Patterned electrolytic device and method of making patterned conductive polymer film
By designing a patterned electrolysis device and applying hydrophilic and hydrophobic treatments, high-resolution, low-cost patterned conductive polymer films were prepared, solving the problems of complex processes and high costs in existing technologies. This method is applicable to various solution-phase electrochemical polymerizations.
Patent Information
- Application Number
- CN202510286490.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-11
- Publication Date
- 2025-12-16
- Estimated Expiration
- 2045-03-11
AI Technical Summary
Existing methods for preparing patterned conductive polymer films suffer from problems such as complex processes, high costs, insufficient pattern resolution, and unstable electrical properties when dealing with complex patterns. In particular, the choice of solvent and subsequent processes affect the integrity of the pattern during the preparation of multiple materials.
The design of the patterned electrolysis device, through the isolation design of the patterned channel and the liquid flow channel, allows the electrolyte and the conductive substrate to directly contact each other at different locations, enabling the simultaneous containment of multiple electrolytes and the formation of patterned thin films. Combined with hydrophilic and hydrophobic treatment and the use of removable adhesive, it ensures the adhesion of the electrolyte to the substrate and the clarity of the pattern.
It achieves high-resolution, low-cost preparation of patterned conductive polymer films with good adhesion, requires no modification to the electrochemical polymerization formulation, avoids the coffee ring effect, and is suitable for electrochemical polymerization in various solution phases.
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Figure CN119980264B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of electropolymerization and electrodeposition, and particularly relates to a patterned electrolysis device and a preparation method of a patterned conductive polymer film. BACKGROUND
[0002] The patterned conductive polymer film refers to a conductive polymer film with a specific pattern. Such a film has applications in many fields, such as electronic devices, wearable sensors, etc. Although there are many existing methods for preparing patterned conductive polymer films, common methods include inkjet printing, printing, photopolymerization, photolithography, oxidant template, self-assembly, etc.
[0003] It should be noted that in the preparation of complex patterns containing multiple materials, the existing methods have certain limitations. 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. In addition to configuring the ink with a suitable viscosity, it is also necessary to ensure that the electrical properties of the polymer are not damaged. The photopolymerization and photolithography processes need to consider the impact of subsequent processes on the solidified material, especially in the preparation process of multiple materials, the solvent of the next material may damage the already solidified conductive polymer layer, thereby affecting the integrity and electrical properties of the pattern, and the configuration of the photopolymerization and photocuring precursor solution also needs to be considered. The oxidant template and self-assembly method require the pattern to be made on the substrate in advance, and the process is complex for complex patterns. In addition, when dealing with high-precision complex patterns, these methods usually require complex process flow and expensive equipment, increasing the cost and time of production. SUMMARY
[0004] In order to solve the above technical problems, the present application provides a patterned electrolysis device and a preparation method of a patterned conductive polymer film, which controls the contact area of the liquid and the electroplating substrate by making a special patterned electrolysis device, thereby preparing a patterned film with different patterns and different components in a single electropolymerization and electrodeposition process.
[0005] To this end, the present application provides the following technical solutions,
[0006] In a first aspect, the present application provides, in an optional embodiment, a patterned electrolysis device, comprising a patterned electrolysis tank, a conductive electrode and a conductive substrate;
[0007] The upper part of the patterned electrolysis tank has a plurality of patterned channels on one side, each channel has a predetermined shape, and the lower end of each patterned channel is in communication with a corresponding liquid flow channel, and each liquid flow channel is isolated from each other and used to transport electrolyte to the corresponding patterned channel.
[0008] The conductive electrode is located at the bottom of the patterned electrolytic cell.
[0009] The conductive substrate is located at the top of the patterned electrolytic cell, and its lower surface is attached to the upper surface of the patterned channel, for forming a patterned polymer film on the conductive area of the lower surface of the conductive substrate after electro-polymerization of the electrolyte.
[0010] In the present application, the liquid flow channel is designed such that the electrolyte in the liquid flow channel directly contacts the conductive substrate at the channel opening of the patterned channel, and the contact surface forms the desired pattern for electro-polymerization. Further, by designing the liquid flow channels to be isolated from each other, the patterned electrolytic device can simultaneously contain different electrolytes, and the different electrolytes directly contact different positions of the conductive substrate.
[0011] Preferably, 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 in communication with each liquid flow channel, for delivering the electrolyte into each liquid flow channel; the height of the liquid injection port is higher than the height of the patterned channel.
[0012] In a second aspect, the present application provides, in optional embodiments, a method for preparing a patterned conductive polymer film, comprising the following steps:
[0013] Preparation of a patterned electrolytic device;
[0014] Non-wetting treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate;
[0015] Wetting treatment of the inner wall of the patterned channel;
[0016] For each channel opening of the patterned channel, the electrolyte corresponding to the polymer film to be formed at the channel opening is injected into the liquid flow channel in communication with the channel opening through the liquid injection port of the patterned electrolytic cell, so that the electrolyte fills the liquid flow channel and the patterned channel in communication with the liquid flow channel, and the horizontal plane of the electrolyte in the patterned channel is attached to the lower surface of the conductive substrate; and the conductive electrode and the conductive substrate are respectively connected to a power source for electro-polymerization, so that the electrolyte in the patterned channel is electro-polymerized on the conductive area of the lower surface of the conductive substrate to form a patterned film.
[0017] In the present application, the power supply is an electrochemical workstation, and when a three-electrode system is needed, a reference electrode can be inserted into the liquid injection port of the patterned electrolytic cell. The present application designs liquid flow channels so that the electrolyte directly contacts the conductive substrate on one side of the cell, and the contact surface forms the pattern required for electropolymerization. Different patterns of channel openings can be designed on different parts of the contact surface, thereby forming different patterns of polymer thin films on different parts of the contact surface. Further, by designing liquid flow channels that are isolated from each other, the electrolytic cell can simultaneously contain different electrolytes, and different electrolytes directly contact different positions of the conductive substrate, thereby enabling the formation of multiple different material conductive polymer thin films.
[0018] In the present application, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate need to be non-wetting treated. If the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are wetted, the electrolyte will spread in the gap between the two, resulting in unclear / blurry final film pattern boundaries, or even the pattern will be connected throughout the surface. In addition, the inner wall of the patterned channel also needs to be wetted. Because the patterned channel is too thin, if it is not wetted, the surface tension is too strong, and the electrolyte will not reach the height of the upper surface of the patterned channel, thereby making it difficult to contact the lower surface of the conductive substrate. Therefore, the patterned channel needs to be wetted to improve the affinity of the electrolyte to the inner wall of the patterned channel and increase the liquid level of the electrolyte in the patterned channel, so that the electrolyte can 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 hydrophobic treated, and the inner wall of the patterned channel is hydrophilic treated; or, when the electrolyte is an oil phase solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are hydrophilic treated, and the inner wall of the patterned channel is hydrophobic treated. The hydrophobic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is by coating the patterned electrolytic cell and the conductive substrate with a hydrophobic material, or by polishing the patterned electrolytic cell and the conductive substrate. The hydrophilic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is by coating the patterned electrolytic cell and the conductive substrate with a hydrophilic material, or by using surface plasma to clean the patterned electrolytic cell and the conductive substrate. The hydrophobic treatment of the inner wall of the patterned channel is by coating the wall of the patterned channel with a hydrophobic material. The hydrophilic treatment of the inner wall of the patterned channel is by coating the wall of the patterned channel with a hydrophilic material.
[0020] Further, the inner wall of the patterned channel is treated with hydrophilic or hydrophobic treatment by filling the patterned channel with gel; the gel filling method includes injecting 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, polyvinylpyrrolidone, polyethylene glycol, silica gel, xanthan gum, carrageenan or paraffin; and / or, when filling the patterned channel with gel, a space for electrolyte injection is reserved at the bottom of the patterned electrolytic cell or the electrolyte is mixed with the gel material.
[0022] In the present application, the hydrophilic or hydrophobic treatment of the inner wall of the patterned channel can further limit the flow direction of the electrolyte, improve the patterned resolution and adhesion of the thin film.
[0023] The further limitation of the flow direction of the electrolyte can be understood 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 not being in contact with the electrolyte liquid level. Therefore, a hydrophilic gel coating is provided on the inner wall of the patterned channel to raise the electrolyte liquid level.
[0024] Preferably, the preparation method further comprises coating a removable adhesive on the top surface of the patterned electrolytic cell after the step of preparing the patterned electrolytic device.
[0025] In the present application, the electrolyte filling method is as follows: first, the electrolyte is subjected to vacuum defoaming treatment, the electrolyte is sucked into an injection container using a long needle, and the injection container is used to inject from the liquid injection port at the top of the patterned electrolytic cell to ensure that the electrolyte fills the liquid flow channel in the patterned electrolytic cell. By coating a removable adhesive on the top surface of the patterned electrolytic cell, the adhesion of the conductive substrate to the patterned electrolytic cell can be increased, further preventing the electrolyte from overflowing, and ensuring that the conductive substrate can be easily removed after the electropolymerization is completed.
[0026] Preferably, the patterned electrolytic cell is prepared by 3D printing technology, silicone reverse molding 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 conductive coating. The electrolyte is a conductive polymer monomer solution or a conductive polymer solution; the conductive polymer monomer solution comprises polymer monomer, dopant, stabilizer and solvent, and the conductive polymer solution comprises conductive polymer, stabilizer and solvent. The conductive polymer monomer is selected from one or more of aniline and its derivatives, thiophene and its derivatives or pyrrole and its derivatives, and there is no special requirement for the selection of the conductive polymer monomer, as long as it is a monomer that can be electropolymerized; and / or, when the electrolyte electrolyte is an aqueous electrolyte, the dopant is a substance that can simultaneously provide protons (hydrogen ions) and anions, 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 electrolyte is an oil-phase electrolyte: the dopant is selected from one or more of organic acid, organic anion salt or ionic liquid, for example: the organic acid can be p-toluenesulfonic acid, octadecyl sulfonic acid, fluorosulfonic acid, methyl sulfonic acid, the organic anion salt can be potassium tetrafluoroborate, lithium hexafluorophosphate, lithium triflate, and the ionic liquid can be 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium triflate, etc.; and / or, the stabilizer is selected from one or more of polyethylene glycol, polyacrylamide, polyvinyl alcohol, polymethyl methacrylate or polyvinylpyrrolidone; and / or, the solvent is selected from water, organic solvent or mixed solvent of water-soluble organic solvent and water.
[0027] In the present application, the mold for preparing the patterned electrolytic cell is a hollow structure, and when the mold is made by silicone reverse molding technology or computer numerical control processing technology, the mold needs to be designed in blocks. The mold is made of one of photosensitive resin, nylon, engineering plastic, polytetrafluoroethylene, organic glass or silicone.
[0028] Preferably, the area of the conductive electrode covers the area of the channel port of the patterned channel.
[0029] Preferably, the conductive area of the lower surface of the conductive substrate is a first shape, the shape area of the channel port of the patterned channel is a second shape, and the shape of the patterned film formed on the conductive substrate is the intersection shape of the first shape and the second shape.
[0030] The conductive substrate is full-area conductive, regionally conductive or partitioned and independently controlled conductive.
[0031] The method for manufacturing the partitioned conductive substrate includes etching a conductive layer of the conductive substrate or printing a partitioned conductive coating.
[0032] The present application further limits the formed pattern by adjusting the actual conductive area and region of the conductive region of the lower surface of the conductive substrate. The formed pattern is the intersection shape of the actual conductive region and the shape region of the channel opening of the patterned channel. The mounting method of the conductive electrode is to insert the conductive electrode material into the bottom of the patterned electrolytic tank by bending, or directly uniformly coat the slurry of the conductive electrode material on the bottom of the patterned electrolytic tank.
[0033] In a third aspect, the present application provides an application of the above-mentioned method for manufacturing the patterned conductive polymer film in the preparation of an electrochromic lateral device.
[0034] In the present application, the method for manufacturing the electrochromic lateral device includes the following steps:
[0035] The conductive layer is arranged on the lower substrate, and then the patterned conductive polymer film is obtained by electroplating on the conductive layer by using the above-mentioned method. Then, the first conductive electrode and the second conductive electrode are arranged on both sides of the conductive layer, and the first conductive electrode and the second conductive electrode have a preset distance from the conductive layer. Then, the barrier walls are arranged on the other two sides of the conductive layer, and the barrier walls are tightly connected with the first conductive electrode and the second conductive electrode to form a frame structure. Finally, the upper substrate is arranged on the first conductive electrode, the electrolyte, the second conductive electrode and the barrier walls, the electrolyte is injected between the first conductive electrode, the second conductive electrode and the conductive layer, and the electrolyte covers the electrochromic layer, so as to obtain the electrochromic lateral device.
[0036] Compared with the prior art, the present application has one or more of the following beneficial effects:
[0037] 1. The present application designs the liquid flow channel, so that the electrolyte in the liquid flow channel directly contacts the conductive substrate at the channel opening of the patterned channel, and the pattern formed by the contact surface is the required pattern of electro-polymerization. Further, by designing the liquid flow channels isolated from each other, the patterned electrolytic device can simultaneously contain different electrolytes, and different electrolytes directly contact different positions of the conductive substrate.
[0038] 2. The preparation method provided by the present application provides a new patterned technical idea. Compared with the printed and electroplated film, the present application has better adhesion, does not need to modify the existing electrochemical polymerization formula, and is suitable for all solution-phase electrochemical polymerization and electrodeposition schemes.
[0039] 3. The method is simple, has low manufacturing cost and good film quality, and compared with the same simple printing and printing, has no coffee ring effect and does not need to prepare high-viscosity ink. BRIEF DESCRIPTION OF DRAWINGS
[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort on the basis of these drawings.
[0041] Figure 1 The schematic diagram of the patterning electro-polymerization technology, the design diagram of the patterning electrolytic cell and the physical diagram of the patterning electrolytic cell of the present application;
[0042] Figure 2 The structural schematic diagram of the patterning electrolytic cell of the present application;
[0043] Figure 3 The model diagram of the patterning electrolytic cell, the physical diagram of the patterning electrolytic device and the physical diagram of the patterning film of Example 1 of the present application;
[0044] Figure 4 The physical diagram of the patterning electrolytic device and the physical diagram of the patterning film of Example 2 of the present application;
[0045] Figure 5 The structural schematic diagram of the patterning electrolytic cell of Example 3 of the present application;
[0046] Figure 6 The physical diagram of the patterning film of Example 3 of the present application;
[0047] Figure 7 The display diagram of the relationship between the patterning electrolytic cell, the conductive substrate and the solution wettability of Example 1 of the present application;
[0048] Figure 8 The model diagram of the patterning electrolytic cell of Example 4 and Comparative Example 1 of the present application;
[0049] Figure 9 The physical diagram of the patterning film prepared in Comparative Example 2 of the present application;
[0050] Figure 10 The physical diagram of the electrochromic transverse device prepared in the application examples and the gradual change spectrum diagram of the three conductive polymer films on the electrochromic transverse device.
[0051] 1-patterning electrolytic cell, 2-conductive electrode, 3-conductive substrate, 4-patterning channel, 5-liquid flow channel, 6-liquid injection port. DETAILED DESCRIPTION
[0052] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.
[0053] With the rapid development of 3D printing technology, it has become simple and low-cost to make high-precision (below 0.1mm) three-dimensional hollow molds. 3D printing technology not only can quickly and accurately manufacture the required mold, but also has a very wide range of material selection, in addition to traditional hard plastic, metal or flexible material can also be selected. Therefore, a micro-channel mold with complex geometric structure can be designed and manufactured according to the needs, which can replace the traditional electrolytic cell for the preparation of complex multi-material conductive polymer patterns.
[0054] Figure 1 a schematically shows the principle of preparing a patterned film by electro-polymerization, wherein the conductive substrate 3 is ITO glass and is located at the top of the patterned electrolytic cell 1, solutions a and b (solutions a and b are different) are respectively filled in the two liquid flow channels 5 of the patterned electrolytic cell 1, the conductive electrode 2 is located at the bottom of the patterned electrolytic cell 1, the conductive substrate 3 and the conductive electrode 2 are respectively connected with the power supply, and two rectangular patterned films are formed on the ITO glass by electro-polymerization.
[0055] Figure 1 b schematically shows the structure of the patterned electrolytic cell, wherein the upper part 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 with the corresponding liquid flow channel 5, and each liquid flow channel 5 is isolated from each other and is used for conveying electrolyte to the corresponding patterned channel 4. Four fluid flow channels 5 are schematically shown in the figure, each liquid flow channel 5 corresponds to three patterned channels 4, and the electrolytes used in the three patterned channels 4 are the same, and the electrolytes in different liquid flow channels 5 can be different from each other.
[0056] Figure 1 c schematically shows the patterned electrolytic cell 1 mold made by the 3D printing technology of stereolithography and the JS-UV-CBY-01 photosensitive resin, which has four types of patterned channels with different sizes in the upper part of the patterned electrolytic cell 1, and further schematically shows that the conductive copper foil is used as the conductive electrode 2. The specific structure is shown in Figure 2 , wherein 1 is the patterned electrolytic cell, 4 is the patterned channel, and 6 is the liquid injection port, and the height of the liquid injection port 6 is higher than the height of the patterned channel 4.
[0057] In Embodiments 1-3, the material of the patterned electrolytic cell is polytetrafluoroethylene, which is inherently hydrophobic, and the electrolyte used in Embodiments 1-3 is an aqueous electrolyte, so no additional non-wetting treatment is required.
[0058] Embodiment 1
[0059] The present embodiment provides a method for preparing a patterned conductive polymer film, comprising the following steps:
[0060] (1) A patterned electrolytic cell made of polytetrafluoroethylene material is prepared using CNC machining technology. The physical diagram of the patterned electrolytic cell is shown in Figure 3 a. The upper part of the patterned electrolytic cell has three patterned channels, and the channel openings of the three patterned channels are rectangular. The lower ends of the three patterned channels are respectively connected to corresponding liquid flow channels, and the three liquid flow channels are isolated from each other and used to transport electrolyte to the respective patterned channels. In the drawings of the present embodiment, the patterned channel and the liquid flow channel are designed in one body, i.e., the shape and area of the channel opening of the patterned channel, the area at the connection position of the patterned channel and the liquid flow channel, and the area of the liquid flow 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, as shown in Figure 3 b.
[0061] (2) In the present embodiment, the relationship between the patterned electrolytic cell, the conductive substrate, and the solution wettability is further studied, and the results are shown in Figure 7 wherein, Figure 7 a schematically shows the effect of hydrophilic and hydrophobic modification of ITO glass using plasma cleaning technology and siloxane hydrophobic technology, respectively. It can be clearly seen that the contact between the electrolyte and the conductive substrate is greatly affected by wettability, which is a key influencing step for patterning using an electrolytic cell; Figure 7 b schematically shows the solvent connection state at the interface between the ITO glass and the hydrophobic reagent after the ITO glass is soaked in deionized water and the hydrophobic reagent is treated for hydrophobicity in a hydrophilic silica gel electrolytic cell. The solvent will fill the entire cavity and cover the ITO film, and it will not overflow along the groove. In addition, removable glue is coated on the top surface of the patterned electrolytic cell, i.e., the top surface of the region separating different patterned channels and the peripheral region of the entire electrolytic cell.
[0062] (3) The inner wall of the patterned channel is treated for wettability (i.e., the inner wall of the patterned channel is treated for hydrophilicity), specifically by providing a hydrophilic gel coating (the gel material is polyacrylamide) on the inner wall of the patterned channel;
[0063] (4) Pour 3 kinds of electrolyte into 3 liquid flow channels respectively, and the electrolyte fills the liquid flow channels and continuously rises to the patterned channels connected with the liquid flow channels, and finally the electrolyte is attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel, wherein the electrolyte a includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5wt% polyethylene glycol with a molecular weight of 20000, the electrolyte b includes 0.1 mol / L 3,4-vinyldioxylthiophene, 0.2 mol / L camphor sulfonic acid and 5wt% polyethylene glycol with a molecular weight of 20000, and the electrolyte c includes 0.1 mol / L pyrrole, camphor sulfonic acid and 5wt% polyethylene glycol with a molecular weight of 20000.
[0064] (5) Connect the conductive electrode with the working electrode alligator clip of the electrochemical workstation through the carbon conductive tape, connect the conductive substrate with the counter electrode alligator clip through the copper foil, and use Ag / AgCl as the reference electrode, and then perform constant voltage electropolymerization respectively, and the electropolymerization time is 600s. The obtained patterned film is shown in Figure 3 c.
[0065] Example 2
[0066] The embodiment provides a preparation method of a patterned conductive polymer film, and the method comprises the following steps:
[0067] (1) Use the CNC processing technology to manufacture a patterned electrolytic cell made of polytetrafluoroethylene material, and the upper part of the patterned electrolytic cell has 2 patterned channels (see Figure 4 b), the channel openings of the 2 patterned channels are horizontal long strip rectangles, the lower ends of the 2 patterned channels are respectively connected with corresponding liquid flow channels, and the 2 liquid flow channels are isolated from each other and are respectively used for conveying electrolyte to the corresponding patterned channel. A carbon rod is used as a conductive electrode and is placed at the bottom of the patterned electrolytic cell, and ITO glass is used as a conductive substrate, and the conductive surface of the conductive substrate faces the patterned electrolytic cell, and the conductive area of the lower surface of the conductive substrate is a vertical long strip rectangle, and the shape of the patterned film is the intersection shape of the horizontal long strip rectangular area of the channel openings of the 2 patterned channels and the vertical long strip rectangular area of the lower surface of the conductive substrate, see Figure 3 a.
[0068] (2) Coat the top surface of the patterned electrolytic cell with removable glue.
[0069] (3) Perform the wetting treatment on the inner wall of the patterned channel (i.e. perform the hydrophilic treatment on the inner wall of the patterned channel), and the specific process is as follows: a hydrophilic gel coating (the gel material is polyacrylamide) is arranged on the inner wall of the patterned channel.
[0070] (4) Pour the electrolyte into the two liquid flow channels respectively. The electrolyte fills the liquid flow channels and the liquid level rises continuously to the patterned channel connected to the liquid flow channels. Finally, the electrolyte is attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. The electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic 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 via carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip via copper foil. Using Ag / AgCl as the reference electrode, constant-voltage electropolymerization was performed for 600 s. The resulting patterned thin film is shown in [reference]. Figure 4 b.
[0072] Example 3
[0073] This embodiment provides a method for preparing a patterned conductive polymer thin film, including the following steps:
[0074] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) was fabricated using CNC machining technology. A schematic diagram of the patterned electrolytic cell can be found in [reference needed]. Figure 5 The patterned electrolytic cell has three patterned channels on one side of its upper part. The openings of these three channels are rectangular, and their lower ends connect to corresponding liquid flow channels. These three liquid flow channels are isolated from each other. A liquid injection port is located on the other side of the upper part of the patterned electrolytic cell, and this port connects to the three liquid flow channels. The height of the injection port is higher than the height of the patterned channels, and it is used to deliver electrolyte to each liquid flow channel. Carbon rods are used as conductive electrodes and placed at the bottom of the patterned electrolytic cell. ITO glass is used as the conductive substrate, with its conductive surface facing the patterned electrolytic cell.
[0075] (2) Apply removable adhesive to the top surface of the patterned electrolytic cell.
[0076] (3) The inner wall of the patterned channel is wetted (i.e., the inner wall of the patterned channel is hydrophilic), specifically: a hydrophilic gel coating (the gel material is polyacrylamide) is applied to the inner wall of the patterned channel.
[0077] (4) Pour 3 kinds of electrolyte into 3 liquid flow channels from the liquid injection port, respectively. The electrolyte fills the liquid flow channel and continuously rises to the patterned channel connected to the liquid flow channel, and finally the electrolyte is attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. Among them, electrolyte a includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5wt% polyethylene glycol with a molecular weight of 20000, electrolyte b includes 0.1 mol / L 3,4-vinyldioxothiophene, 0.2 mol / L camphor sulfonic acid and 5wt% polyethylene glycol with a molecular weight of 20000, and electrolyte c includes 0.1 mol / L pyrrole, camphor sulfonic acid and 5wt% polyethylene glycol with a molecular weight of 20000.
[0078] (5) Connect the conductive electrode to the working electrode alligator clip of the electrochemical workstation through the carbon conductive tape, connect the conductive substrate to the counter electrode alligator clip through the copper foil, and use Ag / AgCl as the reference electrode (inserted into the liquid injection port of the patterned electrolytic cell). Constant voltage electropolymerization is carried out (the polymerization voltage of electrolyte a is 0.8V, the polymerization voltage of electrolyte b is 1.2V, and the polymerization voltage of electrolyte c is 0.625V), and the electropolymerization time is 600s. The obtained patterned film is shown in Figure 6 .
[0079] Example 4
[0080] The embodiment provides a preparation method of a patterned conductive polymer film, comprising the following steps:
[0081] (1) A patterned electrolytic cell made of polytetrafluoroethylene material is prepared by using CNC processing technology. The actual pattern of the patterned electrolytic cell is shown in Figure 8 b. One patterned channel is provided on one side of the upper part of the patterned electrolytic cell, the channel port of the patterned channel is rectangular, the lower end of the patterned channel is in communication with the corresponding liquid flow channel, 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 in communication with the liquid flow channel. The height of the liquid injection port is higher than that of the patterned channel, which is used for delivering electrolyte to each liquid flow channel. A carbon rod is used as a conductive electrode and is placed at the bottom of the patterned electrolytic cell, and ITO glass is used as a conductive substrate with its conductive surface facing the patterned electrolytic cell.
[0082] (2) A removable glue is coated on the top surface of the patterned electrolytic cell.
[0083] (3) Pouring electrolyte into the liquid flow channel from the liquid injection port, making the electrolyte fill the liquid flow channel, and making its liquid level continuously rise into the patterned channel connected with the liquid flow channel, and finally making the electrolyte adhere to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel, wherein the electrolyte comprises 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid, and 5 wt% polyethylene glycol with a molecular weight of 20000.
[0084] (4) Connecting the conductive electrode with the working electrode alligator clip of the electrochemical workstation through the carbon conductive tape, connecting the conductive substrate with the counter electrode alligator clip through the copper foil, and using Ag / AgCl as the reference electrode, respectively, for constant voltage electropolymerization, and the electropolymerization time is 600 s, and a rectangular patterned film is obtained by electropolymerization.
[0085] Comparative Example 1
[0086] The present comparative example provides a preparation method of a patterned conductive polymer film, comprising the following steps:
[0087] (1) Using CNC processing technology to make a patterned electrolytic cell of polytetrafluoroethylene material, and the actual picture of the patterned electrolytic cell is shown in Figure 8 a, the upper part of the patterned electrolytic cell has one patterned channel, the channel port of the patterned channel is rectangular, the lower end of the patterned channel is communicated with the corresponding liquid flow channel, and the liquid flow channel is used to transport electrolyte to the corresponding patterned channel, in the drawing of the present embodiment, the patterned channel and the liquid flow channel are integrated design, that is, the shape area of the channel port of the patterned channel, the area at the connection position of the patterned channel and the liquid flow channel, and the area of the liquid flow 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, and the conductive surface thereof faces the patterned electrolytic cell.
[0088] (2) Coating removable glue on the top surface of the patterned electrolytic cell.
[0089] (3) Pouring electrolyte into the liquid flow channel from the liquid injection port, since the height at the pouring position of the liquid flow channel is the same as the height of the liquid flow channel below the patterned channel, the electrolyte cannot rise into the patterned channel through the liquid flow channel below the patterned channel, so that the electrolyte in the liquid flow channel cannot contact the lower surface of the conductive substrate, wherein the electrolyte comprises 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid, and 5 wt% polyethylene glycol with a molecular weight of 20000.
[0090] (4) The conductive electrode is connected to the working electrode alligator clip of the electrochemical workstation through the carbon conductive tape, the conductive substrate is connected to the counter electrode alligator clip through the copper foil, and Ag / AgCl is used as the reference electrode to perform constant voltage electropolymerization, and the electropolymerization time is 600 s. It is found that the patterned film cannot be electropolymerized.
[0091] Comparative Example 2
[0092] The present comparative example provides a method for preparing a patterned conductive polymer film, comprising the following steps:
[0093] (1) A patterned electrolytic cell made of polytetrafluoroethylene material is prepared using CNC machining technology. The actual drawing of the patterned electrolytic cell is shown in Figure 8 b, one patterned channel is provided on one side of the upper part of the patterned electrolytic cell, the channel opening of the patterned channel is rectangular, the lower end of the patterned channel is in communication with the corresponding liquid flow channel, an injection port is provided on the other side of the upper part of the patterned electrolytic cell, and the injection port is in communication with the liquid flow channel, the height of the injection port is higher than the height of the patterned channel, and the injection port is used to deliver electrolyte to each liquid flow 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.
[0094] (2) The electrolyte is poured into the liquid flow channel from the injection port, so that the electrolyte fills the liquid flow channel and continuously rises to the patterned channel connected to the liquid flow channel, and finally the electrolyte is attached to the horizontal surface of the patterned channel and the lower surface of the conductive substrate (ITO glass). The electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20000.
[0095] (3) The conductive electrode is connected to the working electrode alligator clip of the electrochemical workstation through the carbon conductive tape, the conductive substrate is connected to the counter electrode alligator clip through the copper foil, and Ag / AgCl is used as the reference electrode to perform constant voltage electropolymerization, and the electropolymerization time is 600 s. It is found that the patterned film cannot be electropolymerized out of the patterned electrolytic cell. If the top surface of the patterned electrolytic cell is coated with removable glue, the electrolyte will overflow, the actual area of electroplating will exceed the patterned channel, and the desired pattern cannot be obtained, as shown in Figure 9 .
[0096] Application Example
[0097] The present example provides a method for preparing an electrochromic transverse device using the method of Example 3, comprising the following steps:
[0098] An ITO thin film is provided on an insulating glass, and then 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 water as solvent), 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 water as solvent), and 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 water as solvent) are electroplated in sequence, so that three thin films of polyaniline, polypyrrole and poly-3,4-ethylenedioxythiophene-2-methanol are obtained above the ITO thin film.
[0099] On the insulating glass, two copper foil conductive tapes are respectively attached to two sides of the ITO thin film as a first conductive electrode and a second conductive electrode, and the first conductive electrode and the second conductive electrode have a preset distance from the conductive layer and the electrochromic layer, then on the insulating glass, encapsulating glue is respectively provided on two sides of the first conductive electrode and the second conductive electrode, and the encapsulating glue is tightly connected with the first conductive electrode and the second conductive electrode, a transparent glass is covered above the first conductive electrode, the electrolyte, the second conductive electrode and the barrier wall, then 0.005 mol / L sulfuric acid electrolyte electrolyte is injected between the first conductive electrode and the second conductive electrode by a syringe, and the electrolyte covers the electrochromic layer, so that an electrochromic transverse device is obtained.
[0100] The positive electrode of a constant-voltage power supply is connected with the first conductive electrode, and the negative electrode is connected with the second conductive electrode, and a 3V voltage is applied, and it is found that the three thin films simultaneously have a uniform gradual change effect (as shown in Figure 10 A); the voltage is maintained, and the gradual change spectrum of the three thin films is measured by a thin film transmittance spectrum testing device built by a tungsten lamp light source, a motorized displacement stage and a spectrometer, as shown in Figure 10 B.
[0101] Although the principles of the present application have been described in detail with reference to the preferred embodiments thereof, those skilled in the art should understand that the above embodiments are only illustrative implementations of the present application, and are not a limitation on the scope of the present application. The details in the embodiments do not constitute a limitation on the scope of the present application, and any equivalent transformation, simple replacement, etc. based on the technical solutions of the present application, which do not deviate from the spirit and scope of the present application, all fall within the protection scope of the present application.
Claims
1. A patterned electrolysis apparatus, characterized in that, Includes patterned electrolytic cells, conductive electrodes, and conductive substrates; The patterned electrolytic cell has several patterned channels on one side of its upper part. The opening of each patterned channel has a predetermined shape. The lower end of each patterned channel is connected to a corresponding liquid flow channel. Each liquid flow channel is isolated from the others and is used to deliver electrolyte to its respective patterned channel. The conductive electrode is located at the bottom of the patterned electrolytic cell; The conductive substrate is located at the top of the patterned electrolytic cell, and its lower surface is attached to 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 the electrolyte is electropolymerized. The patterned electrolytic cell has a liquid injection port on the other side of its upper part, and the liquid injection port is connected to each liquid flow channel for delivering the electrolyte to each liquid flow channel. The height of the injection port is higher than the height of the patterned channel.
2. A method for preparing patterned conductive polymer films using the patterned electrolysis apparatus of claim 1, characterized in that, Includes the following steps: Fabrication of patterned electrolysis devices; The upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are subjected to non-wetting treatment; The inner wall of the patterned channel is impregnated. For each channel opening of the patterned channel, the electrolyte corresponding to the polymer film to be formed at the channel opening is injected through the injection port of the patterned electrolytic cell into the liquid flow channel communicating with the channel opening, so that the electrolyte fills the liquid flow channel and the patterned channel communicating with the liquid flow channel, and the horizontal plane 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 for electropolymerization, which causes the electrolyte in the patterned channel to electropolymerize on the conductive area on the lower surface of the conductive substrate to form a patterned thin film.
3. The method according to claim 2, characterized in that, 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 oil-phase 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.
4. The method according to claim 3, characterized in that, The method for hydrophobic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is as follows: coating the patterned electrolytic cell and the conductive substrate with a hydrophobic material; or, The patterned electrolytic cell and the conductive substrate are polished.
5. The method according to claim 3, characterized in that, The method for hydrophilic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is as follows: coating the patterned electrolytic cell and the conductive substrate with a hydrophilic material; or, The patterned electrolytic cell and conductive substrate are cleaned using surface plasma cleaning.
6. The method according to claim 3, characterized in that, The method for hydrophobic treatment of the inner wall of the patterned channel is as follows: coating the inner wall of the patterned channel with a hydrophobic material; and / or, The method for hydrophilic treatment of the inner wall of the patterned channel is to coat the inner wall of the patterned channel with a hydrophilic material.
7. The method according to claim 2, characterized in that, It also includes coating the top surface of the patterned electrolytic cell with a removable adhesive after the step of preparing the patterned electrolytic device; The area of the conductive electrode covers the area of the opening of the patterned channel.
8. The method according to claim 2, characterized in that, The conductive region on the lower surface of the conductive substrate has a first shape, the shape region of the channel opening of the patterned channel has a second shape, and the shape formed by the patterned thin film on the conductive substrate is the intersection of the first shape and the second shape.
9. The application of a patterned conductive polymer film obtained by the method of claim 2 in the fabrication of electrochromic lateral devices.