A kind of electroless plating product, electroless plating method and and application

Abstract

The application discloses a kind of chemical plating products, chemical plating method and and application, wherein, the chemical plating product includes: MXene layer;And, at least one side of the MXene layer surface The chemical plating metal layer;Or, the chemical plating product includes: matrix;MXene layer is arranged on the surface or part of surface of the matrix;And, at the MXene layer surface The chemical plating metal layer;Wherein, the MXene layer includes MXene material.Based on the preparation method of the application, the process steps of chemical plating are greatly simplified, production efficiency is provided, production cost is reduced, and the problem of environmental pollution is avoided.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemistry, and in particular relates to a chemical plating product, a chemical plating method and application. BACKGROUND

[0002] The purpose of plastic chemical plating is to coat the surface of plastic with metal, not only to increase the appearance, but also to compensate for the shortcomings of plastic, to endow the properties of metal, and to fully exert the characteristics of plastic and metal. A large number of plastic chemical plating products have been applied in the industries of energy storage, electronics, automobiles, household appliances, etc.

[0003] Compared with metal parts, plastic chemical plating products not only have a good metallic texture, but also reduce the weight of the product, effectively improve the appearance and decoration of the plastic, and improve the performance in terms of electricity, heat and corrosion resistance. With the rapid development of industry, the application of plastic chemical plating is becoming more and more widespread, and it has become one of the important means of surface decoration for plastic products. Plastic chemical plating has been widely used on the surfaces of ABS, polypropylene, polysulfone, polycarbonate, nylon, phenolic glass fiber reinforced plastic, polystyrene and other plastics at home and abroad.

[0004] The existing plastic chemical plating process generally needs a pretreatment, which includes hydrophilization treatment, sensitization and activation steps, the purpose of which is to make the surface of the plastic compatible with the aqueous plating solution, and to provide a chemical reduction deposition site for the metal ions of the chemical plating. A chemical method is usually used, that is, a strong oxidizing solution containing a mixture of chromic anhydride and sulfuric acid is used for treatment. However, this chemical method uses toxic chemicals, which causes environmental pollution. The purpose of chemical plating treatment is to form a metal conductive film on the surface of the plastic. Through chemical plating treatment, metal ions such as copper, nickel, gold, silver, platinum or palladium with catalytic effect in the plating solution are reduced and deposited on the plastic substrate to form a metal conductive film (thickness about 0.05-0.8 μm). As can be seen, the existing plastic chemical plating must go through hydrophilization treatment, sensitization, activation and chemical plating processes, which has the problems of complex preparation process and low efficiency. SUMMARY

[0005] The present application aims to solve the problems of complex process and low efficiency of the existing plastic chemical plating process, and provides a chemical plating method and a chemical plating product.

[0006] The technical concept of the present application is to form a MXene layer containing MXene material on the surface of a polymer, ceramic, glass fiber or other material substrate, and then chemically plate a chemical plating metal layer on the MXene layer to obtain a chemical plating product.

[0007] The first aspect of the present application provides a chemical plating product, comprising: an MXene layer; and, a chemical plating metal layer disposed on at least one side of the surface of the MXene layer. Or, the chemical plating product comprises: a substrate; an MXene layer disposed on the surface or part of the surface of the substrate; and, a chemical plating metal layer disposed on the surface of the MXene layer. Wherein, the MXene layer comprises an MXene material.

[0008] In some embodiments, the chemical formula of the MXene material is represented as M n+1 X n T x , wherein M represents one or more of transition metal elements; X represents one or more of carbon, nitrogen or boron, T represents a surface functional group; 1≤n≤4, 0

[0009] In some embodiments, the mass content of the MXene material in the MXene layer is between 30% and 100%; preferably, between 50% and 100%, more preferably, between 90% and 100%.

[0010] In some embodiments, the substrate is a non-conductive material.

[0011] In some embodiments, the non-conductive material is selected from a polymer, a ceramic or a glass.

[0012] In some embodiments, the polymer is selected from one or more of acrylonitrile-butadiene-styrene copolymer, polysulfone, polycarbonate, polypropylene, phenolic resin, phenolic glass fiber reinforced plastic, nylon, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene ether, polystyrene, polyamide and derivatives of the above polymers.

[0013] In some embodiments, the MXene material is selected from Ti3C2T x , Ti2CT x , V2CT x , Nb2CT x , Mo2CT x , Ti4C3T x , Ta2CT x , Ta4C3T x , TiNbCT x .

[0014] In some embodiments, the material of the chemical plated metal layer is selected from one or more of copper, nickel, chromium, zinc, cadmium, lead, gold, silver, platinum, iron, cobalt, manganese, antimony, bismuth, gallium, indium, thallium, palladium, rhenium, rhodium, osmium, iridium, niobium, tungsten.

[0015] In some embodiments, the thickness of the MXene layer is between 1 nm and 50 μm; preferably, between 3 nm and 10 μm; more preferably, between 10 nm and 5 μm; in a preferred embodiment, between 100 nm and 2 μm.

[0016] In some embodiments, the thickness of the chemical plated metal layer is between 10 nm and 5 μm; preferably, between 100 nm and 2 μm.

[0017] In some embodiments, the substrate is in the form of a sheet, a film, a tube, a braid, a wire, or a mesh.

[0018] The second aspect of the present application provides a method for preparing the chemical plated product as described above, comprising: a loading step, in which a surface of a substrate is loaded with a MXene material to form a MXene layer; and a chemical plating step, in which a chemical plated metal layer is formed on the surface of the MXene layer.

[0019] In some embodiments, the method further comprises a peeling step after the loading step, in which the substrate is peeled; or the method further comprises a peeling step after the chemical plating step, in which the substrate is peeled.

[0020] In some embodiments, the loading step comprises the following more specific steps: a MXene dispersion liquid is coated and / or sprayed on the substrate, and the MXene layer is obtained after drying.

[0021] In some embodiments, the loading step comprises the following more specific steps: the substrate is immersed and / or taken out of the MXene dispersion liquid, and the MXene layer is formed on the surface of the substrate after drying.

[0022] In some embodiments, the loading step comprises the following more specific steps: the surface of the substrate is contacted with the liquid phase interface of the MXene dispersion liquid, and the MXene layer is formed on the surface of the substrate.

[0023] In some embodiments, the solvent of the MXene dispersion liquid is selected from one or more of water and an alcohol; preferably, the alcohol is selected from one or more of ethanol, propanol, isopropanol, and butanol.

[0024] In some embodiments, the concentration of MXene in the MXene dispersion liquid is between 0.01 mg / ml and 80 mg / ml.

[0025] In some embodiments, the MXene dispersion described above contains a binder.

[0026] In some embodiments, the binder described above is selected from an aqueous binder; preferably, the aqueous binder is selected from one or more of LA133 aqueous adhesive, methyl cellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), and aqueous polyurethane.

[0027] In some embodiments, the MXene dispersion described above is composed of a MXene material and a solvent.

[0028] The third aspect of the present application provides an application of the chemical plating product described above, or the chemical plating product obtained by the preparation method described above, in automobiles, household appliances, and energy storage devices.

[0029] The fourth aspect of the present application provides a current collector, characterized in that the current collector comprises the chemical plating product described above; or, the preparation method of the current collector comprises the preparation method of the chemical plating product described above.

[0030] The fifth aspect of the present application provides a battery comprising the current collector described above.

[0031] The sixth aspect of the present application provides an application of the MXene material for chemical plating on the surface of a non-conductive substrate.

[0032] The present application forms a MXene layer on a substrate by a simple coating or spraying or dipping method, and the MXene material present in the MXene layer has hydrophilicity and can be compatible with water-based chemical plating, thereby avoiding the chemical hydrophilic treatment in the prior art, reducing the activation and sensitization steps before chemical plating in the prior art. It can be seen that the preparation method based on the present application greatly simplifies the process steps of chemical plating, provides production efficiency, reduces production cost, and avoids environmental pollution. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 Figure 1 is a structural schematic diagram of a plastic chemical plating product in Example 1 of the present application.

[0034] Figure 2 Figure 2 is a structural schematic diagram of a plastic chemical plating product in Example 1 of the present application.

[0035] Figure 3 Figure 3 is a structural schematic diagram of a plastic chemical plating product in Example 1 of the present application.

[0036] Figure 4A schematic diagram of the preparation steps of a chemical plating product composite metal foil in Example 1 of the present application, and a schematic diagram of the structure of a composite metal foil.

[0037] Figure 5 A schematic diagram of the preparation steps of a chemical plating product composite metal foil in Example 1 of the present application, and a schematic diagram of the structure of a composite metal foil.

[0038] Figure 6 A schematic diagram of the present application for forming an ultra-thin MXene layer on the surface of a substrate.

[0039] Figure 7 A photo of the chemical plating product obtained in Example 2 of the present application, after peeling off the substrate.

[0040] Figure 8 A photo of the surface of the graphene layer in Comparative Example 1 of the present application.

[0041] Main figure mark explanation:

[0042] 100, 200, 300 chemical plating product; 110, 120 composite metal foil;

[0043] 10 polymer substrate; 20 MXene layer, 21 MXene two-dimensional sheet; 30 chemical plating metal layer. DETAILED DESCRIPTION

[0044] The technical solutions of the present application are illustrated below through specific examples. It should be understood that the one or more steps mentioned in the present application do not exclude other methods and steps before and after the combination steps, or other methods and steps can be inserted between these explicitly mentioned steps. It should also be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. Unless otherwise specified, the numbering of each method step is only for the purpose of identifying each method step, and is not limited to the arrangement order of each method or the scope of the implementation of the present application. Changes or adjustments of the relative relationship, without substantial technical content changes, can also be considered as the implementation scope of the present application.

[0045] The MXene material and graphene in the examples of the present application are purchased from Jinan Sanchuan New Material Technology Co., Ltd., wherein Ti3C2T x The product model of the slurry is SC02003LW, and the concentration is 5 mg / ml, 50 mg / ml. The Ti3C2T x The two-dimensional MXene Ti3C2T x After etching the Al layer in the MAX phase material Ti3AlC2 and ultrasonic peeling, it is obtained. The MXene powder is selected as Ti3C2T x The graphene in the comparative example is prepared by the oxidation-reduction method, and the concentration is 0.5wt%.

[0046] The raw materials and instruments used in the embodiments are not specifically limited in source, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0047] Embodiment 1

[0048] The embodiment provides a chemical plating product 100, as shown in the figure. Figure 1 The chemical plating product 100 comprises a substrate 10, a MXene layer 20 and a chemical plating metal layer 30, wherein the MXene layer 20 contains MXene material; the substrate is in a sheet or film shape, the MXene layer 20 is arranged on one side surface of the substrate 10, and the chemical plating metal layer 30 is arranged on the MXene layer 20. In another embodiment, the MXene layer 20 is arranged on both side surfaces of the substrate 10 (as shown in the figure), and a chemical plating product 200 is obtained. The shape of the substrate is not limited in the embodiment, and in another embodiment, the substrate 10 is in a cylindrical or linear shape (as shown in the figure), and a cylindrical or linear chemical plating product 300 is obtained. In other embodiments, the substrate can also be in a tubular, porous or irregular shape. In some embodiments, the MXene layer 20 covers part of the surface of the substrate. Figure 2 Figure 3

[0049] The embodiment also provides a preparation method of the chemical plating product, and the steps comprise:

[0050] S01: loading MXene material on the surface of the substrate to form a MXene layer;

[0051] S02: chemical plating deposition on the surface of the MXene layer to form a chemical plating metal layer.

[0052] The embodiment also provides another chemical plating product, which is a metal foil with a “sandwich” structure, as shown in the figure. Figure 4 The preparation method of the metal foil with the “sandwich” structure comprises the following steps:

[0053] S11: loading MXene material on the surface of the substrate to form a MXene layer;

[0054] S12: peeling off the substrate in the composite obtained in step S11 to obtain a MXene layer;

[0055] S13: chemical plating deposition on the MXene layer obtained in step S12 to form a chemical plating metal layer, so as to obtain a chemical plating product with a “sandwich” structure, i.e., a composite metal foil 120, which has a chemical plating layer on both sides and a MXene layer in the middle.

[0056] The embodiment also provides another chemical plating product, which is a metal foil with a MXene layer, as shown in the figure. Figure 5 The preparation method of the metal foil with the MXene layer comprises the following steps:​​

[0057] S21: loading the surface of the substrate with MXene material to form a MXene layer;

[0058] S22: electroless plating deposition of the composite obtained in step S21 to form an electroless plated metal layer on the surface of the MXene layer;

[0059] S23: stripping the substrate from the composite obtained in step S22 to obtain another electroless plating product, a composite metal foil 110 having a MXene layer on one side.

[0060] In steps S01, S11 and S21, the loading method of the surface of the substrate with MXene material to form a MXene layer can be a dry process or a wet process. The dry process refers to forming a film layer of MXene material powder and a binder on the surface of the substrate without solvent. The wet process refers to loading the surface of the substrate with a MXene dispersion through spraying, dipping, coating or other methods, and then forming a MXene layer after drying and removing the solvent. The dry process can simplify the process flow by avoiding the step of removing the solvent, but it needs to add a binder to form a stable and continuous conductive layer, which reduces the continuous conductivity of the MXene layer surface. Therefore, the wet process is preferred. The wet process has the beneficial effect that the MXene material can be more uniformly dispersed on the surface of the substrate. Although it includes the step of removing the solvent, since the MXene material has good hydrophilicity, water-based solvents (including water and alcohol solvents) are usually used, which have the advantages of low cost and easy removal. In a specific embodiment, it includes loading the surface of the substrate with a MXene dispersion through one or more times of spraying and / or coating to form a MXene film, and then forming a MXene layer after drying. In another specific embodiment, it includes pulling and / or dipping the substrate from the MXene dispersion several times to make the MXene two-dimensional sheets in the dispersion continuously load on the surface of the substrate under the action of surface tension, and then forming a MXene layer after drying.

[0061] In the present application, the MXene dispersion refers to a liquid or semi-liquid (gel or slurry) mixture containing MXene material. Optionally, the MXene dispersion also contains a certain amount of binder (0.01% to 50% by mass of dry material). The content of the binder is comprehensively judged in combination with the bonding performance and electroless plating performance. Under the premise of ensuring good electroless plating effect and bonding performance, the smaller the content of the binder, the better. Preferably, the binder is a water-based binder, which can be selected from one or more of LA133 water-based adhesive, methyl cellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), water-based polyurethane, etc.

[0062] Optionally, the concentration of the MXene dispersion is between 0.01 mg / ml and 80 mg / ml, which is selected according to the method of coating. The method of coating the MXene dispersion on the substrate optionally includes spraying, coating, dipping, etc. In a specific embodiment, it includes coating 0.01-2 mg / ml of the MXene dispersion on the surface of the substrate by spraying one or several times, and forming a MXene layer after drying; in another specific embodiment, it includes coating 1-10 mg / ml of the MXene dispersion on the surface of the substrate by dipping one or several times, so that the MXene in the dispersion is coated on the surface of the substrate under the action of surface tension, and a MXene layer is formed after drying; in another specific embodiment, it includes coating 10-80 mg / ml of the MXene dispersion on the surface of the substrate by a medium (such as a brush, a doctor blade, etc.), and forming a MXene layer after drying.

[0063] The chemical formula of the MXene material in the MXene layer in the present application can be represented as M n+1 X n T x , wherein M represents one or more of transition metal elements; X represents one or more of carbon, nitrogen or boron, and T represents a surface functional group; 1≤n≤4, 0 x , Ti2CT x , V2CT x , Nb2CT x , Mo2CT x , Ti4C3T x , Ta2CT x , Ta4C3T x , TiNbCT x , etc.

[0064] In some embodiments, a binder is added to the MXene layer as needed to increase the bonding force between the MXene layer and the substrate; that is, the mass content of the MXene material in the MXene layer is between 30% and 100%; the higher the content of the MXene material in the MXene layer, the better the conductivity and hydrophilicity, but the bonding force with the substrate decreases; in other embodiments, the MXene layer also functions as a separation layer, which does not contain a binder. Therefore, preferably, the mass content of the MXene material in the MXene layer is between 50% and 100%, more preferably between 80% and 100%, and even more preferably between 90% and 100%.

[0065] Since the present invention forms a chemically plated metal layer on the surface of the MXene layer by chemical plating, and the substrate surface does not come into contact with the metal layer, but the MXene layer serves as the connecting layer between the substrate and the chemically plated metal layer, the preparation method of the present invention is universally applicable to various substrates.

[0066] In some implementations, the bonding force between the MXene layer and the polymer matrix can be enhanced by roughening the surface of the polymer matrix (such as corona treatment or etching), i.e., etching "pits" on the surface of the polymer matrix, thereby reducing the amount of adhesive used or eliminating the need for adhesive.

[0067] In some embodiments, the polymer matrix may be selected from one or more of the following polymers: acrylonitrile-butadiene-styrene copolymer (ABS), polysulfone (PSF or PSU), polycarbonate (PC), phenolic resin, phenolic glass fiber reinforced plastic, nylon, polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polystyrene (PS), polyamide (PA), and derivatives of the above polymers.

[0068] In some embodiments, the type of metal in the electroless metal plating layer may be one or more of the following: copper, nickel, chromium, zinc, cadmium, lead, gold, silver, platinum, iron, cobalt, manganese, antimony, bismuth, gallium, indium, thallium, palladium, rhenium, rhodium, osmium, iridium, niobium, and tungsten.

[0069] In some embodiments, the thickness of the MXene layer is between 1 nm and 20 μm. The MXene layer can be coated, sprayed, dip-coated, or other methods to coat a polymer matrix with an MXene-containing dispersion (or coating). Since MXene is a typical two-dimensional material, a single layer is only 1 nm thick. When the MXene two-dimensional sheet 21 forms a single layer or a few layers continuously distributed on the substrate surface, for example, through dip-coating or other methods, the thickness of the MXene layer can be as low as 1 nm to 3 nm, forming an ultrathin MXene layer (e.g., ...). Figure 6 (As shown). When using spraying or coating methods, the thickness of the MXene layer can be controlled within a range of several micrometers (1μm to 100μm). Therefore, the thickness of the MXene layer can be adjusted from 1nm to 100μm.

[0070] The thickness of the electroless plated metal layer is controlled by adjusting the conditions of the electroless plating process, and in some embodiments, is between 50 nm and 500 μm. Since the preparation method of the present application only has one electroless plating process, the metal layer of the electroless plated product is only the thickness of the electroless plated metal layer, that is, the present application can obtain an electroless plated product with an ultra-thin metal layer (about 50 nm to 10 μm).

[0071] The role of introducing the MXene layer in electroless plating in the present application is also that the MXene material in the MXene layer has metallic properties and abundant surface functional groups, which can provide nucleation sites for the electroless plated metal and reduce the metal deposition overpotential. In addition, due to the high specific surface area and abundant surface functional groups of MXene, a large amount of metal ions in the electroless plating solution can be adsorbed and complexed, which is beneficial to the uniform deposition of metal in the electroless plating process, and the transition metal elements in MXene can also provide active sites.

[0072] Example 2

[0073] This embodiment provides an electroless plated product and a preparation method thereof. In this embodiment, the polymer matrix is a PET film with a thickness of 10 μm. The preparation method of the plastic electroless plated product of the present application comprises:

[0074] (1) Prepare a Ti3C2T x aqueous dispersion solution with a mass concentration of 2 mg / ml;

[0075] (2) Dip the PET film with a thickness of 10 μm in the Ti3C2T x aqueous dispersion solution, and slowly and uniformly pull out the PET film from the water surface to make the two-dimensional Ti3C2T x in the Ti3C2T x aqueous dispersion solution load on the surface of the PET film under the action of the surface tension of the aqueous solution. After the pulled-out PET film is naturally dried, repeat the pulling and drying process several times (5 times), and place the PET film in a vacuum oven for vacuum drying at 50°C for 4 h to obtain a PET / MXene composite;

[0076] (3) Place the dried PET / MXene composite in an electroless plating device for electroless copper plating treatment. The specific electroless copper plating process comprises:

[0077] a. Prepare an electroless copper plating solution formula: 10 g / L CuSO4·5H2O, 24 g / L NaKC4H4O6·4H2O (potassium sodium tartrate tetrahydrate), 2.2 g / L Na2EDTA (disodium ethylenediaminetetraacetate), 10 g / L K4[Fe(CN)6]3, 20 g / L C 10 H8N2, 10 g / L formaldehyde;

[0078] b. Adjust the pH value of the electroless plating solution to 12 with NaOH, the temperature is 50°C, the electroless plating time is 25 minutes, and the electroless plated copper layer is formed on the surface of the PET / MXene composite layer. After cleaning and drying, the electroless plated copper plastic electroless plated product PET / MXene / Cu composite film is obtained.

[0079] The MXene layer in the embodiment does not contain a binder, and the substrate PET film can be easily peeled off from the PET / MXene / Cu composite film with tweezers, as shown in Figure 7 , a metal copper foil with a MXene layer (black) on one side is obtained. That is, the embodiment also provides an electroless plated product as a metal foil.

[0080] Example 3

[0081] The embodiment provides an electroless plated product and a preparation method thereof, and specifically a composite metal foil. In the embodiment, the polymer substrate is a PET film with a thickness of 10 μm. The preparation method of the electroless plated product of the embodiment includes the following steps:

[0082] (1) Prepare a Ti3C2T x aqueous dispersion solution (not containing a binder) with a mass concentration of 2 mg / ml;

[0083] (2) Dip the PET film with a thickness of 10 μm in the Ti3C2T x aqueous dispersion solution, and slowly and uniformly pull out the PET film from the water surface, so that the two-dimensional Ti3C2T x in the Ti3C2T x aqueous dispersion solution is loaded on the surface of the PET film under the action of the surface tension of the aqueous solution. After the pulled-out PET film is naturally dried, the PET film is repeatedly pulled out and dried for several times (5 times), and then placed in a vacuum oven and vacuum dried at 50°C for 4 h, to obtain a PET / MXene composite;

[0084] (3) Peel off the PET substrate in the PET / MXene composite to obtain a MXene layer;

[0085] (4) Place the MXene layer in an electroless plating device for electroless copper plating treatment. The specific electroless copper plating process is the same as that in Example 3. The MXene layer has a metal copper layer formed by electroless deposition on both sides, to obtain a composite metal copper foil with a “sandwich” structure.

[0086] Similarly, when the type of metal in the electroless plating is replaced by other metals, different types of metal foils can also be obtained by implementing a similar method of Example 2 or 3. Since the metal foils are obtained based on the deposition and growth of metal ions on the MXene layer, inevitably, the surface or interior of the metal foils will contain MXene materials.

[0087] The application also provides a current collector, or in other words, the application of the above-mentioned metal foil as a current collector in energy storage devices such as batteries, supercapacitors, etc.

[0088] Example 4

[0089] This embodiment provides a plastic electroless copper plating product and a preparation method thereof. In this embodiment, the polymer matrix is a PP porous sheet with a thickness of 0.8 mm. The preparation method of the plastic product of the application comprises:

[0090] (1) Prepare a Ti3C2T x aqueous dispersion with a mass concentration of 1 mg / ml, wherein 0.5% of a binder CMC is added;

[0091] (2) The Ti3C2T x aqueous dispersion is sprayed onto the surface of the PP porous sheet by a spraying machine, and after natural air drying, it is placed in a vacuum oven and vacuum dried at 50°C for 4h to obtain a PP / MXene composite;

[0092] (3) The dried PP / MXene composite is placed in an electroless plating device for electroless copper plating treatment. The specific electroless copper plating process is the same as that of Example 2.

[0093] By controlling the electroless plating process conditions, including temperature, current density, electroless plating time, etc., the thickness range of the electroless copper layer can be easily controlled. In some embodiments, the thickness of the electroless copper layer is between 10 nm and 500 μm.

[0094] Example 5

[0095] This embodiment provides a plastic electroless lead plating product and a preparation method thereof. Similar to Example 3, a PP / MXene composite is prepared by the same method, and the dried PP / MXene composite is placed in an electroless plating device for electroless lead plating treatment.

[0096] Example 6

[0097] The embodiment provides a plastic chemical nickel plating product and a preparation method thereof. Similar to the embodiment 4, the PP / MXene composite is prepared by using the same method. The dried PP / MXene composite is placed in a chemical nickel plating device for chemical nickel plating treatment, a chemical nickel plating layer is formed on the surface of the PP / MXene composite layer, and after cleaning and drying, the chemical nickel plating plastic chemical plating product of the application is obtained.

[0098] In other ways, the chemical metal plating layer can also be other metals suitable for chemical plating in an aqueous chemical plating solution, such as chromium, zinc, cadmium, lead, gold, silver, platinum, iron, cobalt, manganese, antimony, bismuth, gallium, indium, thallium, palladium, rhenium, rhodium, osmium, iridium, niobium, tungsten.

[0099] Embodiment 7

[0100] The embodiment provides another specific chemical copper plating product and a preparation method thereof. Similar to the embodiment 2, the difference is that in the embodiment, a high-concentration MXene dispersion liquid (50 mg / ml) is coated on the polymer film by a doctor blade. More specific steps include:

[0101] (1) A Ti3C2T x aqueous dispersion liquid with a mass concentration of 50 mg / ml is prepared;

[0102] (2) The Ti3C2T x aqueous dispersion liquid is coated on one side of a PET film by a doctor blade to form a Ti3C2T x film. The thickness of the Ti3C2T x film can be easily controlled by the gap between the doctor blades on the PET film. After vacuum drying at 50°C for 4h, an MXene layer is formed, and a PET / MXene composite layer is obtained;

[0103] (3) The dried PET / MXene composite layer is placed in a chemical plating device for chemical plating treatment. The specific chemical plating process is the same as that in the embodiment 2, and the chemical copper plating product of the application is obtained.

[0104] Compared with the coating method in the embodiment 7 and the spraying method in the embodiment 4, the immersion and pulling method in the embodiment 2 is more preferred, because in the process of pulling the polymer matrix film out of the liquid, the liquid surface tension causes the MXene two-dimensional sheets in the MXene dispersion liquid to be oriented and laid flat on the surface of the polymer matrix, so that a MXene layer that can completely cover the surface of the polymer matrix and is thinner is obtained. Figure 6As shown in the schematic diagram, the MXene two-dimensional sheet layers are overlapped on the surface of the polymer matrix to form an ultra-thin MXene layer, and the thickness of the MXene layer can be as low as the thickness of several MXene two-dimensional sheet layers. Since the MXene two-dimensional sheet layers are flexible, the ultra-thin MXene layer can be attached to the surface of the polymer matrix.

[0105] It should be noted that Ti3C2T x The MXene has good hydrophilicity and can be stably dispersed in an aqueous solution, so that the use of a dispersant is not required. The conventional dispersant and binder are non-conductive components, and if added to the dispersion, the conductive performance of the coated MXene layer will be affected, and then the effect of electroless plating on the surface of the MXene layer will be affected. Of course, the present application does not exclude the addition of a small amount of binder to the MXene dispersion according to actual needs.

[0106] Example 8

[0107] The chemical plating metal layer in the chemical plating product of the present application can also be more than two layers. In this embodiment, the plastic chemical plating copper product after chemical plating copper treatment is further subjected to chemical plating lead treatment, so that the chemical plating metal copper layer has a chemical plating metal lead layer on the surface.

[0108] Comparative Example 1

[0109] In this embodiment, the MXene dispersion is replaced by a graphene dispersion to prepare a composite with a conductive graphene layer on the surface of PET by using a method similar to that of Example 2. The product is subjected to chemical plating copper under the same conditions, and the product photo is shown in FIG. 2B. Figure 8 It is difficult to achieve chemical plating of metal copper on the surface of the graphene layer, the bonding force between the metal copper and the graphene layer is poor, the plated layer is easy to fall off and peel off, and the effect of electroless plating is poor.

[0110] Since the preparation method of the plastic chemical plating product of the present application involves a chemical plating process, i.e., chemical plating deposition in an aqueous chemical plating solution, the nucleation layer on the polymer matrix is required to have good hydrophilicity and active sites. Although graphene and MXene materials are similar and have a two-dimensional sheet structure, conductive graphene (such as graphene after mechanical exfoliation, electrochemistry or chemical reduction) generally does not have hydrophilicity; and hydrophilic graphene oxide lacks metal-active sites, and both are difficult to apply to the chemical plating process.

[0111] In addition, the MXene material of the present application is different from graphene in that: (1) the MXene material has rich functional groups on the surface, especially halogen-containing functional groups (such as -F). The nucleation overpotential of metal deposition can be reduced, and the uniform growth of the metal plating layer is promoted, so that a dense and uniform chemical plating metal layer is obtained; (2) the MXene material is a transition metal carbon and / or nitride, and the constituent elements include transition metal elements. When MXene is used as a nucleation layer, the transition metal elements contained therein can act as active sites for chemical plating, and the complex hydrophilic, activation, and sensitization steps before chemical plating.

[0112] In a specific embodiment of the present application, MXene Ti3C2T x Since the MXene material is a kind of two-dimensional material, it has similar physical and chemical properties, such as hydrophilicity, rich surface functional groups, and electrical conductivity. In other embodiments, other types of MXene materials can also be used, such as Ti2CT x , V2CT x , Mo2CT x , Nb2CT x , Ta2CT x , Ta3C2T x , Ta4C3T x , Ti4C3T x , etc. It can be reasonably predicted that the same technical effects as MXene Ti3C2T x can also be achieved. The use of these different types of MXene materials in the plastic chemical plating process is within the technical concept of the present application.

[0113] Since the metal plating layer in the chemical plating method of the present application is deposited and grown on the MXene layer, the type of substrate material is not limited, i.e., the chemical plating method of the present application is universal. For other non-polymer substrates, such as metals, ceramics, and glass materials, the chemical plating method of the present application can also be used. The present application also provides a chemical plating product, i.e., a composite material with a chemical plating metal layer. The chemical plating product includes a substrate, a MXene layer on the surface of the substrate, and a chemical plating metal layer on the surface of the MXene layer. The substrate includes: metal, ceramic, glass, and polymer.

[0114] Example 9

[0115] This embodiment provides a chemical plating copper composite material with a glass fiber fabric (GF) substrate. The preparation method steps include:

[0116] (1) Prepare a Ti3C2T x aqueous dispersion with a mass concentration of 1 mg / ml, and add 0.5 wt.% of a binder CMC;

[0117] (2) The glass fiber braid is immersed in Ti3C2T x After being taken out from the aqueous dispersion liquid, dried, and immersed and dried repeatedly for several times, the MXene layer is formed on the surface of the glass fiber; in this embodiment, the immersion is performed for three times, and the drying is performed in a vacuum oven at 50°C for 4h to obtain the GF / MXene composite.

[0118] (3) The dried GF / MXene composite is placed in a chemical plating device to perform the chemical copper plating treatment, and the specific chemical copper plating process is the same as that in Example 2 to obtain the GF / MXene / Cu composite material.

[0119] Example 10

[0120] The glass fiber braid in Example 9 is replaced by a ceramic material, and in one embodiment, the ceramic material is an alumina ceramic. By using the similar method, the ceramic composite with the chemical copper plating layer on the surface is obtained.

[0121] Example 11

[0122] The glass fiber braid in Example 9 is replaced by a metal material, and in one embodiment, the metal material is a metal nickel foil. By using the similar method, the composite metal foil material with the metal nickel / MXene / copper structure can be obtained.

[0123] The foregoing description of specific exemplary embodiments of the application is intended to be illustrative only and is not intended to limit the application to the precise forms described. Many modifications and variations are possible in light of the above teachings without departing from the spirit or essential characteristics of the application. The exemplary embodiments were chosen and described in order to explain the principles of the application and its practical application and to allow others skilled in the art to understand the application for various exemplary embodiments with various modifications being applicable. The scope of the application is intended to be defined by the claims and their equivalents.

Claims

1. A product of electroless plating, characterized by, The electroless plating product comprises: a substrate; a MXene layer disposed on the surface or part of the surface of the substrate; and, an electroless plated metal layer disposed on the surface of the MXene layer; The MXene layer comprises MXene material, the mass content of MXene material in the MXene layer is between 50% and 100%, and the MXene layer is a continuous layer independent of the substrate, configured to be directly electroless plated without the need for hydrophilic treatment, activation or sensitization steps in the electroless plating step. The preparation method of the electroless plating product comprises the following steps: The MXene layer is formed by loading the surface of the substrate with MXene material. The electroless plating step is to directly electroless plate the surface of the MXene layer to form an electroless plated metal layer without the need for hydrophilic treatment, activation or sensitization steps.

2. The electroless plated product of claim 1 wherein, The chemical formula of the MXene material is represented as M n+ 1X n T x wherein M represents one or more of transition metal elements; X represents one or more of carbon, nitrogen or boron, T represents a surface functional group; 1≤ n ≤4, 0< x ≤2.

3. The electroless plated product of claim 2 wherein, The M is selected from one or more of Ti, Nb, Ta, V, Mo, Zr.

4. The electroless plated product of claim 1 wherein, The mass content of MXene material in the MXene layer is between 80% and 100%.

5. The electroless plated product of claim 1 wherein, The mass content of MXene material in the MXene layer is between 90% and 100%.

6. The electroless plated product of claim 1 wherein, The substrate is a non-conductive material.

7. The electroless plated product of claim 6 wherein, The non-conductive material is selected from a polymer, a ceramic or a glass. and / or the MXene material is selected from Ti3C2T x , Ti2CT x , V2CT x , Nb2CT x 、 Mo2CT x , Ti4C3T x , Ta2CT x , Ta4C3T x , TiNbCT x ; The material of the electroless plated metal layer is selected from one or more of copper, nickel, chromium, zinc, cadmium, lead, gold, silver, platinum, iron, cobalt, manganese, antimony, bismuth, gallium, indium, thallium, palladium, rhenium, rhodium, osmium, iridium, niobium, tungsten.

8. The electroless plated product of claim 7 wherein, The polymer is selected from one or more of acrylonitrile-butadiene-styrene copolymer, polysulfone, polycarbonate, polypropylene, phenolic resin, phenolic glass fiber reinforced plastic, nylon, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenyl ether, polystyrene, polyamide and derivatives of the above polymers.

9. The electroless plated product of claim 1 wherein, The thickness of the MXene layer is between 1 nm and 50 μm. The thickness of the electroless plated metal layer is between 10 nm and 5 μm. The substrate is in the form of a sheet, a film, a tube, a braid, a wire or a mesh.

10. The electroless plated product of claim 9 wherein, The thickness of the MXene layer is between 3 nm and 10 μm.

11. The electroless plated product of claim 9 wherein, The thickness of the MXene layer is between 10 nm and 5 μm.

12. The electroless plated product of claim 9 wherein, The thickness of the MXene layer is between 100 nm and 2 μm.

13. A product of electroless plating, characterized by, The electroless plating product comprises: a MXene layer; and, an electroless plated metal layer disposed on at least one side of the surface of the MXene layer; The MXene layer comprises MXene material, the mass content of MXene material in the MXene layer is between 50% and 100%, and the MXene layer is configured to be directly electroless plated without the need for hydrophilic treatment, activation or sensitization steps in the electroless plating step.

14. The electroless plated product of claim 12, wherein, The chemical formula of the MXene material is represented as M n+ 1X n T x wherein M represents one or more of transition metal elements; X represents one or more of carbon, nitrogen or boron, T represents a surface functional group; 1≤ n ≤4, 0< x ≤2.

15. The electroless plated product of claim 14, wherein, The M is selected from one or more of Ti, Nb, Ta, V, Mo, Zr.

16. The electroless plated product of claim 13 wherein, The mass content of MXene material in the MXene layer is between 80% and 100%.

17. The electroless plated product of claim 13 wherein, The mass content of MXene material in the MXene layer is between 90% and 100%.

18. The electroless plated product of claim 13 wherein, the MXene material is selected from Ti3C2T x , Ti2CT x , V2CT x , Nb2CT x 、 Mo2CT x , Ti4C3T x , Ta2CT x , Ta4C3T x , TiNbCT x ; And / or, the material of the electroless plated metal layer is selected from one or more of copper, nickel, chromium, zinc, cadmium, lead, gold, silver, platinum, iron, cobalt, manganese, antimony, bismuth, gallium, indium, thallium, palladium, rhenium, rhodium, osmium, iridium, niobium, tungsten.

19. The electroless plated product of claim 13 wherein, The thickness of the MXene layer is between 1 nm and 50 μm. And / or, the thickness of the electroless plated metal layer is between 10 nm and 5 μm.

20. The electroless plated product of claim 19, wherein, The thickness of the MXene layer is between 3 nm and 10 μm.

21. The electroless plated product of claim 9 wherein, The thickness of the MXene layer is between 10 nm and 5 μm.

22. The electroless plated product of claim 9 wherein, The thickness of the MXene layer is between 100 nm and 2 μm.

23. A method of producing the electroless plated product according to any one of claims 1 to 12, characterized by the steps of Comprising: The surface of the substrate is coated with MXene material to form a MXene layer; The surface of the MXene layer is directly electroless plated to form an electroless plated metal layer without the need for hydrophilic treatment, activation or sensitization steps.

24. A method of producing a electroless plated product according to any one of claims 13 to 22, characterized by the steps of Comprising: A MXene layer is provided, and the mass content of MXene material in the MXene layer is between 50% and 100%; The surface of the MXene layer is directly electroless plated to form an electroless plated metal layer without the need for hydrophilic treatment, activation or sensitization steps.

25. The method for preparing the electroless plating product as described in claim 24, characterized in that, The preparation method further comprises: The surface of the substrate is coated with MXene material to form the MXene layer; After the coating step, the substrate is peeled off; or, after the electroless plating step, the substrate is peeled off.

26. The method for producing an electroless plated product according to claim 23 or 25, wherein In the coating step, the more specific steps include: the MXene dispersion liquid is coated and / or sprayed on the substrate, and after drying, the MXene layer is obtained; Or, the substrate is immersed and pulled out from the MXene dispersion liquid, and after drying, the MXene layer is formed on the surface of the substrate; Or, the surface of the substrate is in contact with the liquid phase interface of the MXene dispersion liquid to form the MXene layer on the surface of the substrate.

27. The method for preparing the electroless plating product as described in claim 26, characterized in that, The substrate is immersed and pulled out from the MXene dispersion liquid, and the MXene two-dimensional sheet is oriented and laid flat under the action of surface tension to form an ultra-thin MXene layer with a thickness of 1 nm to 3 nm.

28. The method for preparing the electroless plating product as described in claim 26, characterized in that, The solvent of the MXene dispersion liquid is selected from one or more of water and alcohol; And / or, the concentration of MXene in the MXene dispersion liquid is between 0.01 mg / ml and 80 mg / ml.

29. The method for preparing the electroless plating product as described in claim 28, characterized in that, The alcohol is selected from one or more of ethanol, propanol, isopropanol, and butanol.

30. The method for preparing the electroless plating product as described in claim 26, characterized in that, The MXene dispersion liquid contains a binder; Or, the MXene dispersion liquid is composed of MXene material and a solvent.

31. The method for preparing the electroless plating product as described in claim 30, characterized in that, The MXene dispersion liquid does not contain a binder, and the mass content of MXene material is between 90% and 100%.

32. The method for preparing the electroless plating product as described in claim 30, characterized in that, The binder is a water-based binder.

33. The method for preparing the electroless plating product as described in claim 32, characterized in that, The water-based binder is selected from one or more of LA133 water-based adhesive, methyl cellulose, polytetrafluoroethylene, polyvinyl alcohol, butadiene styrene rubber, and water-based polyurethane.

34. Use of the electroless plating product according to any one of claims 1 to 22, or the electroless plating product obtained by the preparation method according to any one of claims 23 to 33, in an automobile, a household appliance, an energy storage device.

35. A current collector, comprising: The current collector comprises the electroless plating product according to any one of claims 1 to 22; or, the preparation method of the current collector comprises the preparation method according to any one of claims 23 to 33.

36. A battery comprising the current collector according to claim 35.

37. Use of a MXene material for electroless plating on a substrate surface, characterized in that, The use method step comprises: a coating step of coating a surface of the substrate with MXene material to form a MXene layer; an electroless plating step of directly electroless plating a metal layer on the surface of the MXene layer without performing a hydrophilic treatment, an activation or a sensitization step; a mass content of the MXene material in the MXene layer is between 50% and 100%.

Images