Flexible, transparent, corrosion-resistant silver nanowire-based electromagnetic shielding film and preparation method thereof

Abstract

The present invention discloses a flexible, transparent, corrosion-resistant silver nanowire-based electromagnetic shielding film and a preparation method thereof, wherein the preparation steps are as follows: coating a silver nanowire dispersion on a flexible substrate, coating a conductive network modifier after drying, and protecting the silver nanowire conductive network by nickel plating after drying, thereby preparing a flexible, transparent silver nanowire-based electromagnetic shielding film. The method of the present invention can effectively reduce the contact resistance of the silver nanowire conductive network and improve the corrosion resistance of the electromagnetic shielding film. The product of the present invention has excellent corrosion resistance and electromagnetic shielding capabilities, effectively improves the service life of the electromagnetic shielding material, and is expected to be applied in the outer layer electromagnetic shielding protection of electronic equipment and other directions.

Description

Technical Field

[0001] The invention belongs to the technical field of flexible transparent electromagnetic shielding devices, and in particular relates to a flexible, transparent, corrosion-resistant silver nanowire-based electromagnetic shielding film and a preparation method thereof. Background Art

[0002] Electromagnetic shielding materials are protective materials that can prevent the propagation and diffusion of electromagnetic waves, limit the energy of electromagnetic radiation to a certain range, and thus reduce its harm. They are an important means of achieving electromagnetic radiation protection. The principle of electromagnetic shielding is to use shielding materials to reflect and attenuate electromagnetic waves to prevent them from entering specific areas. With the increasing requirements for electromagnetic compatibility of various electronic equipment and precision instruments, as well as the increasingly urgent demand for electromagnetic protection in optoelectronic detection, human-computer interaction and other systems in the military, aerospace and other fields, higher performance requirements are placed on electromagnetic shielding materials.

[0003] For example, transparent electromagnetic shielding materials are an important method for achieving electromagnetic protection for optical windows of optoelectronic, display and other equipment. Given that light and microwaves are both electromagnetic waves, the essence of transparent electromagnetic shielding is to achieve the passband of the optical band and the stopband of the microwave frequency band. Therefore, there is a lot of research on electromagnetic shielding materials with good visible light transmittance and excellent electromagnetic shielding performance. For example, Wu Chaoxin's research group at Xi'an Jiaotong University (ACS Appl. Mater. Interfaces 2020, 12, 2826-2834) loaded silver nanowires and ferrosoferric oxide nanoparticles on ethylene terephthalate films, and achieved a high transmittance of 90%. It also showed a high electromagnetic shielding effectiveness of 24.9dB at 8.2GHz. Ji Guangbin's research group at Nanjing University of Aeronautics and Astronautics (J.Colloid Interf.Sci.2022;607:89-99) combined biodegradable gelatin with silver nanowires, achieving an electromagnetic shielding performance of up to 37.74dB in the X-band while achieving a light transmittance of 72%, and also achieved good mechanical, durability, antioxidant and antifreeze properties. Currently reported electromagnetic shielding films with silver nanowires as the main electromagnetic shielding network mostly rely on polymer coating to improve their corrosion resistance during use, but this undoubtedly increases the thickness of the film; without adding an additional polymer layer for protection, the silver nanowire network is easily destroyed and ineffective under the action of air, water and sulfur-containing substances;

[0004] Current technology generally uses the following methods to improve the corrosion resistance of silver nanowires:

[0005] (1) Composite graphene, graphene oxide and other materials can be used to cover silver nanowires to achieve anti-corrosion effects. In fact, the cost of adding materials is high, and the corrosion resistance of the coating is only acceptable in a gas environment. Unless these sheet materials are coated very thickly to completely cover the nanowires, they will cause a serious loss of transmittance. If only a thin layer is coated, the silver nanowires cannot be completely covered and protected. Once immersed in a corrosive solution, the exposed points will be severely corroded and the network will basically fail.

[0006] (2) By coating the outer layer with a polymer layer such as various resins, it can achieve the effect of isolating from external corrosion, but the thickness of the coated film has been significantly increased, and the advantage of being "thin" has been lost.

[0007] Therefore, developing a composite film that does not significantly increase the film thickness but can effectively improve the corrosion resistance of silver nanowires will solve the above problems well. Summary of the invention

[0008] The technical problem to be solved by the present invention is to provide a flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film to solve the problem of the silver nanowire network being easily oxidized when exposed.

[0009] In order to solve the above technical problems, the present invention provides a method for preparing a flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film, comprising the following steps:

[0010] 1) Preparation of silver nanowire conductive network:

[0011] Using a silver nanowire dispersion as ink I, coating 1 to 4 layers of the silver nanowire dispersion on a substrate, drying after each layer is coated, thereby removing the solvent in the silver nanowire dispersion to obtain a silver nanowire conductive network on the substrate;

[0012] Description: The silver nanowire conductive network has gaps. The network connected by nanoscale metal wires can not only conduct electricity, but also provide a larger area for visible light to pass through, so its transmittance performance is good;

[0013] 2) Using the conductive network modifier solution as ink II, coating 2 to 4 layers of the conductive network modifier solution on the silver nanowire conductive network obtained in step 1), drying after each layer is coated, thereby removing the solvent in the network modifier solution to obtain a AgNW / network modifier composite transparent conductive film;

[0014] Explanation: Since the conductive network, i.e. the silver nanowires, are not tightly connected, there will be gaps and loose overlaps, so the modifier will penetrate into the gaps to connect the silver nanowires, and also cover the conductive network to improve the uniform distribution of the conductivity of the entire network (the resistance distribution in different places was uneven before the improvement);

[0015] 3) using the AgNW / network modifier composite transparent conductive film obtained in step 2) as a working electrode and a nickel sheet as a counter electrode, immersing the two electrodes in parallel and opposite to each other in a nickel plating solution for electrodeposition; thereby forming a nickel plating layer on the outer surface of the AgNW / network modifier composite transparent conductive film;

[0016] Then, the AgNW / network modifier composite transparent conductive film with nickel plating is rinsed and dried to obtain the AgNW / network modifier@Ni transparent electromagnetic shielding film material.

[0017] Description: The AgNW / network modifier@Ni transparent electromagnetic shielding film material includes a substrate.

[0018] During the deposition process, some of the modifier is stripped off, so part of the coating is in direct contact with the nanowires, while part of the coating has the modifier underneath.

[0019] As an improvement to the preparation method of the flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film of the present invention:

[0020] The conductive network modifier is any one of the following: reduced graphene oxide, graphene oxide, MXene, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polyaniline, polypyrrole;

[0021] In the conductive network modifier solution, the concentration of the conductive network modifier is 0.5-1.5 mg / ml.

[0022] As a further improvement to the method for preparing the flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film of the present invention: the diameter of the silver nanowire is 20 to 100 nm.

[0023] As a further improvement of the method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film of the present invention:

[0024] The substrate in step 1) is a transparent flexible substrate;

[0025] The transparent flexible substrate is any one of the following: polyethylene terephthalate, polycarbonate, colorless transparent polyimide, polymethyl methacrylate, polydimethylsiloxane, and polyurethane.

[0026] As a further improvement of the method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film of the present invention:

[0027] In the step 3), the thickness of the formed nickel plating layer is 5 to 30 nm.

[0028] As a further improvement of the method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film of the present invention:

[0029] The drying in step 1) is as follows: drying at 50-120° C. for 10-30 min;

[0030] The drying in step 2) is as follows: drying at 50-60° C. for 10-30 min;

[0031] In the step 3), the mixture is rinsed with deionized water and anhydrous ethanol in sequence, and then dried at 50-60° C. for 10-30 minutes.

[0032] As a further improvement of the method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film of the present invention:

[0033] The coating method of step 1) is any of the following: spray coating, scraper coating, spin coating, slit coating, screen printing;

[0034] The coating method of step 2) is any of the following: spray coating, blade coating, spin coating, and slit coating.

[0035] As a further improvement of the method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film of the present invention:

[0036] In the step 3):

[0037] The formula of nickel plating solution is NiSO4: 1mol / L, NiCl2: 1mol / L, HBO3: 0.5mol / L and Na3BO3: 0.5mol / L, with deionized water as solvent;

[0038] The specific process parameters of electrodeposition are current of 1 to 5 mA and deposition time of 2 to 3 min;

[0039] The side of the working electrode coated with the conductive network faced parallel to the counter electrode, with a distance of 3 cm.

[0040] The present invention also provides a flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film prepared by any of the above methods.

[0041] The flexible, transparent, corrosion-resistant nickel-silver-plated nanowire-based electromagnetic shielding film obtained by the present invention:

[0042] Transparent conductive network: composed of silver nanowires with a diameter of 20 to 100 nm, so that the transparent conductive network square resistance can be selected in the range of 50 to 80Ω / sq, and the transmittance is greater than 90%;

[0043] Conductive network modifier: Coating the conductive network modifier on the silver nanowire-based transparent conductive network to improve the network uniformity and enhance the network conductivity;

[0044] Nickel plating: After the silver nanowires and network modifiers are coated, an amorphous nickel layer is deposited outside the conductive network by electrodeposition. That is, after the silver nanowires and network modifiers are coated, a protective layer is formed by electrodeposition thereon, and the material of the protective layer is nickel.

[0045] Note: Transmittance refers to the transmittance in air at normal temperature and pressure (at 550nm).

[0046] The present invention deposits a nanometer-level protective layer on the surface of the nanowire by electrochemical deposition, which can effectively isolate corrosive substances and has a very small increase in the thickness of the film, thereby maintaining the low thickness property of the film.

[0047] In the present invention, a nano-scale coating is prepared by controllable electrochemical deposition, which greatly improves the corrosion resistance of silver nanowires. At the same time, the increase in the thickness of the film at the nano-scale does not significantly increase the macroscopic thickness of the film.

[0048] The present invention has the following technical advantages:

[0049] 1) The AgNW / network modifier@Ni corrosion-resistant electromagnetic shielding film of the present invention provides more conductive paths for the connection of silver nanowires through the coating of the network modifier, thereby improving the conductivity and in-plane square resistance uniformity of the silver nanowire network.

[0050] 2) The nickel plating layer of the present invention can form a uniform coating layer to protect the silver nanowire network, reduce the oxidation corrosion rate of the silver nanowires in the air, and enhance the stability of the silver nanowire conductive network.

[0051] 3) The preparation methods of the present invention are all based on solution methods, which are simple in preparation, low in cost, fast in preparation speed and high in efficiency.

[0052] 4) The present invention is simple to prepare, has a thin coating and is corrosion-resistant.

[0053] In summary, the present invention discloses a flexible, transparent, corrosion-resistant silver nanowire-based electromagnetic shielding film and a preparation method thereof, wherein the preparation steps are: coating a silver nanowire dispersion on a flexible substrate, and continuing to coat a conductive network modifier after drying, and protecting the silver nanowire conductive network by electroplating nickel after drying, thereby preparing a flexible, transparent silver nanowire-based electromagnetic shielding film. The method of the present invention can effectively reduce the contact resistance of the silver nanowire conductive network and improve the corrosion resistance of the electromagnetic shielding film. The product of the present invention has excellent corrosion resistance and electromagnetic shielding capabilities, effectively improves the service life of the electromagnetic shielding material, and is expected to be applied in the outer layer electromagnetic shielding protection of electronic equipment and other directions. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] The specific implementation modes of the present invention are further described in detail below with reference to the accompanying drawings.

[0055] Figure 1 This is a flow chart for the preparation of Example 1.

[0056] Figure 2 This is the electron microscope morphology image of Example 3.

[0057] Figure 3 This is the electromagnetic shielding effectiveness diagram of Example 3;

[0058] Figure 4 The resistance changes and microscopic images of AgNW network, AgNW / PEDOT and AgNW / PEDOT:PSS@Ni in Example 3 after corrosion;

[0059] Figure 4 In the figure, (a) represents the resistance change diagram of the three samples after corrosion in 0.5mmol / L Na2S solution for 40s; (b) represents the SEM image of AgNW film after corrosion; (c) represents the SEM image of AgNW / PEDOT:PSS film after corrosion; (d) represents the SEM image of AgNW / PEDOT:PSS@Ni film after corrosion; R s represents the resistance after corrosion, R0 represents the initial resistance, so the vertical axis represents the multiple of the increase in resistance relative to the original resistance. DETAILED DESCRIPTION

[0060] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0061] The thickness of the substrate is about 125±10 microns.

[0062] Embodiment 1: A method for preparing a flexible, transparent, corrosion-resistant silver nanowire-based electromagnetic shielding film, comprising the following steps:

[0063] 1) Preparation of silver nanowire conductive network:

[0064] A silver nanowire dispersion with a diameter of 100 nm (the concentration of the silver nanowires is 0.5 mg / ml, and ethanol is used as the solvent) is used as ink I, and 4 layers of silver nanowire layers (the thickness of each coating is about 300 μm) are coated on a colorless and transparent polyimide substrate by spraying. Each sprayed layer is immediately dried before the next spraying. The drying is performed at 120°C for 10 minutes, thereby removing the solvent in the silver nanowire dispersion to obtain a silver nanowire conductive network with a square resistance of about 50 Ω / sq and a transmittance of about 91%.

[0065] 2) Dissolve poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) as a network modifier in deionized water to obtain a PEDOT:PSS solution with a concentration of 0.5 mg / ml; use this as ink II;

[0066] Using ink II, four layers of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) solution are coated on the silver nanowire conductive network obtained in step 1) by spraying (the thickness of each coating is about 300 μm), and each coated layer is dried immediately before the next coating, and the drying is carried out at 50° C. for 10 minutes, so as to remove the excess solvent in the PEDOT:PSS solution, and obtain a AgNW / PEDOT:PSS composite transparent conductive film with a square resistance of about 36 Ω / sq and uniform distribution in the square resistance plane;

[0067] Explanation: Since the conductive network, i.e. the silver nanowires, are not tightly connected, there will be gaps and loose overlaps, so the modifier PEDOT:PSS will penetrate into the gaps to connect the silver nanowires, and also cover the conductive network to improve the uniform distribution of the conductivity of the entire network (the resistance distribution in different places was uneven before the improvement);

[0068] 3) Using the AgNW / PEDOT:PSS composite transparent conductive film obtained in step 2) as the working electrode and the nickel sheet as the counter electrode, the two electrodes are placed parallel to each other with a distance of 3 cm, immersed in a nickel plating solution, and electroplated to obtain an AgNW / PEDOT:PSS@Ni film.

[0069] The details are as follows:

[0070] The formula of nickel plating solution is NiSO4: 1mol / L, NiCl2: 1mol / L, HBO3: 0.5mol / L and Na3BO3: 0.5mol / L, with deionized water as solvent; the specific process parameters of electrodeposition are current of 5mA and deposition time of 3min;

[0071] The thickness of the formed nickel plating layer is 10 to 30 nm;

[0072] Note: During the deposition process, some modifiers will be stripped off, so part of the coating is in direct contact with the nanowires, while some modifiers exist under the coating. Therefore, the resulting AgNW / PEDOT:PSS@Ni film is an AgNW / PEDOT:PSS@Ni film with a Ni layer covering the outer layer of AgNW and PEDOT:PSS filling the gaps between the AgNW wires under the Ni layer.

[0073] The changes of electromagnetic shielding effectiveness before and after corrosion were 20.01dB and 16.62dB.

[0074] Then, it was rinsed with deionized water and anhydrous ethanol and dried at 50° C. for 10 min to obtain a AgNW / network modifier@Ni transparent electromagnetic shielding thin film material with a transmittance of 75% (550 nm).

[0075] Example 2: A method for preparing a flexible, transparent, corrosion-resistant nickel-silver-plated nanowire-based electromagnetic shielding film, comprising the following steps:

[0076] 1) Preparation of silver nanowire conductive network:

[0077] A silver nanowire dispersion with a diameter of 20 nm (the concentration of the silver nanowires is 0.5 mg / ml) is used as ink I, and two layers of silver nanowire layers (the thickness of each coating is about 300 μm) are coated on a polyethylene terephthalate substrate by spin coating. Each layer is dried immediately after spin coating. The drying is performed at 50°C for 30 minutes to obtain a silver nanowire conductive network with a square resistance of about 80 Ω / sq and a transmittance of about 95%.

[0078] 2) Dissolve poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) as a network modifier in deionized water to obtain a PEDOT:PSS solution with a concentration of 1.5 mg / ml; use this as ink II;

[0079] Ink II is sprayed on the silver nanowire conductive network obtained in step 1) to coat two layers of poly (3, 4-ethylenedioxythiophene) - polystyrene sulfonic acid (PEDOT:PSS) solution (the thickness of each coating is about 300 μm), and each layer is dried immediately at 60°C for 30 minutes to obtain a AgNW / PEDOT:PSS composite transparent conductive film with a square resistance of about 37Ω / sq ​​and uniform distribution in the square resistance plane.

[0080] 3) The AgNW / PEDOT:PSS composite transparent conductive film obtained in step 2) is used as a working electrode, and the rest is basically the same as step 3) of embodiment 1; the deposition time is slightly adjusted so that the thickness of the formed nickel coating is 5 to 15 nm;

[0081] The changes of electromagnetic shielding effectiveness before and after corrosion were 19.55dB and 16.51dB.

[0082] The final AgNW / network modifier@Ni transparent electromagnetic shielding film material has a transmittance of 70% (550nm).

[0083] Example 3: A method for preparing a flexible, transparent, corrosion-resistant nickel-silver-plated nanowire-based electromagnetic shielding film, comprising the following steps:

[0084] 1) Preparation of silver nanowire conductive network:

[0085] A silver nanowire dispersion with a diameter of 45 nm (the concentration of the silver nanowires is 0.5 mg / ml) is used as ink I, and a layer of silver nanowires (the coating thickness is about 300 μm) is coated on a polyethylene terephthalate substrate by spraying, and then dried at 50°C for 10 min to remove the solvent, thereby obtaining a silver nanowire conductive network with a square resistance of about 80 Ω / sq and a transmittance of about 93%.

[0086] 2) Dissolve poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) as a network modifier in deionized water to obtain a PEDOT:PSS solution with a concentration of 0.5 mg / ml; use this as ink II;

[0087] Ink II is sprayed on the silver nanowire conductive network obtained in step 1) to coat 4 layers of poly (3, 4 ethylenedioxythiophene) - polystyrene sulfonic acid (PEDOT:PSS) solution (the thickness of each coating is about 300 μm), and each layer is dried immediately at 50°C for 10 minutes to obtain a AgNW / PEDOT:PSS composite transparent conductive film with a square resistance of about 36Ω / sq and uniform distribution in the square resistance plane.

[0088] 3) The AgNW / PEDOT:PSS composite transparent conductive film obtained in step 2) was used as a working electrode, and the deposition time was slightly adjusted (the deposition time was 2 min), and the rest was the same as step 3) of Example 1; the thickness of the formed nickel coating was 9.7 to 16 nm;

[0089] The changes of electromagnetic shielding effectiveness before and after corrosion were 19.64dB and 16.76dB.

[0090] Finally, the AgNW / network modifier@Ni transparent electromagnetic shielding film material was obtained with a transmittance of 78.1% (550nm).

[0091] The above-mentioned embodiments 1 to 3 all have good corrosion resistance, and embodiment 3 has the highest electromagnetic shielding performance retention ability before and after corrosion, that is, the best performance.

[0092] Experiment: The AgNW / network modifier@Ni transparent electromagnetic shielding film materials obtained in the above-mentioned Examples 1 to 3 were tested according to the waveguide method. The testing process specifically includes placing the sample film according to the electromagnetic shielding test fixture, covering the conductive layer on the test window, generating X-band electromagnetic waves at one end of the window, and detecting the transmission and reflection results of the X-band electromagnetic waves. The test results show that the sample can achieve an average electromagnetic shielding performance of more than 19dB before the corrosion test, and can still maintain an average electromagnetic shielding performance of more than 16.5dB after corrosion.

[0093] The corrosion is to immerse the film in a Na2S solution (0.5 mmol·L-1 ).

[0094] The experimental results of Example 3 are as follows Figure 4 Figure a shows the resistance changes of AgNW / PEODT:PSS and AgNW / PEDOT:PSS@Ni films after being corroded in sodium sulfide solution for 40s. The resistance of the first two films increases several dozen times rapidly, while the resistance of the nickel-plated film increases only slightly. s represents the resistance after corrosion, R0 represents the initial resistance, so the vertical axis represents the multiple of the increase in resistance relative to the original resistance.

[0095] Figures b, c, and d are scanning electron microscope images of the three samples after corrosion: silver nanowire conductive network, AgNW / PEDOT:PSS, and AgNW / PEDOT:PSS@Ni. It can be seen that the first two were severely corroded, while although sulfides were produced in the nickel-plated sample, the network remained intact, indicating that its corrosion resistance was greatly improved.

[0096] Comparative Example 1: The "network modifier" in step 2) of Example 1 was changed from "0.5 mg / ml PEDOT:PSS solution" to the following:

[0097] A reduced graphene oxide solution with a concentration of 0.5 mg / ml (with deionized water as solvent);

[0098] Graphene oxide solution with a concentration of 0.5 mg / ml (with deionized water as solvent);

[0099] MXene solution with a concentration of 0.5 mg / ml (deionized water as solvent);

[0100] A polyaniline solution with a concentration of 0.5 mg / ml (using deionized water as solvent);

[0101] Polypyrrole solution with a concentration of 0.5 mg / ml (deionized water as solvent);

[0102] The rest is the same as Example 1.

[0103] The performance data of the final product are as follows: the electromagnetic shielding effectiveness before and after corrosion are 17.9 and 14.2dB; 18.3 and 15.7dB; 19.2 and 15.2dB; 18.8 and 13.2dB; 19.1 and 15.3dB respectively.

[0104] Comparative Example 2: Step 2) is omitted, that is, the silver nanowire conductive network obtained in Step 1) is directly used to carry out the subsequent Step 3). The rest is the same as in Example 1.

[0105] The final product: the electromagnetic shielding effectiveness before and after corrosion was 12.5 and 7.6dB respectively.

[0106] Comparative Example 3: The working current in step 3) of Example 3 is changed to 1 mA, and the rest is the same as Example 3.

[0107] The final product: the electromagnetic shielding effectiveness before and after corrosion was 15.7 and 7.3dB respectively.

[0108] Comparative Example 4: Change the formula of the nickel plating solution in step 3) of Example 3 to NiSO4: 0.5 mol / L, NiCl2: 0.5 mol / L, HBO3: 0.5 mol / L and Na3BO3: 0.5 mol / L; the rest is the same as Example 3.

[0109] The final product: the electromagnetic shielding effectiveness before and after corrosion was 15.6 and 7.8dB respectively.

[0110] Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there are many variations. All variations that can be directly derived or associated with the content disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. A method for preparing a flexible, transparent, corrosion-resistant nickel-silver-plated nanowire-based electromagnetic shielding film, characterized in that The following steps are involved: 1) Preparation of silver nanowire conductive network: Using a silver nanowire dispersion as ink I, coating 1 to 4 layers of the silver nanowire dispersion on a substrate, drying after each layer is coated, thereby removing the solvent in the silver nanowire dispersion to obtain a silver nanowire conductive network on the substrate; 2) Using the conductive network modifier solution as ink II, coating 2 to 4 layers of the conductive network modifier solution on the silver nanowire conductive network obtained in step 1), drying after each layer is coated, thereby removing the solvent in the network modifier solution to obtain a AgNW / network modifier composite transparent conductive film; 3) using the AgNW / network modifier composite transparent conductive film obtained in step 2) as a working electrode and a nickel sheet as a counter electrode, immersing the two electrodes in parallel and opposite to each other in a nickel plating solution for electrodeposition; thereby forming a nickel plating layer on the outer surface of the AgNW / network modifier composite transparent conductive film; Then, the AgNW / network modifier composite transparent conductive film with nickel plating is rinsed and dried to obtain the AgNW / network modifier@Ni transparent electromagnetic shielding film material.

2. The method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film according to claim 1, characterized in that: The conductive network modifier is any one of the following: reduced graphene oxide, graphene oxide, MXene, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polyaniline, polypyrrole; In the conductive network modifier solution, the concentration of the conductive network modifier is 0.5-1.5 mg / ml.

3. The method for preparing the flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film according to claim 2, characterized in that: The diameter of silver nanowires is 20 to 100 nm.

4. The method for preparing the flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film according to claim 3, characterized in that: The substrate in step 1) is a transparent flexible substrate; The transparent flexible substrate is any one of the following: polyethylene terephthalate, polycarbonate, colorless transparent polyimide, polymethyl methacrylate, polydimethylsiloxane, and polyurethane.

5. The method for preparing the flexible, transparent, corrosion-resistant, nickel-plated silver nanowire-based electromagnetic shielding film according to any one of claims 1 to 4, characterized in that: In the step 3), the thickness of the formed nickel plating layer is 5 to 30 nm.

6. The method for preparing the flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film according to claim 5, characterized in that: The drying in step 1) is as follows: drying at 50-120° C. for 10-30 min; The drying in step 2) is as follows: drying at 50-60° C. for 10-30 min; In the step 3), the mixture is rinsed with deionized water and anhydrous ethanol in sequence, and then dried at 50-60° C. for 10-30 minutes.

7. The method for preparing the flexible, transparent, corrosion-resistant nickel-silver-plated nanowire-based electromagnetic shielding film according to claim 6, characterized in that: The coating method of step 1) is any of the following: spray coating, scraper coating, spin coating, slit coating, screen printing; The coating method of step 2) is any of the following: spray coating, blade coating, spin coating, and slit coating.

8. The method for preparing the flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film according to claim 7, characterized in that: In the step 3): The formula of nickel plating solution is NiSO4: 1mol / L, NiCl2: 1mol / L, HBO3: 0.5mol / L and Na3BO3: 0.5mol / L; electrodeposition: current is 1-5mA, deposition time is 2-3min; The side of the working electrode coated with the conductive network faced the counter electrode in parallel, with a distance of 3 cm.

9. A flexible, transparent, corrosion-resistant nickel-plated silver nanowire-based electromagnetic shielding film prepared by the method of any one of claims 1 to 8.

Images