Preparation method of multifunctional metal coating containing core-shell structure

Abstract

The invention discloses a preparation method of a multifunctional metal coating containing a core-shell structure, and the method comprises the following steps: step S1, selecting a corresponding core material and a shell material according to the requirements of different functions of the core-shell structure, and packaging the core material in the shell material to prepare the core-shell structure with different functions; s2, functionalizing an electrochemical working solution containing metal ions: uniformly mixing the core-shell structures with different functions in the electrochemical working solution containing the metal ions respectively to obtain deposition solutions with different functions; and S3, selecting the deposition liquids with different functions to electrochemically deposit corresponding functional deposition layers on the deposition area on the surface of the conductive substrate layer by layer, and finally obtaining the multifunctional metal coating containing the core-shell structure. Through collaborative innovation of functional modular packaging of a core-shell structure and an electrochemical deposition process, multifunctional integration of the coating, collaborative enhancement of performance and precise and controllable preparation process are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemistry, in particular to a preparation method of a multifunctional metal coating with core-shell structure. BACKGROUND

[0002] With the rapid development of aerospace, biomedical and electronic device fields, the functional coating preparation technology by introducing core-shell structure has made significant progress. Due to the limited multifunctional synergistic enhancement effect, complex coating preparation process and low industrial production efficiency, the application of multifunctional metal coating design and manufacturing in complex harsh environments is limited.

[0003] A preparation method of a polyurea photo-thermal anti-icing coating is disclosed in Chinese patent application No. 202410717770.1 filed on June 4, 2024. The method forms silica / polyurea composite particles by compounding silica nanoparticles into polyurea molecules; then combines these composite particles with graphite microparticles and uniformly disperses them in polysiloxane, developing an ultrahydrophobic photo-thermal coating with excellent wear resistance and durability. The coating surface has high photo-thermal conversion efficiency, can achieve obvious temperature rise under solar irradiation, can delay icing time and reduce ice adhesion strength, and thus achieves good anti-icing and de-icing effect. However, the coating prepared by this method utilizes the multi-coating method for dual functionality of photo-thermal conversion and hydrophobicity, which cannot achieve multifunctionality in one clamping; and this coating preparation method is mainly used for the preparation of multifunctional non-metal coatings, and cannot be used for the preparation of multifunctional metal coatings.

[0004] A barium sulfate material with a photo-thermal conversion surface layer and a preparation method thereof are disclosed in Chinese patent application No. 202210592720.6 filed on May 27, 2022. The barium sulfate material is composed of barium sulfate and a polymer coating with photo-thermal effect, and the barium sulfate is coated with a 10-20 nm thick polymer coating; the method adds barium sulfate ethanol dispersion liquid to the polydopamine solution and stirs, centrifuges, washes and dries, adds iron chloride and pyrrole solution to the barium sulfate ethanol dispersion liquid, and then adds hydrochloric acid and stirs, centrifuges, washes and dries to obtain the material. The material can be used to prepare photo-thermal conversion materials, and the preparation is simple, the material is cheap and easy to obtain, the photo-thermal product can be batch prepared, and the applicability is wide. However, the core-shell structure prepared by this method can only be used to prepare photo-thermal conversion materials, and the metal coating with the core-shell structure cannot directly obtain multifunctionality.

[0005] Chinese patent application No. 202210085306.6 filed on January 25, 2022 discloses a high-temperature phase change heat storage microcapsule with a whisker / fiber coating layer and a preparation method thereof. The method is to place aluminum powder or aluminum-based alloy powder in high-temperature steam for pretreatment, then hydrothermally react with a glucose aqueous solution, take out after cooling, filter, wash, and dry to obtain a core-shell structure. The high-temperature phase change core-shell structure prepared by the invention has high elastic modulus and thermal conductivity, high phase change latent heat retention rate, and good thermal cycle performance, and has a large phase change retention rate. However, the high-temperature phase change core-shell structure prepared by this method mainly reflects a single function, and when applied in a metal coating, the single structure of the core-shell structure is easy to change in volume, thereby affecting the functionality of the coating.

[0006] Chinese patent application No. 200980122531.5 filed on July 10, 2009 discloses a method of electrochemically depositing a metal on a substrate. The method provides a solution and method of electrochemically depositing a metal on a substrate, the solution comprising silica particles co-deposited with nickel. The invention co-deposits silica particles with metal ions on an electrically conductive substrate by a method of electrochemical deposition, and the prepared composite metal coating greatly improves the corrosion prevention effect. However, the coating prepared by the invention uses the material properties of non-metallic particles to enhance the corrosion resistance of the coating, and the multifunctionality under harsh working conditions cannot be satisfied only by the material properties of the non-metallic particles in the method, and the application range is limited.

[0007] The information disclosed in this BACKGROUND section is only for the purpose of increasing the understanding of the general background of the application, and should not be taken as an acknowledgment or any form of suggestion that it forms the prior art that is already known to those of ordinary skill in the art. SUMMARY

[0008] The technical problem to be solved by the present application is to provide a preparation method of a multifunctional metal coating containing a core-shell structure, which solves the problems of single function of existing metal coatings and inability to meet complex requirements in multiple scenes, realizes multifunctional integration of the coating, performance synergistic enhancement, and precise controllability of the preparation process, and solves the problems of existing metal coatings in functional composition, structure regulation, and preparation efficiency.

[0009] To solve the above technical problems, the present application discloses a preparation method of a multifunctional metal coating containing a core-shell structure, characterized in that it comprises the following steps:

[0010] Step S1, selecting corresponding core material and shell material according to the different functional requirements of the core-shell structure, and encapsulating the core material in the shell material to prepare a core-shell structure with different functions;

[0011] Step S2, functionalization of the electrochemical working solution containing metal ions: uniformly mixing the different functional core-shell structures in the electrochemical working solution containing metal ions respectively to obtain different functional deposition solutions;

[0012] Step S3, electrochemical deposition of the corresponding functional deposition layer on the deposition area of the surface of the conductive substrate by selecting the different functional deposition solutions, to finally obtain the multifunctional metal coating containing core-shell structures.

[0013] Specifically, the step S3 comprises: taking the conductive substrate as a cathode, taking an inert electrode as an anode, spacing the conductive substrate and the inert electrode in the deposition solution and connecting the power supply, and electrochemically depositing the corresponding functional deposition layer on the deposition area of the surface of the conductive substrate layer by layer; and the content, arrangement mode, size and shape of the core-shell structure contained in each functional deposition layer, and the size and thickness of each functional deposition layer are regulated by regulating the electrochemical deposition current / voltage, the distance between the cathode and the anode, the temperature of the deposition solution and the electrochemical deposition time.

[0014] Specifically, the multifunctional metal coating is a plurality of single functional layers arranged in layers, and comprises one or a combination of two or more of a heat storage layer, a hydrophobic layer, an anti-electromagnetic interference layer and a wear-resistant and corrosion-resistant layer.

[0015] Alternatively, the multifunctional metal coating is a single functional deposition layer, and the multifunctional is a combination of two or more of heat storage function, hydrophobic function, anti-electromagnetic interference function and wear-resistant and corrosion-resistant function.

[0016] Specifically, the core-shell structure is a multifunctional core-shell structure, which is selected from one of the following:

[0017] The first multifunctional core-shell structure, the shell of the first multifunctional core-shell structure is an anti-electromagnetic interference material shell, and the core of the first multifunctional core-shell structure is a phase change material core;

[0018] The second multifunctional core-shell structure, the shell of the second multifunctional core-shell structure is an anti-electromagnetic interference material shell, and the core of the second multifunctional core-shell structure is a wear-resistant and corrosion-resistant material core;

[0019] The third multifunctional core-shell structure, the shell of the third multifunctional core-shell structure is a wear-resistant and corrosion-resistant material shell, and the core of the third multifunctional core-shell structure is a phase change material core;

[0020] The fourth multifunctional core-shell structure, the shell of the fourth multifunctional core-shell structure is a wear-resistant and corrosion-resistant material shell, and the core of the fourth multifunctional core-shell structure is an anti-electromagnetic interference material core;

[0021] The anti-electromagnetic interference material is selected from a metal-based anti-electromagnetic material, a carbon-based anti-electromagnetic material, an anti-electromagnetic ceramic material, an anti-electromagnetic polymer, or a magnetic material.

[0022] The phase change material is an organic phase change material, an inorganic phase change material, or a composite phase change material.

[0023] The wear-resistant and corrosion-resistant material is a metal-based wear-resistant and corrosion-resistant material, a carbon-based wear-resistant and corrosion-resistant material, a wear-resistant and corrosion-resistant ceramic material, a wear-resistant and corrosion-resistant polymer, a wear-resistant and corrosion-resistant metal oxide, or a hard alloy material.

[0024] Specifically, the core-shell structure is a single-core structure or a multi-core structure.

[0025] The number of cores encapsulated inside the shell of the single-core structure is one.

[0026] The number of cores encapsulated inside the shell of the multi-core structure is two or more.

[0027] In the single-core structure or the multi-core structure, there is a gap between the core and the shell, or the shell is wrapped around the outer surface of the core.

[0028] Specifically, the morphology of the core-shell structure contained in the multifunctional metal coating includes at least one of a spherical shape, a cubic shape, a rod shape, a tubular shape, a lamellar shape, a dendritic shape, or a surface pore shape.

[0029] Specifically, the conductive substrate surface is divided into one or more deposition regions, and the multifunctional metal coating containing the core-shell structure deposited in each deposition region has multifunctionality adapted to the requirements of the deposition region.

[0030] Further, the step S1 further comprises modifying the material of the core and the material of the shell by using a modifier; after modification, the material of the core and the material of the shell have different charges, forming a core-shell structure with uniform structure and self-charging.

[0031] Specifically, the shell of the core-shell structure for the heat storage layer is a directional heat conduction structure, including a shell first part located on a first side and a shell second part located on a side opposite to the first side, the shell first part adopts a high thermal resistance material, and the shell second part adopts a high thermal conductivity material.

[0032] Specifically, when depositing the hydrophobic layer, the deposition is maskless electrochemical deposition or mask electrochemical deposition.

[0033] When the deposition is maskless electrochemical deposition, the part of the core-shell structure exposed on the surface of the coating forms a nano-scale protruding structure for hydrophobicity.

[0034] When the deposition is a mask electrochemical deposition, the hydrophobic layer obtained by the deposition is a micron-scale patterned structure containing core-shell structures, and the part of the core-shell structure exposed on the surface of the micron-scale patterned structure forms a nano-scale protruding structure for hydrophobicity.

[0035] Specifically, the core-shell structure for the anti-electromagnetic interference layer has a core selected from one or more than two combinations of a metal core, a magnetic core and a carbon material metal oxide core, and a shell selected from one or more than two combinations of a metal shell, an insulating / semiconductor shell, a magnetic shell, a polymer shell, a metal oxide shell, a carbon-based shell or a MXenes material shell.

[0036] Specifically, the core-shell structure for the wear-resistant and corrosion-resistant layer has a core selected from one or more than two combinations of a ceramic core, a metal core, a carbon material core, a metal oxide core, a polymer core and a hard alloy core, and a shell selected from one or more than two combinations of a metal shell, a polymer shell, a ceramic shell, a carbon-based shell, a metal oxide shell and a multi-material composite shell.

[0037] Beneficial effects:

[0038] 1. The preparation method of the multifunctional metal coating containing core-shell structures provided by the application realizes efficient design and controllable preparation of the multifunctional metal coating. The method first encapsulates different core materials with shell materials to convert heat storage, anti-electromagnetic interference, wear resistance and corrosion resistance into independent controllable core-shell structure units, thereby providing a basic module for multifunctional integration of the coating. Then, the core-shell structures are uniformly dispersed in an electrochemical working solution and co-deposited under the driving of an electric field, so as to ensure uniform distribution and directional migration of the core-shell structures and metal ions on the surface of the conductive substrate, thereby avoiding the problem of nanoparticle agglomeration. Meanwhile, by adjusting parameters such as current density and deposition time, the thickness, core-shell structure content and distribution gradient of each functional layer can be precisely controlled to meet the differentiated functional requirements of complex components. Finally, the working solution containing different functional core-shell structures is replaced layer by layer, and the heat storage layer, hydrophobic layer, anti-electromagnetic interference layer and wear-resistant and corrosion-resistant layer and other functional layers are sequentially deposited on the surface of the conductive substrate in an orderly manner, supporting single-layer or multi-layer arbitrary combination, thereby realizing preparation of the multifunctional metal coating designed on demand. Moreover, the method improves the preparation efficiency and reduces the process cost, and meanwhile, chemical bonding is generated between the layers, so that the interlayer bonding force is better.

[0039] 2、The preparation method provided by the application realizes multi-scene adaptation of the metal coating function by freely selecting and flexibly combining the heat storage layer, the hydrophobic layer, the anti-electromagnetic interference layer, the wear-resistant and corrosion-resistant layer and other functional layers, and provides a highly flexible and efficient solution for material surface functionalization applied to complex working conditions. Specifically, on the aircraft wing, the front side of the wing has a large air flow, and the coating needs to have an impact resistance effect; the middle part of the wing needs to have an anti-electromagnetic interference coating to protect the internal electronic equipment; and the whole needs to have a hydrophobic layer and a heat storage layer to prevent the surface from being covered with ice, and the preparation method of the application can realize the multifunctional coating under the complex working condition.

[0040] 3、The preparation method provided by the application provides a flexible and efficient implementation path for coating function unit design through diversified structure construction methods, so that the coating can realize function focusing through a single core structure, and can realize multi-performance coupling through a multi-core, cavity and other composite structures.

[0041] 4、The preparation method provided by the application enables a single core-shell structure to carry core functions and derive additional functions through performance complementation of shell materials by targeted combination of core-shell components such as anti-electromagnetic interference materials, high thermal conductivity materials, phase change materials, wear-resistant and corrosion-resistant materials.

[0042] 5、The preparation method provided by the application can achieve precise targeted optimization and efficient material utilization of the coating through regional content and arrangement design, and realizes the optimal balance of coating performance-cost through the synergy of local function strengthening and material simplification in non-critical areas.

[0043] 6、The preparation method provided by the application realizes self-driven uniform dispersion and efficient deposition without post-treatment of the core-shell structure by imparting different charges to the core and shell materials using a modifier during preparation, and forms a stable dispersion system in an electrochemical working solution due to the coulomb force, thereby avoiding the agglomeration or sedimentation problem of traditional core-shell structures caused by surface inertness.

[0044] 7、The preparation method provided by the application realizes precise guidance and on-demand regulation of heat flow in the heat storage layer by selecting a directional heat conduction structure of the core-shell structure, which includes a shell first part located on a first side and a shell second part located on a side opposite to the first side, the shell first part adopts a high thermal resistance material, and the shell second part adopts a high thermal conductivity material, thereby reducing heat loss to non-target directions, reducing heat loss, and improving the net heat storage efficiency of the heat storage layer.

[0045] 8、The preparation method provided by the application realizes efficient preparation and multi-effect synergy of super-hydrophobic performance by constructing nano-scale protrusions and micro-scale patterned structures on the surface of the coating through an electrochemical deposition process, and avoids the post-processing process, thereby significantly reducing maintenance costs and improving service reliability.

[0046] 9、The preparation method provided by the application realizes the breakthrough of coating from single function superposition to system performance multiplication through the cross-layer performance coupling of the functional layer, interlayer synergy, rather than simple function superposition. Specifically, through the cross-layer performance design of the core-shell structure, the anti-electromagnetic interference layer serves the heat conduction strengthening and the wear-resistant layer protects the upper functional unit at the same time, a multi-dimensional collaborative network is formed between the coatings, and the comprehensive performance of the coating under complex working conditions is improved.

[0047] 10、The preparation method provided by the application prepares the multifunctional metal coating containing the core-shell structure through the electrochemical deposition method. The method does not need additional equipment or complex post-processing, and through one clamping of the conductive substrate to be processed, the preparation of the multi-layer functional deposition layer and the construction of the micro-nano structure are simultaneously completed, and the efficient preparation and performance precise control of the multifunctional metal coating containing the core-shell structure are realized. BRIEF DESCRIPTION OF DRAWINGS

[0048] The above and / or other aspects of the application will become more apparent by describing in detail the preferred embodiments thereof with reference to the attached drawings.

[0049] Figure 1 is a process flow diagram of preparing a multifunctional metal coating containing a core-shell structure based on an electrochemical deposition method provided in the embodiment part of the application.

[0050] Figure 2 is a layered design diagram of the multifunctional metal coating containing the core-shell structure provided in the embodiment part of the application.

[0051] Figure 3 is a partial sectional view of a single-core structure provided in the embodiment part of the application;

[0052] Figure 4 is a partial sectional view of a multi-core structure provided in the embodiment part of the application;

[0053] Figure 5 is a partial sectional view of a single-core structure provided in the embodiment part of the application, which has a gap between the core and the shell;

[0054] Figure 6 is a structure diagram of a first multifunctional core-shell structure provided in the embodiment part of the application;

[0055] Figure 7 is a structure diagram of a second multifunctional core-shell structure provided in the embodiment part of the application;

[0056] Figure 8 is a structure diagram of a third multifunctional core-shell structure provided in the embodiment part of the application;

[0057] Figure 9 is a structural schematic diagram of a fourth multifunctional core-shell structure provided in some embodiments of the present application;

[0058] Figure 10 is a schematic diagram of a spherical-like core-shell structure provided in some embodiments of the present application;

[0059] Figure 11 is a schematic diagram of a cubic core-shell structure provided in some embodiments of the present application;

[0060] Figure 12 is a schematic diagram of a rod-like core-shell structure provided in some embodiments of the present application;

[0061] Figure 13 is a schematic diagram of a tubular core-shell structure provided in some embodiments of the present application;

[0062] Figure 14 is a schematic diagram of a sheet-like core-shell structure provided in some embodiments of the present application;

[0063] Figure 15 is a schematic diagram of a dendritic core-shell structure provided in some embodiments of the present application;

[0064] Figure 16 is a schematic diagram of a surface hole-like core-shell structure provided in some embodiments of the present application;

[0065] Figure 17 is a schematic diagram of a sub-region multifunctional coating region division of a multifunctional metal coating containing a core-shell structure provided in some embodiments of the present application.

[0066] Figure 18 is a schematic diagram of a directional heat conduction core-shell structure provided in some embodiments of the present application.

[0067] Figure 19 is a surface topography schematic diagram of a multifunctional metal coating containing a core-shell structure prepared based on a mask-free electrochemical deposition method provided in some embodiments of the present application.

[0068] Figure 20 is a surface topography schematic diagram of a multifunctional metal coating containing a core-shell structure prepared based on a mask electrochemical deposition method provided in some embodiments of the present application.

[0069] Figure 21 is a structural schematic diagram of a multifunctional metal coating one with interlayer synergistic enhancement provided in some embodiments of the present application;

[0070] Figure 22 is a structural schematic diagram of a multifunctional metal coating two with interlayer synergistic enhancement provided in some embodiments of the present application;

[0071] Figure 23is a structural schematic diagram of a heterocharge core-shell structure with a positively charged core provided by an embodiment of the present application.

[0072] Figure 24 is a structural schematic diagram of a heterocharge core-shell structure with a negatively charged core provided by an embodiment of the present application.

[0073] Figure 25 is a schematic diagram of the preparation principle of a multifunctional metal coating containing a core-shell structure prepared based on an electrochemical deposition method provided by an embodiment of the present application. DETAILED DESCRIPTION

[0074] The figure mark of the present application is explained as follows:

[0075] 1, core-shell structure; 11, core; 12, shell; 13, gap; 2, deposition solution; 21, metal ion; 3, deposition solution; 4, multifunctional metal coating; 41, hydrophobic layer; 42, wear-resistant and corrosion-resistant layer; 43, anti-electromagnetic interference layer; 44, heat storage layer; 5, inert electrode; 6, power supply; 7, water droplet; 8, heat release direction; 9, electromagnetic wave; 101, spherical-like; 102, cubic; 103, rod-like; 104, tubular; 105, lamellar; 106, dendritic; 107, surface pore; 120, first multifunctional core-shell structure; 130, second multifunctional core-shell structure; 150, third multifunctional core-shell structure; 160, fourth multifunctional core-shell structure; 112, phase change material core; 113, wear-resistant and corrosion-resistant material core; 114, anti-electromagnetic interference material core; 121, anti-electromagnetic interference material shell; 122, wear-resistant and corrosion-resistant material shell; 401, first multifunctional metal coating; 402, second multifunctional metal coating; 403, third multifunctional metal coating; 411, micron-scale patterned structure; 412, nano-scale protruding structure; 1201, first part of shell; 1202, second part of shell.

[0076] The present application discloses a preparation method of a multifunctional metal coating containing a core-shell structure, which realizes multifunctional integration and precise preparation of the coating by combining core-shell structure 1 functionalization with an electrochemical deposition process. The present application can be applied to the fields of aerospace, electronic and communication equipment, precision electronic components, medical devices, and building and new energy.

[0077] Figure 1 The present application discloses a preparation method of a multifunctional metal coating containing a core-shell structure, which realizes multifunctional integration and precise preparation of the coating by combining core-shell structure 1 functionalization with an electrochemical deposition process. The present application can be applied to the fields of aerospace, electronic and communication equipment, precision electronic components, medical devices, and building and new energy. Figure 1 The present application discloses a preparation method of a multifunctional metal coating containing a core-shell structure, which realizes multifunctional integration and precise preparation of the coating by combining core-shell structure 1 functionalization with an electrochemical deposition process. The present application can be applied to the fields of aerospace, electronic and communication equipment, precision electronic components, medical devices, and building and new energy.

[0078] Step S1, according to the different functional requirements of the core-shell structure 1, the corresponding core material 11 and shell material 12 are selected, the core material 11 is encapsulated in the shell material 12, and the core-shell structure 1 with different functions is prepared;

[0079] Step S2, functionalization of the electrochemical working solution containing metal ions 21: the core-shell structure 1 with different functions is respectively and uniformly mixed in the electrochemical working solution containing metal ions 21, and the deposition solution 2 with different functional properties is obtained;

[0080] Step S3, selecting the deposition solution 2 with different functional properties to electrochemically deposit corresponding functional deposition layers on the deposition area on the surface of the conductive substrate 3 layer by layer, and finally obtaining a multifunctional metal coating containing the core-shell structure.

[0081] The present application realizes the layered integration of the multifunctional coating through the functional matching and synergistic effect of the core material 11 and the shell material 12, and realizes the layered integration of the multifunctional coating through the electrochemical deposition technology. The multifunctional metal coating 4 prepared by the present application has a synergistic enhancement effect between the layers, and realizes the directional optimization and interlayer synergistic enhancement of the coating function through the functional role of the core-shell structure 1 in the coating.

[0082] It should be understood that, in the present application, "selecting the deposition solution 2 with different functional properties to electrochemically deposit corresponding functional deposition layers on the deposition area on the surface of the conductive substrate 3 layer by layer" means that, in the electrochemical deposition process, different functional deposition solutions 2 are replaced layer by layer, and the core-shell structure 1 and the metal ions 21 are sequentially co-deposited on the surface of the conductive substrate 3 under the driving of the electric field or the current.

[0083] Specifically, step S3 includes: taking the conductive substrate 3 as a cathode and taking the inert electrode 5 as an anode, spacing the conductive substrate 3 and the inert electrode 5 in the deposition solution 2 and connecting the power supply 6, and electrochemically depositing corresponding functional deposition layers on the deposition area on the surface of the conductive substrate 3 layer by layer; the content, arrangement mode, size and shape of the core-shell structure 1 contained in each functional deposition layer, and the size and thickness of each functional deposition layer are adjusted by adjusting the electrochemical deposition current / voltage, the distance between the cathode and the anode, the temperature of the deposition solution 2 and the electrochemical deposition time.

[0084] Specifically, the multifunctional metal coating 4 can be a plurality of single-function layers arranged in layers, including one or a combination of two or more of a heat storage layer 44, a hydrophobic layer 41, an anti-electromagnetic interference layer 43 and a wear-resistant and corrosion-resistant layer 42. The stacking order between these single-function layers can be adjusted according to actual needs. In a specific embodiment, referring to Figure 2The multifunctional metal coating with core-shell structure prepared in the embodiment is a multi-layer single-function layer arranged in a stack, including a hydrophobic layer 41, a wear-resistant and corrosion-resistant layer 42, an electromagnetic interference resistant layer 43 and a heat storage layer 44 arranged in turn from outside to inside. The hydrophobic layer 41 located at the outermost layer is a micron-level patterned structure 411 with core-shell structure 1, and the part of the core-shell structure 1 exposed on the surface of the micron-level patterned structure 411 forms a nano-level protruding structure 412 for hydrophobicity. The micron-level patterned structure 411 can adopt the micron-level convex array structure with hydrophobicity disclosed in the prior art. The micron-level patterned structure 411 and the nano-level protruding structure 412 cooperatively form a super-hydrophobic surface, which can effectively block the adhesion of liquid. The wear-resistant and corrosion-resistant layer 42 located under the hydrophobic layer 41 serves as a mechanical support protective layer, which adopts wear-resistant and corrosion-resistant core-shell structure 1 to improve the surface hardness and corrosion resistance of the coating, and to ensure the long-term stable service of the coating. The electromagnetic interference resistant layer 43 located under the wear-resistant and corrosion-resistant layer 42 adopts electromagnetic interference resistant core-shell structure 1, and the electromagnetic interference resistant core-shell structure 1 constructs a conductive shielding network to achieve efficient blocking of electromagnetic interference. The heat storage layer 44 located at the bottom layer adopts phase change material core 112 shell structure 1, which can delay the surface icing speed and maintain the thermal balance of the coating surface by releasing latent heat in an extremely low temperature environment. For the multifunctional metal coating 4 composed of a plurality of single-function layers arranged in a stack, the stacking order of each functional layer can be flexibly adjusted according to the working condition requirements, and is not limited to the order of the embodiment.

[0085] Unlike Figure 2 , the multifunctional metal coating 4 can also be a single-function deposition layer, and the multifunctionality is a combination of two or more of the heat storage function, the hydrophobic function, the electromagnetic interference resistant function and the wear-resistant and corrosion-resistant function. In order to realize the multifunctionality of the single-function deposition layer, as shown in Figures 6 to 9 , the core-shell structure 1 contained therein is a multifunctional core-shell structure, which is selected from one of the following:

[0086] Referring to Figure 6 , the first multifunctional core-shell structure 120, the shell of the first multifunctional core-shell structure 120 is an electromagnetic interference resistant material shell 121, and the core of the first multifunctional core-shell structure 120 is a phase change material core 112;

[0087] Referring to Figure 7 , the second multifunctional core-shell structure 130, the shell of the fourth multifunctional core-shell structure 140 is an electromagnetic interference resistant material shell 121, and the core of the second multifunctional core-shell structure 130 is a wear-resistant and corrosion-resistant material core 113;

[0088] Referring to Figure 8 , the third multifunctional core-shell structure 150, the shell of the third multifunctional core-shell structure 150 is a wear-resistant and corrosion-resistant material shell 122, and the core of the third multifunctional core-shell structure 150 is a phase change material core 112;

[0089] Referring toFigure 9 , the shell of the fourth multifunctional core-shell structure 160 is a wear-resistant and corrosion-resistant material shell 122, and the core of the fourth multifunctional core-shell structure 160 is an electromagnetic interference resistant material core 114;

[0090] The electromagnetic interference resistant material is a metal-based electromagnetic interference resistant material, a carbon-based electromagnetic interference resistant material, an electromagnetic interference resistant ceramic material, an electromagnetic interference resistant polymer, or a magnetic material.

[0091] The phase change material is an organic phase change material, an inorganic phase change material, or a composite phase change material.

[0092] The wear-resistant and corrosion-resistant material is a metal-based wear-resistant and corrosion-resistant material, a carbon-based wear-resistant and corrosion-resistant material, a wear-resistant and corrosion-resistant ceramic material, a wear-resistant and corrosion-resistant polymer, a wear-resistant and corrosion-resistant metal oxide, or a hard alloy material.

[0093] The core 11 and the shell 12 of the core-shell structure 1 of the embodiment can realize composite function design through multi-element combination of functional materials. The above-mentioned combination can meet the demand of multifunctional integration under different working conditions through synergistic matching of material properties.

[0094] The present application can also diversify the functionality of the core-shell structure 1 by regulating the number of the core 11 in the core-shell structure 1. Specifically, the core-shell structure 1 is a single-core structure or a multi-core structure; see Figure 3 The number of the core 11 encapsulated inside the shell 12 of the single-core structure is one; see Figure 4 The number of the core 11 encapsulated inside the shell 12 of the multi-core structure is two or more. As a preferred example of the multi-core structure, the multi-core structure of the present example includes two cores 11, one of which is a high-thermal-conductivity material core, and the other of which is a phase change material core. The coating using the multi-core structure can achieve the effect of wide-range heat storage. Specifically, the heat storage range of each heat storage material is fixed, and when the multi-core core-shell structure has two different heat storage materials with different heat storage ranges, the heat storage range of the multi-core core-shell structure is widened, achieving wide-range heat storage.

[0095] The present application can also regulate the internal structure of the core-shell structure 1 to regulate the stability of the coating during long-term service. In the single-core structure or the multi-core structure, the shell 12 can tightly wrap the outer surface of the core 11, or there can be a gap 13 between the core 11 and the shell 12. As a preferred example of the core-shell structure 1, see Figure 5The core body 11 of the core-shell structure 1 in the example is a phase change material core body 11, and a gap 13 exists between the core body 11 and the shell body 12. When the phase change material core body 11 expands in volume due to phase change, and the metal coating hardly expands, the gap 13 between the core body 11 and the shell body 12 can provide a buffer space, effectively relieve the interface stress, avoid the functional substance, i.e., the phase change material, from leaking due to the rupture of the core-shell structure 1, and thus ensure the long-term stable service of the coating.

[0096] The present application can also further enhance the performance of the multifunctional metal coating containing the core-shell structure by regulating the morphology of the core-shell structure 1. Specifically, as shown in Figures 10 to 16 , the morphology of the core-shell structure 1 contained in the multifunctional metal coating 4 includes at least one of a spherical-like shape 101, a cubic shape 102, a rod-like shape 103, a tubular shape 104, a lamellar shape 105, a dendritic shape 106, or a surface hole shape 107. Among them, referring to Figure 10 , the core-shell structure 1 with a spherical-like shape 101 has isotropic dispersion characteristics and is generally applicable to various scenarios; referring to Figure 11 , the core-shell structure 1 with a cubic shape 102 has a regular geometric shape, which can improve the packing density and enhance the mechanical support performance of the coating; referring to Figure 12 and Figure 13 , the core-shell structure 1 with a rod-like shape 103 and the core-shell structure 1 with a tubular shape 104 can construct a heat conduction or electrical conduction path when distributed in the axial direction, which is suitable for heat management or electromagnetic shielding network design; referring to Figure 14 , the core-shell structure 1 with a lamellar shape 105 has a large aspect ratio characteristic, which can form an interlayer barrier to effectively block the penetration of corrosion medium; referring to Figure 15 , the core-shell structure 1 with a dendritic shape 106 has a multi-stage branch morphology, which can increase the specific surface area and strengthen the interface bonding force and the functional substance loading capacity; referring to Figure 16 , the core-shell structure 1 with a surface hole shape 107 can improve the adsorption efficiency of metal ions 21 through the micro-pore array on its surface, and enhance the uniformity of co-deposition. In this application, the surface hole structure refers to that the outer surface of the shell of the core-shell structure 1 forms an array of micro-pores, and the inner diameter of the micro-pores ranges from 5-20 nm.

[0097] In the embodiment, the above-mentioned morphology diversity provides design freedom for the functional adaptation of the core-shell structure 1, which can optimize the interface action and performance expression according to specific working condition requirements.

[0098] It should be understood that the morphologies of the core-shell structures 1 located in the same functional deposition layer can be the same or different.

[0099] The multifunctional metal coating with core-shell structure can also be designed differently in different regions according to actual functional requirements. Specifically, the surface of the conductive substrate 3 is divided into more than one deposition region, and the multifunctional metal coating with core-shell structure deposited in each deposition region has multifunctionality adapted to the requirements of the deposition region. In a specific embodiment, as shown in FIG. 3, the surface of the conductive substrate 3 is divided into three deposition regions, and the multifunctional metal coating with core-shell structure deposited in each deposition region has multifunctionality adapted to the requirements of the deposition region. Figure 17As shown, the multifunctional metal coating with core-shell structure can be designed differently in different regions according to actual functional requirements. In this embodiment, the typical working conditions of the aircraft wing are taken as an example, and the performance optimization is realized through the precise matching of the coating function of each sub-region and the service environment of the component. In this embodiment, the wing is sequentially divided into a wing front section, a wing middle section and a wing tail section along the direction of air flow. Among them, the wing front section is a high aerodynamic load / low temperature region, which is directly impacted by the air flow as the air flow surface. This area is prone to static electricity accumulation due to high-speed airflow friction, and the low-temperature environment may cause surface icing, affecting the aerodynamic performance. Therefore, a first multifunctional metal coating 401 is prepared on the surface of the wing front section in this embodiment, and the multifunctionality of the first multifunctional metal coating 401 includes heat storage function, hydrophobic function and wear-resistant and corrosion-resistant function. As an example of the first multifunctional metal coating 401, the first multifunctional metal coating 401 can include a heat storage layer 44, a wear-resistant and corrosion-resistant layer 42 and a hydrophobic layer 41 arranged in sequence from inside to outside. The first multifunctional metal coating 401 delays icing by absorbing environmental heat through the heat storage layer 44, reduces the probability of water droplet 7 adhesion by combining the hydrophobic coating, and resists airflow impact by the wear-resistant and corrosion-resistant layer 42. The wing middle section is an internal component protection area, which covers key components such as fuel pipelines and sensors, and needs to meet the requirements of thermal management, electromagnetic shielding and hydrophobicity at the same time. Therefore, a second multifunctional metal coating 402 is prepared on the surface of the wing middle section in this embodiment, and the multifunctionality of the second multifunctional metal coating 402 includes heat storage function, hydrophobic function and anti-electromagnetic interference function. As an example of the second multifunctional metal coating 402, the second multifunctional metal coating 402 can include a heat storage layer 44, an anti-electromagnetic interference layer 43 and a hydrophobic layer 41 arranged in sequence from inside to outside. The second multifunctional metal coating 402 balances the internal thermal environment by using the heat storage layer 44, blocks radar signals and electromagnetic pulses by the anti-electromagnetic interference layer 43, and prevents surface liquid droplets from penetrating into the joint to cause corrosion by the surface super-hydrophobic coating. The wing tail section is an airflow separation / water droplet stripping area. In order to reduce the interference of airflow wake vortex and icing weight gain, this area focuses on strengthening the hydrophobic and drag reduction performance, and is designed as a hydrophobic and anti-electromagnetic interference composite area, i.e. a third multifunctional metal coating 403 is prepared on the surface of the wing tail section in this embodiment, and the multifunctionality of the third multifunctional metal coating 403 includes hydrophobic function and anti-electromagnetic interference function. In an example of the third multifunctional metal coating 403, the third multifunctional metal coating 403 can include an anti-electromagnetic interference layer 43 and a hydrophobic layer 41 arranged in sequence from inside to outside. The hydrophobic layer 41 of the third multifunctional metal coating 403 realizes super-hydrophobic self-cleaning, and the anti-electromagnetic interference layer 43 maintains the electromagnetic compatibility of the whole machine to ensure the stability of the tail wing control signal.

[0100] Specifically, as Figure 18As shown, the shell 12 of the core-shell structure 1 for the heat storage layer 44 is a directional heat-conducting structure, including a first shell part 1201 located on a first side and a second shell part 1202 located on a side opposite to the first side. The first shell part 1201 is made of high thermal resistance material, and the second shell part 1202 is made of high thermal conductivity material. Figure 18 The arrows in the figure represent the direction of heat release. Specifically, in the heat storage layer 44, the core-shell structure 1 achieves directional thermal energy regulation through the following mechanism: On the first side of the shell 12, the outward-facing high-thermal-conductivity material rapidly absorbs heat transferred from the external environment to store it within the core 11. Therefore, the first side of the shell 12 is the heat-conducting side. On the second side of the shell 12, the high-thermal-resistance material facing the conductive substrate 3 inhibits heat loss toward the conductive substrate 3. During the heat absorption and release process, the core 11 material achieves efficient heat storage and controllable release through a directional heat-conducting path. Therefore, the second side of the shell 12 is the heat-resistance side.

[0101] “Controlled release” means that the phase change material in the core-shell structure 1 releases heat only when it reaches the phase change point. The heat release point of the core-shell structure 1 can be controlled by adjusting the internal phase change material.

[0102] Specifically, when depositing the hydrophobic layer 41 , the deposition is maskless electrochemical deposition or masked electrochemical deposition.

[0103] When the deposition is maskless electrochemical deposition, see Figure 19 The exposed portion of the core-shell structure 1 on the coating surface forms a hydrophobic nano-scale protrusion structure 412. Figure 19 As shown, during the masked electrochemical deposition of the hydrophobic layer 41, the core-shell structure 1 and the metal ions 21 are co-deposited in the target deposition area. The exposed portion of the nanoscale core-shell structure 1 on the coating surface forms a nanoscale protrusion structure 412, giving the coating a rough surface with nanoscale protrusions. This rough surface with nanoscale protrusion structure 412 imparts hydrophobicity to the coating surface by reducing the solid-liquid contact area.

[0104] When the deposition is masked electrochemical deposition, see Figure 20 The hydrophobic layer 41 obtained by deposition is a micron-scale patterned structure 411 containing a core-shell structure 1, and the portion of the core-shell structure 1 exposed on the surface of the micron-scale patterned structure 411 forms a hydrophobic nano-scale protrusion structure 412. Specifically, as Figure 20As shown, the embodiment adopts a mask electrochemical deposition method to construct the hydrophobic layer 41 into a micro-nano composite structure with nanoscale protrusions on the surface, and the specific process includes: first, a photoresist is coated on the surface of the target area, such as the conductive substrate 3, by a photolithography process, and a mask plate is used for exposure and development to form a micrometer-scale pattern; then, in the defined area defined by the micrometer-scale pattern, the core-shell structure 1 and the metal ions 21 are electrochemically co-deposited to obtain a micrometer-scale patterned structure 411 containing the core-shell structure 1, and the nanoscale particle size of the core-shell structure 1 exposed on the surface of the micrometer-scale patterned structure 411 forms a nanoscale protrusion. In the composite structure including the micrometer-scale patterned structure 411 and the nanoscale protrusion, the gap 13 in the micrometer-scale patterned structure 411 forms an air retention cavity, which cooperates with the nanoscale protrusion to achieve hydrophobicity.

[0105] The above two hydrophobic layer 41 processes can be flexibly selected according to actual needs.

[0106] Specifically, the core-shell structure 1 for the anti-electromagnetic interference layer 43, the core body 11 thereof is selected from one or more than two combinations of a metal core body, a magnetic core body and a carbon material metal oxide core body, and the shell body 12 thereof is selected from one or more than two combinations of a metal shell body, an insulating / semiconductor shell body, a magnetic shell body, a polymer shell body, a metal oxide shell carbon-based shell body or a MXenes material shell body.

[0107] Specifically, the core-shell structure 1 for the wear-resistant and corrosion-resistant layer 42, the core body 11 thereof is selected from one or more than two combinations of a ceramic core body, a metal core body, a carbon material core body, a metal oxide core body, a polymer core body and a hard alloy core body, and the shell body 12 thereof is selected from one or more than two combinations of a metal shell body, a polymer shell body, a ceramic shell body, a carbon-based shell body, a metal oxide shell body and a multi-material composite shell body.

[0108] The multifunctional metal coating layer containing the core-shell structure prepared by the preparation method of the application also has a synergistic enhancement effect between each layer.

[0109] As an example of a coating layer with a synergistic enhancement effect, see Figure 21The embodiment provides a multifunctional metal coating with a core-shell structure, which comprises a hydrophobic layer 41 on the outside and a heat storage layer 44 on the inside of the hydrophobic layer 41, wherein the hydrophobic layer 41 is a micron-level patterned structure 411 with a core-shell structure 1. The multifunctional metal coating with the core-shell structure provided by the embodiment has a synergistic effect between the heat storage layer 44 and the hydrophobic layer 41, rather than a simple superposition of functions. Specifically, the coordination mechanism of the heat storage layer 44 and the hydrophobic layer 41 is that the heat storage layer 44 absorbs or releases latent heat through the core-shell structure 1, so as to realize dynamic buffering of the surface temperature of the coating; the micro-nano structure on the surface of the hydrophobic layer 41 can form an air retention layer, so as to reduce the surface convective heat transfer coefficient and delay the heat loss speed of the heat storage layer 44 to the environment. The micron-level patterned cavity and the nano protrusion are synergistic, so that the heat retention time of the heat storage layer 44 is prolonged in a low-temperature environment, and the surface icing speed is significantly delayed. Figure 21 The arrow in the figure represents the heat release direction 8, and when the water droplet 7 falls on the surface of the multifunctional coating, the contact area with the coating is reduced due to the hydrophobicity of the coating, and the heat release of the coating delays the condensation time of the water droplet 7, so that the water droplet 7 is more likely to fall off from the surface of the coating.

[0110] As another example of the coating with synergistic enhancement effect, see Figure 22 The embodiment provides a multifunctional metal coating with a core-shell structure, which comprises a hydrophobic layer 41 on the outside and an anti-electromagnetic interference layer 43 on the inside of the hydrophobic layer 41, wherein the hydrophobic layer 41 is a micron-level patterned structure 411 with a core-shell structure 1. The multifunctional metal coating with the core-shell structure provided by the embodiment has a synergistic effect between the anti-electromagnetic interference layer 43 and the hydrophobic layer 41, rather than a simple superposition of functions. Specifically, the coordination mechanism of the anti-electromagnetic interference layer 43 and the hydrophobic layer 41 is that the anti-electromagnetic interference layer 43 constructs an electrically conductive network through the core-shell structure 1, so as to realize efficient shielding of electromagnetic radiation; the hydrophobic surface of the hydrophobic layer 41 can prevent rainwater, salt mist and other corrosive media from being retained on the surface of the anti-electromagnetic interference layer 43, so as to avoid electrochemical corrosion and maintain the long-term integrity of the shielding network. Secondly, the micro-nano structure on the surface of the hydrophobic layer 41 can be extended as an electromagnetic shielding layer, which can scatter and absorb electromagnetic waves, so that the shielding efficiency is additionally improved. When external electromagnetic radiation contacts the multifunctional coating, the micro-nano structure on the surface of the hydrophobic layer 41 reflects the electromagnetic wave 9. At the same time, the anti-electromagnetic interference layer 43 reflects and absorbs the electromagnetic wave 9. Both of them block the electromagnetic radiation at the same time, so as to achieve higher anti-electromagnetic interference characteristics.

[0111] Further, in order to improve the effect of electrochemical co-deposition of the core-shell structure 1 and the metal ions 21, the step S1 further comprises: modifying the material of the core 11 and the material of the shell 12 by using a modifier; after modification, the material of the core 11 and the material of the shell 12 have different charges, forming a core-shell structure 1 with uniform structure and self-charges. There are many methods for preparing the core-shell structure 1, such as microfluidic method and classical sol-gel method.

[0112] Specifically, as shown in Figure 23 and Figure 24 , in the preparation process of the core-shell structure 1, the charge of the material of the core 11 and the material of the shell 12 is regulated by the modifier, so that they have different charges, for example, referring to Figure 23 , the core 11 has a positive charge and the shell 12 has a negative charge, or referring to Figure 24 , the core 11 has a negative charge and the shell 12 has a positive charge. The modification process can realize the directional assembly of the core-shell interface through electrostatic adsorption effect, significantly improve the uniformity of the morphology of the core-shell structure 1, and reduce the agglomeration phenomenon; at the same time, the charged core-shell structure 1 can form synergistic adsorption with the metal ions 21 through Coulomb force in the process of electrochemical deposition, enhance the interfacial bonding strength of the core-shell structure 1 and the metal matrix, and promote the directional migration and uniform dispersion of the core-shell structure 1 under the action of the electric field, so as to ensure the functional consistency of the composite coating.

[0113] The working principle of realizing the synergistic co-deposition of the core-shell structure 1 treated by the modifier and the metal matrix by the electrochemical deposition process and constructing the multifunctional metal composite coating is described in detail below. Figure 25 The deposition principle schematic diagram of the method of the application is shown, and the core mechanism is based on the synergistic effect of the core-shell structure 1 and the electric field driving, and the specific process is as follows:

[0114] The method adopts a double-electrode system, the conductive substrate 3 is used as the cathode, and the inert electrode 5 is used as the anode, and the cathode and the anode are respectively immersed in the electrochemical working solution containing the functionalized core-shell structure 1, that is, the deposition solution 2. Figure 10 The core-shell structure 1 in the deposition solution 2 is the core-shell structure 1 treated by surface charge modification by the modifier, which presents a stable charged state, for example, the core-shell structure 1 has a negative charge or a positive charge.

[0115] The deposition mechanism of the negative charged core-shell structure is: when the core-shell structure 1 has a negative charge, the surface of the core-shell structure 1 adsorbs metal cations in the deposition solution 2 to form a double-layer structure through Coulomb force. Under the action of a direct current electric field, the negatively charged core-shell structure 1 carries the adsorbed metal cations and migrates to the cathode substrate in a directional manner. After the metal cations reach the cathode surface, they are reduced under the action of electrons to deposit in the form of metal elements, and at the same time, the core-shell structure 1 is embedded in the metal matrix to form a composite structure of metal wrapping the core-shell structure.

[0116] The deposition mechanism of the positively charged core-shell structure is that the positively charged core-shell structure 1 has electrostatic repulsion with metal cations, but the surface functional groups can form a complex with metal ions 21 through coordination to achieve stable dispersion. The positively charged core-shell structure directly moves to the cathode in an electric field, and the metal cations reach the cathode by diffusion and electric migration, and reduction deposition occurs. The core-shell structure 1 is anchored in the metal deposition layer by electrostatic adsorption or mechanical embedding effect, forming a composite structure of metal wrapping the core-shell.

[0117] Embodiment 1

[0118] The present embodiment provides a preparation method of a multifunctional metal coating containing core-shell structures, which is used for preparing Figure 2 The multifunctional metal coating 4 containing core-shell structures shown in the figure is a multi-layer single functional layer arranged in layers, including a hydrophobic layer 41, a wear-resistant and corrosion-resistant layer 42, an anti-electromagnetic interference layer 43 and a heat storage layer 44 arranged from outside to inside. Among them, the hydrophobic layer 41 located in the outermost layer is a micron-level patterned structure 411 containing core-shell structures 1. The core-shell structure used in the heat storage layer 44 is a directional heat conduction structure, and the morphology is spherical. One side of the shell is provided with a magnetic material. The magnetic material can be arranged on the heat-conducting side of the shell or on the heat-insulating side of the shell, which can be matched with the subsequent applied magnetic field. The traction of the magnetic field must be in the direction of the deposited conductive substrate. The morphology of the core-shell structure used in the anti-electromagnetic interference layer 43 is lamellar. The morphology of the core-shell structure used in the wear-resistant and corrosion-resistant layer 42 is cubic.

[0119] The preparation method of the present embodiment includes the following steps:

[0120] 1. Prepare the above-mentioned core-shell structures with different functions;

[0121] 2. Mix the core-shell structures 1 with different functions in the electrochemical working solution containing metal ions 21 respectively to obtain deposition solutions 2 with different functional properties;

[0122] Specifically, in the present embodiment, the electrochemical working solution containing metal ions 21 includes nickel sulfate hexahydrate, a complexing agent, an anionic surfactant, an anodic activator, a pH buffer and a brightener. The pH buffer is selected from boric acid, and the anodic activator is selected from nickel chloride.

[0123] 3. Select the deposition solution 2 with different functional properties to electrochemically deposit corresponding functional deposition layers on the deposition area on the surface of the conductive substrate 3 layer by layer, and finally obtain a multifunctional metal coating containing core-shell structures.

[0124] Specifically, in this embodiment, the conductive substrate 3 is a non-magnetic stainless steel plate, and the inert electrode 5 is high-purity electrolytic nickel, preferably 99.5% or higher. Before electrochemical deposition, the cathode and anode are respectively subjected to systematic pretreatment. The pretreated cathode and anode are respectively fixed on both sides of the epoxy resin insulating substrate, and the distance between the two electrodes is adjusted. An electromagnetic plate is added outside the cathode and anode to construct a traction magnetic field. The traction magnetic field exerts a traction force on the directional heat conduction structure towards the direction of the deposited conductive substrate, so that the directional heat conduction structure is deposited in the coating. The specific position of the electromagnetic plate is not marked in the figure. The anode of the power supply 6 is connected to the inert electrode 5, and the cathode of the power supply 6 is connected to the conductive substrate 3. The deposition solution of the heat storage layer is injected into the electrochemical deposition working system, and the power supply is turned on. By using the maskless electrochemical deposition technology combined with the traction effect of the magnetic field force on the magnetic material in the directional heat storage core-shell structure, the first layer, i.e., the heat storage layer containing the directional heat storage core-shell structure, is prepared. The deposition solution in the electrochemical deposition working system is replaced with the anti-electromagnetic interference layer deposition solution and the wear-resistant and corrosion-resistant layer deposition solution in turn, and the anti-electromagnetic interference layer containing the core-shell structure and the wear-resistant and corrosion-resistant layer containing the core-shell structure are prepared in turn by using the maskless electrochemical deposition technology. Then, the prepared coating is subjected to mask processing, and the deposition solution in the electrochemical deposition working system is still the wear-resistant and corrosion-resistant layer deposition solution. The outermost hydrophobic layer containing the core-shell structure is prepared by using the mask electrochemical deposition technology. Thus, the multifunctional metal coating containing the core-shell structure is prepared.

[0125] The present application provides a method for preparing a multifunctional metal coating containing a core-shell structure. There are many methods and approaches to realize this technical solution. The above description is only the preferred embodiment of the present application. It should be noted that for ordinary technical personnel in this technical field, without departing from the principle of the present application, several improvements and refinements can be made, which should be considered as the protection scope of the present application. The components not explicitly described in this embodiment can be realized by existing technology.

Claims

1. A method for preparing a multifunctional metal coating containing a core-shell structure, characterized in that: The following steps are involved: Step S1, selecting corresponding core (11) materials and shell (12) materials according to requirements for different functions of the core-shell structure (1), encapsulating the core (11) material in the shell (12) material, and preparing core-shell structures (1) with different functions; Step S2, functionalization of the electrochemical working solution containing metal ions (21): uniformly mixing the core-shell structures (1) with different functions in the electrochemical working solution containing metal ions (21) to obtain deposition solutions (2) with different functions; Step S3, selecting the deposition liquids (2) with different functionalities to electrochemically deposit corresponding functional deposition layers layer by layer on the deposition area on the surface of the conductive substrate (3), and finally obtaining the multifunctional metal coating (4) containing the core-shell structure (1).

2. The preparation method according to claim 1, characterized in that The multifunctional metal coating (4) is a multi-layered single-functional layer, comprising one or a combination of two or more of a heat storage layer (44), a hydrophobic layer (41), an anti-electromagnetic interference layer (43), and a wear-resistant and corrosion-resistant layer (42); Alternatively, the multifunctional metal coating (4) is a single functional deposition layer, and the multifunctionality is a combination of two or more of the following functions: heat storage function, hydrophobic function, anti-electromagnetic interference function, and wear-resistant and corrosion-resistant function.

3. The preparation method according to claim 2, characterized in that The core-shell structure (1) is a multifunctional core-shell structure (1) selected from one of the following: A first multifunctional core-shell structure (120), wherein the shell of the first multifunctional core-shell structure (120) is an anti-electromagnetic interference material shell (121), and the core of the first multifunctional core-shell structure (120) is a phase change material core (112); A second multifunctional core-shell structure (130), wherein the shell of the second multifunctional core-shell structure (140) is a shell (121) of an anti-electromagnetic interference material, and the core of the second multifunctional core-shell structure (130) is a core (113) of a wear-resistant and corrosion-resistant material; A third multifunctional core-shell structure (150), wherein the shell of the third multifunctional core-shell structure (150) is a wear-resistant and corrosion-resistant material shell (122), and the core of the third multifunctional core-shell structure (150) is a phase change material core (112); A fourth multifunctional core-shell structure (160), wherein the shell of the fourth multifunctional core-shell structure (160) is a wear-resistant and corrosion-resistant material shell (122), and the core of the fourth multifunctional core-shell structure (160) is an anti-electromagnetic interference material core (114); Wherein, the anti-electromagnetic interference material is selected from metal-based anti-electromagnetic materials, carbon-based anti-electromagnetic materials, anti-electromagnetic ceramic materials, anti-electromagnetic polymers or magnetic materials; The phase change material is an organic phase change material, an inorganic phase change material or a composite phase change material; The wear-resistant and corrosion-resistant material is a metal-based wear-resistant and corrosion-resistant material, a carbon-based wear-resistant and corrosion-resistant material, a wear-resistant and corrosion-resistant ceramic material, a wear-resistant and corrosion-resistant polymer, a wear-resistant and corrosion-resistant metal oxide or a hard alloy material.

4. The preparation method according to claim 1, characterized in that The core-shell structure (1) is a single-core structure or a multi-core structure; The number of the core body (11) encapsulated inside the shell (12) of the single-core structure is one; The number of core bodies (11) encapsulated inside the shell (12) of the multi-core structure is two or more; In the single-core structure or the multi-core structure, there is a gap (13) between the core body (11) and the shell (12), or the shell (12) wraps around the outer surface of the core body (11).

5. The preparation method according to claim 1, characterized in that The core-shell structure (1) contained in the multifunctional metal coating (4) has a morphology of at least one of spherical (101), cubic (102), rod (103), tubular (104), lamellar (105), dendritic (106) or surface hole (107).

6. The preparation method according to claim 1, characterized in that The surface of the conductive substrate (3) is divided into more than one deposition area, and the multifunctional metal coating (4) containing the core-shell structure (1) deposited in each deposition area has multifunctionality adapted to the requirements of the deposition area.

7. The preparation method according to claim 1, characterized in that The step S1 further comprises: using a modifier to modify the material of the core (11) and the material of the shell (12); after the modification, the material of the core (11) and the material of the shell (12) have different charges, forming a core-shell structure (1) with uniform structure and self-charge.

8. The preparation method according to claim 2, characterized in that The shell (12) of the core-shell structure (1) used for the heat storage layer (44) is a directional heat-conducting structure, comprising a first shell portion (1201) located on a first side and a second shell portion (1202) located on a side opposite to the first side, wherein the first shell portion (1201) is made of a high thermal resistance material, and the second shell portion (1202) is made of a high thermal conductivity material.

9. The preparation method according to claim 2, characterized in that When depositing the hydrophobic layer (41), the deposition is maskless electrochemical deposition or masked electrochemical deposition; When the deposition is maskless electrochemical deposition, the portion of the core-shell structure (1) exposed on the coating surface forms a nanoscale protrusion structure (412) for hydrophobicity; When the deposition is mask electrochemical deposition, the hydrophobic layer (41) obtained by deposition is a micron-scale patterned structure (411) containing a core-shell structure (1), and the portion of the core-shell structure (1) exposed on the surface of the micron-scale patterned structure (411) forms a nanoscale protrusion structure (412) for hydrophobicity.

10. The preparation method according to claim 1, characterized in that The step S3 comprises: using the conductive substrate (3) as a cathode and the inert electrode (5) as an anode, arranging the conductive substrate (3) and the inert electrode (5) in a deposition liquid (2) with a gap and connecting a power supply (6), and electrochemically depositing corresponding functional deposition layers layer by layer in the deposition area on the surface of the conductive substrate (3); and regulating the content, arrangement, size and shape of the core-shell structure (1) contained in each functional deposition layer, as well as the size and thickness of each functional deposition layer by regulating the electrochemical deposition current / voltage, the distance between the cathode and the anode, the temperature of the deposition liquid (2) and the electrochemical deposition time.

Images