A packaging method for highly integrated flexible supercapacitors

Abstract

The present invention discloses a packaging method for a highly integrated flexible supercapacitor, comprising the following steps: S1, drawing a three-layer flexible mask pattern, wherein the first flexible mask is drawn with a plurality of detection holes and a plurality of electrode opening areas, wherein the electrode opening areas are 0.15-0.25 mm larger in length and width than the actual electrode areas, respectively; S2, patterning; S3, lamination and electrolyte coating; S4, after the electrolyte solidifies, sequentially removing the third and second flexible masks to obtain a packaged highly integrated flexible supercapacitor. The present invention solves the problems of currently used highly integrated flexible supercapacitor packaging, the inconvenience of electrolyte coating, and the inability to measure individual electrode units.

Description

Technical Field

[0001] The present 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 a double-layer interface between electrodes and electrolytes or through electrochemical reactions. They have advantages such as high power density, rapid charge and discharge, and long cycle life, and 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. As a result, 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, 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 internal materials from the external environment. Although this packaging method can ensure the stability and safety of supercapacitors to a certain extent, because metal or plastic materials are used for packaging, the resulting capacitor has a large volume and weight, which is not conducive to the lightweight and miniaturization of the equipment. Moreover, since 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, making 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 single or multiple electrodes and the entire highly integrated series electrode. However, 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 highly integrated flexible supercapacitor packaging, the inconvenience of electrolyte coating, and the 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 flexible mask patterns: Arrange the electrode array of the highly integrated flexible supercapacitor. According to the design pattern of the highly integrated flexible supercapacitor to be assembled, draw three layers of flexible mask patterns, 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, with a detection hole provided on both sides of each electrode opening area, and the electrode opening areas correspond to the electrodes; the second layer of flexible mask and the third layer of flexible mask are respectively drawn with a plurality of matrix arrays, the matrix arrays of the second layer of flexible mask and the matrix arrays 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 after the second layer of flexible mask and the third layer of flexible mask are superimposed, only the electrode area is exposed;

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

[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 and third layers of flexible mask, to obtain a three-layer flexible mask;

[0011] S3, Lamination and Electrolyte Coating: Laminate the three layers of flexible mask on the highly integrated flexible supercapacitor from bottom to top, pressing them during the process, and then coat the electrolyte on the electrode area;

[0012] S4. After the electrolyte solidifies, the third flexible mask and the second flexible mask 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 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 electrodes of the highly integrated flexible supercapacitor are arranged in a matrix, and the electrode edge spacings in the horizontal and vertical directions are different, and the larger the horizontal spacing is compared with the vertical spacing, the wider the spacing is, and the smaller the spacing is, the narrower the spacing is;

[0015] The detection holes are located at a wider spacing, the second flexible mask covers a narrower spacing, the third flexible mask covers the detection holes, and the second flexible mask and the third flexible mask overlap, 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 etching, hot melting, knife carving 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 flexible mask layer is repeatedly pressed with tweezers or an acrylic rod during the lamination process, and the edges of the first flexible mask layer are sealed and fixed with tape.

[0026] The technical solution provided by the present invention can have 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 and second layers of flexible masks 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 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. 4 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] For ease of understanding of the present invention, the present invention will be 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 experiments were carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. All reagents or instruments used without specifying the manufacturer are commercially available conventional products.

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

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

[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. The electrode opening areas 22 correspond to electrodes. 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 arrays of the second layer of flexible mask 3 and the matrix arrays of the third layer of flexible mask 4 are perpendicular to each other. The width of the matrix arrays is equal to the side length of the electrode area. After the second layer of flexible mask 3 and the third layer of flexible mask 4 are superimposed, only the electrode area is exposed.

[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] To solve the problems existing in the prior art, the technical solution proposed in the present invention encapsulates a highly integrated flexible supercapacitor 1 according to the above steps. First, a flexible mask pattern is drawn, and then the flexible mask is patterned. Then, the electrolyte is applied. After the electrolyte solidifies, the second and third flexible masks 3 and 4 are removed according to the direction of the rectangular array of the second and third flexible masks 3 and 4, leaving the first 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 flexible mask 2 is removed, the highly integrated flexible supercapacitor 1 will be completely exposed to the air. In addition, because during the patterning process, each electrode opening area 22 of the first flexible mask 2 is provided with a detection hole 21 on both sides, after the second and third flexible masks 3 and 4 are laminated, only the electrode area is precisely exposed, that is, the detection hole 21 of the first flexible mask 2 is covered. During this process, the mask is pressed to ensure that the mask is fitted and there is no gap between the contact surfaces. When the electrolyte is subsequently applied, the electrolyte will not penetrate into the detection hole 21, avoiding 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 each drawn with a number of mutually perpendicular matrix arrays, the width of the matrix array being equal to the side length of the electrode area, further precisely controlling the coating of the electrolyte. After the second flexible mask 3 and the third flexible mask 4 are superimposed, only the electrode area is precisely exposed. During the coating process, the electrolyte will naturally flow and fill the electrode opening area 22. The second flexible mask 3 and the third flexible mask 4 can ensure that the electrolyte is not 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 process will be removed. In this way, the problem of the electrolyte connecting adjacent electrodes due to the small distance between the electrodes or the small size of the electrodes themselves will not occur, thus solving the problem of inconvenience in electrolyte coating.

[0045] It is worth noting that the matrix arrays of the second layer flexible mask 3 and the third layer flexible mask 4 are perpendicular to each other. When tearing, tearing along the direction of the matrix array can reduce resistance during the tearing process. Because the tearing direction is consistent with the structural direction of the flexible mask, material deformation and stress concentration are reduced, making the flexible mask easier to remove. If a second layer flexible mask that can cover the detection hole 21 and leave corresponding areas according to the electrodes is directly set, the complex structural design may cause stress concentration, especially at the edges and the left-out areas. These stress concentration points can easily cause the second layer flexible mask to tear or remain during the removal process, affecting the packaging effect. In addition, the matrix arrays designed to be perpendicular to each other can simplify the alignment process. When multiple flexible masks are stacked, the vertical matrix array can provide more alignment reference points and reduce alignment errors. If a second layer flexible mask 3 that can cover the detection hole 21 and leave corresponding areas according to the electrodes 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 naturally flow 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 placed in the detection hole 21 with a conductive medium, which can be silver paste or copper foil, and then connected to an external measuring device via a wire for measurement to ensure the accuracy and reliability of the measurement results.

[0048] Furthermore, the material of the three-layer flexible mask is a self-adhesive tape material or 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 can be polyimide (PI) tape, polyethylene terephthalate (PET) film or 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 flexible mask layers gradually decreases from bottom to top. The viscosity of the first flexible mask layer 2 is greater than 2.45N / 25mm, ensuring a perfect sealing effect on the supercapacitor. The viscosity of the second flexible mask layer 3 is 1.47-1.96N / 25mm, and the viscosity of the third flexible mask layer 4 is 0.98-1.47N / 25mm. This ensures that the two mask layers will not easily fall off the capacitor, without affecting the coating of the electrolyte, and are easy to remove later, resulting in the desired packaged highly integrated flexible supercapacitor 1.

[0051] In addition, the three-layer flexible mask is sticky, which can be used to encapsulate the highly integrated flexible supercapacitor 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 electrodes of the highly integrated flexible supercapacitor 1 are arranged in a matrix, and the electrode edge spacings in the horizontal and vertical directions 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 interval, the second flexible mask 3 covers a narrower interval, and the third flexible mask 4 covers the detection holes 21. 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 spacing, it is divided into wider spacing and narrower spacing, that is, the position between the matrix array of the second layer flexible mask 3 and the third layer 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 spacing, and the electrode gap with a smaller width is the narrower spacing, and the wider spacing and the narrower spacing are perpendicular to each other. The detection hole 21 is located at the wider spacing, which is beneficial to patterning the flexible mask in step S2 and reducing the processing difficulty.

[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 spacing and has a larger contact area. Because the third layer of flexible mask 4 is located at the top, when it is torn off, most of the electrolyte can be taken away, and then the second layer of flexible mask 3 can be torn off to separate the electrodes, ensuring that the electrolyte is completely removed.

[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] Furthermore, the thickness of the second and third flexible masks 3 and 4 is 125-200 μm, respectively, which facilitates subsequent removal. The masks have moderate mechanical strength, neither being too fragile to break nor too hard to peel, thus reducing resistance during removal and making them easier to remove. Furthermore, within this thickness range, the masks are more easily flattened during lamination, reducing errors and helping to improve alignment accuracy when stacking multiple masks, ensuring precise electrolyte coverage of the electrodes.

[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 a 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, the electrolyte will not remain too much on their surface, and the coated electrolyte is ensured to be evenly distributed in the electrode opening area 22, effectively preventing the leakage of the electrolyte. 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 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 etching, hot melting, knife carving 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 low 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 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 strong gel structure, improving the stability and reliability of the electrolyte. This allows the 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, exhibiting excellent performance in electrochemical devices and having broad application prospects in flexible electronic devices. The use of PVA-H2SO4 gel electrolyte can effectively form a strong gel structure with high stability and reliability, reducing the occurrence of electrolyte leakage and separation of the electrolyte from the 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, it is vacuumed to remove bubbles in the electrolyte and ensure full contact between the electrolyte and 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, thereby ensuring the packaging effect and capacitor performance.

[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 to prevent gas from entering from the side, ensure that the first flexible mask 2 is completely attached to the highly integrated flexible supercapacitor 1, and prevent 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, arrange the electrode array of the highly integrated flexible supercapacitor 1, and draw a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled as needed, which are the first layer of flexible mask 2, the second layer of flexible mask 3 and the third layer of 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 is provided with 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 size of 2×36mm and a pitch of 1mm, and the third layer of flexible mask 4 is drawn with 5 matrix arrays with a size 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 hole 21 and the electrode opening area 22 of the first layer of flexible mask 2, and removing the rectangular array 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; 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 and the corresponding area is removed. 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 during the process to achieve a tight fit, and then the PVA-H2SO4 gel electrolyte is coated on the electrode area.

[0085] S4. Place the highly integrated flexible supercapacitor 1 with the three-layer mask 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 the packaged highly integrated flexible supercapacitor 1.

[0086] Example 2

[0087] S1. Draw a flexible mask pattern, arrange the electrode array of the highly integrated flexible supercapacitor 1, and draw a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled as needed, which are the first layer of flexible mask 2, the second layer of flexible mask 3 and the third layer of 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 is provided with 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 size of 2×36mm and a pitch of 1mm, and the third layer of flexible mask 4 is drawn with 5 matrix arrays with a size 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: Remove the detection holes 21 and electrode opening areas 22 from the first flexible mask layer 2, and remove the perpendicular rectangular arrays from the second and third flexible masks 3 and 4, to form a three-layer flexible mask. The three-layer flexible mask is made of PI tape. A focused laser beam from a 355nm UV picosecond laser is used, with a power of 9.0W and a scanning speed of 60mm / s. The PI tape is patterned from left to right, following the pattern drawn in step S1, and the corresponding areas are then removed. The thickness of the first flexible mask layer 2 is 60μm, and the thickness of the second and third flexible masks 3 and 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 H2SO4 / PVA gel electrolyte is coated on the electrode area.

[0092] S4. Place the highly integrated flexible supercapacitor 1 with the three-layer mask 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 the packaged highly integrated flexible supercapacitor 1.

[0093] Example 3

[0094] S1. Draw a flexible mask pattern, arrange the electrode array of the highly integrated flexible supercapacitor 1, and draw a three-layer flexible mask pattern according to the design pattern of the highly integrated flexible supercapacitor 1 to be assembled as needed, which are the first layer of flexible mask 2, the second layer of flexible mask 3 and the third layer of 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 is provided with 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 size of 2×36mm and a pitch of 1mm, and the third layer of flexible mask 4 is drawn with 5 matrix arrays with a size 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: Remove the detection holes 21 and electrode opening areas 22 from the first flexible mask layer 2, and remove the perpendicular rectangular arrays from the second and third flexible masks 3 and 4, to form a three-layer flexible mask. The three-layer flexible mask is made of PI tape. A focused laser beam from a 355nm UV picosecond laser is used, with a power of 9.0W and a scanning speed of 60mm / s. The PI tape is patterned from left to right, following the pattern drawn in step S1, and the corresponding areas are then removed. The thickness of the first flexible mask layer 2 is 80μm, and the thickness of the second and third flexible masks 3 and 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 H2SO4 / PVA gel electrolyte is coated on the electrode area.

[0099] S4. Place the highly integrated flexible supercapacitor 1 with the three-layer mask 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 the 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 45×45×15mm aluminum shell, place the prepared 40×40mm 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 into the inner side of the top of the aluminum shell and ensure the seal by crimping to fix the cover;

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

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

[0106] The well-packaged highly integrated flexible supercapacitors obtained in the examples 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 both have relatively good specific capacitance packaging effects, and the overall test results are similar. The specific capacitance of the 50 series-connected electrodes of the packaged highly integrated flexible supercapacitor in 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, nor can it detect the performance of a single or multiple electrodes, lacking 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 are different, that is, the amount of electrolyte coated on the electrode is different, but the present invention ensures that the electrolyte is coated in 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 principles of the present invention have been described above with reference to specific embodiments. These descriptions are intended solely to illustrate the principles of the present invention and are not to be construed in any way as limiting the scope of protection of the present invention. Based on the explanations herein, those skilled in the art will readily conceive of other specific embodiments of the present invention without inventive effort, and such embodiments 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 flexible mask patterns: Arrange the electrode array of the highly integrated flexible supercapacitor. According to the design pattern of the highly integrated flexible supercapacitor to be assembled, draw three layers of flexible mask patterns, 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 the flexible mask is drawn with a plurality of detection holes and a plurality of electrode opening areas, with a detection hole provided on both sides of each electrode opening area, 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 arrays of the second layer of flexible mask and the matrix arrays 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 after the second layer of flexible mask and the third layer of flexible mask are superimposed, only the electrode area is exposed; The electrode opening area is 0.15-0.25 mm larger than the length and width of the electrode area respectively; 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 and third layers of flexible mask, to obtain a three-layer flexible mask; S3, Lamination and Electrolyte Coating: Laminate the three layers of flexible mask on the highly integrated flexible supercapacitor from bottom to top, pressing them during the process, and then coat the electrolyte on the electrode area; S4. After the electrolyte solidifies, the third flexible mask and the second flexible mask 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 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 electrodes of the highly integrated flexible supercapacitor are arranged in a matrix, and the electrode edge spacings in the horizontal and vertical directions 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 covers a narrower spacing, the third flexible mask covers the detection holes, and the second flexible mask and the third flexible mask overlap, 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 carving 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 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 flexible mask layer is repeatedly pressed with tweezers or acrylic rods during the lamination process, and the edges of the first flexible mask layer are sealed and fixed with tape.

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