CN117004934A

CN117004934A - An electroless plating product, electroless plating method and application

Info

Publication number: CN117004934A
Application number: CN202310327678.XA
Authority: CN
Inventors: 杨树斌; 施昱
Original assignee: Beihang University
Current assignee: Beihang University
Priority date: 2023-03-29
Filing date: 2023-03-29
Publication date: 2023-11-07
Anticipated expiration: 2043-03-29
Also published as: CN117004934B

Abstract

The application discloses an electroless plating product, an electroless plating method and application, wherein the electroless plating product comprises the following components: an MXene layer; and a electroless metal layer disposed on at least one side of the surface of the MXene layer; or, the electroless plating product includes: a base; an MXene layer arranged on the surface or part of the surface of the substrate; and a electroless metal layer disposed on the surface of the MXene layer; wherein the MXene layer comprises an MXene material. The preparation method greatly simplifies the process steps of chemical plating, provides production efficiency, reduces production cost and avoids the problem of environmental pollution.

Description

Electroless plating product, electroless plating method and application

Technical Field

The application belongs to the field of chemistry, and particularly relates to an electroless plating product, an electroless plating method and application.

Background

The purpose of plastic electroless plating is to coat metal on the surface of plastic, thereby not only increasing the appearance, but also compensating the defects of the plastic, endowing the metal with the property, fully playing the characteristics of the plastic and the metal into a whole, and a large number of plastic electroless plating products are applied to industries such as energy storage, electronics, automobiles, household appliances and the like.

Compared with metal products, the plastic electroless plating product not only can realize good metal texture, but also can lighten the weight of the product, and improves the electric, thermal and corrosion resistance performances of the plastic electroless plating product while effectively improving the appearance and the decoration of the plastic electroless plating product. With the rapid development of industry and the increasingly wide application of plastic electroless plating, the plastic electroless plating becomes one of the important means for surface decoration in plastic products. The chemical plating is widely performed on the surfaces of ABS, polypropylene, polysulfone, polycarbonate, nylon, phenolic glass fiber reinforced plastic, polystyrene and other plastics at home and abroad.

The existing plastic electroless plating process generally requires pretreatment, and the pretreatment comprises hydrophilization treatment, sensitization and activation steps, so that the plastic surface can be made to be compatible with an aqueous plating solution, and chemical reduction deposition points are provided for electroless plating metal ions, and a chemical method is generally adopted, namely a strong oxidizing solution containing a mixture of chromic anhydride and sulfuric acid is adopted for treatment. However, the chemical method uses toxic chemicals, which has the problem of environmental pollution; the electroless plating treatment is aimed at forming a metal conductive film on the surface of the plastic, and by electroless plating treatment, metal ions such as copper, nickel, gold, silver, platinum or palladium having a catalytic action in the plating solution are deposited on the plastic substrate by reduction to form a metal conductive film (thickness of about 0.05 to 0.8 μm). Therefore, the existing plastic electroless plating has the problems of complex preparation process and low efficiency because the existing plastic electroless plating is required to be subjected to hydrophilization treatment, sensitization, activation and electroless plating processes.

Disclosure of Invention

The application aims to provide an electroless plating method and an electroless plating product, aiming at the problems of complex process and low efficiency of the existing plastic electroless plating process.

The technical conception of the application is that an MXene layer containing an MXene material is formed on the surface of a material matrix such as a polymer, ceramic, glass fiber and the like, and then a electroless plating metal layer is formed on the MXene layer by electroless plating, so that an electroless plating product is obtained.

In a first aspect, the present application provides an electroless plating product comprising: an MXene layer; and a electroless metal layer disposed on at least one side of the surface of the MXene layer. Or, the electroless plating product includes: a base; an MXene layer arranged on the surface or part of the surface of the substrate; and the electroless metal layer is arranged on the surface of the MXene layer. Wherein the MXene layer comprises an MXene material.

In some embodiments, the chemical formula of the MXene material described above is represented by 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; n is more than or equal to 1 and less than or equal to 4, x is more than or equal to 0 and less than or equal to 2; preferably, the M is selected from one or more of Ti, nb, ta, V, mo, zr.

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

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

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

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 terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polystyrene, polyamide, and derivatives of the above polymers;

in some embodiments, the MXene material is selected from Ti ₃ C ₂ T _x 、Ti ₂ CT _x 、V ₂ CT _x 、Nb ₂ CT _x 、Mo ₂ CT _x 、Ti ₄ C ₃ T _x 、Ta ₂ CT _x 、Ta ₄ C ₃ T _x 、TiNbCT _x 。

In some embodiments, the electroless metal layer is made of one or more materials selected from 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.

In some embodiments, the thickness of the MXene layer is between 1nm and 50 μm; preferably between 3nm and 10 μm; more preferably between 10nm and 5 μm; preferably between 100nm and 2 μm;

in some embodiments, the electroless metal layer has a thickness of 10nm to 5 μm; preferably between 100nm and 2 μm.

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

The second aspect of the present application provides a method for preparing the electroless plating product, comprising the steps of: and (3) a loading step: coating the surface of the matrix with an MXene material to form an MXene layer; and (3) chemical plating: and forming a electroless metal layer on the surface of the MXene layer by electroless plating.

In some embodiments, the above-described preparation method further comprises a peeling step of peeling the substrate after the loading step; or, the preparation method further comprises a stripping step after the electroless plating step, and the substrate is stripped.

In some embodiments, in the step of overlaying, more specific steps include: and (3) coating and/or spraying the MXene dispersion liquid on the substrate, and drying to obtain the MXene layer.

In some embodiments, in the step of overlaying, more specific steps include: immersing, pulling and/or immersing the substrate from the MXene dispersion liquid, and forming the MXene layer on the surface of the substrate after drying;

in some embodiments, in the step of overlaying, more specific steps include: and (3) contacting the surface of the matrix with a liquid phase interface of the MXene dispersion liquid to form the MXene layer on the surface of the matrix.

In some embodiments, the solvent of the MXene dispersion is selected from one or more of water, alcohols; preferably, the alcohol is selected from one or more of ethanol, propanol, isopropanol, butanol.

In some embodiments, the concentration of MXene in the MXene dispersion is between 0.01mg/ml to 80mg/ml.

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

In some embodiments, the binder is selected from the group consisting of aqueous binders; preferably, the aqueous binder is selected from one or more of LA133 aqueous binder, methylcellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene Butadiene Rubber (SBR), aqueous polyurethane.

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

The application provides an electroless plating product or an electroless plating product obtained by the preparation method, which is applied to automobiles, household appliances and energy storage devices.

A fourth aspect of the present application provides a current collector comprising the electroless plating product described above; or, the preparation method of the current collector comprises the preparation method of the electroless plating product.

A fifth aspect of the present application provides a battery comprising the current collector described above.

In a sixth aspect, the application provides the use of an MXene material for electroless plating of a non-conductive substrate surface.

The MXene layer is formed on the substrate by simple coating, spraying, dipping or other methods, and the MXene material in the MXene layer has hydrophilicity and can be compatible with the water system chemical plating, so that the chemical method hydrophilic treatment in the prior art is avoided, and the chemical plating pretreatment activation and sensitization steps in the prior art are reduced. Therefore, the preparation method greatly simplifies the process steps of chemical plating, provides production efficiency, reduces production cost and avoids the problem of environmental pollution.

Drawings

Fig. 1 is a schematic structural diagram of a plastic electroless plating product in embodiment 1 of the present application.

FIG. 2 is a second schematic diagram of a plastic electroless plating product according to embodiment 1 of the present application.

FIG. 3 is a third schematic diagram of a plastic electroless plating product according to embodiment 1 of the present application.

Fig. 4 is a schematic diagram of a preparation step of a composite metal foil of an electroless plating product and a schematic diagram of a structure of the composite metal foil in embodiment 1 of the present application.

Fig. 5 is a schematic diagram of a preparation step of a composite metal foil of another electroless plating product in example 1 of the present application, and a schematic diagram of a structure of the composite metal foil.

FIG. 6 is a schematic diagram of the structure of an ultra-thin MXene layer formed on a substrate surface according to the present application.

FIG. 7 is a photograph showing the peeling of a substrate from the electroless plating product obtained in example 2 of the present application.

Fig. 8 is a photograph of electroless plating of the surface of the graphene layer in comparative example 1 of the present application.

The main reference numerals illustrate:

100. 200, 300 electroless plating products; 110. 120 composite metal foil;

10 a polymer matrix; a 20MXene layer, a 21MXene two-dimensional sheet; 30 electroless metal layer.

Detailed Description

The technical scheme of the application is described below through specific examples. It is to be understood that the reference to one or more steps of the application does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the application, which relative changes or modifications may be regarded as the scope of the application which may be practiced without substantial technical content modification.

The MXene material and graphene in the embodiment of the application are purchased from Jinan Sanchuan New Material technologies Co., ltd, wherein Ti ₃ C ₂ T _x Product model SC02003LW of slurry with concentration of 5mg/ml and 50mg/ml, ti ₃ C ₂ T _x Two-dimensional MXene Ti contained in the slurry ₃ C ₂ T _x From MAX phase material Ti ₃ AlC ₂ Etching the Al layer, and then carrying out ultrasonic stripping. The MXene powder is Ti ₃ C ₂ T _x Graphene in the comparative example was prepared by a redox method at a concentration of 0.5wt%.

The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

Example 1

This embodiment provides an electroless plating product 100, as shown in FIG. 1, comprising a substrate 10, an MXene layer 20 and an electroless plating layer 30, wherein the MXene layer 20 contains an MXene material; wherein the substrate is in a sheet shape or a film shape, the MXene layer 20 is arranged on one side surface of the substrate 10, and the electroless metal layer 30 is arranged on the MXene layer 20. In another embodiment, the MXene layer 20 is disposed on both side surfaces of the substrate 10 (FIG. 2), resulting in an electroless plated product 200. The present application is not limited to the shape of the substrate, and in another embodiment, the substrate 10 is cylindrical or linear (fig. 3) to obtain a cylindrical or linear electroless plating product 300. In other embodiments, the substrate may also be tubular, porous, or irregularly shaped. In some embodiments, the MXene layer 20 covers a portion of the surface of the substrate.

The embodiment also provides a preparation method of the electroless plating product, which comprises the following steps:

s01: coating the surface of the matrix with an MXene material to form an MXene layer;

s02: and forming a electroless metal layer on the surface of the MXene layer by electroless deposition.

The embodiment also provides another electroless plating product, which is a metal foil with a sandwich structure, as shown in fig. 4, and the preparation method comprises the following steps:

s11: coating the surface of the matrix with an MXene material to form an MXene layer;

s12: stripping the matrix in the compound obtained in the step S11 to obtain an MXene layer;

s13: and (3) performing electroless deposition on the MXene layer obtained in the step (S12) to form a electroless metal layer, thereby obtaining an electroless plating product with a chemical plating layer on two sides and a sandwich structure with the MXene layer in the middle, namely the composite metal foil 120.

The present embodiment also provides another electroless plating product, which is a metal foil having an MXene layer on one side, as shown in fig. 5, and the preparation method comprises the steps of:

s21: coating the surface of the matrix with an MXene material to form an MXene layer;

s22: depositing the chemical plating of the compound obtained in the step S21, and forming a chemical plating metal layer on the surface of the MXene layer;

s23: the matrix in the composite obtained in step S22 is peeled off to obtain another electroless plating product, the composite metal foil 110 having an MXene layer on one side.

In steps S01, S11, S21, the method of coating the surface of the substrate with the MXene material to form the MXene layer may be a dry method or a wet method, where the dry method refers to forming a film layer on the surface of the substrate by using powder of the MXene material, a binder, and the like under the condition of no solvent; the wet method is to coat the dispersion of MXene on the surface of a substrate by spraying, dipping, coating and the like, and form an MXene layer after drying to remove the solvent. The dry process avoids the step of removing the solvent, can simplify the process flow, but forms a stable continuous conductive layer, requires the addition of a binder, a non-conductive binder, and reduces the continuous conductivity of the surface of the MXene layer. Thus, a wet process is preferably employed. The wet process has the beneficial effects that the MXene material can be more uniformly dispersed on the surface of the matrix; although the solvent removal step is included, because of the good hydrophilicity of the MXene material, aqueous solvents (including water and/or alcohol solvents) are typically employed, which have the advantage of low cost and ease of removal. In a specific embodiment, the method comprises the following steps: coating the MXene dispersion liquid on the surface of a substrate through one or more spraying and/or coating to form an MXene film, and drying to form an MXene layer; in another specific embodiment, the method comprises: the substrate is pulled and/or immersed from the MXene dispersion liquid for a plurality of times, so that the MXene two-dimensional sheets in the dispersion liquid are directionally and continuously coated on the surface of the substrate under the action of surface tension, and the MXene layer is formed after drying.

Wherein, the MXene dispersion liquid in the application refers to a liquid or semi-liquid (gel state or slurry state) mixture containing MXene material; optionally, the MXene dispersion liquid also comprises a certain amount of binder (accounting for 0.01-50% of the mass of the dry material), the content of the binder is comprehensively judged in combination with the bonding performance and the electroless plating performance, and the smaller the content of the binder is, the better the electroless plating effect and the bonding performance are; preferably, the binder is an aqueous binder, optionally selected from one or more of LA133 aqueous binder, methylcellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene Butadiene Rubber (SBR), aqueous polyurethane, etc.

Alternatively, the concentration of the MXene dispersion is between 0.01mg/ml and 80mg/ml, selected according to the method of coating. Methods of coating the substrate with the MXene dispersion optionally include spraying, coating, dipping, and the like. In a specific embodiment, the method comprises the following steps: spraying 0.01-2 mg/ml of MXene dispersion liquid on the surface of a substrate once or for several times, and drying to form an MXene layer; in another embodiment, the method comprises the steps of carrying out one or more times of dipping and pulling on 1-10 mg/ml of MXene dispersion liquid, so that MXene in the dispersion liquid is coated on the surface of a substrate under the action of surface tension, and forming an MXene layer after drying; in another embodiment, the method comprises the steps of coating 10-80 mg/ml of MXene dispersion on the surface of a substrate through a medium (such as a hairbrush, a scraper and the like), and drying to form an MXene layer.

The chemical formula of the MXene material in the MXene layer in the application can be expressed as M _n+1 X _n T _x Wherein M represents a transitionOne or more of metal elements; x represents one or more of carbon, nitrogen or boron, and T represents a surface functional group; n is more than or equal to 1 and less than or equal to 4, x is more than or equal to 0 and less than or equal to 2; in some embodiments M is selected from one or more of Ti, nb, ta, nb, V, mo, zr, cr. The MXene material is typically prepared from a precursor MAX by phase etching the a component therein. Common MXene materials are Ti ₃ C ₂ T _x 、Ti ₂ CT _x 、V ₂ CT _x 、Nb ₂ CT _x 、Mo ₂ CT _x 、Ti ₄ C ₃ T _x 、Ta ₂ CT _x 、Ta ₄ C ₃ T _x 、TiNbCT _x Etc.

In some embodiments, an adhesive is added to the MXene layer as needed to increase the bonding force between the MXene layer and the substrate; i.e. 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 is, the better the conductivity and the hydrophilicity are, but the bonding force between the MXene material and the matrix is reduced; in other embodiments, the MXene layer also functions as a release layer, which does not contain a binder. Thus, preferably, the mass content of the MXene material in the MXene layer is between 50% and 100%, more preferably between 80% and 100%; and still more preferably, between 90% and 100%.

The application forms the electroless plating metal layer on the surface of the MXene layer, and the surface of the substrate is not contacted with the metal layer, but the MXene layer is used as a connecting layer between the substrate and the electroless plating metal layer, so the preparation method of the application has universality for various substrates.

In some embodiments, the bonding force between the MXene layer and the polymer matrix may be enhanced by roughening the surface of the polymer matrix (e.g., corona or etching), i.e., etching "pits" in the surface of the polymer matrix, thereby reducing the amount of binder or eliminating the use of binder.

In some embodiments, the polymer matrix may be selected from the group consisting of acrylonitrile-butadiene-styrene (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, polyvinylchloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene Sulfide (PPs), polyphenylene oxide (PPO), polystyrene (PS), polyamide (PA), and derivatives of one or more of the foregoing polymers.

In some embodiments, the type of metal in the electroless metal layer may be 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.

In some embodiments, the thickness of the MXene layer is between 1nm and 20 μm. The MXene layer may be coated, sprayed, dip-pulled, or the like onto the polymer substrate with a MXene-containing dispersion (which may also be a paint). Since the MXene material is typically a two-dimensional material, the monolayer is only 1nm thick. When the two-dimensional sheet 21 of MXene is formed as a single layer or a continuous distribution of a small number of layers on the surface of the substrate, for example, by dip-coating, the thickness of the MXene layer may be as low as 1nm to 3nm, thereby forming an ultra-thin MXene layer (as shown in FIG. 6). When spraying or coating is used, the thickness of the MXene layer can be controlled to be in the range of several micrometers (1 μm to 100 μm). Thus, the thickness of the MXene layer can be adjusted between 1nm and 100 μm.

The thickness of the electroless metal layer is controlled by adjusting the conditions of the electroless plating process as desired, and in some embodiments, is between 50nm and 500 μm. Because the preparation method of the application only has one electroless plating process, the metal layer of the electroless plating product is only the thickness of the electroless plating metal layer, i.e. the application can obtain an electroless plating piece with an ultrathin metal layer (about 50 nm-10 μm).

The effect of introducing the MXene layer in the electroless plating is that the MXene material in the MXene layer has metallic and rich surface functional groups, and can provide nucleation points for electroless plating of the electroless plating process and reduce metal deposition overpotential. In addition, due to the high specific surface area and rich surface functional groups of the MXene, a large amount of metal ions in the electroless plating solution can be adsorbed and complexed, uniform deposition of metal in the electroless plating process is facilitated, and transition metal elements in the MXene can also provide active sites.

Example 2

The embodiment provides an electroless plating product and a preparation method thereof, wherein a PET film with the thickness of 10 mu m is selected as a polymer matrix in the embodiment, and the preparation method of the plastic electroless plating product comprises the following steps:

(1) Preparing Ti with mass concentration of 2mg/ml ₃ C ₂ T _x Aqueous dispersion (without binder);

(2) A PET film having a thickness of 10 μm was impregnated with Ti ₃ C ₂ T _x After the water-based dispersion, the PET film is slowly pulled out of the water surface at a constant speed to ensure that Ti ₃ C ₂ T _x Two-dimensional Ti in aqueous dispersion ₃ C ₂ T _x Coating the PET film on the surface of the PET film under the action of the surface tension of the aqueous solution, naturally airing the pulled PET film, repeatedly lifting and drying for a plurality of times (5 times), placing the PET film in a vacuum oven, and vacuum drying for 4 hours at 50 ℃ to obtain a PET/MXene compound;

(3) Placing the dried PET/MXene compound in an electroless plating device for electroless copper plating treatment, wherein the specific electroless copper plating process comprises the following steps:

a. preparing an electroless plating solution formula for electroless copper plating: 10g/L CuSO ₄ ·5H ₂ O、24g/L NaKC ₄ H ₄ O ₆ ·4H ₂ O (sodium potassium tartrate tetrahydrate), 2.2g/L Na ₂ EDTA (disodium edetate), 10g/LK ₄ [Fe(CN) ₆ ] ₃ ,20g/L C ₁₀ H ₈ N ₂ 10g/L formaldehyde;

b. and regulating the pH value of the electroless plating solution to 12 by adopting NaOH, wherein the temperature is 50 ℃, the electroless plating time is 25 minutes, forming an electroless plating metal copper layer on the surface of the PET/MXene composite layer, and obtaining the electroless plating plastic product PET/MXene/Cu composite film after cleaning and drying.

In this example, the MXene layer did not contain an adhesive, and the base PET film was easily peeled from the PET/MXene/Cu composite film using tweezers, as shown in fig. 7, to obtain a metal copper foil having an MXene layer (black) on one side. That is, the present embodiment also provides that the electroless plating product is a metal foil.

Example 3

The embodiment provides an electroless plating product and a preparation method thereof, in particular to a composite metal foil, wherein a PET film with the thickness of 10 mu m is selected as a polymer matrix in the embodiment, and the preparation method of the electroless plating product comprises the following steps:

(3) Stripping the PET matrix in the PET/MXene compound to obtain an MXene layer;

(4) The MXene layer was placed in an electroless plating apparatus to perform electroless copper plating, and a specific electroless copper plating process was the same as in example 3, with electroless plating deposited metal copper layers on both sides of the MXene layer, to obtain a composite metal copper foil having a "sandwich" structure.

Similarly, when the kind of electroless plated metal is replaced with other metals, a different kind of metal foil can also be obtained by the similar method of example 2 or 3. Since the metal foils are grown by metal ion deposition onto the MXene layer, it is inevitable that MXene material is present on the surface or inside of the metal foils.

The application also provides a current collector, or application of the obtained metal foil serving as the current collector in energy storage devices such as batteries and super capacitors.

Example 4

The embodiment provides a plastic electroless copper plating product and a preparation method thereof, wherein a PP porous sheet with the thickness of 0.8mm is selected as a polymer matrix in the embodiment, and the preparation method of the plastic part product comprises the following steps:

(1) Preparing Ti with mass concentration of 1mg/ml ₃ C ₂ T _x An aqueous dispersion to which 0.5% of a binder CMC was added;

(2) The Ti is treated with ₃ C ₂ T _x Spraying the water-based dispersion liquid on the surface of the PP porous sheet through a spraying machine, naturally airing, placing in a vacuum oven, and vacuum drying at 50 ℃ for 4 hours to obtain a PP/MXene compound;

(3) The dried PP/MXene composite was placed in an electroless plating apparatus to be subjected to electroless copper plating, and the specific electroless copper plating process was the same as in example 2.

The thickness range of the electroless copper layer, in some embodiments, the electroless copper layer can be easily controlled by controlling electroless plating process conditions, including temperature, current density, electroless plating time, etc., and in some embodiments, the electroless copper layer has a thickness of 10nm to 500 μm.

Example 5

The present example provides a plastic electroless lead plating product and a method for preparing the same, similar to example 3, by preparing a PP/MXene composite by the same method, and placing the dried PP/MXene composite in an electroless lead plating apparatus for electroless lead plating treatment.

Example 6

The embodiment provides a plastic electroless nickel plating product and a preparation method thereof, which are similar to the embodiment 4, PP/MXene compound is prepared by adopting the same method, the PP/MXene compound is placed in an electroless nickel plating device for electroless nickel plating treatment after being dried, an electroless nickel plating layer is formed on the surface of the PP/MXene compound layer, and after the PP/MXene compound is cleaned and dried, the electroless nickel plating plastic electroless nickel plating product is obtained.

In other embodiments, the electroless metal layer may be other metals suitable for electroless plating in aqueous electroless liquids, such as: chromium, zinc, cadmium, lead, gold, silver, platinum, iron, cobalt, manganese, antimony, bismuth, gallium, indium, thallium, palladium, rhenium, rhodium, osmium, iridium, niobium, tungsten.

Example 7

This example provides another specific electroless copper plating product and a method of making the same. Similar to example 2, except that the polymer film was coated with a high concentration of MXene dispersion (50 mg/ml) by doctor blade in this example. More specific steps include:

(1) Preparing Ti with mass concentration of 50mg/ml ₃ C ₂ T _x Aqueous dispersion (viscous slurry);

(2) The Ti is treated with ₃ C ₂ T _x The aqueous dispersion is coated on one side of the PET film by a scraper to form a layer of Ti ₃ C ₂ T _x Film, ti can be conveniently controlled by scraping the gap between PET films ₃ C ₂ T _x The thickness of the film is dried in vacuum for 4 hours at 50 ℃ to form an MXene layer, and a PET/MXene composite layer is obtained;

(3) And (3) placing the dried PET/MXene composite layer into an electroless plating device for electroless plating, wherein the specific electroless plating process is the same as that of the example 2, and the electroless copper plating product of the application is obtained.

The dip-coating method of example 2 is more preferable than the spray-coating method of example 4 and the coating method of example 7 because during the process of the dip-coating, the film of the polymer matrix is pulled out from the liquid, and the surface tension of the liquid acts to orient and lay the two-dimensional sheets of the MXene in the MXene dispersion on the surface of the polymer matrix, so that the MXene layers that can completely cover the surface of the polymer matrix and are thinner are obtained, and as shown in the schematic diagram of fig. 6, the MXene two-dimensional sheets are laid and overlapped on the surface of the polymerized matrix, forming an ultra-thin MXene layer, the thickness of which can be as low as several layers of MXene two-dimensional sheets, which can be laminated on the surface of the polymer matrix due to the flexibility of the MXene two-dimensional sheets.

Since Ti is ₃ C ₂ T _x Has good hydrophilicity, can be stably dispersed in an aqueous solution, and does not needUse of a dispersant. Conventional dispersants and binders are non-conductive components that, if added to the dispersion, necessarily affect the conductive properties of the coated MXene layer and thus the electroless plating effect of the MXene layer surface. Of course, the present application does not exclude the addition of small amounts of binder to the MXene dispersion according to the actual needs.

Example 8

In the embodiment, the electroless plating copper product is subjected to electroless copper plating treatment, and then is subjected to electroless lead plating treatment, and the electroless plating copper layer is provided with an electroless plating lead layer on the surface of the electroless plating copper layer.

Comparative example 1

By adopting a method similar to that of the embodiment 2, replacing the MXene dispersion liquid with the graphene dispersion liquid, preparing a compound with a conductive graphene layer on the surface of PET, and carrying out electroless copper plating under the same conditions, wherein the obtained product photo is shown in figure 8, the electroless plating of metal copper is difficult to realize on the surface of the graphene layer, the binding force between the metal copper and the graphene layer is poor, the plating layer is easy to peel off, and the electroless plating effect is poor.

Because the preparation method of the plastic electroless plating product involves an electroless plating process, i.e. electroless plating deposition by dipping in an aqueous electroless plating solution, the nucleation layer on the polymer matrix is required to have good hydrophilicity and active sites. Although graphene is similar to MXene materials with a two-dimensional lamellar structure, conductive graphene (e.g., mechanically exfoliated, electrochemically or chemically reduced graphene) is generally not hydrophilic; the graphene oxide with hydrophilicity lacks a metallophilic active site, and is difficult to apply to the electroless plating process.

In addition, compared with graphene, the MXene material provided by the application is further different in that: (1) The surface of the MXene material is provided with rich functional groups, especially halogen-containing functional groups (such as-F). The nucleation overpotential of metal deposition can be reduced, the metal plating layer is promoted to uniformly grow, and a compact and uniform electroless metal layer is obtained; (2) The MXene material is transition metal carbon and/or nitride, and the composition elements comprise transition metal elements, when the MXene is used as a nucleation layer, the transition metal elements can be used as active sites of chemical plating, and the chemical plating has complex hydrophilic, activating and sensitizing steps in the early stage.

In the specific embodiment of the application, MXene Ti is adopted ₃ C ₂ T _x As the MXene material is a two-dimensional material, the MXene material has similar physical and chemical characteristics, such as hydrophilicity, abundant surface functional groups, conductivity and the like. In other embodiments, other types of MXene materials, such as Ti ₂ CT _x 、V ₂ CT _x 、Mo ₂ CT _x 、Nb ₂ CT _x 、Ta ₂ CT _x 、Ta ₃ C ₂ T _x 、Ta ₄ C ₃ T _x 、Ti ₄ C ₃ T _x Etc. It is reasonably expected that the same production of MXene Ti is possible ₃ C ₂ T _x The same technical effect. The application of the different MXene materials in the plastic electroless plating process belongs to the technical conception of the application.

The electroless plating method of the present application is not limited in the kind of substrate material, because the metal plating layer is deposited and grown on the MXene layer, i.e., the electroless plating method of the present application is general and can be performed on other non-polymer substrates, such as metal, ceramic, glass materials, etc. The application also provides an electroless plating product, namely a composite material with an electroless plating metal layer, which comprises a matrix, an MXene layer on the surface of the matrix, and an electroless plating metal layer arranged on the surface of the MXene layer. The substrate comprises: including metals, ceramics, glass, polymers.

Example 9

The embodiment provides an electroless copper plating composite material with glass fiber fabric (GF) as a matrix, and the preparation method comprises the following steps:

(1) Preparing Ti with mass concentration of 1mg/ml ₃ C ₂ T _x An aqueous dispersion to which 0.5wt.% of binder CMC was added;

(2) Impregnating glass fiber braid with Ti ₃ C ₂ T _x Taking out the water-based dispersion liquid, drying, soaking and drying again, and repeating for several times to form an MXene layer on the surface layer of the glass fiber; in this example, the impregnation was three times, the drying was performed in a vacuum oven, and vacuum drying was performed at 50℃for 4 hours to obtain a GF/MXene complex;

(3) The dried GF/MXene composite was placed in an electroless plating apparatus for electroless copper plating, and the specific electroless copper plating process was the same as in example 2 to obtain a GF/MXene/Cu composite material.

Example 10

The glass fiber braid of example 9 was replaced with a ceramic material, in one example an alumina ceramic, and a similar process was used to obtain a ceramic composite with an electroless copper plating on the surface.

Example 11

The glass fiber braid of example 9 was replaced with a metallic material, in one embodiment a metallic nickel foil, and a similar approach was used to obtain a metallic nickel/MXene/copper structured composite metallic foil material.

The foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description. It is not intended to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the application and its practical application to thereby enable one skilled in the art to make and utilize the application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.

Claims

1. An electroless plating product, characterized in that the electroless plating product comprises: an MXene layer; and a electroless metal layer disposed on at least one side of the surface of the MXene layer;

or, the electroless plating product includes: a base; an MXene layer arranged on the surface or part of the surface of the substrate; and a electroless metal layer disposed on the surface of the MXene layer;

wherein the MXene layer comprises an MXene material.

2. The electroless plating product of claim 1 wherein said MXene material has a chemical formula of 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; n is more than or equal to 1 and less than or equal to 4, x is more than or equal to 0 and less than or equal to 2; preferably, the M is selected from one or more of Ti, nb, ta, V, mo, zr.

3. The electroless plating product of claim 1 wherein the mass content of MXene material in the MXene layer is between 30% and 100%; preferably 50% to 100%, more preferably 90% to 100%.

4. The electroless plating product of claim 1 wherein said substrate is a non-conductive material; preferably, the non-conductive material is selected from a polymer, ceramic or glass; more preferably, 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 terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polystyrene, polyamide and derivatives of the above polymers;

and/or the MXene material is selected from Ti ₃ C ₂ T _x 、Ti ₂ CT _x 、V ₂ CT _x 、Nb ₂ CT _x 、Mo ₂ CT _x 、Ti ₄ C ₃ T _x 、Ta ₂ CT _x 、Ta ₄ C ₃ T _x 、TiNbCT _x ；

And/or the material of the electroless metal coating 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 and tungsten.

5. The electroless plating product according to claim 1, wherein the MXene layer has a thickness between 1nm and 50 μm; preferably between 3nm and 10 μm; more preferably between 10nm and 5 μm; preferably between 100nm and 2 μm;

and/or the electroless metal layer has a thickness of 10nm to 5 μm; preferably between 100nm and 2 μm;

and/or the substrate is sheet-like, film-like, tubular, braid, wire-like or mesh-like.

6. A method of producing an electroless plating product according to any one of claims 1 to 5, characterized in that the steps include:

and (3) a loading step: coating the surface of the matrix with an MXene material to form an MXene layer;

and (3) chemical plating: and forming a electroless metal layer on the surface of the MXene layer by electroless plating.

7. The method of producing an electroless plating product according to claim 6, wherein the method of producing further comprises a peeling step of peeling the substrate after the loading step;

or, the preparation method further comprises a stripping step after the electroless plating step, and the substrate is stripped.

8. The method of producing an electroless plating product according to claim 6 or 7, wherein in the step of coating, more specific steps include: coating and/or spraying MXene dispersion liquid on the substrate, and drying to obtain the MXene layer;

or immersing, pulling and/or immersing the substrate from the MXene dispersion liquid, and forming the MXene layer on the surface of the substrate after drying;

or, 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.

9. The method of producing an electroless plating product according to claim 8, wherein the solvent of the MXene dispersion is one or more selected from the group consisting of water and alcohols; preferably, the alcohol is selected from one or more of ethanol, propanol, isopropanol and butanol;

and/or the concentration of MXene in the MXene dispersion is between 0.01mg/ml to 80mg/ml.

10. The method of producing an electroless plating product according to claim 6, wherein the MXene dispersion contains a binder; preferably, the binder is selected from aqueous binders; more preferably, the aqueous binder is selected from one or more of LA133 aqueous binder, methylcellulose, polytetrafluoroethylene, polyvinyl alcohol, styrene-butadiene rubber, aqueous polyurethane;

or, the MXene dispersion liquid consists of an MXene material and a solvent.

11. Use of an electroless plated product according to any one of claims 1 to 6 or obtained by a method of preparation according to any one of claims 7 to 10 in automobiles, household appliances, energy storage devices.

12. A current collector comprising the electroless plating product of any one of claims 1 to 6; or, the preparation method of the current collector includes the preparation method according to any one of claims 7 to 10.

13. A battery comprising the current collector of claim 12.

14. An application of an MXene material in chemical plating of a substrate surface.