Preparation method of a flexible three-dimensional electrode

Abstract

The present invention discloses a preparation method of a flexible three-dimensional electrode. First, a flexible polymer solution is added to a processing container and left to stand until completely cured to obtain a flexible substrate. Then, a patterned mold is placed on the surface of the flexible substrate, and a flexible polymer solution and magnetic particles are added into the patterned mold, and then placed in a magnetic field environment to be cured to form a three-dimensional structure layer. After complete curing, a conductive metal material is deposited on the surface to form a metal conductive layer. Finally, the patterned mold is removed, and only the part of the metal conductive layer covering the three-dimensional structure layer is retained to obtain the flexible three-dimensional electrode. The inventive method can achieve the integrated molding of the substrate and the electrode structure, the three-dimensional structure morphology of the electrode is controllable, and the prepared electrode structure has the characteristics of a large specific surface area, improving the electrochemical performance of the electrode. The processing method of the inventive method is simple and has low cost.

Description

Technical Field

[0001] The present invention belongs to the field of flexible electronics technology, and particularly relates to a method for preparing a flexible three-dimensional electrode. Background Art

[0002] With the development of flexible electronics technology, flexible electronic devices show broad application potential in the fields of wearable electronic devices, portable electronic devices, and real-time monitoring medical devices, etc. Flexible electronic devices refer to the electronic technology that integrates components on a flexible substrate. Different from traditional electronic technology, such devices have the characteristics of strong flexibility and good ductility. In order to improve the integration of flexible devices, many electrochemical flexible electronics require electrodes with a large specific surface area to enhance device performance. Three-dimensional electrodes can increase the surface area of the electrode while maintaining a small device volume, and are widely used in the field of electrochemical energy conversion and storage due to their many advantages, such as sewage treatment in electrode reactors, and supercapacitors, sensors, etc. in the energy storage field. Currently, in order to increase the specific surface area of the electrode, the commonly used method is to prepare the electrode substrate using a mesoporous structure, and the commonly used materials include carbon nanoparticles, ZnO nanoparticles, and coarse sugar, etc. However, since the movement of the microparticles is not easily controlled during the preparation process, it affects the morphology of the electrode and is not conducive to further improving the device performance. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for preparing a flexible three-dimensional electrode.

[0004] The method of the present invention is as follows:

[0005] Step (1): Add a flexible polymer solution and a corresponding curing agent into a processing container, and let it stand until completely cured to obtain a flexible substrate.

[0006] Step (2): Place a patterned mold on the surface of the flexible substrate. Add a flexible polymer solution, a corresponding curing agent, and magnetic particles into the patterned mold, and place it in a magnetic field environment and let it stand for 2 to 6 hours. After curing, a three-dimensional structure layer with a designed pattern on the plane is formed. The three-dimensional structure layer has a micro-column morphology with magnetically controlled growth.

[0007] Further, the magnetic particles are iron powder or Fe 2 O 3 particles with a particle size of 50 nm to 10 μm, and the mass ratio to the flexible polymer solution is 1:1 to 20:1.

[0008] Further, the same flexible polymer solution is used in steps (1) and (2), which is polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), or polyethylene terephthalate (PET).

[0009] Step (3): Take out the processing container and the patterning mold as a whole from the magnetic field environment, and let it stand still until it is completely cured to obtain a flexible polymer structure.

[0010] Step (4): Using the method of magnetron sputtering, deposit a conductive metal material on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer. Further, the conductive metal material is gold, silver or copper.

[0011] Step (5): Remove the patterning mold, and only the part of the metal conductive layer covering the three-dimensional structure layer remains to obtain a flexible three-dimensional electrode.

[0012] The present invention has the following beneficial effects compared with the prior art:

[0013] The inventive method is based on a homogeneous polymer substrate, adding magnetic particles with appropriate sizes to the polymer solution, and using a patterning template. By controlling the applied magnetic field, a three-dimensional electrode structure with controllable morphology is obtained through curing. Using the method of metal deposition, a conductive layer is processed on the surface of the structure to obtain a three-dimensional structure electrode. This method can realize the integrated molding of the substrate and the electrode structure, the three-dimensional morphology of the electrode is controllable, and the processing method is applicable to a variety of similar materials, which has important reference significance for the research and development of high-performance flexible electronic devices.

[0014] The method of the present invention can prepare a customizable three-dimensional electrode structure on a flexible substrate. The prepared electrode structure has the characteristic of a large specific surface area, which can effectively improve the electrochemical performance of the electrode. The proposed method has the characteristics of low manufacturing cost, simple operation and strong scalability.

[0015] The present invention utilizes the different forces of magnetic particles with different sizes in magnetic fields with different intensities. By controlling the magnitude of the applied magnetic field and the size of the magnetic particles, the low-cost and controllable preparation of three-dimensional electrodes can be realized. By adding a structure template, the three-dimensional processing of the electrode structure can be graphically realized, which can be applied to the research and development of flexible electronic components, effectively improving the specific surface area of the electrode material and thus improving the electrochemical performance of the device. The method of the present invention has the characteristics of simple manufacturing method and low cost, and at the same time, combined with a graphic template, the preparation of a graphic three-dimensional electrode can be realized. Description of the Drawings

[0016] Figure 1 It is a schematic diagram of the morphology of the three-dimensional structure layer processed on the flexible substrate in the method of the present invention. Detailed Embodiments

[0017] Example 1.

[0018] Step (1): Add polydimethylsiloxane (PDMS) solution and the corresponding curing agent into a processing container with a square bottom surface, and let it stand still until it is completely cured to obtain a square flexible substrate;

[0019] Step (2): Place the patterned mold on the surface of the flexible substrate. Add polydimethylsiloxane (PDMS) solution, the corresponding curing agent, and iron powder with a particle size of 50 nm into the patterned mold, and place it in a magnetic field environment for 2 hours of static settlement. After curing, a three-dimensional structure layer with a planar design pattern is formed. The three-dimensional structure layer has a micro-column morphology grown by magnetic control. The mass ratio of the added iron powder to the polydimethylsiloxane (PDMS) solution is 1:1.

[0020] Step (3): Take out the processing container and the patterned mold as a whole from the magnetic field environment, and let it stand until completely cured to obtain a flexible polymer structure retaining the patterned mold.

[0021] Step (4): Use the method of magnetron sputtering to deposit conductive metal gold on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer.

[0022] Step (5): Remove the patterned mold. Only the part of the metal conductive layer covering the three-dimensional structure layer is retained, and the other parts of the metal conductive layer are removed with the patterned mold to obtain a flexible three-dimensional electrode.

[0023] Example 2.

[0024] Step (1): Add polymethyl methacrylate (PMMA) solution and the corresponding curing agent into a processing container with a circular bottom surface, and let it stand until completely cured to obtain a circular flexible substrate.

[0025] Step (2): Place the patterned mold on the surface of the flexible substrate. Add polymethyl methacrylate (PMMA) solution, the corresponding curing agent, and Fe 2 O 3 particles with a particle size of 100 nm into the patterned mold, and place it in a magnetic field environment for 3 hours of static settlement. After curing, a three-dimensional structure layer with a planar design pattern is formed. The three-dimensional structure layer has a micro-column morphology grown by magnetic control. The mass ratio of the added Fe 2 O 3 particles to the polymethyl methacrylate (PMMA) solution is 3:1.

[0026] Step (3): Take out the processing container and the patterned mold as a whole from the magnetic field environment, and let it stand until completely cured to obtain a flexible polymer structure retaining the patterned mold.

[0027] Step (4): Use the method of magnetron sputtering to deposit conductive metal silver on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer.

[0028] Step (5): Remove the patterned mold. Only the part of the metal conductive layer covering the three-dimensional structure layer is retained, and the other parts of the metal conductive layer are removed with the patterned mold to obtain a flexible three-dimensional electrode.

[0029] Example 3

[0030] Step (1): Add polyethylene terephthalate (PET) solution and the corresponding curing agent into a processing container with a rectangular bottom surface, and let it stand still until it is completely cured to obtain a rectangular flexible substrate.

[0031] Step (2): Place the patterning mold on the surface of the flexible substrate. Add polyethylene terephthalate (PET) solution, the corresponding curing agent, and iron powder with a particle size of 500 nm into the patterning mold, and place it in a magnetic field environment and let it stand still for 3.5 hours. After curing, a three-dimensional structure layer with a designed pattern on the plane is formed, and the three-dimensional structure layer has a micro-column morphology grown by magnetic control; the mass ratio of the added iron powder to the polyethylene terephthalate (PET) solution is 5:1.

[0032] Step (3): Take out the processing container and the patterning mold as a whole from the magnetic field environment, and let it stand still until it is completely cured to obtain a flexible polymer structure retaining the patterning mold.

[0033] Step (4): Use the method of magnetron sputtering to deposit conductive metal copper on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer.

[0034] Step (5): Remove the patterning mold. Only the part of the metal conductive layer covering the three-dimensional structure layer is retained, and the other parts of the metal conductive layer are removed along with the patterning mold to obtain a flexible three-dimensional electrode.

[0035] Example 4

[0036] Step (1): Add polydimethylsiloxane (PDMS) solution and the corresponding curing agent into a processing container with a square bottom surface, and let it stand still until it is completely cured to obtain a square flexible substrate.

[0037] Step (2): Place the patterning mold on the surface of the flexible substrate. Add polydimethylsiloxane (PDMS) solution, the corresponding curing agent, and Fe 2 O 3 particles into the patterning mold, and place it in a magnetic field environment and let it stand still for 4 hours. After curing, a three-dimensional structure layer with a designed pattern on the plane is formed, and the three-dimensional structure layer has a micro-column morphology grown by magnetic control; the mass ratio of the added Fe 2 O 3 particles to the polydimethylsiloxane (PDMS) solution is 10:1.

[0038] Step (3): Take out the processing container and the patterning mold as a whole from the magnetic field environment, and let it stand still until it is completely cured to obtain a flexible polymer structure retaining the patterning mold.

[0039] Step (4) uses the method of magnetron sputtering to deposit conductive metal copper on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer;

[0040] Step (5) removes the patterned mold. Only the part of the metal conductive layer covering the three-dimensional structure layer remains, and the other parts of the metal conductive layer are removed with the patterned mold to obtain a flexible three-dimensional electrode.

[0041] Example 5.

[0042] Step (1) Add polymethyl methacrylate (PMMA) solution and the corresponding curing agent into a processing container with a circular bottom surface, and let it stand until completely cured to obtain a circular flexible substrate;

[0043] Step (2) Place the patterned mold on the surface of the flexible substrate. Add polymethyl methacrylate (PMMA) solution, the corresponding curing agent, and iron powder with a particle size of 5 μm into the patterned mold, and place it in a magnetic field environment and let it stand for 5 hours. After curing, a three-dimensional structure layer with a designed pattern on the plane is formed. The three-dimensional structure layer has a micro-column morphology grown by magnetic control; the mass ratio of the added iron powder to the polymethyl methacrylate (PMMA) solution is 15:1;

[0044] Step (3) Take out the processing container and the patterned mold as a whole from the magnetic field environment, and let it stand until completely cured to obtain a flexible polymer structure retaining the patterned mold;

[0045] Step (4) uses the method of magnetron sputtering to deposit conductive metal copper on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer;

[0046] Step (5) removes the patterned mold. Only the part of the metal conductive layer covering the three-dimensional structure layer remains, and the other parts of the metal conductive layer are removed with the patterned mold to obtain a flexible three-dimensional electrode.

[0047] Example 6.

[0048] Step (1) Add polyethylene terephthalate (PET) solution and the corresponding curing agent into a processing container with a rectangular bottom surface, and let it stand until completely cured to obtain a rectangular flexible substrate;

[0049] Step (2) Place the patterned mold on the surface of the flexible substrate. Add polyethylene terephthalate (PET) solution, the corresponding curing agent, and Fe 2 O 3 particles with a particle size of 10 μm into the patterned mold, and place it in a magnetic field environment and let it stand for 6 hours. After curing, a three-dimensional structure layer with a designed pattern on the plane is formed. The three-dimensional structure layer has a micro-column morphology grown by magnetic control; the added Fe 2 O 3The mass ratio of the particles to the polyethylene terephthalate (PET) solution is 20:1;

[0050] In step (3), the processing container and the patterned mold as a whole are taken out of the magnetic field environment and left to stand until completely cured, obtaining a flexible polymer structure retaining the patterned mold;

[0051] In step (4), by means of magnetic co-sputtering, a conductive metal copper is deposited on one side of the flexible polymer structure having a three-dimensional structure layer to form a metal conductive layer;

[0052] In step (5), the patterned mold is removed, and only the part of the metal conductive layer covering the three-dimensional structure layer remains, and the other parts of the metal conductive layer are removed along with the patterned mold, obtaining a flexible three-dimensional electrode.

[0053] The patterned molds in Examples 1 to 6 are flat molds, the outer edge of which is consistent with the outer edge of the flexible substrate, and the middle part is hollowed out according to the design. The morphology of the three-dimensional structure layer is as Figure 1 shown, Figure 1 the protrusions in which are magnetic particles. It can be seen the morphology of the grown micro-columns after magnetization, and the micro-columns have the property of growing in the same direction.

Claims

1. A preparation method of a flexible three-dimensional electrode, characterized in that, specifically: Step (1) Add a flexible polymer solution and a corresponding curing agent into a processing container, and let it stand until completely cured to obtain a flexible substrate; Step (2): Place the patterned mold on the surface of the flexible substrate. Add a flexible polymer solution, the corresponding curing agent, and magnetic particles into the patterned mold, and place it in a magnetic field environment and let it stand still for 2 to 6 hours. After curing, a three-dimensional structure layer with a designed pattern on the plane is formed. The three-dimensional structure layer has a micro-column morphology for magnetically controlled growth; the magnetic particles are iron powder or Fe 2 O 3 particles, and the mass ratio to the flexible polymer solution is 1:1 to 20:1; The same flexible polymer solution is used in Steps (1) and (2), which is polydimethylsiloxane, polymethyl methacrylate or polyethylene terephthalate; Step (3) Take out the processing container and the patterning mold as a whole from the magnetic field environment, and let it stand until completely cured to obtain a flexible polymer structure; Step (4) Use the method of magnetic co-sputtering to deposit a conductive metal material on one side of the flexible polymer structure with a three-dimensional structure layer to form a metal conductive layer; Step (5) Remove the patterning mold, and only the part of the metal conductive layer covering the three-dimensional structure layer is retained to obtain a flexible three-dimensional electrode.

2. The preparation method of a flexible three-dimensional electrode according to claim 1, characterized in that: The conductive metal material described in Step (4) is gold, silver or copper.

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