An ultra-high voltage graphene film supercapacitor and a highly integrated packaging method thereof

Abstract

The present invention discloses an ultra-high voltage graphene film supercapacitor and a highly integrated packaging method thereof. By pyrolyzing a carbon precursor film on both sides to form a self-supporting graphene film, the prepared graphene electrode has high flexibility and uniformity. This method not only simplifies the process and reduces costs, but also offers strong controllability, making it more conducive to industrial large-scale production. Furthermore, by designing a stacking and flexible packaging method for the supercapacitor, a certain number of second integrated monomers are first connected in series to form a sheet, which is then stacked end-to-end in a "Z" shape to form a highly integrated series structure. This not only addresses the low power and low voltage status of traditional capacitors, but also provides an integrated approach for future high-voltage, high-power flexible electronic devices.

Description

Technical Field

[0001] The present invention relates to the technical field of supercapacitors, and in particular to an ultra-high voltage graphene film supercapacitor and a highly integrated packaging method thereof. Background Art

[0002] In recent years, with the development of electronic components toward miniaturization, flexibility, high integration, and high power, flexible electronic devices, as urgently needed high-voltage output energy storage devices, are indispensable in microelectronic and micromechanical applications such as microrobotics, soft actuators, skin electronics, microsensors, and integrated electronic circuits. In an era of rapidly growing energy demand, energy storage technologies have attracted significant attention, particularly the development of electrochemical energy storage devices, represented by rechargeable batteries (such as sodium-sulfur batteries, flow batteries, lead-acid batteries, and lithium-ion batteries) and supercapacitors. Supercapacitors offer advantages such as efficient space utilization, high device integration, reliable electrochemical performance (such as fast charge and discharge rates, high power output and frequency response, and excellent mechanical flexibility), long cycle life, and environmental friendliness.

[0003] The manufacturing process of supercapacitors involves numerous steps, among which the packaging process is extremely critical. It effectively isolates the electrochemical system within the supercapacitor from the external environment, preventing external interference that could affect its performance. Through specific packaging techniques, the long-term, slow volatilization of the electrolyte gel within the device can be greatly suppressed, and internal short circuits in the capacitor can be prevented, thereby ensuring the supercapacitor's stable and reliable performance, maintaining good working condition during long-term use, and extending its service life and effectiveness.

[0004] Currently, the stable operating voltage of existing supercapacitors is generally around 1V, making it difficult to achieve high voltage output in a small area and unable to meet the high voltage application requirements in fields such as integrated circuits. In view of this, a supercapacitor that can effectively increase the operating voltage is urgently needed. Summary of the Invention

[0005] The purpose of the present invention is to provide an ultra-high voltage graphene film supercapacitor and a highly integrated packaging method thereof, which can effectively increase the operating voltage of the supercapacitor and overcome the shortcomings of the prior art.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] A highly integrated packaging method for ultra-high voltage graphene film supercapacitors comprises the following steps:

[0008] S1, using a laser to emit laser light and act on the two surfaces of the carbon precursor film to pyrolyze and obtain a graphene film;

[0009] S2, cutting the graphene film into long strips to obtain a graphene electrode;

[0010] S3. Cutting the hydrophobic polymer film into a flexible mask, and attaching the flexible mask to at least one end of the graphene electrode; wherein the flexible mask is annular in shape, a bare storage position is defined in the middle of the flexible mask, and the graphene electrode completely covers the storage position;

[0011] S4. Applying a gel solid electrolyte to the storage location, evacuating the vacuum and removing moisture to obtain an integrated monomer; wherein the integrated monomer includes a first integrated monomer and a second integrated monomer, the flexible mask is attached to either end of the first integrated monomer, and the flexible mask is attached to both ends of the second integrated monomer;

[0012] S5, preparing two first integrated units and a plurality of second integrated units;

[0013] S6, connecting the plurality of second integrated monomers end to end in sequence through the gel solid electrolyte and solidifying them to obtain a sheet layer;

[0014] S7. Prepare a plurality of the sheet layers, stack the plurality of sheet layers end to end in a "Z" shape through the gel solid electrolyte, and solidify to obtain an intermediate; connect the two first integrated monomers to the two ends of the intermediate through the gel solid electrolyte, and obtain an ultra-high voltage graphene film supercapacitor after solidification.

[0015] Preferably, step S6 is specifically as follows:

[0016] S6, sequentially connecting the plurality of second integrated monomers end to end with the gel solid electrolyte and curing them, and wrapping the connection between two adjacent second integrated monomers with a packaging tape to encapsulate them to obtain a sheet layer;

[0017] Step S7 is specifically as follows:

[0018] S7, preparing a plurality of the sheet layers, stacking the plurality of the sheet layers end to end in a "Z" shape through the gel solid electrolyte, and curing to obtain an intermediate;

[0019] connecting the two first integrated monomers to the two ends of the intermediate body respectively through the gel solid electrolyte and curing them;

[0020] The connection between two adjacent sheets and the connection between the first integrated monomer and the intermediate body are wrapped with packaging tape to obtain an ultra-high voltage graphene film supercapacitor.

[0021] Preferably, in step S6, the end-to-end connection of the plurality of second integrated monomers in the sheet layer is any one of a step-wise connection and a staggered connection.

[0022] Preferably, in step S3, the thickness of the flexible mask is 125-200 μm.

[0023] Preferably, in step S4, the vacuuming is specifically: placing the integrated monomer in a negative pressure environment with a vacuum degree of -0.9 MPa to -0.7 MPa for 20 to 40 minutes;

[0024] The step of removing moisture specifically includes placing the integrated monomer in the air.

[0025] Preferably, in step S2, the shape of the graphene electrode is rectangular, the ratio of the length to the width of the graphene electrode is 2.2 to 2.3, and the width of the graphene electrode is 3 to 5 mm;

[0026] In step S3, the shape of the flexible mask and the shape of the storage location are both square, and the side length of the flexible mask is 2 mm longer than the side length of the storage location;

[0027] The side length of the flexible mask is greater than the width of the graphene electrode.

[0028] Preferably, in step S4, the gel solid electrolyte is any one of polyvinyl alcohol, gelatin and polyacrylonitrile.

[0029] Preferably, in step S1, the carbon precursor film is any one of a polyimide film, a polyetherimide film and a polyamideimide film;

[0030] In step S3, the polymer film is any one of polyimide tape, polyethylene terephthalate film and polyvinyl chloride tape;

[0031] In steps S6 and S7, the packaging tape is a polyimide tape.

[0032] Preferably, in step S1, the laser is any one of a CO2 laser, a semiconductor laser and an ultraviolet picosecond laser;

[0033] In step S2 and step S3, the cutting is laser cutting, and the laser used for the laser cutting is any one of an ultraviolet picosecond laser and a pulsed CO2 laser.

[0034] An ultra-high voltage graphene film supercapacitor is prepared using the highly integrated packaging method of the ultra-high voltage graphene film supercapacitor.

[0035] The technical solution provided by the present invention can have the following beneficial effects:

[0036] 1. The method of double-sided pyrolysis of carbon precursor films into self-supporting graphene films makes the prepared graphene electrodes highly flexible and uniform. It not only has a simple process and low cost, but also has strong controllability, which is more conducive to industrial large-scale production.

[0037] 2. By designing the stacking and flexible packaging method of supercapacitors, a certain number of second integrated monomers are first connected in series to form a layer, and then stacked end to end in a "Z" shape to form a highly integrated series structure. On the one hand, it solves the low power and low voltage status of traditional capacitors. On the other hand, it also provides an integration idea for future high voltage, high power flexible electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic diagram of the steps of a highly integrated packaging method for an ultra-high voltage graphene film supercapacitor of the present invention.

[0039] Figure 2 It is a schematic structural diagram of a single supercapacitor in the present invention.

[0040] Figure 3 It is a schematic structural diagram of the step-wise connected sheets in the present invention.

[0041] Figure 4 The diagram is a structural diagram of an ultra-high voltage graphene film supercapacitor with a stepped layer structure according to the present invention.

[0042] Figure 5 It is a schematic structural diagram of the interlaced layers in the present invention.

[0043] Figure 6 It is a structural schematic diagram of an ultra-high voltage graphene film supercapacitor with an interlaced layer structure in the present invention.

[0044] Figure 7 This is an equivalent circuit diagram of an ultra-high voltage graphene film supercapacitor integrated with 160 supercapacitors prepared in Example 4 of the present invention.

[0045] Figure 8 CV curves of the ultra-high voltage graphene film supercapacitor integrated with 160 supercapacitors prepared in Example 4 of the present invention at different scan rates.

[0046] Figure 9 3 is a GCD diagram of an ultra-high voltage graphene film supercapacitor integrated with 160 supercapacitors prepared in Example 4 of the present invention at different currents.

[0047] Figure 10 The CV curves of a single supercapacitor and a layer integrated with 10 supercapacitors at a constant scan rate.

[0048] Figure 11 CV curves of the ultra-high voltage graphene film supercapacitors prepared in Examples 1-4 of the present invention at a constant scan rate.

[0049] Figure 12 These are GCD diagrams of a single supercapacitor, a sheet integrated with 10 supercapacitors, and the ultra-high voltage graphene film supercapacitors prepared in Examples 1-4 of the present invention at a constant current density.

[0050] Among them, there are graphene electrode 1, flexible mask 2, storage position 201, and gel solid electrolyte 3. DETAILED DESCRIPTION

[0051] A highly integrated packaging method for ultra-high voltage graphene film supercapacitors comprises the following steps:

[0052] S1, using a laser to emit laser light and act on the two surfaces of the carbon precursor film to pyrolyze and obtain a graphene film;

[0053] S2, cutting the graphene film into long strips to obtain a graphene electrode 1;

[0054] S3. Cutting the hydrophobic polymer film into a flexible mask 2, and adhering the flexible mask 2 to at least one end of the graphene electrode 1; wherein the flexible mask 2 is annular in shape, a bare storage position 201 is defined in the middle of the flexible mask 2, and the graphene electrode 1 completely covers the storage position 201;

[0055] S4, applying the gel solid electrolyte 3 to the storage position 201, evacuating and removing moisture to obtain an integrated monomer; wherein the integrated monomer includes a first integrated monomer and a second integrated monomer, the flexible mask 2 is attached to either end of the first integrated monomer, and the flexible mask 2 is attached to both ends of the second integrated monomer;

[0056] S5, preparing two first integrated units and a plurality of second integrated units;

[0057] S6, connecting the plurality of second integrated monomers end to end in sequence through the gel solid electrolyte 3 and solidifying them to obtain a sheet layer;

[0058] S7. Prepare a plurality of the sheet layers, stack the plurality of the sheet layers end to end in a "Z" shape through the gel solid electrolyte 3, and solidify to obtain an intermediate; connect the two first integrated monomers to the two ends of the intermediate through the gel solid electrolyte 3, and obtain an ultra-high voltage graphene film supercapacitor after solidification.

[0059] In order to solve the technical problem of limited operating voltage of supercapacitors in the existing technology, this solution proposes a highly integrated packaging method for ultra-high voltage graphene film supercapacitors, which combines multiple capacitors in a series stacking manner to effectively increase the operating voltage of the supercapacitor.

[0060] Specifically, if Figure 1 As shown, the high-integration packaging method of this solution includes the following steps:

[0061] First (i.e., step S1), the upper and lower surfaces of the self-supporting carbon precursor film are pyrolyzed using lasers to form double-sided graphene, achieving uniform graphitization of the entire carbon precursor film, thereby achieving the double-sided conductivity required for supercapacitor stacking. This solves the problem of incomplete induction at low laser power in existing induction processes, which prevents the formation of double-sided graphene layers; it also solves the problem of excessive ablation at high laser power, which prevents the formation of uniform graphene layers and may even cause the graphene layers to fall off.

[0062] It should be noted that in step S1, the carbon precursor film can be placed flat on a substrate (such as a glass substrate) for laser induction, which can effectively avoid the phenomenon of ups and downs on the surface of the carbon precursor film and prevent the laser from having large differences in defocus when scanning different areas, resulting in uneven graphene quality in the carbon precursor film. Furthermore, tape (or other clamping devices) can be used to fix the four sides of the carbon precursor film. On the one hand, it can be flattened and tightly attached to the substrate, and on the other hand, it is also convenient to process the other side of the carbon precursor film.

[0063] Then (i.e., step S2), the graphene film is cut into long strips to obtain the graphene electrode 1, which is beneficial to improving the processing efficiency of the supercapacitor electrode. It should be noted that the cutting method can be any one of laser cutting, knife cutting, or hot melting, which is not limited here.

[0064] Next (i.e., step S3), the cut flexible mask 2 is pasted to at least one end of the graphene electrode 1, wherein the storage position 201 opened in the middle of the flexible mask 2 serves as a storage for the next step of coating the gel solid electrolyte 3 to ensure the electrochemical performance of the supercapacitor.

[0065] It should be noted that the flexible mask 2 can be cut by any of laser cutting, knife cutting, or hot melting, which is not limited here. In addition, in order to achieve the adhesion of the flexible mask 2 to the surface of the graphene electrode 1, this solution can use a self-adhesive polymer film tape as the flexible mask 2. One surface of the above-mentioned polymer film tape is self-adhesive, which allows the flexible mask 2 to be tightly adhered to the graphene electrode 1, and the other surface has a hydrophobic effect, which can effectively prevent the gel solid electrolyte 3 in step S4 from diffusing on the surface of the graphene electrode 1. In addition, when sticking the flexible mask 2 to the end of the graphene electrode 1, tweezers or an acrylic rod can be used to repeatedly and gently press it so that the flexible mask 2 is completely adhered to the graphene electrode 1 to prevent the gel solid electrolyte 3 from seeping out of the gap and causing a short circuit.

[0066] Then (i.e., step S4), the gel solid electrolyte 3 is coated on the storage position 201, and the air in the electrolyte is removed by vacuum, and the integrated monomer is obtained after the water in the electrolyte is removed. It should be noted that the coating of the gel solid electrolyte 3 can be done by using a brush pen to coat the electrolyte. The brush pen is a low-cost, easy-to-operate coating tool, and the brush of the brush pen is soft, flexible in coating, and can be applied to occasions with a small coating area. In addition, the vacuum treatment of the integrated monomer can be carried out in a negative pressure device such as a vacuum box, and the water removal treatment can be carried out in a drying box for drying, or directly placed in the air for natural evaporation, which is not limited in this scheme. It should also be noted that the coating amount of the gel solid electrolyte 3 should not be too much to avoid excessive gel solid electrolyte 3 overflowing the storage position 201 of the flexible mask 2 and causing a short circuit; but it should not be too little to avoid weakening the electrochemical performance of the supercapacitor.

[0067] Finally, the supercapacitor is integrated, specifically:

[0068] In the first stage of integration (ie, step S5 ), it is necessary to prepare a first integrated unit and a second integrated unit that match the designed number of supercapacitors.

[0069] In the second stage of integration (i.e., step S6), multiple second integrated monomers with flexible masks 2 and gel solid electrolyte 3 at both ends are connected end to end in sequence to form a layer of ultra-high voltage graphene film supercapacitor. It should be noted that after the ends of two adjacent second integrated monomers are attached to each other, the gel solid electrolyte 3 at the ends of the connection between the two second integrated monomers will fuse with each other and solidify into an electrolyte as a whole, so that the connection between the two adjacent second integrated monomers forms a supercapacitor, such as Figure 2 That is, the sheet layer is integrated with one less supercapacitor than the number of the second integrated monomer.

[0070] In the third stage of integration (i.e., step S7), multiple sheets are stacked end to end and solidified to obtain an intermediate body, and then the first integrated monomer is connected to the head and tail ends of the intermediate body respectively. After solidification, an ultra-high voltage graphene film supercapacitor is obtained. It should be noted that this solution designs a stacking and flexible packaging method for supercapacitors. First, a certain number of second integrated monomers are connected in series to form sheets, such as Figure 3 and 5 As shown, the modules are stacked end to end in a "Z" shape to form a highly integrated series structure, as shown in FIG. Figure 4 and 6 As shown, this method not only solves the low power and low voltage problems of traditional capacitors, but also provides an integration strategy for future high-voltage, high-power flexible electronic devices. It theoretically enables an infinite stacking integration method, greatly improving the high-voltage performance of supercapacitors. Furthermore, during the series stacking of integrated cells, it is important to ensure that the areas coated with electrolyte are aligned and arranged in a straight line, which is more neat, compact, and convenient for subsequent processing.

[0071] The present invention provides a highly integrated packaging method for ultra-high voltage graphene film supercapacitors. By pyrolyzing a carbon precursor film on both sides to form a self-supporting graphene film, the prepared graphene electrode 1 exhibits high flexibility and uniformity. This method not only simplifies the process and reduces costs, but also offers strong controllability, making it more suitable for industrial large-scale production. Furthermore, by designing a stacking and flexible packaging method for the supercapacitor, a certain number of second integrated monomers are first connected in series to form a sheet, which is then stacked end-to-end in a "Z" shape to form a highly integrated series structure. This method addresses the low power and low voltage issues of traditional capacitors while also providing an integrated approach for future high-voltage, high-power flexible electronic devices.

[0072] To further illustrate, step S6 is specifically as follows:

[0073] S6, connecting a plurality of the second integrated monomers end to end in sequence through the gel solid electrolyte 3 and curing them, and wrapping the connection between two adjacent second integrated monomers with a packaging tape to encapsulate them to obtain a sheet layer;

[0074] Step S7 is specifically as follows:

[0075] S7, preparing a plurality of the sheet layers, stacking the plurality of the sheet layers end to end in a "Z" shape through the gel solid electrolyte 3, and curing to obtain an intermediate;

[0076] Connecting the two first integrated monomers to the two ends of the intermediate body respectively through the gel solid electrolyte 3 and curing them;

[0077] The connection between two adjacent sheets and the connection between the first integrated monomer and the intermediate body are wrapped with packaging tape to obtain an ultra-high voltage graphene film supercapacitor.

[0078] In a preferred embodiment of the present technical solution, packaging tape is also used to wrap the connection (i.e., a single supercapacitor). On the one hand, it can play a fixing role to improve the mechanical properties of the supercapacitor, and on the other hand, it can prevent the two graphene electrodes 1 in a single supercapacitor from contacting each other and causing a short circuit.

[0079] To further illustrate, in step S6, the end-to-end connection of the plurality of second integrated units in the sheet layer is any one of a step-wise connection and a staggered connection.

[0080] In another preferred embodiment of the present technical solution, the sheets can be connected in a step-by-step manner, such as Figure 3 As shown, it can also be connected in an interlaced manner, such as Figure 5 As shown, it takes into account both high integration and flexibility.

[0081] To further illustrate, in step S3, the thickness of the flexible mask 2 is 125-200 μm.

[0082] Since the flexible mask 2 of this solution is used to store the gel solid electrolyte 3, if its thickness is too thin, it will affect the electrochemical performance of the supercapacitor on the one hand, and may also cause a short circuit of the supercapacitor on the other hand; if its thickness is too thick, it will easily reduce the flexibility of the supercapacitor.

[0083] Specifically, the flexible mask 2 can be made of thicker material to provide sufficient space for subsequent electrolyte coating to ensure that the electrolyte can be fully coated on the electrode surface. If thicker material is not available, multiple layers of thinner material can be used as a substitute.

[0084] To further illustrate, in step S4, the vacuuming is specifically: placing the integrated monomer in a negative pressure environment with a vacuum degree of -0.9 MPa to -0.7 MPa for 20 to 40 minutes;

[0085] The step of removing moisture specifically includes placing the integrated monomer in the air.

[0086] In this way, the best effect of removing bubbles and moisture is achieved, so that the electrolyte can fully contact the graphene electrode 1 and ensure the electrochemical performance of the supercapacitor.

[0087] To further illustrate, in step S2, the shape of the graphene electrode 1 is rectangular, the ratio of the length to the width of the graphene electrode 1 is 2.2 to 2.3, and the width of the graphene electrode 1 is 3 to 5 mm;

[0088] In step S3, the shape of the flexible mask 2 and the shape of the storage position 201 are both square, and the side length of the flexible mask 2 is 2 mm longer than the side length of the storage position 201;

[0089] The side length of the flexible mask 2 is greater than the width of the graphene electrode 1 .

[0090] In a specific embodiment, the present solution optimizes the shape and size of the graphene electrode 1 and the flexible mask 2, which can further avoid short circuits caused by contact between the two electrodes of a single supercapacitor; in addition, the increase in the area ratio of the storage position 201 can fully expose the electrodes of the supercapacitor and provide sufficient space for the coating of the electrolyte.

[0091] To further illustrate, in step S4, the gel solid electrolyte 3 is any one of polyvinyl alcohol, gelatin and polyacrylonitrile.

[0092] The above electrolyte has excellent electrochemical properties, good mechanical properties and flexibility, good self-healing characteristics and environmental protection, and is an ideal material for use in highly integrated supercapacitors.

[0093] To further illustrate, in step S1, the carbon precursor film is any one of a polyimide film, a polyetherimide film and a polyamideimide film;

[0094] In step S3, the polymer film is any one of polyimide tape, polyethylene terephthalate film and polyvinyl chloride tape;

[0095] In steps S6 and S7, the packaging tape is a polyimide tape.

[0096] Specifically, the polymer film of this scheme is more preferably polyimide tape, which has good flexibility, airtightness and adaptability, can effectively improve the mechanical properties and environmental adaptability of graphene supercapacitors, enhance their performance under bending and stretching conditions, and enable graphene supercapacitors to better adapt to the diverse needs of the modern electronics market.

[0097] To further illustrate, in step S1, the laser is any one of a CO2 laser, a semiconductor laser and an ultraviolet picosecond laser;

[0098] In step S2 and step S3, the cutting is laser cutting, and the laser used for the laser cutting is any one of an ultraviolet picosecond laser and a pulsed CO2 laser.

[0099] Specifically, in step S1, it is preferred to use a continuous wavelength CO2 laser for laser induction, and the graphene processed by focusing, scanning in a progressive manner from left to right, a scanning speed of 150 mm / s, a scanning pitch of 1000 DPI (25.4 microns), and a laser power of 6.7 W is the best.

[0100] In addition, in step S3, the cutting of the flexible mask 2 is more preferably performed by laser cutting using an ultraviolet picosecond laser, and engraving is performed in a focused manner. The laser power needs to be controlled. If it is too small, the polymer film cannot be penetrated, and if it is too large, the substrate will be penetrated. It is best to maintain it at 8.4 to 9 W, and the scanning speed is 60 mm / s.

[0101] An ultra-high voltage graphene film supercapacitor is prepared using the highly integrated packaging method of the ultra-high voltage graphene film supercapacitor.

[0102] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0103] Example 1

[0104] S1. Cut polyimide paper into 100 × 100 mm sheets with scissors. Place the paper flatly on a 100 × 100 × 2 mm glass substrate using tape to secure the four corners. Use a continuous CO2 laser to sequentially scan the top and bottom surfaces of the polyimide paper, pyrolyzing the entire surface into a graphene film. The scanning area is 90 × 90 mm, the laser power is 6.8 W, the scanning pitch is 1000 DPI, the scanning speed is 150 mm / s, and the focus mode is used.

[0105] S2. Using an ultraviolet picosecond laser with a wavelength of 355 nm, the graphene film is engraved from the central area into rectangles with a size of 11×5 mm, distributed in an array of 8×16, to serve as graphene electrode 1; wherein the laser parameters of the ultraviolet picosecond laser are: focusing mode, laser power of 8.5 W, and scanning speed of 60 mm / s.

[0106] S3. A polyimide tape with a thickness of 125 μm is laser cut into a flexible mask 2 using an ultraviolet picosecond laser with a wavelength of 355 nm, and the flexible mask 2 is adhered to at least one end of the graphene electrode 1; wherein the flexible mask 2 is in the shape of a square ring with an outer contour side length of 5.1 mm and an inner contour side length of 3.1 mm, and an exposed storage position 201 is opened in the middle of the flexible mask 2; the laser parameters of the ultraviolet picosecond laser are: focusing mode, laser power of 9 W, and scanning speed of 60 mm / s.

[0107] S4. Apply H2SO4 / PVA hydrogel electrolyte to the storage position 201, place the graphene electrode 1 in a vacuum drying oven, use a vacuum pump to pump the pressure in the vacuum drying oven to 0.8 bar, and maintain it for half an hour; after taking it out, place it in the air for 8 hours, and obtain an integrated monomer after the electrolyte solidifies into a gel; wherein, the integrated monomer includes a first integrated monomer and a second integrated monomer, and a flexible mask 2 is attached to either end of the first integrated monomer, and flexible masks 2 are attached to both ends of the second integrated monomer.

[0108] S5, preparing two first integrated monomers and a plurality of second integrated monomers;

[0109] S6. Connecting multiple second integrated monomers end to end in sequence through H2SO4 / PVA hydrogel electrolyte and curing them, and wrapping the joints of two adjacent second integrated monomers with polyimide tape for packaging to obtain a layer of 10 supercapacitors connected in a stepped manner;

[0110] S7. Prepare multiple layers connected in a stepwise manner and integrated with 10 supercapacitors, stack the layers end to end in a "Z" shape through H2SO4 / PVA hydrogel electrolyte, and solidify to obtain an intermediate; connect two first integrated monomers to the two ends of the intermediate through H2SO4 / PVA hydrogel electrolyte and solidify;

[0111] The connection between two adjacent layers and the connection between the first integrated monomer and the intermediate are wrapped with polyimide tape for packaging to obtain an ultra-high voltage graphene film supercapacitor integrating 60 supercapacitors.

[0112] Example 2

[0113] Steps S1-S5 of Example 2 are the same as steps S1-S5 of Example 1.

[0114] S6. Connecting multiple second integrated monomers end to end in sequence through H2SO4 / PVA hydrogel electrolyte and curing them, and wrapping the joints of two adjacent second integrated monomers with polyimide tape for packaging to obtain a layer of 10 supercapacitors connected in a stepped manner;

[0115] S7. Prepare multiple layers connected in a stepwise manner and integrated with 10 supercapacitors, stack the layers end to end in a "Z" shape through H2SO4 / PVA hydrogel electrolyte, and solidify to obtain an intermediate; connect two first integrated monomers to the two ends of the intermediate through H2SO4 / PVA hydrogel electrolyte and solidify;

[0116] The connection between two adjacent layers and the connection between the first integrated monomer and the intermediate body were wrapped with polyimide tape for packaging to obtain an ultra-high voltage graphene film supercapacitor integrating 80 supercapacitors.

[0117] Example 3

[0118] Steps S1 to S5 of Example 3 are the same as steps S1 to S5 of Example 1.

[0119] S6. Connecting multiple second integrated monomers end to end in sequence through H2SO4 / PVA hydrogel electrolyte and curing them, and wrapping the joints of two adjacent second integrated monomers with polyimide tape for packaging to obtain a layer of 10 supercapacitors connected in a stepped manner;

[0120] S7. Prepare multiple layers connected in a stepwise manner and integrated with 10 supercapacitors, stack the layers end to end in a "Z" shape through H2SO4 / PVA hydrogel electrolyte, and solidify to obtain an intermediate; connect two first integrated monomers to the two ends of the intermediate through H2SO4 / PVA hydrogel electrolyte and solidify;

[0121] The connection between two adjacent layers and the connection between the first integrated monomer and the intermediate body were wrapped with polyimide tape for packaging to obtain an ultra-high voltage graphene film supercapacitor integrating 100 supercapacitors.

[0122] Example 4

[0123] Steps S1-S5 of Example 4 are the same as steps S1-S5 of Example 1.

[0124] S6. Connecting multiple second integrated monomers end to end in sequence through H2SO4 / PVA hydrogel electrolyte and curing them, and wrapping the joints of two adjacent second integrated monomers with polyimide tape for packaging to obtain a layer of 10 supercapacitors connected in a stepped manner;

[0125] S7. Prepare multiple layers connected in a stepwise manner and integrated with 10 supercapacitors, stack the layers end to end in a "Z" shape through H2SO4 / PVA hydrogel electrolyte, and solidify to obtain an intermediate; connect two first integrated monomers to the two ends of the intermediate through H2SO4 / PVA hydrogel electrolyte and solidify;

[0126] The connection between the two adjacent layers and the connection between the first integrated monomer and the intermediate are wrapped with polyimide tape for packaging, and an ultra-high voltage graphene film supercapacitor with 160 supercapacitors is obtained. Its equivalent circuit diagram is shown in the figure below. Figure 7 shown.

[0127] Figure 8 The cyclic voltammetry (CV) curves of an ultra-high voltage graphene film supercapacitor integrated with 160 supercapacitors at different scan rates are shown. Figure 9The constant current charge and discharge (GCD) curves of an ultra-high voltage graphene film supercapacitor integrated with 160 supercapacitors at different currents are shown. Figure 8 and Figure 9 It can be seen that the ultra-high voltage graphene film supercapacitor prepared in Example 4 has excellent electrochemical properties.

[0128] experiment:

[0129] The voltage and specific capacitance of the supercapacitors prepared in Examples 1-4 were measured. In addition, the voltage and specific capacitance of a single supercapacitor and a sheet integrated with 10 supercapacitors in Example 1 were also measured. The results are shown in Table 1 below.

[0130] It is worth noting that when measuring voltage and specific capacitance, in order to ensure the accuracy and reliability of the measurement results, a conductive medium, such as silver paste, can be added to both ends of the supercapacitor, and then connected to an external electrochemical workstation or other measuring device through copper foil or other wires for measurement.

[0131] Table 1 Supercapacitors with different integrated numbers and their corresponding peak voltages and specific capacitances

[0132]

[0133] according to That is, ideally, if the supercapacitors are consistent, then the capacitance of n integrated ultra-low voltage capacitors is 1 / n of the capacitance of a single capacitor. From the measurement results in Table 1, it can be seen that the ultra-high voltage graphene film supercapacitors prepared by this scheme have good consistency.

[0134] in addition, Figure 10 and 11 The cyclic voltammetry (CV) curves of supercapacitors with different numbers of series connections at a constant scan rate are shown. It can be seen that as the number of series connections n increases, the voltage is positively correlated, while the area enclosed by the curve remains basically the same, which also shows that the ultra-high voltage graphene film supercapacitors prepared by this scheme have good consistency. Figure 12 The constant current charge and discharge (GCD) curves of supercapacitors with different numbers of supercapacitors connected in series at a constant current density are shown. It can be seen that as the number of series connections n increases, the voltage is positively correlated, while the sum of the charge and discharge time remains basically the same, which also shows that the ultra-high voltage graphene film supercapacitors prepared by this scheme have good consistency.

[0135] 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 highly integrated packaging method for ultra-high voltage graphene film supercapacitors, characterized in that: The following steps are involved: S1, using a laser to emit laser light and act on the two surfaces of the carbon precursor film to pyrolyze and obtain a graphene film; S2, cutting the graphene film into long strips to obtain a graphene electrode; S3. Cutting the hydrophobic polymer film into a flexible mask, and attaching the flexible mask to at least one end of the graphene electrode; wherein the flexible mask is annular in shape, a bare storage position is defined in the middle of the flexible mask, and the graphene electrode completely covers the storage position; S4. Applying a gel solid electrolyte to the storage location, evacuating the vacuum and removing moisture to obtain an integrated monomer; wherein the integrated monomer includes a first integrated monomer and a second integrated monomer, the flexible mask is attached to either end of the first integrated monomer, and the flexible mask is attached to both ends of the second integrated monomer; S5, preparing two first integrated units and a plurality of second integrated units; S6, connecting the plurality of second integrated monomers end to end in sequence through the gel solid electrolyte and solidifying them to obtain a sheet layer; S7. Prepare a plurality of the sheet layers, stack the plurality of sheet layers end to end in a "Z" shape through the gel solid electrolyte, and solidify to obtain an intermediate; connect two of the first integrated monomers to the two ends of the intermediate through the gel solid electrolyte, and obtain an ultra-high voltage graphene film supercapacitor after solidification.

2. The highly integrated packaging method for ultra-high voltage graphene film supercapacitor according to claim 1, characterized in that: Step S6 is specifically as follows: S6, sequentially connecting the plurality of second integrated monomers end to end with the gel solid electrolyte and curing them, and wrapping the connection between two adjacent second integrated monomers with a packaging tape to encapsulate them to obtain a sheet layer; Step S7 is specifically as follows: S7, preparing a plurality of the sheet layers, stacking the plurality of the sheet layers end to end in a "Z" shape through the gel solid electrolyte, and curing to obtain an intermediate; connecting the two first integrated monomers to the two ends of the intermediate body respectively through the gel solid electrolyte and curing them; The connection between two adjacent sheets and the connection between the first integrated monomer and the intermediate body are wrapped with packaging tape to obtain an ultra-high voltage graphene film supercapacitor.

3. The highly integrated packaging method for ultra-high voltage graphene film supercapacitor according to claim 1, characterized in that: In step S6, the end-to-end connection of the plurality of second integrated units in the sheet layer is either a step-wise connection or a staggered connection.

4. The highly integrated packaging method for ultra-high voltage graphene film supercapacitors according to claim 1, characterized in that: In step S3, the thickness of the flexible mask is 125-200 μm.

5. The highly integrated packaging method for ultra-high voltage graphene film supercapacitor according to claim 1, characterized in that: In step S4, the vacuuming is specifically: placing the integrated monomer in a negative pressure environment with a vacuum degree of -0.9 MPa to -0.7 MPa for 20 to 40 minutes; The step of removing moisture specifically includes placing the integrated monomer in the air.

6. The highly integrated packaging method for ultra-high voltage graphene film supercapacitor according to claim 1, characterized in that: In step S2, the shape of the graphene electrode is rectangular, the ratio of the length to the width of the graphene electrode is 2.2 to 2.3, and the width of the graphene electrode is 3 to 5 mm; In step S3, the shape of the flexible mask and the shape of the storage location are both square, and the side length of the flexible mask is 2 mm longer than the side length of the storage location; The side length of the flexible mask is greater than the width of the graphene electrode.

7. The highly integrated packaging method for ultra-high voltage graphene film supercapacitor according to claim 1, characterized in that: In step S4, the gel solid electrolyte is any one of polyvinyl alcohol, gelatin and polyacrylonitrile.

8. The highly integrated packaging method for ultra-high voltage graphene film supercapacitors according to claim 2, characterized in that: In step S1, the carbon precursor film is any one of a polyimide film, a polyetherimide film and a polyamideimide film; In step S3, the polymer film is any one of polyimide tape, polyethylene terephthalate film and polyvinyl chloride tape; In steps S6 and S7, the packaging tape is a polyimide tape.

9. The highly integrated packaging method for ultra-high voltage graphene film supercapacitors according to claim 1, characterized in that: In step S1, the laser is any one of a CO2 laser, a semiconductor laser and an ultraviolet picosecond laser; In step S2 and step S3, the cutting is laser cutting, and the laser used for the laser cutting is any one of an ultraviolet picosecond laser and a pulsed CO2 laser.

10. An ultra-high voltage graphene film supercapacitor, characterized in that: The ultra-high voltage graphene film supercapacitor is prepared using the highly integrated packaging method according to any one of claims 1 to 9.

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