Patterned electrolysis device and preparation method of patterned conductive polymer film

Abstract

The invention relates to the technical field of electropolymerization and electrodeposition, in particular to a patterned electrolysis device and a preparation method of a patterned conductive polymer film. The patterned electrolysis device provided by the invention comprises a patterned electrolytic tank, a conductive electrode and a conductive substrate, a plurality of patterning channels are formed in the upper portion of the patterning electrolytic cell, a channel opening of each patterning channel is in a preset shape, the lower ends of the patterning channels are communicated with the corresponding liquid circulation channels, and the liquid circulation channels are isolated from one another and used for conveying electrolyte to the corresponding patterning channels respectively; the conductive electrode is positioned at the bottom of the patterned electrolytic cell; the conductive substrate is located at the top of the patterning electrolytic tank, the lower surface of the conductive substrate is attached to the upper surface of the patterning channel, and the conductive substrate is used for forming a polymer film on a conductive area on the lower surface of the conductive substrate after electrolyte electropolymerization. According to the invention, the liquid flowing channels which are isolated from each other are designed, so that the formation of conductive polymer films made of various different materials can be realized.

Description

Technical Field

[0001] The invention relates to the technical field of electropolymerization and electrodeposition, and in particular to a patterned electrolysis device and a method for preparing a patterned conductive polymer film. Background Art

[0002] Patterned conductive polymer films refer to conductive polymer films with specific patterns. Such films are used in many fields, such as electronic devices, wearable sensors, etc. Although there are many methods for preparing patterned conductive polymer films, the common ones include inkjet printing, printing, photopolymerization, photolithography, oxidant templates, self-assembly, etc.

[0003] It should be noted that existing methods have certain limitations when preparing complex patterns containing multiple materials. For example, inkjet printing and printing technology require that the polymer ink have a suitable viscosity, otherwise it may result in insufficient pattern resolution or ink diffusion. While configuring the ink with a suitable viscosity, it is also necessary to ensure that the electrical properties of the polymer are not damaged. Photopolymerization and photolithography processes need to consider the impact of subsequent processes on the cured materials, especially in the preparation of multiple materials. The solvent of the next material may destroy the already cured conductive polymer layer, thereby affecting the integrity and electrical properties of the pattern, and the configuration of photopolymerization and photocuring precursor solutions also needs to be considered. Oxidant templates and self-assembly methods require patterns to be made on the substrate in advance, and the process is complicated for complex patterns. In addition, these methods usually require complex process flows and expensive equipment when processing high-precision complex patterns, which increases manufacturing costs and time. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a method for preparing a patterned electrolytic device and a patterned conductive polymer film. By making a special patterned electrolytic device to control the contact area between the liquid and the electroplating substrate, patterned films with different patterns and different compositions can be prepared in a single electropolymerization and electrodeposition process.

[0005] To this end, the present invention provides the following technical solutions:

[0006] In a first aspect, the present invention provides, in an optional embodiment, a patterned electrolysis device, comprising a patterned electrolytic cell, a conductive electrode, and a conductive substrate;

[0007] A plurality of patterned channels are provided on one side of the upper portion of the patterned electrolytic cell, the channel opening of each patterned channel has a predetermined shape, the lower end of the patterned channel is connected to the corresponding liquid circulation channel, and the liquid circulation channels are isolated from each other and are respectively used to transport electrolyte to the respective patterned channels;

[0008] The conductive electrode is located at the bottom of the patterned electrolytic cell;

[0009] The conductive substrate is located on the top of the patterned electrolytic tank, and its lower surface is in contact with the upper surface of the patterned channel, so as to form a polymer film on the conductive area on the lower surface of the conductive substrate after electropolymerization of the electrolyte.

[0010] In the present invention, by designing the liquid flow channel, the electrolyte in the liquid flow channel is in direct contact with the conductive substrate at the channel opening of the patterned channel, and the pattern formed on the contact surface is the pattern required for electropolymerization. Further, by designing liquid flow channels that are isolated from each other, the patterned electrolysis device can simultaneously accommodate different electrolytes, and different electrolytes are in direct contact with different positions of the conductive substrate.

[0011] Preferably, a liquid injection port is provided on the other side of the upper portion of the patterned electrolytic cell, and the liquid injection port is connected to each liquid circulation channel for transporting the electrolyte to each liquid circulation channel; the height of the liquid injection port is higher than the height of the patterned channel.

[0012] In a second aspect, the present invention provides a method for preparing a patterned conductive polymer film in an optional embodiment, comprising the following steps:

[0013] preparing a patterned electrolytic device;

[0014] performing a non-wetting treatment on the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate;

[0015] performing an infiltration treatment on the inner wall of the patterned channel;

[0016] For each channel opening of the patterned channel, an electrolyte corresponding to the polymer film to be formed at the channel opening is injected into the liquid circulation channel connected to the channel opening through the injection port of the patterned electrolytic cell, so that the electrolyte fills the liquid circulation channel and the patterned channel connected to the liquid circulation channel, and the horizontal plane of the electrolyte in the patterned channel is in contact with the lower surface of the conductive substrate; and the conductive electrode and the conductive substrate are respectively connected to a power source to perform electropolymerization, so that the electrolyte in the patterned channel is electropolymerized on the conductive area on the lower surface of the conductive substrate to form a patterned film.

[0017] In the present invention, the power source is an electrochemical workstation. When a three-electrode system is required, a reference electrode can be inserted at the injection port of the patterned electrolytic cell. The present invention designs a liquid circulation channel so that the electrolyte is in direct contact with the conductive substrate on one side of the cell. The pattern formed on the contact surface is the pattern required for electropolymerization. Channel openings with different patterns can be designed at different parts of the contact surface, thereby forming polymer films with different patterns at different parts of the contact surface. Further, by designing liquid circulation channels that are isolated from each other, the electrolytic cell can accommodate different electrolytes at the same time, and different electrolytes are in direct contact with different positions of the conductive substrate, so that the formation of conductive polymer films of multiple different materials can be achieved.

[0018] In the present invention, it is necessary to perform non-wetting treatment on the upper surface of the patterned electrolytic tank and the lower surface of the conductive substrate. This is because, if the upper surface of the patterned electrolytic tank and the lower surface of the conductive substrate are wetted, the electrolyte will spread in the gap between the two, resulting in unclear / blurred boundaries of the final thin film pattern, and even the pattern will connect the entire surface. In addition, it is also necessary to perform wetting treatment on the inner wall of the patterned channel. This is because, since the patterned channel is too thin, if the wetting treatment is not performed, the surface tension is too strong, and the electrolyte will not reach the height of the upper surface of the patterned channel, making it difficult to contact the lower surface of the conductive substrate. Therefore, the patterned channel is subjected to wettability treatment to improve the affinity of the electrolyte to the inner wall of the patterned channel, increase the liquid level of the electrolyte in the patterned channel, and enable the electrolyte to contact the lower surface of the conductive substrate.

[0019] Preferably, when the electrolyte is an aqueous solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are treated to be hydrophobic, and the inner wall of the patterned channel is treated to be hydrophilic; or, when the electrolyte is an oily solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are treated to be hydrophilic, and the inner wall of the patterned channel is treated to be hydrophobic. The method of treating the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate to be hydrophobic is: coating the patterned electrolytic cell and the conductive substrate with a hydrophobic material; or, polishing the patterned electrolytic cell and the conductive substrate. The method of treating the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate to be hydrophilic is: coating the patterned electrolytic cell and the conductive substrate with a hydrophilic material; or, surface plasma cleaning the patterned electrolytic cell and the conductive substrate. The method of treating the inner wall of the patterned channel to be hydrophobic is: coating the wall of the patterned channel with a hydrophobic material. The method of performing hydrophilic treatment on the inner wall of the patterned channel is: coating the wall of the patterned channel with a hydrophilic material.

[0020] Furthermore, the method of performing hydrophilic treatment on the inner wall of the patterned channel or performing hydrophobic treatment on the inner wall of the patterned channel is: filling the patterned channel with gel; the method of filling the gel includes: injecting the gel material into the patterned channel for solidification; or, filling the solidified gel material into the patterned channel.

[0021] Preferably, the gel material is selected from one or more of polyacrylamide, agarose, dextran sulfate, cellulose acetate, starch, siloxane, polystyrene-divinylbenzene, polyvinyl pyrrolidone, polyethylene glycol, silica gel, xanthan gum, carrageenan or paraffin; and / or, when filling the patterned channel with gel, it is necessary to reserve space for electrolyte injection at the bottom of the patterned electrolytic cell, or, the electrolyte is mixed in the gel material.

[0022] In the present invention, the inner wall of the patterned channel filling is subjected to hydrophilic or hydrophobic treatment, which can further restrict the flow direction of the electrolyte and improve the patterning resolution and adhesion of the film.

[0023] The flow direction of the electrolyte can be further restricted as follows: if the electrolyte is an aqueous phase, when the electrolytic cell material itself is a hydrophobic material, the electrolyte cannot enter the through hole, resulting in the ITO glass being unable to contact the electrolyte surface. Therefore, a hydrophilic gel coating is provided on the inner wall of the patterned channel to increase the electrolyte surface height.

[0024] Preferably, the preparation method further comprises, after the step of preparing the patterned electrolytic device, coating the top surface of the patterned electrolytic tank with removable glue.

[0025] In the present invention, the electrolyte is injected by vacuum defoaming treatment, the electrolyte is sucked into an injection container by a long needle, and the injection container is used to inject from the injection port on the upper part of the patterned electrolytic cell to ensure that the electrolyte fills the liquid flow channel in the patterned electrolytic cell. By coating the top surface of the patterned electrolytic cell with removable glue, the fit between the conductive substrate and the patterned electrolytic cell can be increased, and the electrolyte can be further prevented from overflowing, while ensuring that the conductive substrate is easy to remove after the electropolymerization is completed.

[0026] Preferably, the patterned electrolytic cell is prepared by 3D printing technology, silicone mold technology or computer numerical control processing technology. The material of the conductive electrode is selected from one of platinum sheet, graphite sheet, silver sheet or conductive glass; and / or, the conductive substrate is selected from one of conductive glass, metal or flexible substrate coated with a conductive coating. The electrolyte is a conductive polymer monomer solution or a conductive polymer solution; the conductive polymer monomer solution includes polymer monomers, dopants, stabilizers and solvents, and the conductive polymer solution includes conductive polymers, stabilizers and solvents. The conductive polymer monomer is selected from one or more of aniline and its derivatives, thiophene and its derivatives or pyrrole and its derivatives. There are no special requirements for the selection of conductive polymer monomers, as long as they are monomers that can be electropolymerized; and / or, when the electrolyte of the electrolyte is an aqueous electrolyte, the dopant is a substance that can provide protons (hydrogen ions) and anions at the same time, and there is no requirement for the specific type, for example: polystyrene sulfonic acid, camphor sulfonic acid, hydrochloric acid, sulfuric acid, benzene sulfonic acid, etc. When the electrolyte of the electrolyte is an oil phase electrolyte: the dopant is selected from one or more of organic acids, organic anion salts or ionic liquids, for example, the organic acid can be p-toluenesulfonic acid, octadecylsulfonic acid, fluorosulfonic acid, methanesulfonic acid, the organic anion salt can be potassium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, and the ionic liquid can be 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, etc.; and / or, the stabilizer is selected from one or more of polyethylene glycol, polyacrylamide, polyvinyl alcohol, polymethyl methacrylate or polyvinyl pyrrolidone; and / or, the solvent is selected from water, an organic solvent or a mixed solvent of an organic solvent miscible with water and water.

[0027] In the present invention, the mold for preparing the patterned electrolytic cell is a hollow structure. When the mold is made by using the silicone mold turning technology or the computer numerical control processing technology, the mold needs to be designed in blocks. The mold is made of a material selected from photosensitive resin, nylon, engineering plastics, polytetrafluoroethylene, organic glass or silicone.

[0028] Preferably, the area of ​​the conductive electrode covers the area of ​​the channel opening of the patterned channel.

[0029] Preferably, the conductive area on the lower surface of the conductive substrate is a first shape, the shape area of ​​the channel opening of the patterned channel is a second shape, and the shape formed by the patterned film on the conductive substrate is an intersection of the first shape and the second shape.

[0030] The conductive substrate is conductive over the entire surface, conductive in a region, or conductive in regions independently controlled.

[0031] The method for manufacturing the partitioned independently conductive substrate includes etching a conductive layer of a conductive substrate, or printing a partitioned conductive coating.

[0032] The present invention further limits the formed pattern by adjusting the actual conductive area and area of ​​the conductive area on the lower surface of the conductive substrate. The formed pattern is the intersection shape of the actual conductive area and the shape area of ​​the channel opening of the patterned channel. The conductive electrode is installed by inserting the conductive electrode material into the bottom of the patterned electrolytic cell by bending, or directly coating the conductive electrode material slurry evenly on the bottom of the patterned electrolytic cell.

[0033] In a third aspect, the present invention provides, in an optional embodiment, an application of the method for preparing the patterned conductive polymer film in preparing an electrochromic lateral device.

[0034] In the present invention, the method for preparing the electrochromic lateral device comprises the following steps:

[0035] A conductive layer is arranged on the lower substrate, and then the above method is used to electroplate a patterned conductive polymer film on the conductive layer, and then a first conductive electrode and a second conductive electrode are arranged on both sides of the conductive layer, and there is a preset distance between the first conductive electrode and the second conductive electrode and the conductive layer, and then retaining walls are respectively arranged on the other two sides of the conductive layer, and the retaining walls are tightly connected to the first conductive electrode and the second conductive electrode to enclose a frame structure together, and finally the upper substrate is covered above the first conductive electrode, the electrolyte, the second conductive electrode and the retaining wall, and the electrolyte is injected between the first conductive electrode, the second conductive electrode and the conductive layer, and the electrolyte covers the electrochromic layer to obtain an electrochromic lateral device.

[0036] Compared with the prior art, the present invention has one of the following beneficial effects:

[0037] 1. The present invention designs a liquid flow channel so that the electrolyte in the liquid flow channel is in direct contact with the conductive substrate at the channel opening of the patterned channel, and the pattern formed on the contact surface is the pattern required for electropolymerization. Further, by designing liquid flow channels that are isolated from each other, the patterned electrolysis device can simultaneously accommodate different electrolytes, and different electrolytes are in direct contact with different positions of the conductive substrate.

[0038] 2. The preparation method provided by the present invention provides a new patterning technology idea, which has better adhesion than printed and electroplated films, does not require modification of the existing electrochemical polymerization formula, and is suitable for all solution-phase electrochemical polymerization and electrodeposition schemes.

[0039] 3. This method is simple, has low production cost and good film quality. Compared with the equally simple printing and printing, there is no coffee ring effect and no need to prepare high-viscosity ink. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0041] Figure 1 The schematic diagram of the patterned electropolymerization technology of the present invention, the design diagram of the patterned electrolytic cell and the actual diagram of the patterned electrolytic cell;

[0042] Figure 2 It is a schematic structural diagram of a patterned electrolytic cell of the present invention;

[0043] Figure 3 A model diagram of a patterned electrolytic cell, a physical diagram of a patterned electrolytic device, and a physical diagram of a patterned thin film according to Example 1 of the present invention;

[0044] Figure 4 A physical picture of a patterned electrolysis device and a physical picture of a patterned thin film according to Example 2 of the present invention;

[0045] Figure 5 Schematic diagram of the structure of the patterned electrolytic cell of Example 3 of the present invention;

[0046] Figure 6 This is a physical picture of the patterned thin film of Example 3 of the present invention;

[0047] Figure 7 This is a diagram showing the relationship between the patterned electrolytic cell, the conductive substrate and the solution wettability of Example 1 of the present invention;

[0048] Figure 8 The model diagram of the patterned electrolytic cell of Example 4 of the present invention and Comparative Example 1;

[0049] Fig. 9 This is a physical picture of the patterned film prepared in Comparative Example 2 of the present invention;

[0050] Fig.10 A real picture of the electrochromic lateral device prepared according to the application example of the present invention and a gradient spectrum diagram of three conductive polymer films on the electrochromic lateral device.

[0051] 1- patterned electrolytic cell, 2- conductive electrode, 3- conductive substrate, 4- patterned channel, 5- liquid flow channel, 6- liquid injection port. DETAILED DESCRIPTION

[0052] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0053] With the rapid development of 3D printing technology, it has become simple and low-cost to make high-precision (less than 0.1mm) three-dimensional hollow molds. 3D printing technology can not only quickly and accurately manufacture the required molds, but also has a wide range of material choices. In addition to traditional hard plastics, metals or flexible materials can also be selected. Therefore, microfluidic molds with complex geometric structures can be designed and manufactured according to needs to replace the traditional electropolymerization electrolytic cell, thereby realizing the preparation of complex multi-material conductive polymer patterns.

[0054] Figure 1 a schematically illustrates the principle of preparing a patterned film by electropolymerization of the present invention, wherein the conductive substrate 3 is ITO glass and is located at the top of the patterned electrolytic cell 1, and the two liquid flow channels 5 of the patterned electrolytic cell 1 are respectively filled with solution a and solution b (solution a and solution b are different), and the conductive electrode 2 is located at the bottom of the patterned electrolytic cell 1, and the conductive substrate 3 and the conductive electrode 2 are respectively connected to a power source, and two rectangular patterned films are formed on the ITO glass through electropolymerization.

[0055] Figure 1 b schematically shows a schematic structural diagram of a patterned electrolytic cell, wherein the upper portion of the patterned electrolytic cell 1 has a plurality of patterned channels 4, the channel opening of each patterned channel 4 is rectangular, the lower end of the patterned channel 4 is connected to the corresponding liquid circulation channel 5, and each liquid circulation channel 5 is isolated from each other and is used to transport electrolyte to each patterned channel 4. Four fluid circulation channels 5 are schematically drawn in the figure, each liquid circulation channel 5 corresponds to three patterned channels 4, the electrolyte used in the three patterned channels 4 is the same, and the electrolytes in different liquid circulation channels 5 may be different from each other.

[0056] Figure 1 c schematically shows a patterned electrolytic cell 1 mold made using 3D printing technology of stereolithography and JS-UV-CBY-01 photosensitive resin, with four types of patterns of different sizes on the upper part of the patterned electrolytic cell 1, and further schematically shows the use of conductive copper foil as a conductive electrode 2. For a specific structural schematic diagram, see Figure 2 , wherein 1 is a patterned electrolytic cell, 4 is a patterned channel, 6 is a liquid injection port, and the height of the liquid injection port 6 is higher than the height of the patterned channel 4.

[0057] In Examples 1-3, since the material of the patterned electrolytic bath is polytetrafluoroethylene, which is hydrophobic in itself, and the electrolyte used in Examples 1-3 is an aqueous electrolyte, no additional non-wetting treatment is required.

[0058] Example 1

[0059] This embodiment provides a method for preparing a patterned conductive polymer film, comprising the following steps:

[0060] (1) The patterned electrolytic cell made of polytetrafluoroethylene material is made using CNC processing technology. The actual picture of the patterned electrolytic cell can be found in Figure 3 a. The upper part of the patterned electrolytic cell has three patterned channels, the channel openings of the three patterned channels are rectangular, the lower ends of the three patterned channels are connected to the corresponding liquid circulation channels respectively, the three liquid circulation channels are isolated from each other, and are used to transport electrolyte to their respective patterned channels. In the drawings of this embodiment, the patterned channel and the liquid circulation channel are integrated, that is, the shape area of ​​the channel opening of the patterned channel, the area at the connection position of the patterned channel and the liquid circulation channel, and the area of ​​the liquid circulation channel in the horizontal direction are the same. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell. ITO glass is used as a conductive substrate with its conductive surface facing the patterned electrolytic cell, see Figure 3 b.

[0061] (2) In this example, the relationship between the patterned electrolytic cell, the conductive substrate and the solution wettability is further studied. Figure 7 ,in, Figure 7 a schematically shows the effect of using plasma cleaning technology and siloxane hydrophobic technology to modify the hydrophilicity and hydrophobicity of ITO glass. It can be clearly seen that the contact between the electrolyte and the conductive substrate is greatly affected by the wettability, which is also the key influencing step of patterning using an electrolytic cell; Figure 7 b schematically shows the solvent connection state of the interface between the two after adding deionized water to the hydrophilic silica gel electrolytic cell and soaking the ITO glass in a hydrophobic reagent for hydrophobic treatment. The solvent will fill the entire cavity and cover the ITO film, and it will not overflow along the tank. In addition, a removable glue is applied to the top surface of the patterned electrolytic cell (i.e., the top surface of the area used to separate different patterned channels and the peripheral area of ​​the entire electrolytic cell).

[0062] (3) performing an infiltration treatment on the inner wall of the patterned channel (i.e., performing a hydrophilic treatment on the inner wall of the patterned channel), specifically: providing a hydrophilic gel coating (the gel material is polyacrylamide) on the inner wall of the patterned channel;

[0063] (4) Three electrolytes are poured into three liquid flow channels respectively, the electrolytes fill the liquid flow channels, and the liquid levels are continuously raised to the patterned channels connected to the liquid flow channels, and finally the electrolytes are bonded to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channels, wherein electrolyte a comprises 0.1 mol / L aniline, 0.2 mol / L camphorsulfonic acid and 5 wt% of polyethylene glycol with a molecular weight of 20,000, electrolyte b comprises 0.1 mol / L 3,4-ethylenedioxythiophene, 0.2 mol / L camphorsulfonic acid and 5 wt% of polyethylene glycol with a molecular weight of 20,000, and electrolyte c comprises 0.1 mol / L pyrrole, camphorsulfonic acid and 5 wt% of polyethylene glycol with a molecular weight of 20,000.

[0064] (5) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation through a carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip through a copper foil. Ag / AgCl was used as a reference electrode, and constant voltage electropolymerization was performed respectively. The electropolymerization time was 600 s. The obtained patterned film was shown in FIG. Figure 3 c.

[0065] Example 2

[0066] This embodiment provides a method for preparing a patterned conductive polymer film, comprising the following steps:

[0067] (1) A patterned electrolytic cell made of polytetrafluoroethylene material was fabricated using CNC processing technology. The upper portion of the patterned electrolytic cell had two patterned channels (see Figure 4 b), the channel openings of the two patterned channels are both horizontal long rectangular strips, the lower ends of the two patterned channels are respectively connected to the corresponding liquid flow channels, the two liquid flow channels are isolated from each other, and are respectively used to transport electrolyte to their respective patterned channels. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell, and an ITO glass is used as a conductive substrate with its conductive surface facing the patterned electrolytic cell. The conductive area on the lower surface of the conductive substrate is a vertical long rectangular strip, and the shape of the patterned film is the intersection of the horizontal long rectangular area of ​​the channel openings of the two patterned channels and the vertical long rectangular area on the lower surface of the conductive substrate, see Figure 3 a.

[0068] (2) Coating a removable glue on the top surface of the patterned electrolytic cell.

[0069] (3) performing an infiltration treatment on the inner wall of the patterned channel (i.e., performing a hydrophilic treatment on the inner wall of the patterned channel), specifically: providing a hydrophilic gel coating (the gel material is polyacrylamide) on the inner wall of the patterned channel;

[0070] (4) The electrolyte is poured into two liquid flow channels respectively, the electrolyte fills the liquid flow channels, and the liquid level is continuously raised to the patterned channel connected to the liquid flow channel, and finally the electrolyte is bonded to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel, wherein the electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphorsulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.

[0071] (5) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation through a carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip through a copper foil. Ag / AgCl was used as a reference electrode, and constant voltage electropolymerization was performed respectively. The electropolymerization time was 600 s. The obtained patterned film was shown in FIG. Figure 4 b.

[0072] Example 3

[0073] This embodiment provides a method for preparing a patterned conductive polymer film, comprising the following steps:

[0074] (1) A patterned electrolytic cell made of polytetrafluoroethylene material is made using CNC processing technology. The structural schematic diagram of the patterned electrolytic cell is shown in Figure 5 , one side of the upper part of the patterned electrolytic cell has three patterned channels, the channel openings of the three patterned channels are rectangular, the lower ends of the three patterned channels are connected to the corresponding liquid circulation channels respectively, the three liquid circulation channels are isolated from each other, and a liquid injection port is provided on the other side of the upper part of the patterned electrolytic cell, and the liquid injection port is connected to the three liquid circulation channels, the height of the liquid injection port is higher than the height of the patterned channel, and is used to transport the electrolyte to each liquid circulation channel. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell, and an ITO glass is used as a conductive substrate, with its conductive surface facing the patterned electrolytic cell.

[0075] (2) Coating a removable glue on the top surface of the patterned electrolytic cell.

[0076] (3) performing an infiltration treatment on the inner wall of the patterned channel (i.e., performing a hydrophilic treatment on the inner wall of the patterned channel), specifically: providing a hydrophilic gel coating (the gel material is polyacrylamide) on the inner wall of the patterned channel;

[0077] (4) Three electrolytes are poured into three liquid flow channels from the injection ports respectively, the electrolytes fill the liquid flow channels, and the liquid levels are continuously raised to the patterned channels connected to the liquid flow channels, and finally the electrolytes are bonded to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channels, wherein electrolyte a comprises 0.1 mol / L aniline, 0.2 mol / L camphorsulfonic acid and 5 wt% of polyethylene glycol with a molecular weight of 20,000, electrolyte b comprises 0.1 mol / L 3,4-ethylenedioxythiophene, 0.2 mol / L camphorsulfonic acid and 5 wt% of polyethylene glycol with a molecular weight of 20,000, and electrolyte c comprises 0.1 mol / L pyrrole, camphorsulfonic acid and 5 wt% of polyethylene glycol with a molecular weight of 20,000.

[0078] (5) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation through a carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip through a copper foil. Ag / AgCl was used as a reference electrode (inserted into the injection port of the patterned electrolytic cell) to perform constant voltage electropolymerization (the polymerization voltage of electrolyte a was 0.8 V, the polymerization voltage of electrolyte b was 1.2 V, and the polymerization voltage of electrolyte c was 0.625 V). The electropolymerization time was 600 s. The obtained patterned film was shown in FIG. Figure 6 .

[0079] Example 4

[0080] This embodiment provides a method for preparing a patterned conductive polymer film, comprising the following steps:

[0081] (1) The patterned electrolytic cell made of polytetrafluoroethylene material is made using CNC processing technology. The actual picture of the patterned electrolytic cell can be found in Figure 8 b. One side of the upper part of the patterned electrolytic cell has a patterned channel, the channel opening of the patterned channel is rectangular, the lower end of the patterned channel is connected to the corresponding liquid circulation channel, and the other side of the upper part of the patterned electrolytic cell is provided with a liquid injection port, and the liquid injection port is connected to the liquid circulation channel, and the height of the liquid injection port is higher than the height of the patterned channel, which is used to transport the electrolyte to each liquid circulation channel. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell, and an ITO glass is used as a conductive substrate, so that its conductive surface faces the patterned electrolytic cell.

[0082] (2) Coating a removable glue on the top surface of the patterned electrolytic cell.

[0083] (3) pouring the electrolyte into the liquid flow channel from the injection port, so that the electrolyte fills the liquid flow channel, and the liquid level continues to rise to the patterned channel connected to the liquid flow channel, and finally the electrolyte is bonded to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel, wherein the electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphorsulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.

[0084] (4) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation via carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip via copper foil. Ag / AgCl was used as a reference electrode. Constant voltage electropolymerization was performed for 600 s to obtain a rectangular patterned film.

[0085] Comparative Example 1

[0086] This comparative example provides a method for preparing a patterned conductive polymer film, comprising the following steps:

[0087] (1) The patterned electrolytic cell made of polytetrafluoroethylene material is made using CNC processing technology. The actual picture of the patterned electrolytic cell can be found in Figure 8 a, the upper part of the patterned electrolytic cell has a patterned channel, the channel opening of the patterned channel is rectangular, and the lower end of the patterned channel is connected to the corresponding liquid circulation channel for transporting electrolyte to each patterned channel. In the drawings of this embodiment, the patterned channel and the liquid circulation channel are integrated, that is, the shape area of ​​the channel opening of the patterned channel, the area at the connection position of the patterned channel and the liquid circulation channel, and the area of ​​the liquid circulation channel in the horizontal direction are the same. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell, and ITO glass is used as a conductive substrate so that its conductive surface faces the patterned electrolytic cell.

[0088] (2) Coating a removable glue on the top surface of the patterned electrolytic cell.

[0089] (3) pouring the electrolyte into the liquid flow channel. Since the height of the liquid flow channel pouring position is the same as the height of the liquid flow channel below the patterned channel, the electrolyte cannot rise through the liquid flow channel below the patterned channel to the patterned channel, resulting in the electrolyte in the liquid flow channel being unable to contact the lower surface of the conductive substrate, wherein the electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphorsulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.

[0090] (4) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation via carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip via copper foil. Ag / AgCl was used as a reference electrode. Constant voltage electropolymerization was performed for 600 s. It was found that no patterned film could be electropolymerized.

[0091] Comparative Example 2

[0092] This comparative example provides a method for preparing a patterned conductive polymer film, comprising the following steps:

[0093] (1) The patterned electrolytic cell made of polytetrafluoroethylene material is made using CNC processing technology. The actual picture of the patterned electrolytic cell can be found in Figure 8 b. One side of the upper part of the patterned electrolytic cell has a patterned channel, the channel opening of the patterned channel is rectangular, the lower end of the patterned channel is connected to the corresponding liquid circulation channel, and the other side of the upper part of the patterned electrolytic cell is provided with a liquid injection port, and the liquid injection port is connected to the liquid circulation channel, and the height of the liquid injection port is higher than the height of the patterned channel, which is used to transport the electrolyte to each liquid circulation channel. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell, and an ITO glass is used as a conductive substrate, so that its conductive surface faces the patterned electrolytic cell.

[0094] (2) pouring the electrolyte into the liquid flow channel from the injection port, so that the electrolyte fills the liquid flow channel, and the liquid level continues to rise to the patterned channel connected to the liquid flow channel, and finally the electrolyte is bonded to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel, wherein the electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphorsulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.

[0095] (3) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip through copper foil. Ag / AgCl was used as the reference electrode, and constant voltage electropolymerization was performed for 600 s. It was found that if the top surface of the patterned electrolytic cell was not coated with removable glue, the electrolyte would overflow and the actual electroplating area would exceed the patterned channel, resulting in the inability to obtain the desired electroplating pattern. See Fig. 9 .

[0096] Application Examples

[0097] This embodiment provides a method for preparing an electrochromic lateral device using the method of embodiment 3, comprising the following steps:

[0098] An indium tin oxide (ITO) film is arranged on an insulating glass, and is electroplated in an aniline monomer solution (0.1 mol / L aniline, 0.025 mol / L sodium polystyrene sulfonate, 0.025 mol / L camphor sulfonic acid, 0.05 mol / L sulfuric acid, and a solvent of water), a thiophene monomer solution (0.1 mol / L thiophene, 0.025 mol / L sodium polystyrene sulfonate, 0.025 mol / L camphor sulfonic acid, 0.05 mol / L sulfuric acid, and a solvent of water) and a poly (3,4-ethylenedioxythiophene-2-methanol) monomer solution (0.1 mol / L 3,4-ethylenedioxythiophene-2-methanol, 0.025 mol / L sodium polystyrene sulfonate, 0.025 mol / L camphor sulfonic acid, 0.05 mol / L sulfuric acid, and a solvent of water) in sequence, so that three films of polyaniline, polypyrrole, and poly (3,4-ethylenedioxythiophene-2-methanol) are electroplated on the top of the ITO film;

[0099] On the insulating glass, a copper foil conductive tape is respectively attached to both sides of the ITO film as the first conductive electrode and the second conductive electrode, and a preset distance is provided between the first conductive electrode and the second conductive electrode and the conductive layer and the electrochromic layer. Then, on the insulating glass, packaging glue is respectively arranged on both sides of the first conductive electrode and the second conductive electrode, and the packaging glue is tightly connected to the first conductive electrode and the second conductive electrode. Transparent glass is covered above the first conductive electrode, the electrolyte, the second conductive electrode and the retaining wall. Then, a 0.005 mol / L sulfuric acid electrolyte is injected between the first conductive electrode, the second conductive electrode and the conductive layer with a syringe, and the electrolyte covers the electrochromic layer to obtain an electrochromic lateral device.

[0100] Connect the positive electrode of the constant voltage power supply to the first conductive electrode, and the negative electrode to the second conductive electrode, and apply a 3V voltage. It will be found that the three films will have a uniform gradient effect at the same time (such as Fig.10 A); keep the voltage, use the tungsten lamp light source, the electric translation stage and the spectrometer to build the film transmission spectrum test device to measure the gradient spectrum of the three films as shown in Fig.10 As shown in B.

[0101] Although the principles of the present invention are described in detail above in conjunction with the preferred embodiments of the present invention, those skilled in the art should understand that the above embodiments are merely explanations of the exemplary implementations of the present invention, and are not intended to limit the scope of the present invention. The details in the embodiments do not constitute limitations on the scope of the present invention, and any obvious changes such as equivalent transformations, simple replacements, etc. based on the technical solution of the present invention, without departing from the spirit and scope of the present invention, fall within the protection scope of the present invention.

Claims

1. A patterned electrolysis device, characterized in that: comprising a patterned electrolytic cell, a conductive electrode and a conductive substrate; A plurality of patterned channels are provided on one side of the upper portion of the patterned electrolytic cell, the channel opening of each patterned channel has a predetermined shape, the lower end of the patterned channel is connected to the corresponding liquid circulation channel, and the liquid circulation channels are isolated from each other and are respectively used to transport electrolyte to the respective patterned channels; The conductive electrode is located at the bottom of the patterned electrolytic cell; The conductive substrate is located on the top of the patterned electrolytic tank, and its lower surface is in contact with the upper surface of the patterned channel, so as to form a polymer film on the conductive area on the lower surface of the conductive substrate after electropolymerization of the electrolyte.

2. The patterned electrolysis device according to claim 1, characterized in that: A liquid injection port is provided on the other side of the upper portion of the patterned electrolytic cell, and the liquid injection port is communicated with each liquid circulation channel, and is used to transport the electrolyte to each liquid circulation channel; The height of the injection port is higher than the height of the patterned channel.

3. A method for preparing a patterned conductive polymer film, characterized in that: The following steps are involved: preparing a patterned electrolytic device; performing a non-wetting treatment on the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate; performing an infiltration treatment on the inner wall of the patterned channel; For each channel opening of the patterned channel, injecting an electrolyte corresponding to the polymer film to be formed at the channel opening into the liquid circulation channel connected to the channel opening through the injection port of the patterned electrolytic cell, so that the electrolyte fills the liquid circulation channel and the patterned channel connected to the liquid circulation channel, and the horizontal surface of the electrolyte in the patterned channel is in contact with the lower surface of the conductive substrate; as well as The conductive electrode and the conductive substrate are respectively connected to a power source to perform electropolymerization, so that the electrolyte in the patterned channel is electropolymerized on the conductive area on the lower surface of the conductive substrate to form a patterned film.

4. The method for preparing a patterned conductive polymer film according to claim 3, characterized in that: When the electrolyte is an aqueous solution, the upper surface of the patterned electrolytic tank and the lower surface of the conductive substrate are treated to be hydrophobic, and the inner wall of the patterned channel is treated to be hydrophilic; or, When the electrolyte is an oil phase solution, the upper surface of the patterned electrolytic tank and the lower surface of the conductive substrate are treated to be hydrophilic, and the inner wall of the patterned channel is treated to be hydrophobic.

5. The method for preparing a patterned conductive polymer film according to claim 4, characterized in that: The method of performing hydrophobic treatment on the upper surface of the patterned electrolytic tank and the lower surface of the conductive substrate is: coating the patterned electrolytic tank and the conductive substrate with a hydrophobic material; or, The patterned electrolytic cell and the conductive substrate are polished.

6. The method for preparing a patterned conductive polymer film according to claim 4, characterized in that: The method of performing hydrophilic treatment on the upper surface of the patterned electrolytic tank and the lower surface of the conductive substrate is: coating the patterned electrolytic tank and the conductive substrate with a hydrophilic material; or, The patterned electrolytic cell and the conductive substrate are cleaned using surface plasma.

7. The method for preparing a patterned conductive polymer film according to claim 4, characterized in that: The inner wall of the patterned channel is treated to be hydrophobic by: coating the wall of the patterned channel with a hydrophobic material; and / or, The method of performing hydrophilic treatment on the inner wall of the patterned channel is: coating the wall of the patterned channel with a hydrophilic material.

8. The method for preparing a patterned conductive polymer film according to claim 3, characterized in that: The method further comprises coating a removable glue on the top surface of the patterned electrolytic tank after the step of preparing the patterned electrolytic device; The area of ​​the conductive electrode covers the area of ​​the channel opening of the patterned channel.

9. The method for preparing a patterned conductive polymer film according to claim 3, characterized in that: The conductive area on the lower surface of the conductive substrate is of a first shape, the shape area of ​​the channel opening of the patterned channel is of a second shape, and the shape formed by the patterned film on the conductive substrate is an intersection of the first shape and the second shape.

10. Use of the method for preparing the patterned conductive polymer film according to claim 3 in preparing an electrochromic lateral device.

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