Packaging method of high-integration flexible supercapacitor

Abstract

The invention discloses a packaging method for a high-integration flexible supercapacitor, and the method comprises the following steps: S1, drawing three layers of flexible mask patterns, a first layer of flexible mask is provided with a plurality of detection holes and a plurality of electrode opening regions, and the length and width of the electrode opening regions are 0.15-0.25 mm larger than those of an actual electrode region; s2, carrying out patterning processing; s3, laminating and electrolyte coating are carried out; and S4, after the electrolyte is solidified, sequentially removing the third layer of flexible mask and the second layer of flexible mask to obtain the packaged high-integration flexible supercapacitor. The problems that packaging and electrolyte coating of an existing high-integration flexible supercapacitor are inconvenient, and each electrode monomer cannot be measured are solved.

Description

Technical Field

[0001] The invention relates to the field of electronic technology, and in particular to a packaging method for a highly integrated flexible supercapacitor. Background Art

[0002] Supercapacitors are energy storage components between traditional capacitors and batteries. They store energy through the double layer or electrochemical reaction between the electrode and the electrolyte interface. They have the advantages of high power density, fast charge and discharge, and long cycle life. They are widely used in electronics, transportation, energy and other fields. With the continuous development of science and technology, the demand for miniaturized, wearable and implantable microelectronic devices is increasing, and the demand for energy storage devices with small size, high integration and stable performance is also increasing. Therefore, highly integrated flexible supercapacitors have emerged, which can meet the needs of high integration and flexibility.

[0003] However, the traditional supercapacitor packaging technology usually uses aluminum shells or plastic shells for packaging, assembling electrodes, electrolytes and conductive media inside the shell, and then sealing and packaging to achieve the purpose of protecting the internal materials from the external environment. Although this packaging method can ensure the stability and safety of the supercapacitor to a certain extent, because metal or plastic materials are used for packaging, the volume and weight of the resulting capacitor are large, which is not conducive to the lightweight and miniaturization of the equipment, and because these shells generally have strong rigidity, they cannot meet the flexibility requirements under special conditions during packaging. It can be seen that the traditional shell packaging method cannot meet the packaging requirements of highly integrated flexible supercapacitors. In addition, the distance between each electrode of the highly integrated flexible supercapacitor is too small and the size of the electrode itself is too small, which makes it inconvenient to coat the electrolyte. Moreover, it is composed of multiple electrodes, and the performance difference of each electrode may affect the performance of the entire module. It is necessary to test the performance of a single or multiple electrodes and the entire highly integrated series electrode, and the existing packaging technology is difficult to ensure the precise coating of the electrolyte while providing a reliable way to measure each electrode monomer. Summary of the invention

[0004] In view of the above-mentioned defects, the purpose of the present invention is to propose a packaging method for a highly integrated flexible supercapacitor to solve the problems of the current packaging of highly integrated flexible supercapacitors, inconvenient coating of electrolytes, and inability to measure each electrode monomer.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] A packaging method for a highly integrated flexible supercapacitor comprises the following steps:

[0007] S1. Drawing a flexible mask pattern: Arrangement of the electrode array of the highly integrated flexible supercapacitor. According to the design pattern of the highly integrated flexible supercapacitor to be assembled, draw a three-layer flexible mask pattern, which are the first layer of flexible mask, the second layer of flexible mask and the third layer of flexible mask from bottom to top;

[0008] The first layer of flexible mask is drawn with a plurality of detection holes and a plurality of electrode opening areas, each electrode opening area is provided with a detection hole on both sides, and the electrode opening area corresponds to the electrode; the second layer of flexible mask and the third layer of flexible mask are respectively drawn with a plurality of matrix arrays, the matrix array of the second layer of flexible mask and the matrix array of the third layer of flexible mask are perpendicular to each other, the width of the matrix array is equal to the side length of the electrode area, and only the electrode area is exposed after the second layer of flexible mask and the third layer of flexible mask are superimposed;

[0009] The electrode opening area is 0.15-0.25 mm larger than the length and width of the electrode area;

[0010] S2, patterning processing: removing the detection holes and electrode opening areas of the first layer of flexible mask, and removing the rectangular arrays perpendicular to each other of the second layer of flexible mask and the third layer of flexible mask, to obtain a three-layer flexible mask;

[0011] S3, lamination and electrolyte coating: laminating the three-layer flexible mask on the highly integrated flexible supercapacitor from bottom to top, pressing it during the process, and then coating the electrolyte on the electrode area;

[0012] S4. After the electrolyte solidifies, the third flexible mask layer and the second flexible mask layer are removed in sequence to obtain a packaged highly integrated flexible supercapacitor.

[0013] Furthermore, the material of the three-layer flexible mask is a self-adhesive tape material or a thin film material, and the viscosity of the three-layer flexible mask decreases from bottom to top. The viscosity of the first layer of flexible mask is greater than 2.45N / 25mm, the viscosity of the second layer of flexible mask is 1.47-1.96N / 25mm, and the viscosity of the third layer of flexible mask is 0.98-1.47N / 25mm.

[0014] Furthermore, in step S1, the electrode matrix of the highly integrated flexible supercapacitor is arranged, and the electrode edge spacing in the horizontal direction and the vertical direction are different. Compared with the vertical spacing, the larger the horizontal spacing is, the wider spacing is, and the smaller the spacing is, the narrower spacing is.

[0015] The detection holes are located at a wider spacing, the second flexible mask layer covers a narrower spacing, the third flexible mask layer covers the detection holes, and the second flexible mask layer overlaps with the third flexible mask layer, exposing only the electrode area.

[0016] Preferably, the thickness of the first flexible mask layer is 20-80 μm, and the thickness of the second flexible mask layer and the third flexible mask layer are 125-200 μm respectively.

[0017] Preferably, the materials of the second flexible mask layer and the third flexible mask layer have hydrophobic properties;

[0018] Alternatively, a hydrophobic treatment is performed on the surfaces of the second flexible mask layer and the third flexible mask layer.

[0019] Preferably, in step S2, the patterning process is performed by one of etching, hot melting, knife engraving and laser engraving.

[0020] Preferably, in step S2, the three-layer flexible mask is patterned using an ultraviolet picosecond laser;

[0021] Among them, the laser power is 8.5-9.5W and the scanning speed is 50-100mm / s.

[0022] Preferably, the coated electrolyte is a hydrogel-based electrolyte.

[0023] Further, in step S4, the coated electrolyte is a PVA-H2SO4 gel electrolyte;

[0024] After the electrolyte is coated on the electrode area, a vacuum treatment is performed with a vacuum pressure of 0.8-0.9 bar and a vacuum time of 0.5-1 h.

[0025] Preferably, in step S3, the first layer of flexible mask is repeatedly pressed with tweezers or acrylic rods during the lamination process, and the edges of the first layer of flexible mask are sealed and fixed with tape.

[0026] The technical solution provided by the present invention may include the following beneficial effects:

[0027] By using three layers of flexible masks, the electrolyte can be accurately covered in the high-resolution electrode area. Subsequently, the third layer of flexible mask and the second layer of flexible mask are torn off in turn to obtain a highly integrated flexible supercapacitor encapsulated by the first layer of flexible mask and the electrolyte. The first layer of flexible mask is provided with a detection hole, which is located near the electrode. A single electrode unit can be measured by connecting the measuring device with a wire. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic structural diagram of an embodiment of the present invention.

[0029] Figure 2 It is a schematic diagram of the structure of an embodiment of the present invention after packaging.

[0030] Figure 3 1 is a cyclic voltammetry curve of a single electrode according to an embodiment of the present invention.

[0031] Figure 4 FIG. 5 is an overall cyclic voltammetry curve of an embodiment of the present invention.

[0032] Among them: a highly integrated flexible supercapacitor 1, a first layer of flexible mask 2, a detection hole 21, an electrode opening area 22, a second layer of flexible mask 3, and a third layer of flexible mask 4. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0034] In order to facilitate the understanding of the present invention, the present invention is described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0035] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0036] The present invention provides a packaging method for a highly integrated flexible supercapacitor, comprising the following steps:

[0037] S1. Drawing a flexible mask pattern: Arrangement of the electrode array of the highly integrated flexible supercapacitor 1. Drawing a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled, which are respectively the first layer flexible mask 2, the second layer flexible mask 3 and the third layer flexible mask 4 from bottom to top;

[0038] The first layer of flexible mask 2 is drawn with a plurality of detection holes 21 and a plurality of electrode opening areas 22, each electrode opening area 22 is provided with a detection hole 21 on both sides thereof, and the electrode opening area 22 corresponds to the electrode; the second layer of flexible mask 3 and the third layer of flexible mask 4 are respectively drawn with a plurality of matrix arrays, the matrix array of the second layer of flexible mask 3 and the matrix array of the third layer of flexible mask 4 are perpendicular to each other, the width of the matrix array is equal to the side length of the electrode area, and only the electrode area is exposed after the second layer of flexible mask 3 and the third layer of flexible mask 4 are superimposed;

[0039] The electrode opening area 22 is 0.15-0.25 mm larger than the length and width of the electrode area;

[0040] S2, patterning processing: removing the detection holes 21 and the electrode opening area 22 of the first layer of flexible mask 2, and removing the rectangular arrays perpendicular to each other of the second layer of flexible mask 3 and the third layer of flexible mask 4, to obtain a three-layer flexible mask;

[0041] S3, lamination and electrolyte coating: laminating the three-layer flexible mask on the highly integrated flexible supercapacitor 1 from bottom to top, pressing during the process, and then coating the electrolyte on the electrode area;

[0042] S4, after the electrolyte solidifies, the third flexible mask 4 and the second flexible mask 3 are removed in sequence to obtain a packaged highly integrated flexible supercapacitor 1.

[0043] In order to solve the problems existing in the prior art, the technical solution proposed in the present invention encapsulates the highly integrated flexible supercapacitor 1 according to the above steps, first draws the flexible mask pattern, then patterns the flexible mask, and then applies the electrolyte. After waiting for the electrolyte to solidify, the second layer of flexible mask 3 and the third layer of flexible mask 4 are torn off according to the direction of the rectangular array of the second layer of flexible mask 3 and the third layer of flexible mask 4, leaving the first layer of flexible mask 2 and the hydrogel electrolyte in the electrode opening area 22 to achieve the encapsulation of the highly integrated flexible supercapacitor 1. If the first layer of flexible mask 2 is removed, the highly integrated flexible supercapacitor 1 will be completely exposed to the air. And because during the patterning process, each electrode opening area 22 of the first layer of flexible mask 2 is provided with a detection hole 21 on both sides, after the second layer of flexible mask 3 and the third layer of flexible mask 4 are superimposed, only the electrode area is accurately exposed, that is, the detection hole 21 of the first layer of flexible mask 2 has been covered, and pressed during the process to ensure that the mask is fitted, there is no gap between the contact surfaces, and when the electrolyte is subsequently coated, the electrolyte will not penetrate into the detection hole 21 to avoid contamination or short circuit. After the second layer of flexible mask 3 and the third layer of flexible mask 4 are removed, the well-packaged highly integrated flexible supercapacitor 1 has a detection hole 21, which can detect the performance of a single or multiple electrodes and the entire highly integrated series electrode, providing a simple and feasible channel for measuring each electrode of the highly integrated flexible supercapacitor 1, solving the problem in the prior art that it is impossible to measure each electrode monomer.

[0044] At the same time, the second flexible mask 3 and the third flexible mask 4 are respectively drawn with a number of mutually perpendicular matrix arrays, the width of the matrix array is equal to the side length of the electrode area, and the coating of the electrolyte is further accurately controlled. After the second flexible mask 3 and the third flexible mask 4 are superimposed, only the electrode area is accurately exposed. During the coating process, the electrolyte will naturally flow and fill the electrode opening area 22, and the second flexible mask 3 and the third flexible mask 4 can ensure that the electrolyte will not be coated on unnecessary areas. After the electrolyte solidifies, the second flexible mask 3 and the third flexible mask 4 are torn off, and the electrolyte attached to the second flexible mask 3 and the third flexible mask 4 during the coating of the electrolyte will be removed. In this way, there will be no problem that the electrolyte connects the adjacent electrodes due to the small distance between the electrodes and the small size of the electrodes themselves, causing a short circuit, and the problem of inconvenience in electrolyte coating will be solved.

[0045] It is worth noting that the matrix arrays of the second layer of flexible mask 3 and the third layer of flexible mask 4 are perpendicular to each other. When tearing, tearing along the direction of the matrix array can reduce the resistance during the tearing process, because the tearing direction is consistent with the structural direction of the flexible mask, reducing the deformation and stress concentration of the material, making the flexible mask easier to remove. If a second layer of flexible mask that can cover the detection hole 21 and leave a corresponding area according to the electrode is directly set, the complex structural design may cause stress concentration, especially at the edge and the empty area. These stress concentration points are easy to cause the second layer of flexible mask to tear or remain during the removal process, affecting the packaging effect. In addition, the matrix arrays designed perpendicular to each other can simplify the alignment process. When multiple layers of flexible masks are stacked, the vertical matrix array can provide more alignment reference points and reduce alignment errors. If a second layer of flexible mask 3 that can cover the detection hole 21 and leave a corresponding area according to the electrode is directly set, the alignment error is large and the desired packaging effect cannot be achieved.

[0046] In addition, the electrode opening area 22 is 0.15-0.25 mm larger than the length and width of the electrode area, respectively. In step S3, when the electrolyte is coated, it will flow naturally and fill all available space, that is, the electrolyte will automatically fill the electrode opening area 22. The second layer of flexible mask 3 and the third layer of flexible mask 4 can further accurately control the coating area of ​​the electrolyte to ensure that the electrolyte will not be coated on unnecessary areas, and the electrode opening area 22 is larger than the electrode area, which effectively prevents the mismatch with the actual electrode area during bonding, resulting in insufficient electrode exposure or damage to the electrode structure.

[0047] Furthermore, the well-packaged highly integrated flexible supercapacitor 1 can be provided with a conductive medium in the detection hole 21, and then connected to an external measuring device through a wire for measurement, thereby ensuring the accuracy and reliability of the measurement result. The conductive medium can be silver paste or copper foil.

[0048] Furthermore, the material of the three-layer flexible mask is a self-adhesive tape material or a thin film material, and the viscosity of the three-layer flexible mask decreases from bottom to top. The viscosity of the first layer of flexible mask 2 is greater than 2.45N / 25mm, the viscosity of the second layer of flexible mask 3 is 1.47-1.96N / 25mm, and the viscosity of the third layer of flexible mask 4 is 0.98-1.47N / 25mm.

[0049] Specifically, the material of the three-layer flexible mask is a self-adhesive tape material or film material, which may be a polyimide (PI) tape, a polyethylene terephthalate (PET) film or a polyvinyl chloride (PVC) tape, which has good high temperature resistance, corrosion resistance or high flatness performance, and is suitable for capacitor packaging.

[0050] Furthermore, the viscosity of the three layers of flexible masks gradually decreases from bottom to top, and the viscosity of the first layer of flexible mask 2 is greater than 2.45N / 25mm, ensuring a good sealing effect on the supercapacitor. The viscosity of the second layer of flexible mask 3 is 1.47-1.96N / 25mm, and the viscosity of the third layer of flexible mask 4 is 0.98-1.47N / 25mm, ensuring that the two layers of masks will not easily fall off the capacitor, will not affect the coating of the electrolyte, and are easy to remove later, so as to obtain the desired packaged high-integrated flexible supercapacitor 1.

[0051] In addition, the three-layer flexible mask is sticky, which can realize the packaging of highly integrated flexible supercapacitors 1. Not only is the process simple and the cost low, but it is also highly controllable, making it easy to control the pattern design of the mask, and is more conducive to industrial large-scale production.

[0052] Furthermore, in step S1, the electrode matrix of the highly integrated flexible supercapacitor 1 is arranged, and the electrode edge spacings in the horizontal direction and the vertical direction are different. Compared with the vertical spacing, the larger the horizontal spacing is, the wider spacing is, and the smaller the spacing is, the narrower spacing is.

[0053] The detection holes 21 are located at a wider spacing, the second flexible mask 3 covers a narrower spacing, the third flexible mask 4 covers the detection holes 21, and the second flexible mask 3 and the third flexible mask 4 overlap, exposing only the electrode area.

[0054] Specifically, the electrode matrix is ​​arranged, and the electrode gaps in the horizontal and vertical directions are different, that is, the distances between adjacent electrode edges are different. According to the size of the electrode gaps, they are divided into wider gaps and narrower gaps, that is, the position between the matrix arrays of the second flexible mask 3 and the third flexible mask 4, wherein "wider" and "narrower" are obtained by comparing the widths of the electrode gaps in the horizontal and vertical directions. Among them, the electrode gap with a larger width is the wider gap, and the electrode gap with a smaller width is the narrower gap, and the wider gap and the narrower gap are perpendicular to each other. The detection hole 21 is located at the wider gap, which is beneficial to patterning the flexible mask in step S2 and reduces the difficulty of processing.

[0055] The second layer of flexible mask 3 separates the electrodes, and the third layer of flexible mask 4 covers the detection hole 21, that is, the third layer of flexible mask 3 covers a wider interval and has a larger contact area. Because the third layer of flexible mask 4 is located at the top, most of the electrolyte can be taken away when it is torn off, and then the second layer of flexible mask 3 can be torn off to separate the electrodes, ensuring that the electrolyte is removed cleanly.

[0056] Preferably, the thickness of the first flexible mask layer 2 is 20-80 μm, and the thickness of the second flexible mask layer 3 and the third flexible mask layer 4 are 125-200 μm respectively.

[0057] It is worth noting that the thickness of the first flexible mask 2 is 20-80 μm. Within this thickness range, the electrode opening area 22 provides sufficient space for subsequent electrolyte coating, while using less electrolyte and reducing electrolyte waste.

[0058] In addition, the thickness of the second flexible mask 3 and the third flexible mask 4 is 125-200 μm, which is conducive to the subsequent tearing of the second flexible mask 3 and the third flexible mask 4, and has moderate mechanical strength, and will not be easily broken due to being too fragile, nor too hard to be peeled off, reducing the resistance during the tearing process, making the mask easier to remove. Moreover, within this thickness range, it is easier to keep it flat during lamination, reduce errors, and help improve the alignment accuracy when multiple masks are superimposed, ensuring accurate coverage of the electrolyte on the electrode.

[0059] Preferably, the materials of the second flexible mask layer 3 and the third flexible mask layer 4 have hydrophobic properties; or, the surfaces of the second flexible mask layer 3 and the third flexible mask layer 4 are subjected to hydrophobic treatment.

[0060] Specifically, in step S3, electrolyte coating is required. Since the second flexible mask 3 and the third flexible mask 4 have hydrophobic properties, electrolyte will not remain too much on their surfaces, and the coated electrolyte is ensured to be evenly distributed in the electrode opening area 22, effectively preventing electrolyte leakage. In addition, the pollution to the surrounding environment and equipment is reduced to a certain extent.

[0061] Preferably, the materials of the second flexible mask layer 3 and the third flexible mask layer 4 have super hydrophobic properties and may be a composite film of perfluoroethylene propylene copolymer (FEP) and PI or a Teflon tape.

[0062] Furthermore, the second flexible mask 3 and the third flexible mask 4 can be materials with poor hydrophobic properties coated with a super hydrophobic coating, such as polyethylene terephthalate (PET) film, polyvinyl chloride (PVC) tape and other materials with poor hydrophobic properties. The specific hydrophobic treatment is: coating the surface with fluorine / silicon materials such as perfluoroethylene propylene copolymer (FEP), polytetrafluoroethylene (PTFE), polydimethylsiloxane (PDMS) to improve its hydrophobic properties.

[0063] Preferably, in step S2, the patterning process is performed by one of etching, hot melting, knife engraving and laser engraving.

[0064] It is worth noting that the electrode size and electrode spacing of the highly integrated flexible supercapacitor are small. Therefore, in step S2, the patterning process needs to have a certain precision so that the flexible mask can correspond one-to-one with the electrodes of the highly integrated flexible supercapacitor 1. Etching, hot melting and laser engraving can all achieve high-precision effects, and can realize fine patterning at the micron or even nanometer level, and can be quickly formed, which is suitable for large-scale production and improves production efficiency.

[0065] Preferably, when used in a laboratory or small-scale production, a patterned processing method such as knife engraving can be used, which has high reproducibility, low cost and flexible operation.

[0066] Preferably, in step S2, the three-layer flexible mask is patterned using an ultraviolet picosecond laser;

[0067] Among them, the laser power is 8.5-9.5W and the scanning speed is 50-100mm / s.

[0068] Specifically, engraving is performed in a focused manner, wherein the laser power is maintained at 8.5-9.5W and the scanning speed is maintained at 50-100mm / s. This can effectively prevent carbonization of the mask edge, surface roughness, and surface unevenness caused by excessive laser power or slow scanning speed. If the laser power is too small or the scanning speed is too fast, the mask may not be engraved smoothly due to insufficient energy, and the desired pattern cannot be obtained.

[0069] Preferably, the coated electrolyte is a hydrogel-based electrolyte.

[0070] In step S4, the electrolyte to be coated is a hydrogel electrolyte, which can be an electrolyte of polyvinyl alcohol (PVA), gelatin, polyacrylamide or polymethyl acrylate. The hydrogel electrolyte can achieve a high ionic conductivity at room temperature and has excellent electrochemical properties, good mechanical flexibility and temperature stability, and is very suitable for application in highly integrated flexible supercapacitors.

[0071] Further, in step S4, the coated electrolyte is a PVA-H2SO4 gel electrolyte;

[0072] After the electrolyte is coated on the electrode area, a vacuum treatment is performed with a vacuum pressure of 0.8-0.9 bar and a vacuum time of 0.5-1 h.

[0073] Specifically, sulfuric acid (H2SO4) is a strong acid with good ionic conductivity, which can significantly improve the conductivity of hydrogel electrolytes. (PVA) polyvinyl alcohol is a highly flexible polymer that can form a firm gel structure and improve the stability and reliability of the electrolyte. This allows PVA-H2SO4 gel electrolyte to achieve high ionic conductivity at room temperature, and has excellent electrochemical properties, good mechanical flexibility and temperature stability. It is an ideal material for use in highly integrated flexible supercapacitors 1, exhibits excellent performance in electrochemical devices, and has broad application prospects in flexible electronic devices. The use of PVA-H2SO4 gel electrolyte can effectively form a firm gel structure with high stability and reliability, reducing the occurrence of electrolyte leakage and separation of electrolyte from electrodes due to the electrode size of the highly integrated flexible supercapacitor 1 and the close distance between the electrodes.

[0074] After the electrolyte is coated on the electrode area, a vacuum treatment is performed to remove bubbles in the electrolyte so that the electrolyte is in full contact with the electrode. The vacuum pressure is 0.8-0.9 bar and the vacuum time is 0.5-1h to ensure that the moisture and gas in the electrolyte are effectively removed while avoiding damage to the electrolyte structure and performance, so as to ensure the packaging effect and the performance of the capacitor.

[0075] Preferably, in step S3, the first flexible mask 2 is repeatedly pressed with tweezers or an acrylic rod during the lamination process, and the edges of the first flexible mask 2 are sealed and fixed with tape.

[0076] Specifically, the edge of the first flexible mask 2 is sealed and fixed with tape, which can prevent gas from entering from the side and ensure that the first flexible mask 2 is completely attached to the highly integrated flexible supercapacitor 1, while also preventing the electrolyte from penetrating from the gap to cause a short circuit.

[0077] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0078] Example Group

[0079] Example 1

[0080] S1. Draw a flexible mask pattern and arrange the electrode array of the highly integrated flexible supercapacitor 1. Draw a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled, which are the first flexible mask 2, the second flexible mask 3 and the third flexible mask 4 from bottom to top; wherein, in this embodiment, the specification of the highly integrated flexible supercapacitor 1 is 40×40mm, the number of electrodes is 50, the specification of a single electrode is 2×3mm, and it is distributed in a 10×5 array, with 10 electrodes horizontally and an electrode spacing of 1mm, and 5 electrodes vertically and a spacing of 3mm.

[0081] The first layer of flexible mask 2 is drawn with 60 detection holes 21 and 50 electrode opening areas 22, each electrode opening area 22 has a detection hole 21 on both sides, and the electrode opening area 22 corresponds to the electrode; wherein, the size of the detection hole 21 is 0.5×0.5mm, located at a spacing of 3mm, and the size of the electrode opening area 22 is 2.2×3.2mm.

[0082] The second layer of flexible mask 3 is drawn with 10 matrix arrays with a specification of 2×36mm and a pitch of 1mm, and the third layer of flexible mask 4 is drawn with 5 matrix arrays with a specification of 3×30mm and a pitch of 3mm. The matrix arrays of the second and third layers of flexible masks 4 are perpendicular to each other. After the second layer of flexible mask 3 and the third layer of flexible mask 4 are superimposed, only the electrode area is exposed.

[0083] S2, patterning processing, removing the detection holes 21 and the electrode opening area 22 of the first layer of flexible mask 2, and removing the rectangular arrays of the second layer of flexible mask 3 and the third layer of flexible mask 4 that are perpendicular to each other, to obtain a three-layer flexible mask; wherein, the material of the three-layer flexible mask is PI tape, and a focused laser is emitted by a UV picosecond laser with a wavelength of 355nm, the laser power is set to 9.0W, and the scanning speed is 60mm / s. According to the three-layer flexible mask pattern drawn in step S1, the PI tape is surface patterned by scanning from left to right to remove the corresponding area. In addition, the thickness of the first layer of flexible mask 2 is 20μm, and the thickness of the second layer of flexible mask 3 and the third layer of flexible mask 4 is 125μm.

[0084] S3, electrolyte coating, the three-layer flexible mask is sequentially attached to the highly integrated flexible supercapacitor 1 from bottom to top, and pressed in the process to achieve a close fit, and then the PVA-H2SO4 gel electrolyte is coated on the electrode area.

[0085] S4. Place the highly integrated flexible supercapacitor 1 with three layers of masks attached in a vacuum drying oven and let it stand for 30 minutes at a pressure of 0.8 bar. After the electrolyte solidifies into a gel, take it out of the vacuum drying oven and remove the third flexible mask 4 and the second flexible mask 3 in turn to obtain a packaged highly integrated flexible supercapacitor 1.

[0086] Example 2

[0087] S1. Draw a flexible mask pattern and arrange the electrode array of the highly integrated flexible supercapacitor 1. Draw a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled, which are the first flexible mask 2, the second flexible mask 3 and the third flexible mask 4 from bottom to top; wherein, in this embodiment, the specification of the highly integrated flexible supercapacitor 1 is 40×40mm, the number of electrodes is 50, the specification of a single electrode is 2×3mm, and it is distributed in a 10×5 array, with 10 electrodes horizontally and an electrode spacing of 1mm, and 5 electrodes vertically and a spacing of 3mm.

[0088] The first layer of flexible mask 2 is drawn with 60 detection holes 21 and 50 electrode opening areas 22, each electrode opening area 22 has a detection hole 21 on both sides, and the electrode opening area 22 corresponds to the electrode; wherein, the size of the detection hole 21 is 0.5×0.5mm, located at a spacing of 3mm, and the size of the electrode opening area 22 is 2.2×3.2mm.

[0089] The second layer of flexible mask 3 is drawn with 10 matrix arrays with a specification of 2×36mm and a pitch of 1mm, and the third layer of flexible mask 4 is drawn with 5 matrix arrays with a specification of 3×30mm and a pitch of 3mm. The matrix arrays of the second and third layers of flexible masks 4 are perpendicular to each other. After the second layer of flexible mask 3 and the third layer of flexible mask 4 are superimposed, only the electrode area is exposed.

[0090] S2, patterning processing, removing the detection hole 21 and the electrode opening area 22 of the first layer of flexible mask 2, removing the rectangular array perpendicular to each other of the second layer of flexible mask 3 and the third layer of flexible mask 4, and obtaining a three-layer flexible mask; wherein the material of the three-layer flexible mask is PI tape, and the laser power is set to 9.0W and the scanning speed is 60mm / s by the focused laser emitted by the ultraviolet picosecond laser with a wavelength of 355nm. According to the three-layer flexible mask pattern drawn in step S1, the PI tape is subjected to surface patterning processing by scanning from left to right and the corresponding area is removed. The thickness of the first layer of flexible mask 2 is 60μm, and the thickness of the second layer of flexible mask 3 and the third layer of flexible mask 4 is 175μm.

[0091] S3, electrolyte coating, the three-layer flexible mask is sequentially attached to the highly integrated flexible supercapacitor 1 from bottom to top, and pressed during the process to achieve a tight fit, and then the H2SO4 / PVA gel electrolyte is coated on the electrode area.

[0092] S4. Place the highly integrated flexible supercapacitor 1 with three layers of masks attached in a vacuum drying oven and let it stand for 30 minutes at a pressure of 0.8 bar. After the electrolyte solidifies into a gel, take it out of the vacuum drying oven and remove the third flexible mask 4 and the second flexible mask 3 in turn to obtain a packaged highly integrated flexible supercapacitor 1.

[0093] Example 3

[0094] S1. Draw a flexible mask pattern and arrange the electrode array of the highly integrated flexible supercapacitor 1. Draw a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled, which are the first flexible mask 2, the second flexible mask 3 and the third flexible mask 4 from bottom to top; wherein, in this embodiment, the specification of the highly integrated flexible supercapacitor 1 is 40×40mm, the number of electrodes is 50, the specification of a single electrode is 2×3mm, and it is distributed in a 10×5 array, with 10 electrodes horizontally and an electrode spacing of 1mm, and 5 electrodes vertically and a spacing of 3mm.

[0095] The first layer of flexible mask 2 is drawn with 60 detection holes 21 and 50 electrode opening areas 22, each electrode opening area 22 has a detection hole 21 on both sides, and the electrode opening area 22 corresponds to the electrode; wherein, the size of the detection hole 21 is 0.5×0.5mm, located at a spacing of 3mm, and the size of the electrode opening area 22 is 2.2×3.2mm.

[0096] The second layer of flexible mask 3 is drawn with 10 matrix arrays with a specification of 2×36mm and a pitch of 1mm, and the third layer of flexible mask 4 is drawn with 5 matrix arrays with a specification of 3×30mm and a pitch of 3mm. The matrix arrays of the second and third layers of flexible masks 4 are perpendicular to each other. After the second layer of flexible mask 3 and the third layer of flexible mask 4 are superimposed, only the electrode area is exposed.

[0097] S2, patterning processing, removing the detection hole 21 and the electrode opening area 22 of the first layer of flexible mask 2, removing the rectangular array perpendicular to each other of the second layer of flexible mask 3 and the third layer of flexible mask 4, and obtaining a three-layer flexible mask; wherein the material of the three-layer flexible mask is PI tape, and the laser power is set to 9.0W and the scanning speed is 60mm / s by the focused laser emitted by the ultraviolet picosecond laser with a wavelength of 355nm. According to the three-layer flexible mask pattern drawn in step S1, the PI tape is subjected to surface patterning processing by scanning from left to right and the corresponding area is removed. The thickness of the first layer of flexible mask 2 is 80μm, and the thickness of the second layer of flexible mask 3 and the third layer of flexible mask 4 is 200μm.

[0098] S3, electrolyte coating, the three-layer flexible mask is sequentially attached to the highly integrated flexible supercapacitor 1 from bottom to top, and pressed during the process to achieve a tight fit, and then the H2SO4 / PVA gel electrolyte is coated on the electrode area.

[0099] S4. Place the highly integrated flexible supercapacitor 1 with three layers of masks attached in a vacuum drying oven and let it stand for 30 minutes at a pressure of 0.8 bar. After the electrolyte solidifies into a gel, take it out of the vacuum drying oven and remove the third flexible mask 4 and the second flexible mask 3 in turn to obtain a packaged highly integrated flexible supercapacitor 1.

[0100] Comparative Example 1

[0101] Compared with Example 1, Comparative Example 1 uses a traditional shell packaging technology, and the specific steps are:

[0102] A. Prepare a 45×45×15 mm aluminum shell, place the prepared 40×40 mm highly integrated flexible supercapacitor 1 inside the aluminum shell, and install a sealing ring and a sealing gasket on the edge of the aluminum shell;

[0103] B. Press the cover plate into the inner side of the top of the aluminum shell, and ensure the seal by crimping to fix the cover plate;

[0104] C. Lead out the electrode lead through the through hole on the cover plate to ensure that the capacitor can be connected to the external circuit, and inject glue to seal the electrode lead through hole to ensure the sealing and stability of the capacitor;

[0105] D. Apply epoxy resin to the inside of the sealed end of the capacitor case and apply curing agent to the side of the cover, and then perform heat packaging to form an adhesive sealing layer.

[0106] The well-packaged highly integrated flexible supercapacitors obtained in the embodiments and comparative examples were tested by using cyclic voltammetry to obtain CV (cyclic voltammetry) curves of the highly integrated flexible supercapacitors, and the specific capacitance of the capacitors was obtained by using the basic formula for calculating capacitance.

[0107] The basic formula for calculating specific capacitance using the CV method is:

[0108]

[0109] Where i is the current in the CV curve, v is the voltage scan rate, V is the voltage window, and A is the electrode area. The specific test results are shown in the following table:

[0110] Table 1 Specific capacitance of capacitors

[0111]

[0112] As shown in Table 1, the well-packaged highly integrated flexible supercapacitors obtained in the embodiment group and the comparative example 1 have relatively good specific capacitance packaging effects, and the overall test results are similar. The specific capacitance of 50 series-connected electrodes of the packaged highly integrated flexible supercapacitor of the embodiment group is 0.381-0.385 mF / cm 2 The specific capacitance of 50 series-connected electrodes of the packaged highly integrated flexible supercapacitor of Comparative Example 1 is 0.388 mF / cm 2 , which is similar to the specific capacitance value obtained in the example group. However, comparative example 1 cannot test the specific capacitance of a single electrode, cannot detect the performance of a single or multiple electrodes, and lacks a reliable test and measurement method.

[0113] Moreover, in the embodiment group, the thickness of the first flexible mask, the second flexible mask and the third flexible mask of each embodiment is different, that is, the amount of electrolyte coated on the electrode is different, but the present invention ensures that the electrolyte is coated at the desired position by using three layers of flexible masks, and at the same time uses a hydrogel electrolyte and performs a vacuum treatment during solidification to ensure that the electrolyte can penetrate into the electrode as much as possible. Therefore, the specific capacitance of each embodiment is similar, and the purpose of measuring a single electrode can be achieved. Specifically, the CV curves of a single electrode and its overall measurement of the highly integrated flexible supercapacitor in Example 1 are as follows: Figure 3 and Figure 4 The embodiment group proves that the present invention is feasible and can effectively achieve the desired packaging purpose.

[0114] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A packaging method for a highly integrated flexible supercapacitor, characterized in that: The following steps are involved: S1. Drawing a flexible mask pattern: Arrangement of the electrode array of the highly integrated flexible supercapacitor. According to the design pattern of the highly integrated flexible supercapacitor to be assembled, draw a three-layer flexible mask pattern, which are the first layer of flexible mask, the second layer of flexible mask and the third layer of flexible mask from bottom to top; The first layer of flexible mask is drawn with a plurality of detection holes and a plurality of electrode opening areas, each electrode opening area is provided with a detection hole on both sides, and the electrode opening area corresponds to the electrode; The second layer of flexible mask and the third layer of flexible mask are respectively drawn with a plurality of matrix arrays, the matrix array of the second layer of flexible mask and the matrix array of the third layer of flexible mask are perpendicular to each other, the width of the matrix array is equal to the side length of the electrode area, and only the electrode area is exposed after the second layer of flexible mask and the third layer of flexible mask are superimposed; The electrode opening area is 0.15-0.25 mm larger than the length and width of the electrode area; S2, patterning processing: removing the detection holes and electrode opening areas of the first layer of flexible mask, and removing the rectangular arrays perpendicular to each other of the second layer of flexible mask and the third layer of flexible mask, to obtain a three-layer flexible mask; S3, lamination and electrolyte coating: laminating the three-layer flexible mask on the highly integrated flexible supercapacitor from bottom to top, pressing it during the process, and then coating the electrolyte on the electrode area; S4. After the electrolyte solidifies, the third flexible mask layer and the second flexible mask layer are removed in sequence to obtain a packaged highly integrated flexible supercapacitor.

2. The packaging method of a highly integrated flexible supercapacitor according to claim 1, characterized in that: The material of the three-layer flexible mask is a self-adhesive tape material or a film material, and the viscosity of the three-layer flexible mask decreases from bottom to top. The viscosity of the first layer of flexible mask is greater than 2.45N / 25mm, the viscosity of the second layer of flexible mask is 1.47-1.96N / 25mm, and the viscosity of the third layer of flexible mask is 0.98-1.47N / 25mm.

3. The packaging method of a highly integrated flexible supercapacitor according to claim 2, characterized in that: In step S1, the electrode matrix of the highly integrated flexible supercapacitor is arranged, and the electrode edge spacing in the horizontal direction and the vertical direction are different. Compared with the vertical spacing, the larger the horizontal spacing is, the wider spacing is, and the smaller the spacing is, the narrower spacing is; The detection holes are located at a wider spacing, the second flexible mask layer covers a narrower spacing, the third flexible mask layer covers the detection holes, and the second flexible mask layer overlaps with the third flexible mask layer, exposing only the electrode area.

4. The packaging method of a highly integrated flexible supercapacitor according to claim 2, characterized in that: The thickness of the first flexible mask layer is 20-80 μm, and the thickness of the second flexible mask layer and the third flexible mask layer are 125-200 μm respectively.

5. The packaging method of a highly integrated flexible supercapacitor according to claim 1, characterized in that: The materials of the second flexible mask layer and the third flexible mask layer have hydrophobic properties; Alternatively, a hydrophobic treatment is performed on the surfaces of the second flexible mask layer and the third flexible mask layer.

6. The packaging method of a highly integrated flexible supercapacitor according to claim 1, characterized in that: In step S2, the patterning process is performed by etching, hot melting, knife engraving and laser engraving.

7. The packaging method of a highly integrated flexible supercapacitor according to claim 6, characterized in that: In step S2, a three-layer flexible mask is patterned using an ultraviolet picosecond laser; Among them, the laser power is 8.5-9.5W and the scanning speed is 50-100mm / s.

8. The packaging method of a highly integrated flexible supercapacitor according to claim 1, characterized in that: The coated electrolyte is a hydrogel-based electrolyte.

9. The packaging method of a highly integrated flexible supercapacitor according to claim 8, characterized in that: In step S4, the coated electrolyte is a PVA-H2SO4 gel electrolyte; After the electrolyte is coated on the electrode area, a vacuum treatment is performed with a vacuum pressure of 0.8-0.9 bar and a vacuum time of 0.5-1 h.

10. The packaging method of a highly integrated flexible supercapacitor according to claim 1, characterized in that: In step S3, the first layer of flexible mask is repeatedly pressed with tweezers or acrylic rods during the bonding process, and the edges of the first layer of flexible mask are sealed and fixed with tape.

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