference between this comparative example and Example 2 is that a higher content of zinc powder is used: the content of zinc powder sacrificial anode particles is 20 parts (16.7% of the total mass), and the other components and processes are the same as in Example 2.

[0080] Due to the excessive zinc powder content, the viscosity of the adhesive functional layer increases significantly during preparation, making mixing difficult, resulting in poor leveling during coating and increased surface roughness. Conductive pathways easily form between zinc powder particles, causing localized short circuits and uneven distribution of the sacrificial anode protection current. Excessive zinc powder is rapidly consumed during long-term service, generating large amounts of zinc hydroxide corrosion products, leading to expansion and cracking of the adhesive layer and a decrease in bond strength.

[0081] Comparative Example 2 The only difference between this comparative example and Example 1 is that a very low content of zinc powder is used: the content of zinc powder sacrificial anode particles is 2 parts (1.8% of the total mass), and the other components and processes are the same as in Example 1.

[0082] Due to the low zinc powder content, an effective distributed electrochemical protection network cannot be formed, and the particle spacing is too large (>5mm), resulting in discontinuous protection range. During system startup or when the energy management unit fails, the concrete reinforcement does not receive sufficient primary protection, and the self-corrosion potential shifts negatively by only 50-80mV, far below the requirements for effective protection.

[0083] Comparative Example 3 The only difference between this comparative example and Example 3 is that the content of cement-based filler (calcium silicate) is 18 parts, while the other components and processes are the same as in Example 3.

[0084] Excessive cement-based filler makes the bonding layer rigid and reduces its flexibility, making it prone to cracking under structural deformation caused by wave impact and temperature changes. An excessively high elastic modulus of the bonding layer worsens its compatibility with the butyl rubber matrix, reducing interfacial bond strength. Excessive inorganic filler also increases system weight and installation difficulty.

[0085] Comparative Example 4 The only difference between this comparative example and Example 1 is that the magnesium oxide content is too high: the magnesium oxide content is 7 parts, and the other components and processes are the same as in Example 1.

[0086] Excessive magnesium oxide content can cause the adhesive layer to absorb too much water and swell excessively in humid environments. Magnesium oxide reacts with water to form magnesium hydroxide, which expands in volume by about 2 times, increasing internal stress in the adhesive layer and causing cracks and blistering. An excessively alkaline environment (pH>12) can also accelerate the degradation of butyl rubber, reducing adhesive strength and service life.

[0087] Comparative Example 5 The only difference between this comparative example and Example 2 is that the negatively charged triboelectric material layer uses a smooth FEP film and is not subjected to micro / nano-structuring treatment; the other components and processes are the same as in Example 2.

[0088] Due to its smooth surface, the frictional contact area is reduced, and the charge density is only 20-35 μC / m². 2 Compared to Example 2, this represents a reduction of over 80%. Under the same wave conditions, power generation is reduced by 75%, to only 2.5-12 mW / m. 2 This makes it difficult to meet the power requirements of cathodic protection. The system is basically unable to provide effective protective current during low wave periods (wave height <0.5m).

[0089] Comparative Example 6 The only difference between this comparative example and Example 1 is that the crease depth of the Miura folding structure is 0.2 mm, while the other components and processes are the same as in Example 1.

[0090] Shallow creases result in insufficient deformation of the protective power generation layer under wave action, with a relative displacement of only 0.1-0.4 mm, inadequate contact separation, and low power generation efficiency. Shallow creases also have weak mechanical buffering capacity, making them prone to plastic deformation or fracture under large wave impacts (wave height > 5 m), reducing impact resistance by more than 60%.

[0091] Performance tests were conducted on the above embodiments and comparative examples, including tests on bond strength, power generation, cathodic protection effectiveness, and system durability. The test methods were as follows: The bond strength of each bonding functional layer was measured using ASTM D4541 standard, with the failure mode being concrete substrate failure. Potential values ​​were recorded continuously for 30 days using ASTM C876 standard. The corrosion rates of the steel reinforcement were compared between unprotected and reinforced concrete specimens protected with the self-functional protective systems of the examples / comparative cases. The corrosion rates were quantified using electrochemical impedance spectroscopy (EIS) and polarization curves. The steel reinforcement potentials in Table 1 are the average values ​​after 30 days of stable system operation; the corrosion rates were determined by weight loss after 180 days of testing; the unprotected control group consisted of reinforced concrete specimens without the protective system under the same conditions.

[0092] Power generation test steps: Install the protection system on the wave simulation test bench; set the wave parameters: wave height 0.5-3m, period 1-4s; connect the output terminal (DC side) of the rectifier module to a digital storage oscilloscope (bandwidth 100MHz, sampling rate 1GSa / s) and a precision resistor load (100Ω), continuously record the voltage and current waveforms for 30 minutes, and finally calculate the average power and peak power.

[0093] System durability testing (accelerated aging test): The protective system was installed in a marine environment simulation chamber and tested for 180 days (simulating 10 years of actual service); environmental conditions were set as follows: temperature cycling (-10℃ to 40℃, one cycle every 24 hours), salt spray (compliant with ASTM B117 standard, NaCl concentration 5%), and ultraviolet aging (UVA-340 lamp, irradiance 0.89W / m²). 2 / nm), wave impact (wave height 2m, period 2s, continuous action); test the bonding strength, power generation and cathodic protection effect every 30 days; observe the changes in the appearance of the system and record defects such as cracks, blistering and peeling.

[0094] System reliability testing: Tests were conducted at the Marine Atmospheric Corrosion Test Station on Xiaomaidao Island in Qingdao City. The mean wave period (MWP) was 4-8 seconds (frequency 0.125-0.25Hz), the average water depth was 44 meters, and the average wave height was 0.8-1.2 meters. Ten sets of protection systems were installed. The system was operated continuously for 180 days, and the number and type of system failures were recorded. The mean time between failures (MTBF) and availability of the system were calculated. Maintenance checks were performed monthly, and maintenance time and costs were recorded.

[0095] The performance test results of the above embodiments and comparative examples are shown in Table 1.

[0096] Table 1 Performance test results of the examples and comparative examples

[0097] Example 2 illustrates the system reliability test results, which are the test results of 10 systems over 180 days, as detailed in Table 2.

[0098] Table 2 System Reliability Test Results of Example 2

[0099] Test Result Analysis: The bond strength of Examples 1-6 was all within the range of 1.42-2.12 MPa, meeting the requirements of the marine concrete repair material standard (≥1.5 MPa). Example 3, using the upper limit formulation, achieved the highest bond strength (2.12 MPa). Comparative Example 1 showed a decrease in bond strength to 1.25 MPa due to excessive zinc powder; Comparative Examples 3 and 4, due to improper filler ratios, saw their bond strengths drop to 1.02 MPa and 0.88 MPa respectively, below the standard requirements.

[0100] The power generation range of Examples 1-6 under a wave height of 1m is 18.6-48.5mW / m. 2 All can meet the cathodic protection current requirements (20-50mA / m). 2 The corresponding power is 15-60mW / m 2 Comparative Example 5, lacking micro / nano structures, had a power generation capacity of only 8 mW / m. 2 The power generation of Comparative Example 6 was reduced by 77% due to insufficient crease depth, resulting in a power output of only 11 mW / m. 2 .

[0101] The surface potential of the reinforcing bars in Examples 1-6 remained stable within the range of -832 to -905 mV, meeting the requirements of GB / T 21447-2018 standard (-800 to -1000 mV). The corrosion rate of the reinforcing bars decreased to 2.8-6.5 μm / year, a reduction of 97-98.5% compared to the unprotected control group (215 μm / year), demonstrating extremely high protection efficiency. Comparative Example 2, due to insufficient zinc powder, had a potential of only -785 mV and a corrosion rate of 18.5 μm / year; Comparative Example 5, due to insufficient power generation, had a potential of -758 mV, failing to meet the adequate protection standard.

[0102] Examples 1-6 exhibited excellent long-term stability after 180 days of accelerated aging, maintaining 87.4-95.3% of the bond strength and 83.2-92.1% of the power generation. Example 3 showed the best durability, with bond strength and power generation retention rates of 95.3% and 92.1%, respectively. Comparative Examples 1, 4, and 5, due to defects in the adhesive layer formulation, showed bond strength retention rates reduced to 58.3-72.3%, exhibiting significant cracking and blistering. Comparative Examples 5 and 6, due to insufficient power generation performance or structural defects, showed power generation retention rates reduced to 62.3-65.3%.

[0103] Example 2 demonstrated high reliability after 365 days of continuous operation in a real marine environment, achieving a system availability rate of 98.5% and a mean time between failures (MTBF) of 8760 hours (1 year). The main failures were reference electrode failure (with a lifespan of approximately 1.5-2 years, requiring periodic replacement) and communication module failure (affected by marine environmental interference), both of which could be quickly repaired through modular design. The annual maintenance cost was approximately 1200 RMB per set, representing an 80% saving compared to an external power supply solution (which incurs approximately 6000 RMB per set annually for cable laying, equipment depreciation, and electricity costs), demonstrating significant economic benefits.

[0104] The self-powered protection system for marine concrete structures of the present invention has the following significant advantages: The distributed zinc powder sacrificial anode of the bonding functional layer provides primary protection, while the energy harvesting layer and the protective power generation layer provide continuous and stable impressed current cathodic protection through wave energy conversion. The two mechanisms work together to reduce the corrosion rate of steel bars by 97-98.5%.

[0105] The system utilizes the abundant wave energy in the marine environment to generate electricity, with a power output of 18-48 mW / m. 2 It requires no external power supply, truly achieving energy self-sufficiency. Compared to traditional impressed current cathodic protection solutions, it saves 60-80% on cable laying and power equipment investment, and reduces annual operation and maintenance costs by 70-80%.

[0106] Equipped with an intelligent energy management unit and a distributed reference electrode network, it monitors the system status and concrete potential in real time, and dynamically adjusts the protection current according to the energy storage status and corrosion rate, with a potential control accuracy of ±2%, achieving precise and efficient adaptive protection.

[0107] The system adopts high-performance materials resistant to marine environments and biomimetic structural design. After 180 days of accelerated aging test (simulating 10 years of service), the bonding strength retention rate is 87-95%, the power generation retention rate is 83-92%, and the system design life is 20-30 years, which is 3-8 times longer than the traditional sacrificial anode method (life 3-8 years).

[0108] Use 1-3m 2 The modular units are spliced ​​together with flexible connectors, allowing for quick installation, modular replacement, convenient maintenance, and a system availability of 98.5%.

[0109] Utilizing renewable wave energy, with zero pollution emissions, it aligns with the concept of green development; the Miura folded structure provides mechanical buffering, reducing the direct impact of waves on concrete; the superhydrophobic surface reduces marine organism attachment, minimizing ecological impact.

[0110] The self-powered protection system of this invention has broad application prospects in the field of long-term protection of marine concrete structures such as offshore platforms, cross-sea bridges, wharves, and offshore wind power foundations. It has important theoretical significance and engineering application value for extending the service life of marine engineering, reducing maintenance costs, and ensuring structural safety.

[0111] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A self-powered protection system for marine concrete structures, characterized by: The energy management unit, the bonding functional layer (1), and the energy collection layer and the protective power generation layer arranged in sequence on the bonding functional layer (1); The bonding functional layer (1) is used for adhering to the concrete base body (100), and comprises a viscoelastic matrix and functional components distributed therein, the functional components at least including a hydrophobic agent, aerogel slow-release particles, a cement-based filler, magnesium oxide and zinc powder sacrificial anode particles; The energy collection layer comprises an elastic support structure (4) and a lower electrode layer and a negative electric friction material layer arranged in sequence on the bonding functional layer (1), the lower electrode layer is adhered to the bonding functional layer (1) by an insulating adhesive, and the elastic support structure (4) is connected between the bonding functional layer (1) and the protective power generation layer; The protective power generation layer comprises a protective steel plate (6) with a textured structure on an outer surface and having super-hydrophobic properties, and a sealing structure (5) sealingly connected between a steel edge and the bonding functional layer (1); The energy management unit comprises a rectification module, an energy storage module and a control module, and is used for converting alternating current pulses generated by friction between the energy collection layer and the protective power generation layer into direct current and storing the direct current in the energy storage module, and supplying power to the bonding functional layer (1) as needed.

2. The self-powered protection system for marine concrete structures according to claim 1, characterized in that: The bonding functional layer (1) comprises the following raw materials by mass fraction: 100 parts of butyl rubber, 5-15 parts of a hydrophobic agent, 3-5 parts of aerogel slow-release particles, 5-10 parts of a cement-based filler, 2-4 parts of magnesium oxide, 5-15 parts of zinc powder sacrificial anode particles, and 3-5 parts of a plasticizer.

3. The self-powered protection system for the marine concrete structure according to claim 2, characterized in that: The butyl rubber has a molecular weight of 300-500 thousand and an unsaturation degree of less than 2%; the hydrophobic agent is one or a mixture of several of nano-silicon dioxide hydrophobic agent, fluorosilane or organosilicon hydrophobic agent; the aerogel slow-release particles are silica aerogel particles with a particle size of 0.5-5 mm; the cement-based filler is one or a mixture of several of calcium silicate, silica fume or metakaolin; the zinc powder sacrificial anode particles have a particle size of 10-100 μm and a purity of greater than 99%; and the plasticizer is one or a mixture of several of dioctyl phthalate, dioctyl sebacate or epoxy soybean oil.

4. The self-powered protection system for marine concrete structures according to claim 2, characterized in that: The preparation method of the bonding functional layer (1) comprises the following steps: Step one, butyl rubber is added to a planetary mixer, and the temperature is controlled at 15-25 ℃, and low-speed stirring is started; Step two, the hydrophobic agent, the aerogel slow-release particles, the cement-based filler and the magnesium oxide are added in batches, each batch accounts for 20-30% of the total amount, and stirring is performed for 5-10 minutes after each addition; Step three, the zinc powder sacrificial anode particles are added, and stirring is continued for 20-30 minutes; Step four, the plasticizer is added, and stirring is performed for 10-20 minutes; Step five, vacuum degassing is performed for 15-25 minutes, and the vacuum degree is 0.1-1 kPa, thereby obtaining the bonding functional layer (1) material.

5. The self-powered protection system for marine concrete structures of claim 2, wherein: The bonding functional layer (1) has a thickness of 3-8 mm; the zinc powder sacrificial anode particles in the bonding functional layer (1) have a content of 5%-12% of the total mass and are uniformly dispersed to form a distributed primary electrochemical protection network.

6. The self-powered protection system for marine concrete structures of claim 1, wherein: The lower electrode layer is made of a flexible conductive material, such as a graphene composite conductive film, a carbon nanotube film or a metalized polymer film, and has a thickness of 0.05-0.3 mm and an electrical conductivity greater than 1000 S / m; The negative electric friction material layer has a thickness of 0.1-1 mm and is made of polytetrafluoroethylene, fluorinated ethylene propylene copolymer or polyvinylidene fluoride; the surface of the negative electric friction material layer is subjected to micro-nano structuring to form a multi-level composite morphology; The elastic support structure (4) is made of silicone rubber, polyurethane or shape memory polymer and is formed into a micro-spring array or a porous elastomer by injection molding or 3D printing; the elastic support structure (4) has a compression modulus of 5-20 MPa and a resilience rate greater than 80%.

7. The self-powered protection system for marine concrete structures of claim 1, wherein: The energy collection layer comprises a plurality of distributed array design power generation units, the power generation unit comprises a unit electrode layer (2) and a unit friction layer (3) arranged in sequence on a bonding functional layer (1); the effective area of a single power generation unit is 0.01-0.25m 2 ; a plurality of power generation units are connected in parallel.

8. The self-powered protection system for marine concrete structures of claim 1, wherein: The protective steel plate (6) is made of 316L or 2205 duplex stainless steel plate and has a thickness of 1-3 mm; the protective steel plate (6) is processed into a Miura folded texture structure; the outer surface of the protective steel plate (6) is subjected to laser texturing or chemical etching to form a micro-nano composite rough structure, and is coated with a low surface energy substance layer; the low surface energy substance is perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane.

9. The self-powered protection system for marine concrete structures of claim 1, wherein: The top angle of the folded unit of the Miura folded texture structure of the protective steel plate (6) is 60-120°, the fold depth is 1-2 mm, a rhombic or hexagonal unit array is formed, and the unit side length is 5-15 cm; The Miura folded texture structure can produce controllable deformation under the action of waves, the deformation amount is 50%-200% of the fold depth, a relative displacement is generated between the protective layer and the energy collection layer, the displacement amplitude is 1-20 mm, and the movement frequency is 0.3-5 Hz.

10. The self-powered protection system for marine concrete structures of claim 1, wherein: A reference electrode network uniformly arranged on the surface of the bonding functional layer (1) is further included, and the reference electrode network is used to collect the potential of the concrete substrate (100) in real time; The control module monitors the friction power generation, the energy storage state of the energy storage module, the surface potential and corrosion rate of the concrete substrate (100) in real time, and controls the output of the protective current density, so that the concrete surface potential is maintained in the range of -800 to -950 mV. When the energy storage state is higher than 80% and the power generation power is sufficient, the output protection current density is 50-100 mA / m 2 ; When the energy storage state is 30%-80%, the output protection current density is 20-50 mA / m 2 ; When the state of charge is below 30%, the output protection current density is 10-20 mA / m 2 .

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