Self-healing electrodes based on plasmon-enhanced liquid metal-solid matrix heterointerfaces, their fabrication methods and applications

Abstract

A self-healing electrode based on plasmon resonance-enhanced liquid metal-solid substrate heterojunction interface, its preparation method, and its application. This invention belongs to the field of electrochemical electrode and flexible electronic device technology. In the electrode preparation stage, this invention introduces a nanostructure layer with plasmon resonance effect and uses a light source matched to the plasmon resonance wavelength for photo-sintering. The photothermal effect of plasmon resonance generates localized, high-efficiency heating at the heterojunction interface, significantly strengthening the interfacial bonding between the liquid metal and the solid electrode substrate. The electrode prepared in this way retains the inherent passive self-healing capability of liquid metal during subsequent service, and also exhibits superior cycle life and structural reliability due to improved interfacial stability.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical electrode and flexible electronic device technology, specifically relating to a self-healing electrode based on plasmon-reinforced liquid metal-solid matrix heterointerface, its preparation method and application. Background Technology

[0002] With the rapid development of flexible electronics, wearable sensing, and portable energy storage devices, electrode materials not only need to withstand conventional electrochemical loads during service, but also inevitably face dynamic mechanical deformations such as repeated bending, stretching, and torsion. These deformations can induce the initiation and propagation of microcracks within the electrode, interfacial delamination between the active material and the current collector, and localized breakage of the conductive network, leading to irreversible interruptions of electrical pathways and rapid degradation of device performance. For rigid or semi-rigid electrodes such as traditional metal foils, carbon-based thin films, or conductive polymer coatings, once structural damage forms penetrating defects, electrical contacts will permanently fail, severely shortening device lifespan.

[0003] To address this challenge, endowing electrode materials with self-healing capabilities has become a research hotspot in this field. Among these, utilizing the flow properties of gallium-based liquid metals near room temperature to construct self-healing electrodes is a particularly promising technological approach. When cracks develop in the electrode substrate, liquid metal pre-placed inside or on the surface of the electrode can spontaneously migrate towards the damaged area through capillary action and its own fluidity, filling the crack gaps and restoring conductive connections, thus achieving passive self-healing without external material replenishment. Based on this principle, researchers have developed various liquid metal composite electrode structures, such as anchoring liquid metal in nanowire gaps, carbon fiber skeleton pores, or micro / nano trench arrays, to impart damage repair capabilities while maintaining the mechanical integrity of the electrode. Furthermore, introducing liquid metal as a heterogeneous interface filling layer between solid electrodes and electrolytes has also been shown to effectively improve interfacial contact uniformity and alleviate interfacial failure problems.

[0004] However, the aforementioned self-healing electrode schemes based on the passive flow of liquid metal generally share a key common problem: insufficient interfacial bonding strength between the liquid metal and the solid electrode substrate. Whether combined with carbon materials, metal nanowires, or metal oxide frameworks, the interaction between the liquid metal and the solid surface mainly relies on van der Waals forces and capillary forces, resulting in limited interfacial bonding. Under long-term, frequent mechanical deformation, the solid-liquid interface is prone to slippage, liquid metal extrusion and loss, and interfacial delamination. Once the liquid metal detaches from the pores or microstructures of the solid framework, its self-healing function is lost, severely limiting the electrode's electrical integrity and cycle life. Therefore, effectively strengthening the interfacial bonding between the liquid metal and the solid electrode substrate during the fabrication stage and improving interfacial stability is crucial for enhancing the overall performance of liquid metal self-healing electrodes.

[0005] On the other hand, surface plasmon resonance, as a unique physical effect generated by the interaction between light and nanostructures, has been explored in recent years for interfacial bonding and structural strengthening in various material systems. For example, by utilizing the localized thermal field generated by plasmon resonance in silver nanostructures, selective nanoconnections can be achieved at the intersection nodes of silver nanowires, significantly reducing film resistance and improving the mechanical stability of conductive networks without damaging the flexible polymer substrate. However, existing research on interfacial strengthening based on the localized photothermal effect of plasmon resonance mainly focuses on the bonding within homogeneous metal nanomaterial systems, with the target being the strengthening of the bond between the same or similar metal materials. The interfacial bonding between liquid metal and solid substrate differs fundamentally from the bonding in homogeneous metal systems: liquid metals are fluid, and under the localized photothermal effect of plasmon resonance, not only does interfacial atomic diffusion occur, but also viscosity changes, wetting and spreading, and flow behavior, making the interfacial strengthening mechanism more complex. Therefore, how to achieve controllable strengthening of the bonding strength of heterogeneous interfaces while preserving the inherent self-healing ability of liquid metals has become a technical challenge that urgently needs to be overcome in this field. Summary of the Invention

[0006] The present invention aims to overcome the above-mentioned shortcomings of the prior art and provide a self-healing electrode based on plasmon-reinforced liquid metal-solid matrix heterostructure interface, its preparation method and application.

[0007] The technical solution of the present invention is as follows: One objective of this invention is to provide a method for preparing a self-healing electrode based on a plasmonic-reinforced liquid metal-solid matrix heterointerface, the method comprising the following steps: (1) Surface activation pretreatment of substrate and conductive current collector layer: Activation pretreatment is carried out through physical or chemical means to remove adsorbed pollutants, organic residues and natural oxide layers from the surface, while introducing active functional groups or increasing surface roughness. (2) Solid electrode active material layer forming: A porous solid electrode active material layer is constructed on the surface of the conductive current collector layer. By controlling the material deposition kinetics, solvent evaporation rate and curing conditions, a connected or semi-connected pore network is formed inside the active material layer. (3) Controllable construction of plasmonic nanostructures: Plasmon nanostructures with discrete nanoparticle assembly morphology or ordered nanoarray structure are constructed on the surface and internal pore walls of the active material layer of solid electrode using micro-nano fabrication or self-assembly methods. (4) Controlled introduction of liquid metal: When liquid metal is in a flowing state, it is filled into the pores of the solid electrode active material layer by coating, printing transfer or vacuum-assisted infiltration. (5) Plasmon local photothermal interface enhancement treatment: Irradiation was performed using a light source whose emission spectrum matched the surface plasmon resonance band of the plasmon nanostructure layer, with a total irradiation time of 1 ms to 30 min. (6) Integration of encapsulation and protective layer.

[0008] Further specifying, the physical or chemical means described in step (1) include, but are not limited to, one or more of the following: plasma cleaning, ultraviolet ozone irradiation, acid / alkali etching, organic solvent ultrasonic cleaning, ion beam bombardment, surface modification, and surface grafting polymerization modification.

[0009] Further specifying, the substrate in step (1) is a flexible substrate, preferably one or more of polydimethylsiloxane, polyimide, polyethylene terephthalate, polyurethane, and polyethylene naphthalate.

[0010] Further specifying, the conductive current collector layer in step (1) is one or more of the following: metal foil, carbon cloth, carbon paper, graphene film, carbon nanotube film, conductive polymer film, or transparent conductive oxide film.

[0011] Further specifying, the forming method described in step (2) includes, but is not limited to, scraping, spin coating, spraying, dip coating, electrohydraulic inkjet printing, screen printing, gravure printing, inkjet printing, electrochemical deposition, chemical vapor deposition, physical vapor deposition, magnetron sputtering, atomic layer deposition, or filtration film formation.

[0012] Further specifying, the solid electrode active material layer in step (2) is a composite of one or more of the following: carbon-based materials, silicon-based materials, metal oxides, and conductive polymers.

[0013] Furthermore, the carbon-based materials include, but are not limited to, one or more of activated carbon, graphite, graphene, carbon nanotubes, and carbon fibers; the metal oxides include, but are not limited to, one or more of manganese dioxide, iron tetroxide, ruthenium oxide, and indium tin oxide; and the conductive polymers include, but are not limited to, one or more of polyaniline, polypyrrole, and polythiophene.

[0014] Further, the thickness of the solid electrode active material layer in step (2) is 100 nm to 100 μm.

[0015] Further, the micro / nano fabrication or self-assembly described in step (3) includes, but is not limited to, chemical reduction in situ growth, electrochemical deposition, self-assembly, template-assisted growth, photolithography, electron beam etching, nanoimprinting, or template stripping.

[0016] Further specifying, the plasmonic nanostructure material described in step (3) is selected from at least one of pure metals such as gold, silver, platinum, palladium, copper, and aluminum or their alloys.

[0017] Further, the particle size of the discrete nanoparticles in step (3) is 5 nm to 500 nm.

[0018] Further specifying, the ordered nanoarray structure in step (3) includes one or more of the following nanostructures: nanograting array, nanopore array, nanorod array, or nanocone array, with a characteristic size of 10 nm to 500 nm.

[0019] Further specifying, the coating method in step (4) includes drop coating, spin coating, spray coating, scraping coating or dip-coating, the printing transfer method includes screen printing, gravure printing, inkjet printing or roll transfer, and the vacuum-assisted infiltration method includes vacuum-assisted infiltration or capillary self-filling.

[0020] Further specifying, the liquid metal in step (4) is selected from gallium-based room temperature liquid metals, preferably at least one of GaIn alloy, GaInSn alloy, GaSn alloy, GaInZn alloy, and GaInSnZn alloy.

[0021] Further, the contact interface between the liquid metal in step (4) and the isotropic nanostructure in step (3) is located in the region of 0~20 μm from the light incident surface.

[0022] Further specifying, the mass ratio of the solid electrode active material in step (2), the ionotropic nanostructure material in step (3), and the liquid metal in step (4) is 1:(0.5~200):(0.5~200).

[0023] Further specifying, the light source mentioned in step (5) includes a continuous light source, a quasi-continuous light source, and a pulsed laser light source.

[0024] Furthermore, when the light source is a continuous or quasi-continuous light source, the irradiance power density is 0.01 W / cm². 2 ~100 MW / cm 2 When the light source is a pulsed source, the pulse width is 1 fs to 1 s, the repetition frequency is 1 Hz to 100 MHz, and the pulse energy density is 0.1 μJ / cm². 2 ~100 J / cm 2 The peak power density is 0.01 W / cm³. 2 ~100 MW / cm 2 The average power density is 0.01 W / cm³. 2 ~10 kW / cm 2 The number of pulses is 1 to 10. 9 Second-rate.

[0025] Further, the emission wavelength range of the light source in step (5) is 200~2000 nm, and the emission wavelength at least partially overlaps with the local surface plasmon resonance absorption band of the plasmon nanostructure layer.

[0026] Further specifying, the light source illumination method in step (5) is fixed-point illumination, surface illumination, line scan illumination, point-by-point scan illumination, array illumination, or mask selective illumination.

[0027] Further, the application method of the encapsulation protective layer in step (6) includes, but is not limited to, thin film bonding, coating and curing, or vapor deposition.

[0028] To further define, film bonding methods include lamination or bonding methods; coating and curing methods include spin coating, spraying, drop coating and curing, slot coating or screen printing; vapor deposition methods include chemical vapor deposition, plasma-enhanced chemical vapor deposition or atomic layer deposition.

[0029] Further specifying, the material of the encapsulation protective layer in step (6) includes, but is not limited to, organic polymers, inorganic films, or organic-inorganic composite materials.

[0030] Furthermore, the organic polymer includes at least one of flexible polymer films, elastomer films, UV-curable resins, thermosetting resins, and silicone encapsulants; the inorganic film includes at least one of inorganic oxide films and nitride films; and the organic-inorganic composite material includes organic-inorganic hybrid barrier films.

[0031] The second objective of this invention is to obtain a self-healing electrode based on a plasmonic-reinforced liquid metal-solid matrix heterointerface using the method described above, wherein the electrode comprises, from bottom to top: Base; Conductive current collector layer; The solid electrode active material layer, plasmonic nanostructures, and liquid metal; wherein the plasmonic nanostructures are attached to, embedded in, or grown in situ on the light-incident side surface, near-surface pore walls, or microcrack inner walls of the solid electrode active material layer; and the liquid metal is distributed within the pores of the solid electrode active material layer and forms an interface contact with the plasmonic nanostructures. Encapsulation and protective layer.

[0032] The third objective of this invention is to provide a method for preparing a self-healing electrode based on a plasmonic-reinforced liquid metal-solid matrix heterointerface, the method comprising the following steps: (1) Surface activation pretreatment of substrate and conductive current collector layer: Activation pretreatment is carried out through physical or chemical means to remove adsorbed pollutants, organic residues and natural oxide layers from the surface, while introducing active functional groups or increasing surface roughness. (2) Preparation of composite functional layer: Solid electrode active materials and plasmonic nanostructure materials are mixed uniformly with liquid metal in a liquid medium to obtain a composite slurry, which is then integrally formed into a film and cured. Alternatively, solid electrode active materials, plasmonic nanostructure materials, and liquid metals are dispersed uniformly in a liquid medium to obtain three slurries, and then the three slurries are deposited alternately to form a composite functional layer with a stacked interpenetrating structure. (3) Plasmon local photothermal interface enhancement treatment: Irradiation was performed using a light source whose emission spectrum matched the surface plasmon resonance band of the plasmon nanostructure layer, with a total irradiation time of 1 ms to 30 min. (4) Integration of encapsulation and protective layer.

[0033] Further specifying, the physical or chemical means described in step (1) include, but are not limited to, one or more of the following: plasma cleaning, ultraviolet ozone irradiation, acid / alkali etching, organic solvent ultrasonic cleaning, ion beam bombardment, surface modification, and surface grafting polymerization modification.

[0034] Further specifying, the substrate in step (1) is a flexible substrate, preferably one or more of polydimethylsiloxane, polyimide, polyethylene terephthalate, polyurethane, and polyethylene naphthalate.

[0035] Further specifying, the conductive current collector layer in step (1) is one or more of the following: metal foil, carbon cloth, carbon paper, graphene film, carbon nanotube film, conductive polymer film, or transparent conductive oxide film.

[0036] Further specifying, the solid electrode active material in step (2) is one or more composites of carbon-based materials, silicon-based materials, metal oxides, and conductive polymers.

[0037] Furthermore, the carbon-based materials include, but are not limited to, one or more of activated carbon, graphite, graphene, carbon nanotubes, and carbon fibers; the metal oxides include, but are not limited to, one or more of manganese dioxide, iron tetroxide, ruthenium oxide, and indium tin oxide; and the conductive polymers include, but are not limited to, one or more of polyaniline, polypyrrole, and polythiophene.

[0038] Further specifying, the plasmonic nanostructure material described in step (2) is selected from at least one of pure metals such as gold, silver, platinum, palladium, copper, and aluminum or their alloys.

[0039] Further specifying, the liquid metal in step (2) is selected from gallium-based room temperature liquid metals, preferably at least one of GaIn alloy, GaInSn alloy, GaSn alloy, GaInZn alloy, and GaInSnZn alloy.

[0040] Further specifying, the film-forming method described in step (2) includes, but is not limited to, spraying, screen printing, gravure printing, inkjet printing, scraping, spin coating, drop coating, slot coating, roller coating, transfer printing, dip coating, or electrophoretic deposition.

[0041] Further specified, the slurry supply rate in step (2) is 0.01 mL / min to 100 mL / min.

[0042] Further, the thickness of the composite functional layer in step (2) is 100 nm to 800 μm.

[0043] Further, the curing temperature in step (2) is -200℃ to 150℃, and the time is 1 min to 120 min.

[0044] Further specifying, in step (2), the mass ratio of solid electrode active material, plasmonic nanostructure material and liquid metal is 1:(0.5~200):(0.5~200).

[0045] Further specifying, the light source mentioned in step (3) includes a continuous light source, a quasi-continuous light source, and a pulsed laser light source.

[0046] Furthermore, when the light source is a continuous or quasi-continuous light source, the irradiance power density is 0.01 W / cm². 2 ~100 MW / cm 2 When the light source is a pulsed source, the pulse width is 1 fs to 1 s, the repetition frequency is 1 Hz to 100 MHz, and the pulse energy density is 0.1 μJ / cm². 2 ~100 J / cm 2 The peak power density is 0.01 W / cm³. 2 ~100 MW / cm 2 The average power density is 0.01 W / cm³. 2 ~10 kW / cm 2 The number of pulses is 1 to 10. 9 Second-rate.

[0047] Further, the emission wavelength range of the light source in step (3) is 200~2000 nm, and the emission wavelength at least partially overlaps with the local surface plasmon resonance absorption band of the plasmon nanostructure layer.

[0048] Further specifying, the light source illumination method in step (3) is fixed-point illumination, surface illumination, line scan illumination, point-by-point scan illumination, array illumination, or mask selective illumination.

[0049] Further, the application method of the encapsulation protective layer in step (4) includes, but is not limited to, thin film bonding, coating and curing, or vapor deposition.

[0050] To further define, film bonding methods include lamination or bonding methods; coating and curing methods include spin coating, spraying, drop coating and curing, slot coating or screen printing; vapor deposition methods include chemical vapor deposition, plasma-enhanced chemical vapor deposition or atomic layer deposition.

[0051] Further specifying, the material of the encapsulation protective layer in step (4) includes, but is not limited to, organic polymers, inorganic films, or organic-inorganic composite materials.

[0052] Furthermore, the organic polymer includes at least one of flexible polymer films, elastomer films, UV-curable resins, thermosetting resins, and silicone encapsulants; the inorganic film includes at least one of inorganic oxide films and nitride films; and the organic-inorganic composite material includes organic-inorganic hybrid barrier films.

[0053] The fourth objective of this invention is to obtain a self-healing electrode based on a plasmonic-enhanced liquid metal-solid matrix heterointerface obtained by the above method, wherein the electrode comprises, from bottom to top: Base; Conductive current collector layer; Composite functional layer; solid electrode active material and plasmonic nanostructure material mixed with liquid metal; Encapsulation and protective layer.

[0054] The fifth objective of this invention is to provide an application of the above-mentioned self-healing electrode based on plasmon-reinforced liquid metal-solid matrix heterostructure in the fields of electrochemistry or flexible electronic devices.

[0055] The advantages of this invention compared to existing technologies are: This invention introduces a nanostructure layer with plasmon resonance effect during the electrode fabrication stage and uses a light source matched to the plasmon resonance wavelength for photo-sintering. The photothermal effect of plasmon resonance generates localized, high-efficiency heating at the heterogeneous interface, significantly strengthening the interfacial bonding between the liquid metal and the solid electrode substrate. The electrode prepared in this way retains the inherent passive self-healing capability of liquid metal during subsequent service, and also exhibits superior cycle life and structural reliability due to improved interfacial stability. Specific advantages are as follows: (1) Significantly enhanced heterogeneous interface bonding and improved electrode cycle stability: By introducing nanostructure units with plasmon resonance effect into the electrode system and applying wavelength-matched local photothermal treatment during the preparation stage, the plasmon nonradiative relaxation process generates an efficient and localized photothermal effect at the interface between the liquid metal and the solid substrate, significantly improving the wetting behavior of the liquid metal on the solid surface and promoting inter-diffusion of interfacial atoms, forming an enhanced solid-liquid interface bonding that far exceeds the dependence of traditional van der Waals forces and capillary forces. This enhanced interface effectively suppresses the extrusion loss, interfacial slippage, and structural delamination of liquid metal under long-term mechanical deformation, fundamentally solving the core problem of insufficient heterogeneous interface bonding in existing liquid metal self-healing electrodes, and greatly improving the cycle life and structural reliability of the electrode; (2) The passive self-healing ability of liquid metal is fully preserved: the plasmon effect only acts on the interface strengthening process in the electrode preparation stage. The self-healing behavior of the electrode in subsequent service is still driven by the fluidity of the liquid metal itself. No external light field, thermal field or artificial intervention is required. The self-healing mechanism is reliable and timely, and it is suitable for long-term stable operation under various dynamic deformation conditions. (3) Two implementation paths are provided: layered order structure and hybrid order structure, with strong process adaptability: Both layered order structure and hybrid order structure can achieve integrated preparation of composite functional layers through large-area, low-cost film formation processes such as spraying and printing, which are particularly suitable for the large-scale production of flexible wearable electronic devices. Both implementation paths can effectively strengthen heterogeneous interfaces while retaining the self-healing function of liquid metal; (4) Local heating protects flexible substrates and temperature-sensitive materials: The heat field is concentrated on the surface of the nanostructure and its surrounding tens to hundreds of nanometers by utilizing the highly localized heating region of the plasmonic resonance photothermal effect. This has minimal thermal impact on the substrate, current collector and solid electrode active material layer far from the interface, effectively avoiding the thermal damage to flexible polymer substrates and temperature-sensitive functional materials caused by traditional integral hot sintering or hot annealing processes. It is especially suitable for low-temperature and non-destructive fabrication of flexible electronic devices. (5) Strong controllability and good repeatability of process parameters: Plasmon local photothermal treatment process can achieve precise design of resonant wavelength and photothermal conversion efficiency by controlling the material type, size, morphology and distribution density of plasmon nanostructures; at the same time, the degree of interface heating and strengthening effect can be precisely controlled by adjusting the light source wavelength, irradiation power density and irradiation time. This method is highly compatible with existing micro-nano processing, printed electronics and thin film preparation processes, with a wide process window, excellent controllability and repeatability, and is easy to scale up and promote application; (6) Plasmon nanostructures can provide auxiliary functions to electrodes: After completing the interface strengthening function in the preparation stage, the plasmon nanostructure layer or plasmon nanostructure unit in the electrode system is still retained in the electrode system and can provide auxiliary functions in subsequent service, such as enhancing the electrode's response to light of a specific wavelength, improving electromagnetic shielding performance, or providing an optical signal channel for monitoring the structural health of the electrode, thus further expanding the functional application range of the electrode. Attached Figure Description

[0056] Figure 1 This is a schematic diagram of the layered electrode structure of Example 1; Figure 2 This is a schematic diagram of the electrode structure of the hybrid sequence structure in Example 2. Detailed Implementation

[0057] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0058] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0059] The present invention provides a method for preparing the above-mentioned electrode. This method is applicable to the preparation of electrode structures with a clear hierarchical structure, and is also applicable to the process route of directly preparing plasmonic nanostructures, solid electrode active materials and liquid metals in a mixed form on a substrate or current collector. It has the advantages of wide process adaptability and large-scale production.

[0060] The method for preparing the hierarchical ordered structure includes the following steps: (1) Surface activation pretreatment of substrate and conductive current collector layer: Activation pretreatment is carried out through physical or chemical means to remove adsorbed pollutants, organic residues and natural oxide layers from the surface, while introducing active functional groups or increasing surface roughness. Adsorbed contaminants, organic residues, and natural oxide layers on the substrate and current collector surfaces are removed by physical or chemical means, while active functional groups are introduced or surface roughness is increased, thereby improving surface energy states and wetting properties. The pretreatment process can be carried out in a suitable temperature range and atmosphere conditions according to the thermal stability, chemical resistance, and initial surface state of the substrate and current collector materials. After this step, the substrate and current collector surfaces obtain a clean and activated interface state suitable for subsequent nanostructure assembly or thin film deposition, so as to improve the uniformity of subsequent functional layer adhesion and bonding reliability on their surfaces. (2) Solid electrode active material layer forming: A porous solid electrode active material layer is constructed on the surface of the conductive current collector layer. By controlling the material deposition kinetics, solvent evaporation rate and curing conditions, a connected or semi-connected pore network is formed inside the active material layer. A solid electrode active material layer with predetermined pore characteristics is constructed on the substrate and current collector surface layer. This layer is the main carrier of the electrode's electrochemical activity. During the molding process, by controlling the material deposition kinetics, solvent evaporation rate, and curing conditions, a connected or semi-connected pore network is formed inside the active material layer, providing spatial channels for the subsequent penetration and storage of liquid metal. The composition of the solid electrode active material layer can be adapted to the target application scenario of the electrode. The thickness, porosity, and pore structure parameters of this layer can be controlled by the molding process conditions to achieve optimized matching of liquid metal filling capacity and electron transport path. (3) Controllable construction of plasmonic nanostructures: Plasmon nanostructures with discrete nanoparticle assembly morphology or ordered nanoarray structure are constructed on the surface and internal pore walls of the active material layer of solid electrode using micro-nano fabrication or self-assembly methods. The plasmonic nanostructure layer is composed of a metal or alloy thereof with surface plasmonic resonance activity. Its structural morphology includes an assembled layer of discrete nanoparticles or an ordered nanoarray structure. During the construction process, the surface plasmonic resonance wavelength and photothermal conversion efficiency can be precisely controlled by adjusting the size, morphology, spacing, and distribution density of the nanostructure units. The specific construction method can be selected from micro-nano fabrication or self-assembly techniques based on the target structural characteristics and substrate tolerance. The resulting plasmonic nanostructure layer can efficiently absorb specific wavelength light energy and convert it into a localized thermal field under subsequent illumination. In this step, the plasmonic nanostructure layer is mainly constructed on the light-incident surface of the solid electrode active material layer, near-surface pore walls, microcrack inner walls, or pre-designed microstructure inner walls, rather than directly on the current collector or substrate surface. The plasmonic nanostructure units are at least partially exposed in the light incident path or distributed in the near-surface region reachable by the incident light to ensure that they can be effectively excited by a matching wavelength light source during subsequent photothermal treatment. (4) Controlled introduction of liquid metal: When liquid metal is in a flowing state, it is filled into the pores of the solid electrode active material layer by coating, printing transfer or vacuum-assisted infiltration. The introduction process is carried out in a flowing state of liquid metal, utilizing mechanisms such as capillary force, pressure assistance, or mechanical spreading to ensure that the liquid metal fully fills the micro-nano pores, crack channels, or pre-set trench structures of the active material layer. The introduction method can be selected and combined according to the viscosity characteristics of the liquid metal, the target filling depth, and the electrode geometry to achieve efficient and uniform distribution of the liquid metal within the framework. After this step, a dispersed or continuous solid-liquid interface is formed between the liquid metal and the plasmonic nanostructure layer, providing a precursor state for the interface reaction in subsequent photothermal treatment. (5) Plasmon local photothermal interface enhancement treatment: Irradiation was performed using a light source whose emission spectrum matched the surface plasmon resonance band of the plasmon nanostructure layer, with a total irradiation time of 1 ms to 30 min. After the liquid metal is introduced but before encapsulation, or when a transparent encapsulation layer is provided, a light source is used to irradiate the functional layer side of the porous solid electrode active material layer. The emission spectrum of the light source matches the surface plasmon resonance band of the plasmon nanostructure layer. Under light irradiation, the plasmon nanostructure layer undergoes localized surface plasmon resonance, efficiently converting the absorbed light energy into heat energy through a non-radiative relaxation process, forming a highly localized temperature rise region on the nanostructure surface and at its interface with the liquid metal. This localized temperature rise effect causes the viscosity of the liquid metal at the interface to decrease and the wetting angle to decrease, accelerating the spreading and wetting of the liquid metal on the solid surface and the sintering between liquid metals. At the same time, it enhances the interdiffusion behavior of atoms on both sides of the interface, thereby forming a transition layer with significantly improved bonding strength at the solid-liquid interface. During photothermal treatment, the heat is highly confined to the micro- and nano-scale regions of the interface, and the thermal impact on the substrate, current collector, and solid electrode active material layer is suppressed to a negligible level. The treatment atmosphere can be selected based on the oxidation sensitivity of the liquid metal to prevent excessive oxidation during the treatment process. This step utilizes the local photothermal effect of plasmon resonance to selectively heat and strengthen the contact interface between the liquid metal and the plasmon nanostructure layer. (6) Integration of encapsulation and protective layer.

[0061] A flexible encapsulation protective layer is applied to the electrode system prepared through the aforementioned steps to isolate it from the erosion and damage caused by moisture, oxygen, and physical and mechanical damage (such as scratches and abrasion) in the external environment, thereby improving the long-term stability and reliability of the electrode during its service life. The encapsulation layer material has flexible and deformable properties, and can deform synchronously with the bending and stretching deformation of the electrode, without restricting the mechanical compliance of the electrode. The encapsulation process is carried out with the electrical leads of the electrode reserved, ensuring that the electrode can still establish a reliable electrical connection with the external circuit after encapsulation. The method of applying the encapsulation layer can be flexibly selected according to the material properties and electrode geometry.

[0062] The method for preparing the hybrid ordered structure includes the following steps: (1) Surface activation pretreatment of substrate and conductive current collector layer: Activation pretreatment is carried out through physical or chemical means to remove adsorbed pollutants, organic residues and natural oxide layers from the surface, while introducing active functional groups or increasing surface roughness. (2) Preparation of composite functional layer: Solid electrode active materials and plasmonic nanostructure materials are mixed uniformly with liquid metal in a liquid medium to obtain a composite slurry, which is then integrally formed into a film and cured. Alternatively, solid electrode active materials, plasmonic nanostructure materials, and liquid metals are dispersed uniformly in a liquid medium to obtain three slurries, and then the three slurries are deposited alternately to form a composite functional layer with a stacked interpenetrating structure. Plasmon nanostructure units, solid electrode active material units, and liquid metal units are mixed in a liquid medium according to a preset ratio to form a composite ink or dispersion with good dispersion uniformity and film-forming suitability; the viscosity, solid content, and component distribution uniformity of the prepared composite ink or dispersion should meet the construction requirements of the subsequent film-forming process. The film-forming process allows for effective control over the thickness, porosity, and spatial distribution of the composite functional layer by adjusting parameters such as ink supply rate, deposition thickness, drying temperature, and curing time. The film-forming atmosphere can be selected based on the oxidation sensitivity of the liquid metal and the solvent evaporation characteristics to ensure the chemical stability of each component during film formation. After this step, multiple dispersed heterogeneous interface contact points or regions are formed within the composite functional layer between liquid metal units and plasmonic nanostructure units, providing numerous interfacial reaction precursor sites for subsequent photothermal interface strengthening treatment. (3) Plasmon local photothermal interface enhancement treatment: Irradiation was performed using a light source whose emission spectrum matched the surface plasmon resonance band of the plasmon nanostructure layer, with a total irradiation time of 1 ms to 30 min. (4) Integration of encapsulation and protective layer.

[0063] Example 1: Layered ordered electrode (Au + CNT + GaInSn) (1) Surface activation pretreatment of substrate and conductive current collector layer A 100 μm thick polyimide film was selected as a flexible substrate, and a 200 nm thick gold film was deposited on its surface by magnetron sputtering as a conductive current collector layer. The substrate and the conductive current collector layer were ultrasonically cleaned with acetone, ethanol and deionized water for 10 min each, dried with nitrogen, and then placed in an ultraviolet ozone cleaner for 15 min to obtain a clean and activated surface. (2) Solid electrode active material layer forming Carbon nanotubes and polyvinylidene fluoride were mixed at a mass ratio of 9:1, and 5 mL of N-methylpyrrolidone was added to grind them into a uniform slurry. The slurry was coated onto the surface of the conductive current collector layer by a blade coating method with a blade gap of 50 μm. After coating, the material was vacuum dried at 80℃ for 6 h to form a solid electrode active material layer with a thickness of 30 μm and a porosity of 40%. (3) Controllable construction of plasmonic nanostructures Take 50 mL of commercially available citrate buffer with a concentration of 0.5 mg / mL for stable suspension of gold nanoparticles. The average particle size of the gold nanoparticles is 30 nm. Immerse the substrate / conductive current collector layer with the solid electrode active material layer in it and let it stand at room temperature for 2 h to self-assemble. After taking it out, rinse it with deionized water and blow it dry with nitrogen. Gold nanoparticle plasmonic nanostructures are obtained on the surface and internal pore walls of the solid electrode active material layer. (4) Controlled introduction of liquid metal GaInSn alloy liquid metal was selected, and 0.5 g of liquid metal was dropped onto the surface of the active material layer of the solid electrode using a drop-casting method. The electrode was then placed under a vacuum of 1×10⁻⁶. -2 The liquid metal was kept in the vacuum chamber of Pa for 5 minutes to fully fill the pore network of the solid electrode active material layer by vacuum-assisted infiltration. After removal, the excess liquid metal on the surface was wiped off with lint-free paper. (5) Plasmon local photothermal interface enhancement treatment The resulting electrode was placed in an argon protective atmosphere and irradiated with a 532 nm continuous-wave laser. The power density of the light source was set to 1.5 W / cm². 2 The irradiation time was 5 min; the laser wavelength matched the plasmon resonance peak of the gold nanoparticles. During the irradiation process, the plasmon nanostructure layer generated a local photothermal effect, forming a local high temperature at the interface between the liquid metal and the gold nanoparticles, which promoted interface wetting and atomic diffusion. (6) Integration of encapsulation and protective layer A 50 μm thick polydimethylsiloxane film was used as the encapsulation layer and was attached to the electrode surface by lamination. After reserving electrode leads, performance testing was performed.

[0064] Example 2: Hybrid ordered electrode - three-component system (Ag + Graphene + EGaIn) (1) Surface activation pretreatment of substrate and conductive current collector layer: Same as step (1) in Example 1, except that the current collector material is changed to carbon cloth; (2) Preparation of composite functional layer: Silver nanoparticles, graphene nanosheets, and EGaIn alloy liquid metal were weighed out at a mass ratio of 1:40:40. The silver nanoparticles had an average particle size of 20 nm, and the graphene nanosheets had a thickness of 2–5 nm and a diameter of 5–10 μm. The silver nanoparticles and graphene nanosheets were ultrasonically dispersed in anhydrous ethanol for 30 min to form a uniform suspension. Then, the EGaIn alloy was added to the suspension under mechanical stirring, and stirring was continued for 1 h to obtain a three-component composite slurry. The slurry viscosity was 800 mPa·s, and the solid content was 15 wt%. The obtained composite slurry was uniformly sprayed onto the surface of the carbon cloth conductive current collector layer using a spraying method. During the spraying process, the substrate temperature was maintained at 60℃ and the slurry supply rate was 2 mL / min. After the spraying was completed, the composite functional layer was dried and cured in a vacuum oven at 80℃ for 30 min to form a composite functional layer with a thickness of 150 μm. (3) Plasmon local photothermal interface enhancement treatment The resulting electrode was placed in a nitrogen protective atmosphere and irradiated with a 405 nm laser. The power density of the light source was set to 0.8 W / cm². 2 With an irradiation time of 8 min, the silver nanoparticles exhibit strong local surface plasmon resonance absorption near 405 nm. Photothermal treatment simultaneously generates local temperature rise at each silver-liquid metal contact interface within the composite functional layer, achieving multi-site interface strengthening. (4) Integration of encapsulation and protection layer: Same as step (6) in Example 1.

[0065] Example 3: Layered sequential electrode (Pt + MnO2 + GaInZn) (1) Activation pretreatment of substrate and conductive current collector layer surface: Same as step (1) in Example 1; (2) Solid electrode active material layer forming A manganese dioxide active material layer was deposited on the surface of a conductive current collector layer using an electrochemical deposition method. The electrolyte was a mixed aqueous solution of 0.1 mol / L manganese acetate and 0.1 mol / L sodium sulfate. A constant current deposition mode was used with a current density of 1 mA / cm² and a deposition time of 10 min. After deposition, the layer was annealed at 100 °C for 2 h to obtain a manganese dioxide active layer with a thickness of 5 μm and a mesoporous structure. (3) Controllable construction of plasmonic nanostructure layers Using the substrate / current collector with manganese dioxide active layer obtained in step (2) as the working electrode, a platinum sheet as the counter electrode, and a saturated calomel electrode as the reference electrode, the electrode was placed in an electrolyte containing 0.5 mmol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L sodium sulfate (Na2SO4). Electrochemical deposition was performed using cyclic voltammetry with a potential scan range of -0.2 V to 0.6 V (vs. SCE), a scan rate of 50 mV / s, and 30 cyclic deposition cycles. After deposition, the electrode was removed, rinsed with deionized water, and dried with nitrogen to obtain a plasmonic nanostructure in which platinum nanoparticles are uniformly loaded on the surface of the manganese dioxide layer and near the surface pore walls. (4) Controlled introduction of liquid metal GaInZn alloy liquid metal was selected and heated to 50℃ to reduce its viscosity. 0.3 g of the liquid metal was then uniformly coated onto the surface of the manganese dioxide active layer using a scraping method with a scraper gap of 20 μm. After coating, the electrode was placed under a vacuum of 1×10⁻⁶. -1 The liquid metal was kept in a vacuum chamber for 10 minutes to promote the penetration of liquid metal into the mesopores. (5) Plasmon local photothermal interface enhancement treatment The resulting electrode was placed in a reducing atmosphere of argon and hydrogen in a volume ratio of 95:5 and irradiated with a 633 nm laser at a power density of 3.0 W / cm². 2 The irradiation time was 2 min, and the laser wavelength matched the plasmonic resonance peak of the platinum nanoparticles to achieve efficient interfacial photothermal enhancement. (6) Integration of encapsulation and protective layer: Same as step (6) in Example 1.

[0066] Example 4: Hybrid Sequential Electrode – Three-component System (Au + Activated Carbon + GaInSn) (1) Activation pretreatment of substrate and conductive current collector layer surface: Same as Example 1 (1).

[0067] (2) Preparation of composite functional layer Three slurries were prepared: ① a gold nanorod ethanol dispersion with a gold nanorod aspect ratio of 3:1, a longitudinal plasmon resonance peak at 680 nm, and a concentration of 1 mg / mL; ② an activated carbon / N-methylpyrrolidone slurry with activated carbon having a specific surface area of ​​1500 m². 2 / g, with a solid content of 10 wt%; ③GaInSn liquid metal microdroplet dispersion, in which liquid metal is dispersed in ethanol by ultrasonic dispersion, with an average droplet size of 5 μm and a solid content of 20 wt%; The three slurries were deposited alternately by spraying: first, a gold nanorod dispersion was sprayed to form the bottom layer and dried at 60°C; second, an activated carbon slurry was sprayed and dried at 80°C; and finally, a liquid metal droplet dispersion was sprayed and dried at room temperature. The above cycle was repeated 3 times to construct a composite functional layer with a stacked interpenetrating structure and a total thickness of 200 μm. (3) Plasmon local photothermal interface enhancement treatment The resulting electrode was placed under a vacuum of 1×10⁻⁶. -3 In a vacuum chamber of Pa, irradiation was performed using a 680 nm laser with a power density of 1.0 W / cm². 2 The irradiation time is 10 minutes; (4) Integration of encapsulation and protection layer: Same as step (6) in Example 1.

[0068] Comparative Example 1: Traditional liquid metal electrode without plasmonic photothermal treatment The difference from Example 1 is that step (3) of constructing the plasmonic nanostructure layer and step (5) of strengthening the plasmonic local photothermal interface are omitted; that is, a solid electrode active material layer is directly prepared on the conductive current collector, followed by the introduction of liquid metal and direct encapsulation. The remaining materials and process parameters are the same as in Example 1.

[0069] Comparative Example 2: Electrodes treated with integral thermal annealing instead of plasmonic photothermal treatment The difference from Example 1 is that step (5) of the plasmonic local photothermal interface strengthening process is replaced by overall thermal annealing; specifically, the electrode after the introduction of liquid metal is placed in a vacuum oven and heated at 150°C for 30 minutes. All other materials and process parameters are the same as in Example 1.

[0070] Comparative Example 3: Electrodes in hybrid ordered structures without the introduction of plasmon units The difference from Example 2 is that: in step (2) the composite slurry is prepared without adding silver nanoparticles, but only by mixing graphene nanosheets and liquid metal at a mass ratio of 1:1, and the plasmon local photothermal interface strengthening process in step (3) is omitted. All other materials and process parameters are the same as in Example 2.

[0071] Comparative Example 4: Traditional electrode without liquid metal (no self-healing function) The difference from Example 1 is that step (4) of introducing liquid metal is completely omitted, that is, the controlled introduction of liquid metal and the plasmonic local photothermal interface strengthening treatment in step (5) are not performed. All other materials and process parameters are the same as in Example 1.

[0072] The following performance tests were performed on the electrodes prepared in the above embodiments and comparative examples: (1) Interface bonding test Referring to GB / T1457-2005 "Test Method for Roller Peel Strength of Sandwich Structures", the peel test method was adopted. 3M tape was attached to the liquid metal layer on the electrode surface and peeled vertically at a constant rate, and the peel strength was recorded. Each sample was tested 5 times and the average value was taken.

[0073] (2) Bending cycle stability test Referring to GB / T38001.61-2019 / IEC62715-6-1:2014 "Flexible display devices – Part 6-1: Mechanical stress test methods", the electrodes were fixed on a bending tester with a curvature radius of 5 mm and repeatedly bent at a frequency of 1 Hz. After every 100 bends, the change in electrode resistance was measured, and the number of bending cycles when the rate of resistance change exceeded 20% of the initial value was recorded.

[0074] (3) Liquid metal retention rate test Place the electrode in a centrifuge and centrifuge at 500 rpm for 10 minutes. Weigh the electrode before and after centrifugation and calculate the liquid metal retention rate. A higher retention rate indicates a better interface anchoring effect.

[0075] (4) Electrochemical cycling performance test Referring to GB / T34870.1-2017 "Supercapacitors - Part 1: General Rules", the electrodes were used as supercapacitor electrodes, and constant current charge-discharge tests were performed in a three-electrode system. The electrolyte was a 1 mol / L sodium sulfate aqueous solution, the current density was 1 A / g, and the capacity retention rate was recorded after 10,000 cycles.

[0076] The performance test results are shown in Table 1.

[0077] Results Analysis As can be seen from the comparison between Example 1 and Comparative Example 1, the peel strength of Example 1 is increased by about 4.7 times, the bending cycle life is increased by more than 8 times, and the liquid metal retention rate is increased by about 34%, which fully demonstrates that the introduction of plasmonic nanostructure layer and photothermal treatment can significantly enhance the heterogeneous interface bonding.

[0078] A comparison of Example 1 and Comparative Example 2 shows that although the overall hot annealing in Comparative Example 2 has a certain improvement effect, the peel strength and retention rate are significantly lower than those in Example 1, and the bending cycle life is much lower than that in Example 1. This demonstrates the advantage of plasmonic localized photothermal treatment, namely, localized heating avoids thermal damage to the substrate and active materials.

[0079] As can be seen from the comparison between Example 1 and Comparative Example 4, the electrode prepared in this way does not contain a liquid metal layer and therefore does not have self-healing ability. After the electrode develops cracks under mechanical deformation, the conductive path is permanently interrupted and cannot recover on its own, which proves the contribution of the introduction of the liquid metal layer to the electrode's self-healing function and cycle stability.

[0080] As can be seen from the comparison between Example 2 and Comparative Example 3, the peel strength of Example 2 is increased by about 2.9 times and the capacity retention rate is increased by about 39%, which verifies the necessity of introducing plasmonic nanostructure units into the hybrid ordered structure to strengthen the interface.

[0081] A comparison of Examples 1 and 2 shows that the interfacial bonding strength and stability of the layered ordered structure are slightly better than those of the hybrid ordered structure, because the interface position is clear and the photothermal enhancement effect is more concentrated in the layered structure; however, the hybrid ordered structure process is simpler and suitable for large-area, low-cost preparation.

[0082] As can be seen from the comparison between Example 4 and Example 1, Example 4, which uses an ordered structure of platinum nanograting array, is slightly better than Example 1, which uses disordered self-assembly of gold nanoparticles, in terms of peeling strength and retention rate. This indicates that the ordered nanoarray structure has a higher utilization efficiency of the plasmonic photothermal effect.

[0083] The test results of the above embodiments and comparative examples show that, by introducing plasmonic nanostructure units and applying wavelength-matched local photothermal treatment, the present invention can significantly enhance the heterogeneous interface bonding between liquid metal and solid substrate, greatly improve the cycling stability of the electrode under mechanical deformation and the liquid metal retention rate, while fully preserving the passive self-healing capability of the liquid metal. Both hierarchical and hybrid ordered structures can achieve the technical effects of the present invention, and can be flexibly selected according to actual application requirements.

[0084] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and 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 method for preparing a self-healing electrode based on a plasmonic-reinforced liquid metal-solid matrix heterointerface, characterized in that, The method described: (1) Surface activation pretreatment of substrate and conductive current collector layer: Activation pretreatment is carried out through physical or chemical means to remove adsorbed pollutants, organic residues and natural oxide layers from the surface, while introducing active functional groups or increasing surface roughness. (2) Solid electrode active material layer forming: A porous solid electrode active material layer is constructed on the surface of the conductive current collector layer. By controlling the material deposition kinetics, solvent evaporation rate and curing conditions, a connected or semi-connected pore network is formed inside the active material layer. (3) Controllable construction of plasmonic nanostructures: Plasmon nanostructures with discrete nanoparticle assembly morphology or ordered nanoarray structure are constructed on the surface and internal pore walls of the active material layer of solid electrode using micro-nano fabrication or self-assembly methods. (4) Controlled introduction of liquid metal: When liquid metal is in a flowing state, it is filled into the pores of the solid electrode active material layer by coating, printing transfer or vacuum-assisted infiltration. (5) Plasmon local photothermal interface enhancement treatment: Irradiation was performed using a light source whose emission spectrum matched the surface plasmon resonance band of the plasmon nanostructure layer, with a total irradiation time of 1 ms to 30 min. (6) Integration of encapsulation and protective layer.

2. A method for preparing a self-healing electrode based on a plasmon-reinforced liquid metal-solid matrix heterointerface, characterized in that, The method described: (1) Surface activation pretreatment of substrate and conductive current collector layer: Activation pretreatment is carried out through physical or chemical means to remove adsorbed pollutants, organic residues and natural oxide layers from the surface, while introducing active functional groups or increasing surface roughness. (2) Preparation of composite functional layer: Solid electrode active materials and plasmonic nanostructure materials are mixed uniformly with liquid metal in a liquid medium to obtain a composite slurry, which is then integrally formed into a film and cured. Alternatively, solid electrode active materials, plasmonic nanostructure materials, and liquid metals are dispersed uniformly in a liquid medium to obtain three slurries, and then the three slurries are deposited alternately to form a composite functional layer with a stacked interpenetrating structure. (3) Plasmon local photothermal interface enhancement treatment: Irradiation was performed using a light source whose emission spectrum matched the surface plasmon resonance band of the plasmon nanostructure layer, with a total irradiation time of 1 ms to 30 min. (4) Integration of encapsulation and protective layer.

3. The method according to claim 1 or 2, characterized in that, The physical or chemical means mentioned in step (1) include, but are not limited to, one or more of the following: plasma cleaning, ultraviolet ozone irradiation, acid / alkali etching, organic solvent ultrasonic cleaning, ion beam bombardment, surface modification, and surface grafting polymerization modification; the substrate is one or more of the following: polydimethylsiloxane, polyimide, polyethylene terephthalate, polyurethane, and polyethylene naphthalate; the conductive current collector layer is one or more of the following: metal foil, carbon cloth, carbon paper, graphene film, carbon nanotube film, conductive polymer film, or transparent conductive oxide film.

4. The method according to claim 1, characterized in that, The forming methods described in step (2) include, but are not limited to, scraping, spin coating, spraying, dip coating, electrohydraulic inkjet printing, screen printing, gravure printing, inkjet printing, electrochemical deposition, chemical vapor deposition, physical vapor deposition, magnetron sputtering, atomic layer deposition, or filtration film formation; the micro / nano fabrication or self-assembly described in step (3) includes, but are not limited to, chemical reduction in situ growth, electrochemical deposition, self-assembly, template-assisted growth, photolithography, electron beam etching, nanoimprinting, or template peeling; the coating methods described in step (4) include drop coating, spin coating, spraying, scraping, or dip-coating; the printing transfer methods include screen printing, gravure printing, inkjet printing, or roll transfer; the vacuum-assisted infiltration methods include vacuum-assisted infiltration or capillary self-filling; the thickness of the solid electrode active material layer described in step (2) is 100 nm to 100 μm; the particle size of the discrete nanoparticles described in step (3) is 5 nm. nm ~ 500 nm; the ordered nanoarray structure mentioned in step (3) includes one or more of the following nanostructures: nanograting array, nanopore array, nanorod array or nanocone array, with a characteristic size of 10 nm ~ 500 nm; the contact interface between the liquid metal and the ionotropic nanostructure in step (3) in step (4) is located in a region of 0 ~ 20 μm from the light incident surface; the mass ratio of the solid electrode active material in step (2), the ionotropic nanostructure material in step (3) and the liquid metal in step (4) is 1:(0.5 ~ 200):(0.5 ~ 200).

5. The method according to claim 2, characterized in that, The film-forming methods mentioned in step (2) include, but are not limited to, spraying, screen printing, gravure printing, inkjet printing, scraping, spin coating, drop coating, slot coating, roller coating, transfer printing, dip coating, or electrophoretic deposition; the slurry supply rate is 0.01 mL / min to 100 mL / min; the thickness of the composite functional layer is 100 nm to 800 μm; the curing temperature is -200℃ to 150℃, and the time is 1 min to 120 min; the mass ratio of solid electrode active material, plasmonic nanostructure material and liquid metal is 1:(0.5 to 200):(0.5 to 200).

6. The method according to claim 1 or 2, characterized in that, The solid electrode active material layer in step (2) is a composite of one or more of the following: carbon-based materials, silicon-based materials, metal oxides, and conductive polymers; the plasmonic nanostructure material in step (2) or step (3) is selected from at least one of pure metals such as gold, silver, platinum, palladium, copper, and aluminum, or their alloys; the liquid metal in step (2) or step (4) is selected from gallium-based room-temperature liquid metals; the light source in step (3) or step (5) includes a continuous light source, a quasi-continuous light source, and a pulsed laser light source; the emission wavelength range of the light source in step (3) or step (5) is 200~2000 nm. nm, and the emission wavelength at least partially overlaps with the local surface plasmon resonance absorption band of the plasmon nanostructure layer; the irradiation method of the light source in step (3) or step (5) is fixed-point irradiation, surface irradiation, line scanning irradiation, point-by-point scanning irradiation, array irradiation or mask selective irradiation; the application method of the encapsulation protective layer in step (4) or step (6) includes, but is not limited to, thin film bonding method, coating curing method or vapor deposition method; the material of the encapsulation protective layer in step (4) or step (6) includes, but is not limited to, organic polymer, inorganic thin film or organic-inorganic composite material.

7. The method according to claim 6, characterized in that, Carbon-based materials include, but are not limited to, one or more of activated carbon, graphite, graphene, carbon nanotubes, and carbon fibers; metal oxides include, but are not limited to, one or more of manganese dioxide, iron tetroxide, ruthenium oxide, and indium tin oxide; conductive polymers include, but are not limited to, one or more of polyaniline, polypyrrole, and polythiophene; gallium-based room-temperature liquid metals are at least one of GaIn alloy, GaInSn alloy, GaSn alloy, GaInZn alloy, and GaInSnZn alloy; when the light source is a continuous or quasi-continuous light source, the irradiation power density is 0.01 W / cm². 2 ~100MW / cm 2 When the light source is a pulsed source, the pulse width is 1 fs to 1 s, the repetition frequency is 1 Hz to 100 MHz, and the pulse energy density is 0.1 μJ / cm². 2 ~100 J / cm 2 The peak power density is 0.01 W / cm³. 2 ~100 MW / cm 2 The average power density is 0.01 W / cm³. 2 ~10 kW / cm 2 The number of pulses is 1 to 10. 9 Second-rate; Thin film application methods include lamination or bonding methods; Coating and curing methods include spin coating, spray coating, drop coating and curing, slot coating or screen printing; vapor deposition methods include chemical vapor deposition, plasma-enhanced chemical vapor deposition or atomic layer deposition; organic polymers include at least one of flexible polymer films, elastomer films, UV-curable resins, thermosetting resins, and silicone encapsulants; inorganic films include at least one of inorganic oxide films and nitride films; organic-inorganic composite materials include organic-inorganic hybrid barrier films.

8. The self-healing electrode based on a plasmonic-reinforced liquid metal-solid matrix heterointerface obtained by the method of claim 1, characterized in that, The electrodes, from bottom to top, include: Base; Conductive current collector layer; The solid electrode active material layer, plasmonic nanostructures, and liquid metal; wherein the plasmonic nanostructures are attached to, embedded in, or grown in situ on the light-incident side surface, near-surface pore walls, or microcrack inner walls of the solid electrode active material layer; and the liquid metal is distributed within the pores of the solid electrode active material layer and forms an interface contact with the plasmonic nanostructures. Encapsulation and protective layer.

9. The self-healing electrode based on a plasmonic-enhanced liquid metal-solid matrix heterointerface obtained by the method of claim 2, characterized in that, The electrodes, from bottom to top, include: Base; Conductive current collector layer; Composite functional layer; solid electrode active material and plasmonic nanostructure material mixed with liquid metal; Encapsulation and protective layer.

10. The application of the self-healing electrode based on plasmon-reinforced liquid metal-solid matrix heterostructure interface as described in claim 8 or 9 in the fields of electrochemistry or flexible electronic devices.

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