Preparation method and application of flexible conductive film with polyaryletherketone protective layer

Abstract

The application relates to a preparation method and application of a flexible conductive film with a polyaryletherketone protective layer. The application aims to solve the technical problems of poor weather resistance, mechanical performance to be improved, additional pretreatment before depositing a conductive layer and poor bonding force between a substrate and the conductive layer of an existing flexible substrate material. The application comprises the following steps: 1, preparing a polyaryletheramine film; 2, preparing a polyaryletherketone protective layer; 3, preparing a conductive layer; and 4, preparing an electrochromic / supercapacitor device. The polyaryletherketone protective layer used in the application has excellent mechanical performance and weather resistance, improves the mechanical performance of the whole substrate while protecting the flexible substrate material; the polyaryletherketone protective layer is synchronously generated in situ to form a polyaniline activation layer when the polyaryletherketone protective layer is prepared, nucleation sites are provided for the conductive layer deposition and the bonding force between the conductive layer and the substrate is enhanced; the polyaryletherketone protective layer used in the application has no selectivity to the flexible substrate material and is universally applicable to various flexible substrate materials.

Description

Technical Field

[0001] This invention belongs to the field of electrochromic / supercapacitor and conductive film technology, specifically relating to a flexible conductive film with a polyaryletherketone protective layer, its preparation method and application. Background Technology

[0002] With the development of flexible optoelectronic devices, various electronic devices in production and daily life are gradually moving towards modularization, thinning, and even miniaturization. In recent years, the ever-increasing demand for flexible devices has undoubtedly placed higher demands on the development of materials. As is well known, optoelectronic devices have always played an important role in people's production and daily lives, and flexible conductive films are an indispensable component of these devices.

[0003] Currently, the basic components of flexible conductive films consist of a flexible material as a substrate and a conductive layer deposited on its surface. Due to the process requirements of different deposition methods and the inherent limitations of the flexible materials themselves, the production conditions for achieving both mechanical properties and weather resistance in flexible conductive films are relatively demanding. Furthermore, given the intrinsic characteristics of flexible substrates being mostly insulating and having stable surface properties, the bonding force between the substrate and the conductive layer must be considered during the material selection process for preparing flexible conductive films, which further limits the universality of flexible conductive film preparation methods.

[0004] Therefore, finding a method to improve the mechanical properties and weather resistance of flexible substrate materials while providing active sites for subsequent conductive layer deposition, so that the preparation of flexible conductive films is no longer limited by specific material combinations and process conditions, thereby fundamentally reducing production and processing costs, is of great research value for the rapid development and performance improvement of optoelectronic devices such as electrochromic / supercapacitors. Summary of the Invention

[0005] The purpose of this invention is to solve the technical problems of existing flexible substrate materials having poor weather resistance in extreme environments, needing to improve mechanical properties, requiring additional pretreatment before depositing the conductive layer, and having poor adhesion between the substrate and the conductive layer, and to provide a method for preparing a flexible conductive film with a polyaryletherketone protective layer.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A method for preparing a flexible conductive film with a polyaryletherketone protective layer, characterized by comprising the following steps:

[0008] A. Preparation of polyaryletheramine films:

[0009] A1. Prepare a polyaryletheramine solution with a mass fraction of 0.1% to 40% using a good polar polymer solvent;

[0010] A2. Using the above-mentioned polyaryletheramine solution as the casting solution, a film is formed on a flexible substrate;

[0011] A3. The film described in step A2 is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 60–180°C, and the annealing time is 0.5–24 h.

[0012] B. Preparation of the polyaryletherketone protective layer:

[0013] B1. Prepare an acid solution of the oxidant by adding the oxidant to the acid solution and mixing thoroughly at room temperature. The concentration of the oxidant is 0.01M to 2.0M, and the concentration of the acid is 0.1M to 10.0M. The mixing method is one or any combination of stirring, shaking, and ultrasonication.

[0014] B2. Add the polyarylene ether amine membrane obtained in step A to the acidic solution of the oxidant mentioned above, and react at a constant temperature. The reaction temperature is 10-100℃, and the reaction time is 0.5-48h; the ratio of the amount of polyarylene ether amine membrane to the acidic solution of the oxidant is 0.1g:5-300mL.

[0015] B3. Clean the polyaryletherketone film obtained in step B2. The solvent is ethanol and water, and the cleaning is performed 1 to 10 times. The cleaning method is one or any combination of immersion, ultrasonication, vibration, and reflux.

[0016] B4. Remove the solvent from the cleaned polyaryletherketone film to obtain a polyaryletherketone protective layer. The solvent removal method is either freeze-drying or drying, for 0.5 to 12 hours. The freeze-drying temperature is -80 to -20°C, and the drying temperature is 30 to 100°C.

[0017] C. Preparation of conductive layer:

[0018] A flexible conductive film with a polyaryletherketone protective layer can be obtained by depositing a metal conductive layer on a flexible substrate with a polyaryletherketone protective layer and performing simple post-processing.

[0019] Furthermore, the polyaryletheramine described in step A has the structure shown in formula (I):

[0020] Equation (I)

[0021] Where A, B, and C are any of the following structures, and n is a positive integer representing the degree of aggregation;

[0022]

[0023]

[0024]

[0025] Furthermore, the film-forming method described in step A2 is one or any combination of spin coating, spray coating, scraping coating, drip coating, casting, impregnation, casting, slot extrusion coating, screen printing, inkjet printing, spray pyrolysis, and roll-to-roll coating.

[0026] Further, the flexible substrate mentioned in step A2 is one of the following: film, fiber or fabric of PET, PEN, PI, PC, PVDF, PDMS, TPU, PVA, PES, PPSU and their derivatives.

[0027] Preferably, the good solvent for the polar polymer in step A1 is one or any combination of common polar solvents such as NMP, DMAc, DMF, THF, Me-THF, DCM, TCM, EA, CB, DCB, TCB, MB, DMB, TMB, TMB, and AC.

[0028] Furthermore, the thickness of the polyaryletherketone protective layer in step B is 5 μm to 50 μm.

[0029] Preferably, the oxidant in step B1 is one or any combination of hydrogen peroxide, peroxidase, ammonium persulfate, potassium dichromate, ferric chloride, aluminum chloride, copper chloride, tellurium, potassium permanganate, and silver nitrate.

[0030] Preferably, the acid mentioned in step B1 is hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, or phosphoric acid.

[0031] One or any combination of hydrobromic acid, fluoroboric acid, phytic acid, formic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, sulfosalicylic acid, trifluoroacetic acid, trifluorobenzenesulfonic acid, dodecylbenzenesulfonic acid, dioctyl succinate sulfonic acid, and camphor sulfonic acid.

[0032] Furthermore, the deposited metal in step C is one or any combination of gold, silver, copper, nickel, palladium, tin, and cobalt.

[0033] Furthermore, the metal deposition method described in step C is one or any combination of electroplating, electroless plating, spraying, and physical vapor deposition.

[0034] A flexible conductive film with a polyaryletherketone protective layer is characterized in that it is prepared by the method described in the above technical solution.

[0035] Furthermore, the application of a flexible conductive film with a polyaryletherketone protective layer in the field of electrochromic / supercapacitors involves supplementing the flexible conductive film with a polyaryletherketone protective layer with active materials and electrolytes, and then assembling it to obtain an electrochromic / supercapacitor device based on the flexible conductive film with a polyaryletherketone protective layer.

[0036] Furthermore, the electrochromic / supercapacitor device has a sandwich structure or a parallel structure.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. The polyaryletherketone protective layer obtained by the present invention has excellent mechanical properties and weather resistance, and improves the overall mechanical properties of the substrate while protecting the flexible substrate material;

[0039] 2. In this invention, a polyaniline activation layer is simultaneously generated in situ during the preparation of the polyaryletherketone protective layer, providing nucleation sites for subsequent conductive layer deposition and enhancing its adhesion to the substrate;

[0040] 3. The polyaryletherketone protective layer used in this invention has virtually no selectivity for flexible substrate materials and is generally applicable to various flexible substrate materials;

[0041] 4. The method of the present invention is compatible with various film-forming processes and is low in cost, and can be applied to large-scale industrial production. Attached Figure Description

[0042] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; obviously, the drawings described below are some embodiments of the present invention, and those skilled in the art can obtain other drawings based on these drawings without creative effort.

[0043] Figure 1 This is a schematic flowchart of a method for preparing a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention.

[0044] Figure 2 This is a structural illustration of a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention.

[0045] intention;

[0046] Figure 3 This is a physical image of a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention;

[0047] Figure 4 This is an SEM image of a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention, wherein (1) is a planar SEM of a flexible conductive film with a polyaryletherketone protective layer, and (2) is a cross-sectional SEM of a flexible substrate with a polyaryletherketone protective layer.

[0048] Figure 5This is a sheet resistance data diagram of a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention, wherein (1) is the parallel test data of the sheet resistance of a flexible conductive film with a polyaryletherketone protective layer, and (2) is the long-term stability test data of the sheet resistance of a flexible conductive film with a polyaryletherketone protective layer.

[0049] Figure 6 This is a mechanical property data sheet of a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention;

[0050] Figure 7 This is a schematic diagram of a parallel structure device illustrating a method for preparing a flexible conductive film with a polyaryletherketone protective layer according to an embodiment of the present invention and its application in an electrochromic / supercapacitor.

[0051] Figure 8 This invention relates to a method for preparing a flexible conductive film with a polyaryletherketone protective layer and its application in electrochromic / supercapacitors, as well as an electrochromic device performance data sheet.

[0052] Figure 9 This invention relates to a method for preparing a flexible conductive film with a polyaryletherketone protective layer and its application in electrochromic / supercapacitors, as well as a supercapacitor performance data sheet.

[0053] Figure 10 This is a schematic diagram of a sandwich structure device according to an embodiment of the present invention, which describes a method for preparing a flexible conductive film with a polyaryletherketone protective layer and its application in an electrochromic / supercapacitor. Detailed Implementation

[0054] To make the objectives, technical effects, and technical solutions of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention. Based on the embodiments disclosed in the present invention, other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0055] Specific Implementation Method 1: This implementation method describes a preparation method and application of a flexible conductive film with a polyaryletherketone protective layer, which is completed according to the following steps:

[0056] I. Preparation of polyaryletheramine films:

[0057] ① Prepare a polyaryletheramine solution with a mass fraction of 0.1% to 40% using a good polar polymer solvent;

[0058] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0059] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 60–180℃, and the annealing time is 0.5–24 h.

[0060] II. Preparation of polyaryletherketone protective layer:

[0061] ① Prepare an acid solution of the oxidant by adding the oxidant to the acid solution at a certain concentration ratio and mixing thoroughly at room temperature. The concentration of the oxidant is 0.01M to 2.0M, and the concentration of the acid is 0.1M to 10.0M. The mixing method described in step ② is one or any combination of stirring, shaking, and sonication.

[0062] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react at a constant temperature. The reaction temperature is 10–100℃, and the reaction time is 0.5–48 h;

[0063] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g: 5-300mL.

[0064] ③ The polyaryletherketone film obtained after the reaction in step ② is washed. The solvents are ethanol and water, and the washing process is repeated 1 to 10 times.

[0065] The cleaning method described in step 2③ is one or any combination of soaking, ultrasonication, vibration, and reflux.

[0066] ④ Remove the solvent from the polyaryletherketone film obtained in step 2.③ to obtain the polyaryletherketone protective layer. The solvent removal method is either freeze-drying or drying, for a time of 0.5 to 12 hours. The freeze-drying temperature is -80 to -20°C, and the drying temperature is 30 to 100°C.

[0067] III. Preparation of the conductive layer:

[0068] A flexible conductive film with a polyaryletherketone protective layer can be obtained by depositing a metal conductive layer on a flexible substrate with a polyaryletherketone protective layer and performing simple post-processing.

[0069] Furthermore, by supplementing a flexible conductive film with a polyaryletherketone protective layer with active materials and an electrolyte, an electrochromic / supercapacitor device with a flexible conductive film with a polyaryletherketone protective layer as the substrate can be obtained after assembly. The device structure is either a sandwich structure or a parallel structure.

[0070] The principle and advantages of this implementation method:

[0071] I. This embodiment utilizes the characteristic that polyaryletheramine can be converted into polyaryletherketone in one step in an acidic solution environment of oxidant, while simultaneously forming polyaniline in situ, to process the substrate of flexible conductive film, thereby achieving the purpose of simultaneously forming a protective layer and an activation layer between the flexible substrate material and the conductive layer.

[0072] II. The polyaryletherketone protective layer obtained in this embodiment has excellent mechanical properties and weather resistance, which improves the overall mechanical properties of the substrate while protecting the flexible substrate material.

[0073] Third, in this embodiment, a polyaniline activation layer is simultaneously generated in situ during the preparation of the polyaryletherketone protective layer, providing nucleation sites for subsequent conductive layer deposition and enhancing its adhesion to the substrate;

[0074] IV. The polyaryletherketone protective layer used in this embodiment has virtually no selectivity for flexible substrate materials.

[0075] It is widely applicable to various flexible substrate materials;

[0076] V. The method described in this embodiment is compatible with various film-forming processes and is low in cost, making it applicable to large-scale industrial production.

[0077] This embodiment provides a flexible conductive film with a polyaryletherketone protective layer.

[0078] Specific Implementation Method Two: This specific implementation method differs from Specific Implementation Method One in that: in step one, a polyaryletheramine solution with a mass fraction of 5-20% is prepared using a good solvent for polar polymers, the annealing temperature is 120-180℃, and the annealing time is 5-15 hours. Other steps are the same as in Specific Implementation Method One.

[0079] Specific Implementation Method Three: This specific implementation method differs from Specific Implementation Method One or Two in that the oxidant concentration in step two is 0.1M to 1.0M, and the acid concentration is 0.1M to 5.0M. The other steps are the same as in Specific Implementation Method One or Two.

[0080] Specific Implementation Method Four: This specific implementation method differs from Specific Implementation Methods One to Three in that the ratio of the amount of polyaryletheramine film to the acid solution of the oxidant is 0.1g:5-100mL. The other steps are the same as in Specific Implementation Methods One to Three.

[0081] Specific Implementation Method Five: The difference between this specific implementation method and Specific Implementation Methods One through Four is: Step...

[0082] The flexible substrate mentioned in step one① is one of the following: a film, fiber, or fabric made of PET, PEN, PI, PC, PVDF, PDMS, TPU, PVA, PES, PPSU, and their derivatives. The other steps are the same as in specific embodiments one to four.

[0083] Specific Implementation Method Six: This specific implementation method differs from Specific Implementation Methods One to Five in that: the good solvent for the polar polymer mentioned in step one ① is one or any combination of common polar solvents such as NMP, DMAc, DMF, THF, Me-THF, DCM, TCM, EA, CB, DCB, TCB, MB, DMB, TMB, and AC. The other steps are the same as in Specific Implementation Methods One to Five.

[0084] Specific Implementation Method Seven: This specific implementation method differs from Specific Implementation Methods One to Six in that the thickness of the polyaryletherketone protective layer in step two is 5 μm to 50 μm. The other steps are the same as in Specific Implementation Methods One to Six.

[0085] Specific Implementation Method Eight: This specific implementation method differs from Specific Implementation Methods One to Seven in that the oxidant mentioned in step two ① is one or any combination of hydrogen peroxide, peroxidase, ammonium persulfate, potassium dichromate, ferric chloride, aluminum chloride, copper chloride, tellurium, potassium permanganate, and silver nitrate. The other steps are the same as in Specific Implementation Methods One to Seven.

[0086] Specific Implementation Method Nine: This specific implementation method differs from Specific Implementation Methods One to Eight in that: the acid mentioned in step two① is one or any combination of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, phosphoric acid, hydrobromic acid, fluoroboric acid, phytic acid, formic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, sulfosalicylic acid, trifluoroacetic acid, trifluorobenzenesulfonic acid, dodecylbenzenesulfonic acid, dioctyl succinate sulfonic acid, and camphorsulfonic acid. The other steps are the same as in Specific Implementation Methods One to Eight.

[0087] Specific Implementation Method Ten: This specific implementation method differs from Specific Implementation Methods One to Seven in that the deposited metal in step three is one or any combination of gold, silver, copper, nickel, palladium, tin, and cobalt. The other steps are the same as in Specific Implementation Methods One to Nine.

[0088] Specific Implementation Method Eleven: This specific implementation method differs from Specific Implementation Methods One through Ten in that the metal deposition method described in step three is one of electroplating, electroless plating, spraying, or physical vapor deposition. The other steps are the same as in Specific Implementation Methods One through Ten.

[0089] Specific Implementation Method Twelve: This specific implementation method differs from Specific Implementation Methods One to Eleven in that the electrochromic / supercapacitor device structure described in step four is either a sandwich structure or a parallel structure. The other steps are the same as in Specific Implementation Methods One to Eleven.

[0090] The beneficial effects of the present invention are verified using the following embodiments:

[0091] Example 1: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0092] I. Preparation of polyaryletheramine films:

[0093] ① Prepare a 0.1% polyaryletheramine solution using a good polar polymer solvent;

[0094] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0095] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 120℃ and the annealing time is 4h.

[0096] The good solvent for the polar polymer mentioned in step 1① is NMP;

[0097] The polyaryletheramine structure described in step 1① is as follows:

[0098]

[0099] The flexible substrate mentioned in step 1② is PET;

[0100] The film-forming method described in step 1② is casting film formation.

[0101] II. Preparation of polyaryletherketone protective layer:

[0102] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.2M and an acid concentration of 1.5M;

[0103] The mixing method described in step 2① is stirring.

[0104] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 40℃, and the reaction time is 40h;

[0105] The oxidant mentioned in step 2① is ammonium persulfate;

[0106] The acid mentioned in step 2① is hydrochloric acid;

[0107] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:60mL.

[0108] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and clean it three times.

[0109] The cleaning method described in step 2③ is soaking.

[0110] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0111] The method for removing solvent described in step 2④ is drying;

[0112] The solvent removal time mentioned in step 2④ is 0.5 hours;

[0113] The solvent removal temperature mentioned in step 2④ is 100℃;

[0114] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 12 μm;

[0115] The polyaryletherketone structure described in step 2④ is as follows:

[0116]

[0117] III. Preparation of the conductive layer:

[0118] Ag nanowires are sprayed onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0119] The concentration of the Ag nanowire dispersion in step three is 1 mg / mL, and the dispersant is ethanol;

[0120] The spraying pressure in step three is 20 psi, the distance is 4 cm, and the temperature is 50 °C.

[0121] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0122] Figure 3 This is a photograph of the flexible conductive film with a polyaryletherketone protective layer obtained in step three of Example 1. From... Figure 3 The macroscopic morphology of the flexible conductive film with a polyaryletherketone protective layer can be seen.

[0123] Figure 4 These are SEM images of the flexible conductive film with a polyaryletherketone protective layer obtained in step three of Example 1, wherein (1) is a planar SEM of a flexible conductive film with a polyaryletherketone protective layer, and (2) is a cross-sectional SEM of a flexible substrate with a polyaryletherketone protective layer. Figure 4 The microstructure and thickness of the flexible conductive film with a polyaryletherketone protective layer are known.

[0124] Figure 5This is a sheet resistance data graph of the flexible conductive film with a polyaryletherketone protective layer obtained in step three of Example 1, where (1) is the parallel test data of the sheet resistance of a flexible conductive film with a polyaryletherketone protective layer, and (2) is the long-term stability test data of the sheet resistance of a flexible conductive film with a polyaryletherketone protective layer. Figure 5 It can be seen that the sheet resistance of the five sets of flexible conductive films with polyaryletherketone protective layers is less than 13Ω / sq, and they have good long-term stability, which can meet the requirements of optoelectronic devices.

[0125] Figure 6 This is a table showing the mechanical properties of the flexible conductive film with a polyaryletherketone (PAEK) protective layer obtained in step three of Example 1. Compared to the flexible conductive film without a PAEK protective layer, the introduction of the protective layer significantly improves the overall mechanical properties of different flexible substrate materials.

[0126] Figure 7 This is a schematic diagram of the parallel structure device of electrochromic / supercapacitor in Example 1. In the figure, 1 is a flexible conductive film with a polyaryletherketone protective layer, 2 is a PEDOT:PSS layer, 3 is a WO3 layer, and 4 is an electrolyte layer.

[0127] Figure 8 This is a performance data table for the electrochromic device obtained in Example 1. The transmittance change of the electrochromic device is 49.65%, the color-changing and fading times are 5.4s and 2.1s respectively, and the coloring efficiency is 346.9cm. 2 / C.

[0128] Figure 9 This is a performance data table of the supercapacitor obtained in Example 1. The supercapacitor has a performance of 1 mA / cm². -2 At the current density, the areal capacitance is 386 mF cm⁻¹. 2 .

[0129] Example 2: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0130] I. Preparation of polyaryletheramine films:

[0131] ① Prepare a 1.5% polyaryletheramine solution using a good polar polymer solvent;

[0132] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0133] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 70℃ and the annealing time is 10h.

[0134] The good solvent for the polar polymer mentioned in step 1① is DMAc;

[0135] The polyaryletheramine structure described in step 1① is as follows:

[0136]

[0137] The flexible substrate mentioned in step 1② is PEN;

[0138] The film formation method described in step 1② is spin coating, with a rotation speed of 2000 rpm and a time of 40 s.

[0139] II. Preparation of polyaryletherketone protective layer:

[0140] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 2.0 M and an acid concentration of 10.0 M;

[0141] The mixing method described in step 2① is oscillation.

[0142] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 10℃, and the reaction time is 48h;

[0143] The oxidant mentioned in step 2① is hydrogen peroxide;

[0144] The acid mentioned in step 2① is phosphoric acid;

[0145] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:300mL.

[0146] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 5 times.

[0147] The cleaning method described in step 2③ is reflux.

[0148] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0149] The method for removing solvent described in step 2④ is drying;

[0150] The solvent removal time mentioned in step 2④ is 3 hours;

[0151] The solvent removal temperature mentioned in step 2④ is 80℃;

[0152] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 5 μm;

[0153] The polyaryletherketone structure described in step 2④ is as follows:

[0154]

[0155] III. Preparation of the conductive layer:

[0156] A flexible conductive film with a polyaryletherketone protective layer can be obtained by electroless plating of Cu on a flexible substrate with a polyaryletherketone protective layer and simple post-processing.

[0157] The chemical plating formula described in step three is as follows: potassium sodium tartrate (tetrahydrate): disodium ethylenediaminetetraacetate (dihydrate): copper sulfate pentahydrate: nickel sulfate (hexahydrate): sodium hydroxide: potassium ferrocyanide (trihydrate): 2,2'-bipyridine = 32.0g: 2.5g: 12.5g: 3.5g: 10.0g: 0.02g: 0.01g.

[0158] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0159] Figure 10 This is a schematic diagram of the electrochromic / supercapacitor sandwich structure device obtained in Example 1. In the figure, 1 and 5 are flexible conductive films with polyaryletherketone protective layers, 2 is a PEDOT:PSS layer, 3 is an electrolyte layer, and 4 is a WO3 layer.

[0160] Example 3: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0161] I. Preparation of polyaryletheramine films:

[0162] ① Prepare a 10% polyaryletheramine solution using a good polar polymer solvent;

[0163] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0164] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 60℃ and the annealing time is 24h.

[0165] The good solvent for the polar polymer mentioned in step 1① is DMF;

[0166] The polyaryletheramine structure described in step 1① is as follows:

[0167]

[0168] The flexible substrate mentioned in step 1② is PI;

[0169] The film formation method described in step 1② is blade coating, with a thickness of 200μm, a speed of 2.5mm / min, and a temperature of 35℃.

[0170] II. Preparation of polyaryletherketone protective layer:

[0171] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.01M and an acid concentration of 0.1M;

[0172] The mixing method described in step 2① is ultrasound.

[0173] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 80℃, and the reaction time is 8 hours.

[0174] The oxidant mentioned in step 2① is potassium dichromate;

[0175] The acid mentioned in step 2① is sulfuric acid;

[0176] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:5mL.

[0177] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and clean it once.

[0178] The cleaning method described in step 2③ is oscillation.

[0179] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0180] The solvent removal method described in step 2④ is lyophilization;

[0181] The solvent removal time mentioned in step 2④ is 2 hours;

[0182] The solvent removal temperature mentioned in step 2④ is -80℃;

[0183] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 37 μm;

[0184] The polyaryletherketone structure described in step 2④ is as follows:

[0185]

[0186] III. Preparation of the conductive layer:

[0187] Ni is electroplated onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0188] The electroplating formula described in step three is: nickel sulfate (heptahydrate): nickel chloride (hexahydrate): boric acid

[0189] =200g:60g:37.5g, bath temperature is 50℃, pH is 3.

[0190] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0191] Example 4: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0192] I. Preparation of polyaryletheramine films:

[0193] ① Prepare a 23% polyaryletheramine solution using a good polar polymer solvent;

[0194] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0195] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 100℃ and the annealing time is 1.5h.

[0196] The good solvent for the polar polymer mentioned in step 1① is THF;

[0197] The polyaryletheramine structure described in step 1① is as follows:

[0198]

[0199] The flexible substrate mentioned in step 1② is PC;

[0200] The film-forming method described in step 1② is spray coating, with a pressure of 20 psi, a distance of 10 cm, and a temperature of 60℃.

[0201] II. Preparation of polyaryletherketone protective layer:

[0202] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.8M and an acid concentration of 2.0M;

[0203] The mixing method described in step 2① is ultrasound.

[0204] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 60℃, and the reaction time is 15h;

[0205] The oxidant mentioned in step 2① is peroxidase;

[0206] The acid mentioned in step 2① is perchloric acid;

[0207] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:100mL.

[0208] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 10 times.

[0209] The cleaning method described in step 2③ is ultrasound.

[0210] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0211] The solvent removal method described in step 2④ is lyophilization;

[0212] The solvent removal time mentioned in step 2④ is 12 hours;

[0213] The solvent removal temperature mentioned in step 2④ is -20℃;

[0214] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 50 μm;

[0215] The polyaryletherketone structure described in step 2④ is as follows:

[0216]

[0217] III. Preparation of the conductive layer:

[0218] Au nanowires are sprayed onto a flexible substrate with a polyaryletherketone (PAK) protective layer, and a flexible conductive film with a PAK protective layer can be obtained after simple post-processing.

[0219] The concentration of the Au nanowire dispersion in step three is 0.5 mg / mL, and the dispersant is isopropanol;

[0220] The spraying pressure in step three is 40 psi, the distance is 10 cm, and the temperature is 45 °C.

[0221] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0222] Example 5: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0223] I. Preparation of polyaryletheramine films:

[0224] ① Prepare a 17% polyaryletheramine solution using a good polar polymer solvent;

[0225] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0226] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 180℃ and the annealing time is 0.5h.

[0227] The good solvent for the polar polymer mentioned in step 1① is Me-THF;

[0228] The polyaryletheramine structure described in step 1① is as follows:

[0229]

[0230] The flexible substrate mentioned in step 1② is PVDF;

[0231] The film-forming method described in step 1② is drop coating.

[0232] II. Preparation of polyaryletherketone protective layer:

[0233] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.0 M and an acid concentration of 0.5 M;

[0234] The mixing method described in step 2① is ultrasound.

[0235] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 100℃, and the reaction time is 0.5h;

[0236] The oxidizing agent mentioned in step 2① is silver nitrate;

[0237] The acid mentioned in step 2① is acetic acid;

[0238] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:230mL.

[0239] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and clean it 8 times.

[0240] The cleaning method described in step 2③ is soaking.

[0241] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0242] The solvent removal method described in step 2④ is lyophilization;

[0243] The solvent removal time mentioned in step 2④ is 5 hours;

[0244] The solvent removal temperature mentioned in step 2④ is -50℃;

[0245] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 7 μm;

[0246] The polyaryletherketone structure described in step 2④ is as follows:

[0247]

[0248] III. Preparation of the conductive layer:

[0249] Palladium is electroplated onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0250] The electroplating formula described in step three is: Pd(NH3)2Br2:(NH4)2HPO:NH4Br:Pyridine-3-sulfonic acid:Urea = 50g:50g:3g:15g, with a bath temperature of 50℃ and a pH of 7.5.

[0251] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0252] Example 6: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0253] I. Preparation of polyaryletheramine films:

[0254] ① Prepare a 6% polyaryletheramine solution using a good polar polymer solvent;

[0255] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0256] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 150℃ and the annealing time is 5h.

[0257] The good solvent for the polar polymer mentioned in step 1① is DCM;

[0258] The polyaryletheramine structure described in step 1① is as follows:

[0259]

[0260] The flexible substrate mentioned in step 1② is PDMS;

[0261] The film-forming method described in step 1② is immersion film formation, with a time of 3 hours.

[0262] II. Preparation of polyaryletherketone protective layer:

[0263] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.8M and an acid concentration of 5.5M;

[0264] The mixing method described in step 2① is oscillation.

[0265] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 70℃, and the reaction time is 4 hours.

[0266] The oxidant mentioned in step 2① is copper chloride;

[0267] The acid mentioned in step 2① is hydrobromic acid;

[0268] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:5mL.

[0269] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 7 times.

[0270] The cleaning method described in step 2③ is ultrasound.

[0271] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0272] The method for removing solvent described in step 2④ is drying;

[0273] The solvent removal time mentioned in step 2④ is 12 hours;

[0274] The solvent removal temperature mentioned in step 2④ is 30℃;

[0275] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 36 μm;

[0276] The polyaryletherketone structure described in step 2④ is as follows:

[0277]

[0278] III. Preparation of the conductive layer:

[0279] Cobalt is physically vapor-deposited on a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0280] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0281] Example 7: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0282] I. Preparation of polyaryletheramine films:

[0283] ① Prepare a 30% polyaryletheramine solution using a good polar polymer solvent;

[0284] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0285] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 85℃ and the annealing time is 22h.

[0286] The good solvent for the polar polymer mentioned in step 1① is TCM;

[0287] The polyaryletheramine structure described in step 1① is as follows:

[0288]

[0289] The flexible substrate mentioned in step 1② is TPU;

[0290] The film formation method described in step 1② is casting film formation at a temperature of 80℃.

[0291] II. Preparation of polyaryletherketone protective layer:

[0292] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.04M and an acid concentration of 1.5M;

[0293] The mixing method described in step 2① is stirring.

[0294] ② The polyaryletheramine membrane obtained in step one is added to the acidic solution of the oxidant mentioned in step two ①, and the reaction is carried out. The reaction temperature is 20℃, and the reaction time is 43h;

[0295] The oxidant mentioned in step 2① is ammonium persulfate;

[0296] The acid mentioned in step 2① is fluoroboric acid;

[0297] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:150mL.

[0298] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat the process four times.

[0299] The cleaning method described in step 2③ is oscillation.

[0300] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0301] The solvent removal method described in step 2④ is lyophilization;

[0302] The solvent removal time mentioned in step 2④ is 10 hours;

[0303] The solvent removal temperature mentioned in step 2④ is -35℃;

[0304] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 43 μm;

[0305] The polyaryletherketone structure described in step 2④ is as follows:

[0306]

[0307] III. Preparation of the conductive layer:

[0308] A flexible conductive film with a polyaryletherketone protective layer can be obtained by chemically plating tin onto a flexible substrate with a polyaryletherketone protective layer and then performing simple post-treatment.

[0309] The chemical plating formula described in step three is: sodium hydroxide: sodium nitrate: ammonium hydroxide: potassium dichromate: tin acetate: water = 50g: 20g: 20g: 1.5g: 10mL: 1L, and the bath temperature is 70℃.

[0310] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0311] Example 8: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0312] I. Preparation of polyaryletheramine films:

[0313] ① Prepare a 27% polyaryletheramine solution using a good polar polymer solvent;

[0314] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0315] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 125℃ and the annealing time is 8h.

[0316] The good solvent for the polar polymer mentioned in step 1① is EA;

[0317] The polyaryletheramine structure described in step 1①:

[0318]

[0319] The flexible substrate mentioned in step 1② is PVA;

[0320] The film formation method described in step 1② is slit extrusion coating with a pressure of 0.5 kPa and a flow rate of 28 L / h.

[0321] II. Preparation of polyaryletherketone protective layer:

[0322] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.15M and an acid concentration of 6.0M;

[0323] The mixing method described in step 2① is stirring.

[0324] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 50℃, and the reaction time is 38h;

[0325] The oxidant mentioned in step 2① is potassium permanganate;

[0326] The acid mentioned in step 2① is phytic acid;

[0327] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:230mL.

[0328] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 6 times.

[0329] The cleaning method described in step 2③ is reflux.

[0330] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0331] The method for removing solvent described in step 2④ is drying;

[0332] The solvent removal time mentioned in step 2④ is 8 hours;

[0333] The solvent removal temperature mentioned in step 2④ is -40℃;

[0334] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 28 μm;

[0335] The polyaryletherketone structure described in step 2④ is as follows:

[0336]

[0337] III. Preparation of the conductive layer:

[0338] A flexible conductive film with a polyaryletherketone protective layer can be obtained by electroless plating of Cu on a flexible substrate with a polyaryletherketone protective layer and simple post-processing.

[0339] The chemical plating formula described in step three is as follows: potassium sodium tartrate (tetrahydrate): disodium ethylenediaminetetraacetate (dihydrate): copper sulfate pentahydrate: nickel sulfate (hexahydrate): sodium hydroxide: potassium ferrocyanide (trihydrate): 2,2'-bipyridine = 32.0g: 2.5g: 12.5g: 3.5g: 10.0g: 0.02g: 0.01g.

[0340] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0341] Example 9: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0342] I. Preparation of polyaryletheramine films:

[0343] ① Prepare a polyaryletheramine solution with a mass fraction of 18% using a good polar polymer solvent;

[0344] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0345] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 140℃ and the annealing time is 3h.

[0346] The good solvent for the polar polymer mentioned in step 1① is CB;

[0347] The polyaryletheramine structure described in step 1① is as follows:

[0348]

[0349] The flexible substrate mentioned in step 1② is PES;

[0350] The film-forming method described in step 1② is screen printing.

[0351] II. Preparation of polyaryletherketone protective layer:

[0352] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.75M and an acid concentration of 0.8M;

[0353] The mixing method described in step 2① is ultrasound.

[0354] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 90℃, and the reaction time is 3 hours.

[0355] The oxidant mentioned in step 2① is aluminum chloride;

[0356] The acid mentioned in step 2① is formic acid;

[0357] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:25mL.

[0358] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and clean it three times.

[0359] The cleaning method described in step 2③ is ultrasound.

[0360] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0361] The method for removing solvent described in step 2④ is drying;

[0362] The solvent removal time mentioned in step 2④ is 8 hours;

[0363] The solvent removal temperature mentioned in step 2④ is 75℃;

[0364] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 16 μm;

[0365] The polyaryletherketone structure described in step 2④ is as follows:

[0366]

[0367] III. Preparation of the conductive layer:

[0368] Ni is electroplated onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0369] The electroplating formula described in step three is: nickel sulfate (heptahydrate): nickel chloride (hexahydrate): boric acid

[0370] =200g:60g:37.5g, bath temperature is 50℃, pH is 3.

[0371] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0372] Example 10: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0373] I. Preparation of polyaryletheramine films:

[0374] ① Prepare a 40% polyaryletheramine solution using a good polar polymer solvent;

[0375] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0376] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 165℃ and the annealing time is 1.5h.

[0377] The good solvent for the polar polymer mentioned in step 1① is DCB;

[0378] The polyaryletheramine structure described in step 1① is as follows:

[0379]

[0380] The flexible substrate mentioned in step 1② is PPSU;

[0381] The film formation method described in step 1② is inkjet printing at a speed of 2.5 μmm / s.

[0382] II. Preparation of polyaryletherketone protective layer:

[0383] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.25M and an acid concentration of 2.5M;

[0384] The mixing method described in step 2① is oscillation.

[0385] ② The polyaryletheramine membrane obtained in step one is added to the acidic solution of the oxidant mentioned in step two ①, and the reaction is carried out. The reaction temperature is 30℃, and the reaction time is 44h;

[0386] The oxidant mentioned in step 2① is tellurium;

[0387] The acid mentioned in step 2① is methanesulfonic acid;

[0388] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:80mL.

[0389] ③ Clean the polyaryletherketone film obtained in step ②. Use ethanol and water as solvents, and clean twice.

[0390] The cleaning method described in step 2③ is reflux.

[0391] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0392] The method for removing solvent described in step 2④ is drying;

[0393] The solvent removal time mentioned in step 2④ is 7 hours;

[0394] The solvent removal temperature mentioned in step 2④ is 40℃;

[0395] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 33 μm;

[0396] The polyaryletherketone structure described in step 2④ is as follows:

[0397]

[0398] III. Preparation of the conductive layer:

[0399] Au nanowires are sprayed onto a flexible substrate with a polyaryletherketone (PAK) protective layer, and a flexible conductive film with a PAK protective layer can be obtained after simple post-processing.

[0400] The concentration of the Au nanowire dispersion in step three is 0.5 mg / mL, and the dispersant is isopropanol;

[0401] The spraying pressure in step three is 40 psi, the distance is 10 cm, and the temperature is 45 °C.

[0402] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0403] Example 11: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0404] I. Preparation of polyaryletheramine films:

[0405] ① Prepare a 0.5% polyaryletheramine solution using a good polar polymer solvent;

[0406] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0407] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 100℃ and the annealing time is 6h.

[0408] The good solvent for the polar polymer mentioned in step 1① is TCB;

[0409] The polyaryletheramine structure described in step 1① is as follows:

[0410]

[0411] The flexible substrate mentioned in step 1② is PET;

[0412] The film formation method described in step 1② is spray pyrolysis film formation at a temperature of 170℃.

[0413] II. Preparation of polyaryletherketone protective layer:

[0414] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.8M and an acid concentration of 5.0M;

[0415] The mixing method described in step 2① is oscillation.

[0416] ② The polyarylene ether amine membrane obtained in step one is added to the acidic solution of the oxidant mentioned in step two ①, and the reaction is carried out. The reaction temperature is 70℃, and the reaction time is 26h;

[0417] The oxidant mentioned in step 2① is ferric chloride;

[0418] The acid mentioned in step 2① is benzenesulfonic acid;

[0419] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:160mL.

[0420] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 10 times.

[0421] The cleaning method described in step 2③ is oscillation.

[0422] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0423] The solvent removal method described in step 2④ is lyophilization;

[0424] The solvent removal time mentioned in step 2④ is 2.5 hours;

[0425] The solvent removal temperature mentioned in step 2④ is -65℃;

[0426] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 42 μm;

[0427] The polyaryletherketone structure described in step 2④ is as follows:

[0428]

[0429] III. Preparation of the conductive layer:

[0430] Ag nanowires are sprayed onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0431] The concentration of the Ag nanowire dispersion in step three is 1 mg / mL, and the dispersant is ethanol;

[0432] The spraying pressure in step three is 20 psi, the distance is 4 cm, and the temperature is 50 °C.

[0433] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0434] Example 12: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0435] I. Preparation of polyaryletheramine films:

[0436] ① Prepare a 35% polyaryletheramine solution using a good polar polymer solvent;

[0437] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0438] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 95℃ and the annealing time is 12h.

[0439] The good solvent for the polar polymer mentioned in step 1① is MB;

[0440] The polyaryletheramine structure described in step 1① is as follows:

[0441]

[0442] The flexible substrate mentioned in step 1② is PVDF;

[0443] The film-forming method described in step 1② is roll-to-roll film formation.

[0444] II. Preparation of polyaryletherketone protective layer:

[0445] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.08M and an acid concentration of 0.2M;

[0446] The mixing method described in step 2① is stirring.

[0447] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 20℃, and the reaction time is 45h;

[0448] The oxidant mentioned in step 2① is ammonium persulfate;

[0449] The acid mentioned in step 2① is p-toluenesulfonic acid;

[0450] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:270mL.

[0451] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and clean it 8 times.

[0452] The cleaning method described in step 2③ is soaking.

[0453] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0454] The solvent removal method described in step 2④ is lyophilization;

[0455] The solvent removal time mentioned in step 2④ is 1 hour;

[0456] The solvent removal temperature mentioned in step 2④ is -75℃;

[0457] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 18 μm;

[0458] The polyaryletherketone structure described in step 2④ is as follows:

[0459]

[0460] III. Preparation of the conductive layer:

[0461] Cobalt is physically vapor-deposited on a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0462] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0463] Example 13: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0464] I. Preparation of polyaryletheramine films:

[0465] ① Prepare a 22% polyaryletheramine solution using a good polar polymer solvent;

[0466] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0467] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 80℃ and the annealing time is 18h.

[0468] The good solvent for the polar polymer mentioned in step 1① is DMB;

[0469] The polyaryletheramine structure described in step 1① is as follows:

[0470]

[0471] The flexible substrate mentioned in step 1② is TPU;

[0472] The film formation method described in step 1② is blade coating, with a thickness of 160μm, a speed of 3mm / min, and a temperature of 50℃.

[0473] II. Preparation of polyaryletherketone protective layer:

[0474] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.6M and an acid concentration of 9.5M;

[0475] The mixing method described in step 2① is ultrasound.

[0476] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 45℃, and the reaction time is 12h;

[0477] The oxidizing agent mentioned in step 2① is silver nitrate;

[0478] The acid mentioned in step 2① is sulfosalicylic acid;

[0479] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:15mL.

[0480] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat the process four times.

[0481] The cleaning method described in step 2③ is ultrasound.

[0482] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0483] The solvent removal method described in step 2④ is lyophilization;

[0484] The solvent removal time mentioned in step 2④ is 10 hours;

[0485] The solvent removal temperature mentioned in step 2④ is -25℃;

[0486] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 39 μm;

[0487] The polyaryletherketone structure described in step 2④ is as follows:

[0488]

[0489] III. Preparation of the conductive layer:

[0490] A flexible conductive film with a polyaryletherketone protective layer can be obtained by chemically plating tin onto a flexible substrate with a polyaryletherketone protective layer and then performing simple post-treatment.

[0491] The chemical plating formula described in step three is: sodium hydroxide: sodium nitrate: ammonium hydroxide: potassium dichromate: tin acetate: water = 50g: 20g: 20g: 1.5g: 10mL: 1L, and the bath temperature is 70℃.

[0492] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0493] Example 14: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0494] I. Preparation of polyaryletheramine films:

[0495] ① Prepare a 5% polyaryletheramine solution using a good polar polymer solvent;

[0496] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0497] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 140℃ and the annealing time is 3h.

[0498] The good solvent for the polar polymer mentioned in step 1① is TMB;

[0499] The polyaryletheramine structure described in step 1① is as follows:

[0500]

[0501] The flexible substrate mentioned in step 1② is PI;

[0502] The film-forming method described in step 1② is casting film formation.

[0503] II. Preparation of polyaryletherketone protective layer:

[0504] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.15M and an acid concentration of 3.0M;

[0505] The mixing method described in step 2① is oscillation.

[0506] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 65℃, and the reaction time is 7 hours.

[0507] The oxidant mentioned in step 2① is potassium permanganate;

[0508] The acid mentioned in step 2① is trifluoroacetic acid;

[0509] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:210mL.

[0510] ③ Clean the polyaryletherketone film obtained in step ②. Use ethanol and water as solvents, and clean twice.

[0511] The cleaning method described in step 2③ is oscillation.

[0512] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0513] The method for removing solvent described in step 2④ is drying;

[0514] The solvent removal time mentioned in step 2④ is 3 hours;

[0515] The solvent removal temperature mentioned in step 2④ is 70℃;

[0516] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 6 μm;

[0517] The polyaryletherketone structure described in step 2④ is as follows:

[0518]

[0519] III. Preparation of the conductive layer:

[0520] Ni is electroplated onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0521] The electroplating formula described in step three is: nickel sulfate (heptahydrate): nickel chloride (hexahydrate): boric acid

[0522] =200g:60g:37.5g, bath temperature is 50℃, pH is 3.

[0523] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0524] Example 15: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0525] I. Preparation of polyaryletheramine films:

[0526] ① Prepare a 33% polyaryletheramine solution using a good polar polymer solvent;

[0527] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0528] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 165℃ and the annealing time is 1 hour.

[0529] The good solvent for the polar polymer mentioned in step 1① is AC;

[0530] The polyaryletheramine structure described in step 1① is as follows:

[0531]

[0532] The flexible substrate mentioned in step 1② is PPSU;

[0533] The film formation method described in step 1② is spin coating, with a rotation speed of 1500 rpm and a time of 60 s.

[0534] II. Preparation of polyaryletherketone protective layer:

[0535] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.7M and an acid concentration of 7.5M;

[0536] The mixing method described in step 2① is ultrasound.

[0537] ② The polyaryletheramine membrane obtained in step one is added to the acidic solution of the oxidant mentioned in step two ①, and the reaction is carried out. The reaction temperature is 75℃, and the reaction time is 4.5h;

[0538] The oxidant mentioned in step 2① is hydrogen peroxide;

[0539] The acid mentioned in step 2① is trifluorobenzenesulfonic acid;

[0540] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:65mL.

[0541] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and clean it three times.

[0542] The cleaning method described in step 2③ is oscillation.

[0543] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0544] The solvent removal method described in step 2④ is lyophilization;

[0545] The solvent removal time mentioned in step 2④ is 6.5 hours;

[0546] The solvent removal temperature mentioned in step 2④ is -55℃;

[0547] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 24 μm;

[0548] The polyaryletherketone structure described in step 2④ is as follows:

[0549]

[0550] III. Preparation of the conductive layer:

[0551] Palladium is electroplated onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0552] The electroplating formula described in step three is: Pd(NH3)2Br2:(NH4)2HPO:NH4Br:Pyridine-3-sulfonic acid:Urea = 50g:50g:3g:15g, with a bath temperature of 50℃ and a pH of 7.5.

[0553] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0554] Example 16: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0555] I. Preparation of polyaryletheramine films:

[0556] ① Prepare a 12% polyaryletheramine solution using a good polar polymer solvent;

[0557] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0558] ③ The film described in step 1, ② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 70℃ and the annealing time is 21h.

[0559] The good solvent for the polar polymer mentioned in step 1① is NMP;

[0560] The polyaryletheramine structure described in step 1① is as follows:

[0561]

[0562] The flexible substrate mentioned in step 1② is PES;

[0563] The film formation method described in step 1② is spray pyrolysis film formation at a temperature of 200℃.

[0564] II. Preparation of polyaryletherketone protective layer:

[0565] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.25M and an acid concentration of 6.5M;

[0566] The mixing method described in step 2① is ultrasound.

[0567] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 40℃, and the reaction time is 30h;

[0568] The oxidant mentioned in step 2① is copper chloride;

[0569] The acid mentioned in step 2① is dodecylbenzenesulfonic acid;

[0570] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:50mL.

[0571] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 5 times.

[0572] The cleaning method described in step 2③ is soaking.

[0573] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0574] The method for removing solvent described in step 2④ is drying;

[0575] The solvent removal time mentioned in step 2④ is 1.5 hours;

[0576] The solvent removal temperature mentioned in step 2④ is 95℃;

[0577] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 32 μm;

[0578] The polyaryletherketone structure described in step 2④ is as follows:

[0579]

[0580] III. Preparation of the conductive layer:

[0581] A flexible conductive film with a polyaryletherketone protective layer can be obtained by electroless plating of Cu on a flexible substrate with a polyaryletherketone protective layer and simple post-processing.

[0582] The chemical plating formula described in step three is as follows: potassium sodium tartrate (tetrahydrate): disodium ethylenediaminetetraacetate (dihydrate): copper sulfate pentahydrate: nickel sulfate (hexahydrate): sodium hydroxide: potassium ferrocyanide (trihydrate): 2,2'-bipyridine = 32.0g: 2.5g: 12.5g: 3.5g: 10.0g: 0.02g: 0.01g.

[0583] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0584] Example 17: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0585] I. Preparation of polyaryletheramine films:

[0586] ① Prepare a 24% polyaryletheramine solution using a good polar polymer solvent;

[0587] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0588] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 115℃ and the annealing time is 5h.

[0589] The good solvent for the polar polymer mentioned in step 1① is DMAc;

[0590] The polyaryletheramine structure described in step 1① is as follows:

[0591]

[0592] The flexible substrate mentioned in step 1② is PDMS;

[0593] The film-forming method described in step 1② is screen printing.

[0594] II. Preparation of polyaryletherketone protective layer:

[0595] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.8M and an acid concentration of 4.5M;

[0596] The mixing method described in step 2① is oscillation.

[0597] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 85℃, and the reaction time is 2 hours.

[0598] The oxidizing agent mentioned in step 2① is silver nitrate;

[0599] The acid mentioned in step 2① is dioctyl succinate sulfonic acid;

[0600] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:280mL.

[0601] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 9 times.

[0602] The cleaning method described in step 2③ is soaking.

[0603] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0604] The method for removing solvent described in step 2④ is drying;

[0605] The solvent removal time mentioned in step 2④ is 8 hours;

[0606] The solvent removal temperature mentioned in step 2④ is 45℃;

[0607] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 45 μm;

[0608] The polyaryletherketone structure described in step 2④ is as follows:

[0609]

[0610] III. Preparation of the conductive layer:

[0611] Au nanowires are sprayed onto a flexible substrate with a polyaryletherketone (PAK) protective layer, and a flexible conductive film with a PAK protective layer can be obtained after simple post-processing.

[0612] The concentration of the Au nanowire dispersion in step three is 0.5 mg / mL, and the dispersant is isopropanol;

[0613] The spraying pressure in step three is 40 psi, the distance is 10 cm, and the temperature is 45 °C.

[0614] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor parallel structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0615] Example 18: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0616] I. Preparation of polyaryletheramine films:

[0617] ① Prepare a polyaryletheramine solution with a mass fraction of 18% using a good polar polymer solvent;

[0618] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0619] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 135℃ and the annealing time is 9 hours.

[0620] The good solvent for the polar polymer mentioned in step 1① is DMF;

[0621] The polyaryletheramine structure described in step 1① is as follows:

[0622]

[0623] The flexible substrate mentioned in step 1② is PC;

[0624] The film-forming method described in step 1② is immersion film formation, with a time of 8 hours.

[0625] II. Preparation of polyaryletherketone protective layer:

[0626] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 0.06M and an acid concentration of 1.8M;

[0627] The mixing method described in step 2① is stirring.

[0628] ② The polyaryletheramine membrane obtained in step one is added to the acidic solution of the oxidant mentioned in step two ①, and the reaction is carried out. The reaction temperature is 30℃, and the reaction time is 39h;

[0629] The oxidant mentioned in step 2① is peroxidase;

[0630] The acid mentioned in step 2① is camphor sulfonic acid;

[0631] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:135mL.

[0632] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 6 times.

[0633] The cleaning method described in step 2③ is reflux.

[0634] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0635] The solvent removal method described in step 2④ is lyophilization;

[0636] The solvent removal time mentioned in step 2④ is 11 hours;

[0637] The solvent removal temperature mentioned in step 2④ is -30℃;

[0638] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 46 μm;

[0639] The polyaryletherketone structure described in step 2④ is as follows:

[0640]

[0641] III. Preparation of the conductive layer:

[0642] Palladium is electroplated onto a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0643] The electroplating formula described in step three is: Pd(NH3)2Br2:(NH4)2HPO:NH4Br:Pyridine-3-sulfonic acid:Urea = 50g:50g:3g:15g, with a bath temperature of 50℃ and a pH of 7.5.

[0644] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0645] Example 19: A method for preparing a flexible conductive film with a polyaryletherketone protective layer, comprising the following steps:

[0646] I. Preparation of polyaryletheramine films:

[0647] ① Prepare a 36% polyaryletheramine solution using a good polar polymer solvent;

[0648] ② Using the solution described in step ① as the casting solution, a film is formed on a flexible substrate;

[0649] ③ The film described in step 1② is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 150℃ and the annealing time is 15h.

[0650] The good solvent for the polar polymer mentioned in step 1① is THF;

[0651] The polyaryletheramine structure described in step 1① is as follows:

[0652]

[0653] The flexible substrate mentioned in step 1② is PEN;

[0654] The film formation method described in step 1② is blade coating, with a thickness of 95μm, a speed of 5mm / min, and a temperature of 40℃.

[0655] II. Preparation of polyaryletherketone protective layer:

[0656] ① Prepare an acid solution for the oxidizing agent, with an oxidizing agent concentration of 1.35M and an acid concentration of 7.5M;

[0657] The mixing method described in step 2① is stirring.

[0658] ② Add the polyaryletheramine membrane obtained in step one to the acidic solution of the oxidant mentioned in step two ①, and react. The reaction temperature is 75℃, and the reaction time is 10h;

[0659] The oxidant mentioned in step 2① is potassium dichromate;

[0660] The acid mentioned in step 2① is nitric acid;

[0661] In step 2②, the ratio of the amount of polyaryletheramine membrane to the acid solution of the oxidant is 0.1g:220mL.

[0662] ③ Clean the polyaryletherketone film obtained in step 2. Use ethanol and water as solvents, and repeat 5 times.

[0663] ④ Remove the solvent from the polyaryletherketone film obtained in step 2 ③ to obtain a polyaryletherketone protective layer.

[0664] The method for removing solvent described in step 2④ is drying;

[0665] The solvent removal time mentioned in step 2④ is 9.5 hours;

[0666] The solvent removal temperature mentioned in step 2④ is 85℃;

[0667] The thickness of the polyaryletherketone protective layer mentioned in step 2④ is 15 μm;

[0668] The polyaryletherketone structure described in step 2④ is as follows:

[0669]

[0670] III. Preparation of the conductive layer:

[0671] Cobalt is physically vapor-deposited on a flexible substrate with a polyaryletherketone protective layer, and a flexible conductive film with a polyaryletherketone protective layer can be obtained after simple post-processing.

[0672] Furthermore, using PEDOT:PSS and WO3 as active materials, supplemented with an electrolyte, an electrochromic / supercapacitor sandwich structure device can be obtained after assembly, with a flexible conductive film with a polyaryletherketone protective layer as the substrate. The electrolyte formulation is PMMA:PC:LiClO4 = 5g:10mL:1g.

[0673] The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can still make modifications or equivalent substitutions to the specific implementation of the present invention. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention are within the protection scope of the claims of the present invention pending approval.

Claims

1. A method for preparing a flexible conductive film with a polyaryletherketone protective layer, characterized in that, Includes the following steps: A. Preparation of polyaryletheramine films: A1. Prepare a polyaryletheramine solution with a mass fraction of 0.1% to 40% using a good polar polymer solvent; A2. Using the above-mentioned polyaryletheramine solution as the casting solution, a film is formed on a flexible substrate; A3. The film described in step A2 is subjected to thermal annealing to obtain a polyaryletheramine film. The annealing temperature is 60-180℃ and the annealing time is 0.5-24h. B. Preparation of the polyaryletherketone protective layer: B1. Prepare an acid solution of the oxidant by adding the oxidant to the acid solution and mixing thoroughly at room temperature. The concentration of the oxidant is 0.01M to 2.0M, and the concentration of the acid is 0.1M to 10.0M. The mixing method is one or any combination of stirring, shaking, and ultrasonication. B2. Add the polyarylene ether amine membrane obtained in step A to the acid solution of the above-mentioned oxidant, and react at a constant temperature of 10-100℃ for 0.5-48h; the ratio of the amount of polyarylene ether amine membrane to the acid solution of the oxidant is 0.1g:5-300mL. B3. The polyaryletherketone film obtained in step B2 is cleaned with ethanol and water as solvents, and the cleaning is performed 1 to 10 times. The cleaning method is one or any combination of immersion, ultrasonication, vibration, and reflux. B4. Remove the solvent from the cleaned polyaryletherketone film to obtain a polyaryletherketone protective layer. The solvent removal method is either freeze-drying or drying, with a time of 0.5 to 12 hours. The freeze-drying temperature is -80 to -20°C, and the drying temperature is 30 to 100°C. C. Preparation of conductive layer: A flexible conductive film with a polyaryletherketone protective layer can be obtained by depositing a metal conductive layer on a flexible substrate with a polyaryletherketone protective layer and performing simple post-processing.

2. The method for preparing a flexible conductive film with a polyaryletherketone protective layer according to claim 1, characterized in that, The polyaryletheramine described in step A has the structure shown in formula (I): Equation (I) Where A, B, and C are any of the following structures, and n is a positive integer representing the degree of aggregation; 。 3. The method for preparing a flexible conductive film with a polyaryletherketone protective layer according to claim 1, characterized in that, The film-forming method described in step A2 is one or any combination of spin coating, spray coating, scraping coating, drip coating, casting, impregnation, casting, slot extrusion coating, screen printing, inkjet printing, spray pyrolysis, and roll-to-roll coating.

4. The method for preparing a flexible conductive film with a polyaryletherketone protective layer according to claim 1, characterized in that, The flexible substrate mentioned in step A2 is one of PET, PEN, PI, PC, PVDF, PDMS, TPU, PVA, PES, PPSU film, fiber or fabric.

5. The method for preparing a flexible conductive film with a polyaryletherketone protective layer according to claim 1, characterized in that, The thickness of the polyaryletherketone protective layer in step B is 5 μm to 50 μm.

6. The method for preparing a flexible conductive film with a polyaryletherketone protective layer according to claim 1, characterized in that, The deposited metal in step C is one or any combination of gold, silver, copper, nickel, palladium, tin, and cobalt.

7. The method for preparing a flexible conductive film with a polyaryletherketone protective layer according to claim 1, characterized in that... The metal deposition method described in step C is one or any combination of electroplating, electroless plating, spraying, and physical vapor deposition.

8. A flexible conductive film with a polyaryletherketone protective layer, characterized in that, It is prepared by the method described in any one of claims 1 to 7.

9. The application of the flexible conductive film with a polyaryletherketone protective layer according to claim 8 in the field of electrochromic / supercapacitors, characterized in that, By combining a flexible conductive film with a polyaryletherketone protective layer with active materials and an electrolyte, an electrochromic / supercapacitor device with a flexible conductive film with a polyaryletherketone protective layer as the substrate can be obtained after assembly.

10. The application of the flexible conductive film with a polyaryletherketone protective layer according to claim 9 in the field of electrochromic / supercapacitors, characterized in that, The electrochromic / supercapacitor device has a structure that is either a sandwich structure or a parallel structure.

Images