CN104810163A - Graphene supercapacitor and preparation method thereof, and energy storage system - Google Patents
Graphene supercapacitor and preparation method thereof, and energy storage system Download PDFInfo
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- CN104810163A CN104810163A CN201410344330.2A CN201410344330A CN104810163A CN 104810163 A CN104810163 A CN 104810163A CN 201410344330 A CN201410344330 A CN 201410344330A CN 104810163 A CN104810163 A CN 104810163A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a graphene supercapacitor and a preparation method thereof, and an energy storage system. The method comprises two pads are prepared on a PCB and serve as first and second current collector substrates of the graphene supercapacitor; a graphite oxide solution is dropped in a to-be-dropped areas formed on the first and second current collector substrates; laser engraving reduction is carried out on graphite oxide films formed by drying and molding the graphite oxide solution to form first and second patterned graphene electrodes; and the first and second graphene electrodes are packaged by filling an electrolyte to form the graphene supercapacitor. According to the scheme, the pads on the circuit board serve as the current collector substrates, the preparation technology of the graphene supercapacitor is optimized, the procedure of welding is omitted, and the integrated level of the PCB is improved.
Description
Technical Field
The invention relates to the field of electronic elements, in particular to a preparation method of a graphene super capacitor, the graphene super capacitor and an energy storage system.
Background
At present, energy storage devices generally adopted in an energy storage circuit are a super capacitor, a lithium battery, a lead-acid battery and the like. And usually, the super capacitor is used as a primary energy storage unit, and the lithium battery is used as a secondary energy storage unit. The super capacitor has uniqueness in the process of storing and releasing energy, not only embodies a high pulse rate charging and discharging process, but also has the advantages of high energy and high specific power, namely the charging and discharging time is only tens of seconds, and the power density is 10-100 times higher than that of a storage battery.
Since the graphene is a carbon molecule formed by arranging and connecting carbon atoms in a hexagon shape, the structure of the graphene is very stable, and the graphene has the characteristics of high conductivity, high toughness, high strength, ultra-large specific surface area and the like, so that the supercapacitor taking the graphene as an electrode material has excellent performance and is more suitable for energy storage.
A common energy storage system utilizing the graphene super capacitor takes a PCB (printed circuit board) as a carrier, a circuit element and the graphene super capacitor are installed on the PCB, the graphene super capacitor is integrated with the outside of the PCB, and the manufactured graphene super capacitor is installed on the PCB.
This kind of external integration's mode, at first, need carry out the secondary to independent graphite alkene ultracapacitor system and encapsulate, carry out electronic components and parts to graphite alkene ultracapacitor system promptly, with the graphite alkene ultracapacitor system welding after the secondary encapsulation on PCB, the cost is higher to because the secondary encapsulation leads to graphite alkene ultracapacitor system occupation space too big, energy storage system's integrated level is lower, space utilization is low.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene super capacitor, the graphene super capacitor and an energy storage system aiming at the defects of the prior art, wherein an energy storage circuit and the graphene super capacitor are directly integrated internally, and the graphene super capacitor is directly manufactured on a printed circuit board, so that the welding process and the packaging cost are saved, and the integration level of the energy storage system is improved.
According to one aspect of the invention, a preparation method of a graphene supercapacitor is provided, and the preparation method comprises the following steps: manufacturing two bonding pads on a printed circuit board to serve as a first current collector substrate and a second current collector substrate of the graphene supercapacitor; dripping graphite oxide solution in a region to be dripped formed by the first current collector substrate and the second current collector substrate; carrying out laser engraving reduction treatment on a graphite oxide film formed after the graphite oxide solution is dried and molded to obtain a first patterned graphene electrode and a second patterned graphene electrode; and filling electrolyte and packaging the first graphene electrode and the second graphene electrode to form the graphene super capacitor.
Optionally, two parallel pads with preset sizes are manufactured to serve as a first current collector substrate and a second current collector substrate of the graphene supercapacitor; dripping graphite oxide solution on the surfaces of the first current collector substrate and the second current collector substrate; and carrying out laser engraving and reduction on the graphite oxide films formed after the graphite oxide solutions on the surfaces of the first current collector substrate and the second current collector substrate are dried and molded into a first graphene electrode and a second graphene electrode which are in parallel strips.
Optionally, two pads with preset relative positions are manufactured on a printed circuit board to serve as a first current collector substrate and a second current collector substrate of the graphene supercapacitor; dripping graphite oxide solution on the surface of the printed circuit board between the first current collector substrate and the second current collector substrate or the surface formed by the printed circuit board between the first current collector substrate and the second current collector substrate and partial areas of the first current collector substrate and the second current collector substrate; and carrying out laser engraving and reduction on a graphite oxide film formed after drying and forming of a graphite oxide solution between the first current collector substrate and the second current collector substrate into an interdigital first graphene electrode and a second graphene electrode.
Optionally, the method further comprises: and arranging a mold made of polyethylene terephthalate or polymethyl methacrylate around a region to be dripped, which is formed by the first current collector substrate and the second current collector substrate, wherein the thickness of the polyethylene terephthalate or the polymethyl methacrylate is 0.1mm-1 mm.
Optionally, the method further comprises: and removing the polyethylene terephthalate mould or the polymethyl methacrylate mould.
Optionally, the method further comprises: and brushing first conductive silver paint and second conductive silver paint on the leading-out sides of the first graphene electrode and the second graphene electrode respectively, wherein the first conductive silver paint is in contact with the first graphene electrode and the first current collector substrate, and the second conductive silver paint is in contact with the second graphene electrode and the second current collector substrate.
Optionally, putting the printed circuit board with the first graphene electrode and the second graphene electrode into a glove box, and filling electrolyte into the first graphene electrode and the second graphene electrode; and packaging the first graphene electrode and the second graphene electrode filled with the electrolyte into the graphene supercapacitor.
Optionally, the electrolyte is a semi-solid mixture of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide ionic liquid and nano-silica, wherein the mass ratio of the 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide ionic liquid to the nano-silica is 100: 3.
According to another aspect of the present invention, there is provided a graphene supercapacitor fabricated on a printed circuit board, including: two bonding pads manufactured on a printed circuit board are respectively used as a first current collector substrate and a second current collector substrate of the graphene supercapacitor; the method comprises the steps that a first current collector substrate and a second current collector substrate are subjected to laser engraving reduction treatment to form a first graphical graphene electrode and a second graphical graphene electrode, wherein the first graphical graphene electrode and the second graphical graphene electrode are made of graphite oxide films located in a to-be-dripped coating area formed by the first current collector substrate and the second current collector substrate, and the graphite oxide films are formed by drying and molding graphite oxide solutions; and the first graphene electrode, the second graphene electrode and the electrolyte are packaged into the graphene supercapacitor by the packaging structure.
Optionally, the first graphene electrode and the second graphene electrode are parallel strips and are respectively located on the first current collector substrate and the second current collector substrate; the first current collector substrate and the second current collector substrate are parallel and have a predetermined size.
Optionally, the first graphene electrode and the second graphene electrode are interdigitated, the first graphene electrode and the second graphene electrode are located on a surface formed by a printed circuit board between the first current collector substrate and the second current collector substrate or a partial area of the printed circuit board between the first current collector substrate and the second current collector substrate, and the first current collector and the second current collector have a preset relative position.
Optionally, the graphene super ground container further comprises: the first conductive silver paint is positioned on the leading-out side of the first graphene electrode, and the second conductive silver paint is positioned on the leading-out side of the second graphene electrode; the first conductive silver paint is in contact with the first graphene electrode and the first current collector substrate, and the second conductive silver paint is in contact with the second graphene electrode and the second current collector substrate.
Optionally, the electrolyte is a semi-solid mixture of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide ionic liquid and nano-silica, wherein the mass ratio of the 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide ionic liquid to the nano-silica is 100: 3.
Optionally, the package structure further comprises: and the mold is arranged around the region to be dripped and is made of polyethylene terephthalate or polymethyl methacrylate, wherein the thickness of the polyethylene terephthalate or the polymethyl methacrylate is 0.1mm-1 mm.
According to another aspect of the present invention, there is provided an energy storage system including: the printed circuit board is provided with a reserved area, and the graphene supercapacitor is manufactured on the reserved area; the printed circuit board is further provided with: a rectifying element and a filter element; the input/output end of the filter element is connected with the output end of the rectifying element, and the input/output end of the filter element is respectively connected with a first graphene electrode and a second graphene electrode of the graphene supercapacitor; the energy storage system further includes: a nano-generator; the output end of the nano generator is connected with the input end of the rectifying element on the printed circuit board.
According to the preparation method of the graphene supercapacitor, the graphene supercapacitor and the energy storage system, the bonding pad on the printed circuit board is used as the current collector substrate, the preparation process of the graphene supercapacitor is optimized, the graphene supercapacitor which is electrically connected with the printed conductor is directly manufactured on the printed circuit board, the welding process is saved, and the occupied space of the thin-film graphene supercapacitor is remarkably reduced.
Drawings
Fig. 1 shows a flowchart of a method for manufacturing a graphene supercapacitor according to an embodiment of the present invention;
fig. 2 shows a flowchart of a method for manufacturing a graphene supercapacitor according to another embodiment of the present invention;
fig. 3 shows a flowchart of a method for manufacturing a graphene supercapacitor according to another embodiment of the present invention;
fig. 4a is a schematic structural diagram of a graphene supercapacitor fabricated on a printed circuit board according to an embodiment of the present invention;
fig. 4b is a schematic structural diagram of a graphene supercapacitor fabricated on a printed circuit board according to a preferred embodiment of the present invention;
fig. 5 is a schematic structural diagram of a graphene supercapacitor fabricated on a printed circuit board according to another embodiment of the present invention;
FIG. 6 shows a charging curve diagram of a graphene supercapacitor provided by the present invention;
fig. 7 shows a block diagram of an energy storage system provided by an embodiment of the invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
Fig. 1 shows a flowchart of a method for manufacturing a graphene supercapacitor according to an embodiment of the present invention, and as shown in fig. 1, the method includes the following steps:
step S110, two pads are fabricated on the printed circuit board as a first current collector substrate and a second current collector substrate of the graphene supercapacitor.
Determining the relative position and size of the bonding pad according to the size, electrode shape and the like of the graphene super capacitor to be prepared, reserving an area with a proper size on the printed circuit board, and manufacturing the bonding pad with a proper shape and size.
The material of the bonding pad is generally copper foil, the conductivity is high, and the bonding pad is a proper choice as a super capacitor current collector material. According to the invention, the bonding pad on the printed circuit board is used as the current collector substrate of the super capacitor, so that compared with an external integration mode, on one hand, the current collector material is saved, and the graphene super capacitor is thinner; on the other hand, because the bonding pad is directly connected with the wiring layer on the printed circuit board, the first current collector substrate and the second current collector substrate are used as leading-out ends of the graphene supercapacitor and are electrically connected with other elements on the printed circuit board through printed wires, so that the traditional welding process of integrating the graphene supercapacitor with the circuit board is omitted, the electrical packaging of the graphene supercapacitor is avoided, and the occupied space of the graphene supercapacitor is remarkably reduced.
Step S120, dropping a graphite oxide solution in a region to be dropped formed by the first current collector substrate and the second current collector substrate.
First, a graphite oxide solution is prepared, and a person skilled in the art can obtain the graphite oxide solution in various ways, which is not limited herein. For example, graphite oxide can be prepared using the Hummer method or a modified Hummer method, and then a graphite oxide solution of suitable concentration, e.g., a graphite oxide solution concentration of 2.7mg/ml, 5mg/ml, etc., can be prepared using the graphite oxide.
Specifically, the graphite oxide solution may be further subjected to ultrasonic dispersion treatment. Wherein, the main effect of ultrasonic dispersion treatment lies in: the layers in the multi-layer graphite oxide solution are separated from each other, so that the multi-layer graphite oxide solution is converted into a single-layer (or less-layer) graphite oxide solution. Preferably, the time of the ultrasonic dispersion treatment is 5 to 10 minutes.
The area to be dripped is selected according to the size and the electrode shape of the graphene supercapacitor to be manufactured, for example, for a parallel strip-shaped graphene supercapacitor, the area to be dripped is the surfaces of the first and second current collector substrates, and for an interdigital graphene supercapacitor, the area to be dripped is the surface of a printed circuit board between the first and second current collector substrates or a partial area between the surface of the printed circuit board between the first and second current collector substrates and the surfaces of the first and second current collector substrates.
Step S130, performing laser engraving reduction processing on the graphite oxide film formed after the graphite oxide solution is dried and molded, so as to obtain a first graphene electrode and a second graphene electrode which are patterned.
First, the drop-coated graphite oxide solution is subjected to a drying molding treatment. Naturally placing the graphite oxide solution dripped on the surface of the area to be dripped for a period of time to completely dry the graphite oxide solution, or drying the graphite oxide solution in a drying oven, preferably, the temperature in the drying oven is 30-50 ℃, and the drying time is 0.5-10 h. During the drying process, the solvent in the graphite oxide solution is evaporated, and the residual solute is attached to the surface of the region to be dripped to form a dry and solidified graphite oxide film.
And engraving the graphite oxide film formed after the graphite oxide solution is dried and formed into a preset electrode pattern, such as an interdigital shape, a parallel strip shape, a spiral shape and the like, and simultaneously reducing the graphite oxide film into a graphene film. Specifically, irradiation with an infrared laser having a predetermined wavelength (for example, 780nm) may be performed. In addition, the working parameters such as the power range and the engraving speed of the laser engraving can be set according to the thickness of the graphite oxide film. When the thickness of the graphite oxide film is thicker, the power and the speed of laser engraving can be properly increased; conversely, the power and speed of the laser engraving can be reduced appropriately. Preferably, the power range of laser engraving is 2.5W-6W, and the engraving speed is 20mm/s-200 mm/s.
Step S140, filling electrolyte and packaging the first graphene electrode and the second graphene electrode to form the graphene supercapacitor.
Specifically, reference may be made to a packaging method in the prior art, for example, packaging by using PDMS (polydimethylsiloxane), which is not described herein again.
Fig. 2 is a flowchart illustrating a method for manufacturing a graphene supercapacitor according to another embodiment of the present invention, which is specifically a method for manufacturing a parallel stripe graphene supercapacitor, and as shown in fig. 2, the method includes the following steps:
step S210, two parallel pads with a preset size are manufactured on a printed circuit board as a first current collector substrate and a second current collector substrate of the graphene supercapacitor.
According to the method for preparing the parallel strip-shaped graphene supercapacitor, the size of each bonding pad is determined according to the required capacitance value, the two bonding pads are close to each other, the distance is generally 0.4mm-1mm, the distance is not too large or too small, short circuit between graphene electrodes is easily caused if the distance is too small, the distance is too large, migration of ions between the electrodes is not facilitated, and the charging and discharging time of the graphene supercapacitor is prolonged.
The capacitance value is determined according to specific requirements, and then the size of the bonding pad is determined, for example, for a low-power consumption single chip microcomputer chip, a graphene supercapacitor with the capacitance of 5-10mF can be selected, at this time, the overall size range of the graphene supercapacitor is generally between 3mm × 8mm and 10mm × 20mm, the size of each graphene electrode is between 3mm × 4mm and 10mm × 10mm, the size of the bonding pad can be slightly larger than that of the electrode, and the redundant part can be used for preparing conductive silver paint and the like, which is described in the following steps. Of course, the above values can be adjusted according to the power supply voltage, power consumption, etc. required by the integrated circuit components on the printed circuit board.
Step S220, a mold made of PET (polyethylene terephthalate) or PMMA (polymethyl methacrylate) is disposed around the first current collector substrate and the second current collector substrate, wherein the thickness of the PET or PMMA is 0.1mm to 1 mm.
A PET mold or a PMMA mold is used to define the region of the graphite oxide solution to be dripped. Specifically, the PET mold or the PMMA mold may be bonded around the regions to be dripped on the first current collector substrate and the second current collector substrate by means of bonding or the like. Of course, other molds of material may be used, such as polyimide tape of suitable thickness.
Step S230, dripping the graphite oxide solution into a region to be dripped formed by a PET (polyethylene terephthalate) mould or a PMMA (polymethyl methacrylate) mould.
In the embodiment of the invention, the copper foil on the bonding pad is in direct large-area contact with the graphite oxide solution, the copper foil can play a role in pre-reducing the graphite oxide in the drying process, the graphite oxide can be prevented from agglomeration in the reducing process, and a small amount of copper element enters the graphite oxide solution, so that the conductivity of the reduced graphene electrode in the subsequent step can be improved.
The amount of the graphite oxide solution is determined according to the concentration of the graphite oxide solution and the size of the graphene supercapacitor to be prepared, and taking an 8mf graphene supercapacitor as an example, the sizes of the first and second graphene electrodes are both 4mm × 4mm, and the concentration of the graphite oxide solution is 5mg/ml, 0.01ml of the graphite oxide solution can be selectively and dropwise coated on the first and second current collector substrates, respectively.
And step S240, removing the PET mould or the PMMA mould.
And after the graphite oxide solution is dried and formed, removing the PET mould or the PMMA mould.
This step is an optional step, and if the PET mold or the PMMA mold is not removed, the PET mold or the PMMA mold can be used to form part of the encapsulation structure, forming a cavity for accommodating the electrolyte, and functioning similarly to the cushion sheet.
Step S250, reducing the graphite oxide thin films on the surfaces of the first current collector substrate and the second current collector substrate to be parallel strip-shaped first graphene electrode and second graphene electrode by laser engraving.
Due to the fact that the graphene has high conductivity and an ultra-large specific surface area, the graphene reduced by laser engraving can be directly used as an electrode of a graphene super capacitor.
In the embodiment of the invention, the contact areas of the first graphene electrode and the second graphene electrode in parallel strips and the first current collector substrate and the second current collector substrate are larger, so that a stronger charge collection effect is achieved.
Step S260, brushing first conductive silver paint and second conductive silver paint on the leading-out sides of the first graphene electrode and the second graphene electrode respectively.
The first conductive silver paint is in contact with the first graphene electrode and the first current collector substrate, and the second conductive silver paint is in contact with the second graphene electrode and the second current collector substrate. The leading-out sides of the first graphene electrode and the second graphene electrode are the sides, which are corresponding to the graphite oxide films on the first current collector substrate and the second current collector substrate and are directly subjected to laser engraving reduction treatment.
The conductive silver paint is used as an extraction electrode and is used for further improving the charge collection characteristic of the graphene electrode. Because first, second graphite alkene electrode lead-out side has directly received laser sculpture reduction processing, compares with the one side that contacts with the mass flow body substrate, and reduction degree is higher, possesses better performance, for example, has higher conductivity, and specific surface area is bigger etc. consequently, has guaranteed high performance's electric connection between graphite alkene electrode and the mass flow body substrate.
Step S270, placing the printed circuit board on which the first graphene electrode and the second graphene electrode are fabricated into a glove box, and filling an electrolyte into the first graphene electrode and the second graphene electrode.
The electrolyte can be electrolyte solution commonly used in graphene super capacitors, such as electrolyte of polyvinyl alcohol/sulfuric acid system, polyvinyl alcohol/phosphoric acid system, and the like.
Compared with the common aqueous electrolyte solution, the ionic liquid has higher ionic conductivity and thermal stability, so that the super capacitor can achieve higher charge and discharge speed. According to the invention, the ionic liquid and the polymer or the nano silicon dioxide are mixed to form the gel electrolyte, so that a larger charging and discharging interval can be obtained, the electrolyte can be prevented from leaking, and the graphene supercapacitor can be conveniently packaged.
Specifically, the amount of nanosilicon dioxide is determined by the viscosity of the electrolyte, and an intuitive method is to fill the semi-solid mixture into a vial, and after inversion, the ionic liquid has no obvious sign of downflow.
The electrolyte in this embodiment may be 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and nano-silica, 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and nano-silica, and 1-butyl-2, 3-methylimidazole bistrifluoromethylsulfonyl imide salt and nano-silica. Preferably, the electrolyte is a semi-solid mixture of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ionic liquid and nano-silica, wherein the mass ratio of the 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ionic liquid to the nano-silica is 100: 3.
Step S280, packaging the first graphene electrode and the second graphene electrode filled with the electrolyte into the graphene supercapacitor.
And after the electrolyte is filled, standing for a period of time, fully impregnating the electrode with the electrolyte, evaporating redundant moisture, and packaging the first graphene electrode, the second graphene electrode and the electrolyte.
Fig. 3 shows a flow chart of a method for manufacturing a graphene supercapacitor according to another embodiment of the present invention, which is a method for manufacturing an interdigitated graphene supercapacitor, as shown in fig. 3, the method includes the following steps:
step S310, two pads with preset relative positions are manufactured on the printed circuit board as a first current collector substrate and a second current collector substrate of the graphene supercapacitor.
According to the method, the graphene electrode is manufactured on the surface of the insulating layer on the surface of the printed circuit board between the first current collector substrate and the second current collector substrate, and the preset relative position of the first graphene electrode and the second graphene electrode is determined according to the size of the graphene super capacitor to be manufactured. There are no strict requirements on the dimensions of the first and second current collector substrates compared to the previous embodiment.
Step S320, a PET mold or a PMMA mold is disposed around a region to be dripped, which is formed by the printed circuit board between the first current collector substrate and the second current collector substrate or the printed circuit board between the first current collector substrate and the second current collector substrate and the partial regions of the first current collector substrate and the second current collector substrate.
Specifically, a mold made of PET (polyethylene terephthalate) or PMMA (polymethyl methacrylate) is arranged around a region to be dripped, which is formed by a printed circuit board between a first current collector substrate and a second current collector substrate or a part of regions of the printed circuit board between the first current collector substrate and the second current collector substrate, wherein the thickness of the PET or PMMA is 0.1mm-1 mm. This step is an optional step, and functions in the same way as the PET mold or PMMA mold shown in fig. 2, and is not described herein again.
Step S330, the graphite oxide solution is dripped into a region to be dripped formed by a PET (polyethylene terephthalate) mold or a PMMA (polymethyl methacrylate) mold.
The graphite oxide solution to be dripped can not coincide with the first current collector substrate and the second current collector substrate, namely the graphite oxide solution to be dripped is a printed circuit board between the first current collector substrate and the second current collector substrate, at the moment, an additional extraction electrode is required to be prepared to play a role in collecting charges, and the graphene electrode is connected with the current collector substrate and is further electrically connected with other elements through a printed wire. The extraction electrode is described in detail in step S360.
The area to be dripped of the graphite oxide solution can also be partially overlapped with the first current collector substrate and the second current collector substrate, namely, the area to be dripped is an area formed by a printed circuit board between the first current collector substrate and the second current collector substrate and partial areas of the first current collector substrate and the second current collector substrate, and then the first graphene electrode and the second graphene electrode formed after laser engraving reduction treatment are respectively in direct contact with the first current collector substrate and the second current collector substrate, and the first current collector substrate and the second current collector substrate play a role in collecting charges. The partial areas of the first and second current collector substrates refer to the overlapping parts of the first and second current collector substrates and the dripped graphite oxide solution. In this case, of course, the extraction electrode may be provided to further improve the charge collection property of the graphene electrode.
The amount of the graphite oxide solution can be referred to the previous embodiment, and is not described herein.
Step S340, uncovering the PET mould or the PMMA mould.
After the graphite oxide solution is dried and formed, the PET mould or PMMA mould can be removed; alternatively, the PET mold or PMMA mold is retained as part of the encapsulation structure.
Step S350, performing laser engraving and reducing the graphite oxide thin film formed by drying the graphite oxide solution between the first current collector substrate and the second current collector substrate into interdigital first graphene electrode and second graphene electrode.
Due to the high insulating property of the graphene oxide, the graphite oxide realizes the isolation between the positive and negative graphene interdigital electrodes, and a diaphragm structure in the traditional graphene super capacitor can be omitted, so that the preparation process is simplified.
The first graphene electrode and the second graphene electrode which are in an interdigital shape can increase the electrochemical surface area of the graphene supercapacitor, and compared with the graphene supercapacitor with parallel strip-shaped electrodes of the same size, the storage capacity and the power density are improved.
Furthermore, when the size of the graphene supercapacitor is miniaturized, the number of the interdigital electrodes is increased, so that the moving path of ions between two adjacent interdigital electrodes is reduced, and the charging and discharging time of the graphene supercapacitor is remarkably reduced.
Step S360, brushing first conductive silver paint and second conductive silver paint on the leading-out sides of the first graphene electrode and the second graphene electrode respectively.
The first conductive silver paint is in contact with the first graphene electrode and the first current collector substrate, and the second conductive silver paint is in contact with the second graphene electrode and the second current collector substrate.
As in the previous embodiment, the leading-out sides of the first graphene electrode and the second graphene electrode are the sides of the graphite oxide thin film between the first current collector substrate and the second current collector substrate directly subjected to the laser engraving reduction treatment, and the functions of the graphite oxide thin film are also the same as those of the previous embodiment, which are not described herein again.
If the region to be coated of the graphite oxide solution partially overlaps the first and second current collector substrates in step S330, the formed first and second graphene electrodes are in contact with the first and second current collector substrates, respectively, and then step S360 is an optional step and may be used to further enhance the charge collection effect.
Step S370, placing the printed circuit board on which the first graphene electrode and the second graphene electrode are fabricated into a glove box, and filling an electrolyte into the first graphene electrode and the second graphene electrode.
The electrolyte is selected in step S270 of the previous embodiment, and is not described herein again.
And step S380, packaging the first graphene electrode and the second graphene electrode filled with the electrolyte into the graphene supercapacitor.
According to the preparation method of the graphene supercapacitor provided by the embodiment of the invention, the bonding pad on the printed circuit board is used as the current collector substrate of the supercapacitor to manufacture the graphene supercapacitor with a planar structure, so that the internal integration of the graphene supercapacitor and other circuit elements on a printed circuit is realized. The welding process is omitted, the electric packaging of the graphene super capacitor is avoided, and the occupied space of the graphene super capacitor is obviously reduced.
The invention also provides a graphene supercapacitor manufactured on a printed circuit board, which is manufactured according to the preparation method of the graphene supercapacitor, and comprises the following steps: two bonding pads manufactured on a printed circuit board are respectively used as a first current collector substrate and a second current collector substrate of the graphene supercapacitor; the method comprises the steps that a first current collector substrate and a second current collector substrate are subjected to laser engraving reduction treatment to form a first graphical graphene electrode and a second graphical graphene electrode, wherein the first graphical graphene electrode and the second graphical graphene electrode are made of graphite oxide films located in a to-be-dripped coating area formed by the first current collector substrate and the second current collector substrate, and the graphite oxide films are formed by drying and molding graphite oxide solutions; and the packaging structure packages the first graphene electrode and the second graphene electrode into the graphene supercapacitor.
Fig. 4a is a schematic structural diagram of a graphene supercapacitor fabricated on a printed circuit board according to an embodiment of the present invention, and as shown in fig. 4a, the graphene supercapacitor includes: the first graphene electrode 41A and the second graphene electrode 42A in parallel strips are respectively located on the first current collector substrate 43A and the second current collector substrate 44A; in this embodiment, the areas to be dripped are the surfaces of the first current collector substrate 43A and the second current collector substrate 44A on which the graphite oxide solution is dripped; the first current collector substrate 43A and the second current collector substrate 44A are pads with a preset size manufactured on the printed circuit board; a gap 47A is left between the first current collector substrate 43A and the second current collector substrate 43B, the gap 47A is usually 0.4mm-1mm, and should not be too large or too small, if the gap 47A is less than 0.4mm, a short circuit between the first graphene electrode 41A and the second graphene electrode 42A is easily caused, and if the gap 47A is too large, migration of ions between the electrodes is not facilitated, which may increase the charging and discharging time of the graphene supercapacitor. Optionally, the graphene supercapacitor further comprises: a first conductive silver paint 4a5 on the lead-out side of the first graphene electrode 41A and a second conductive silver paint 46A on the lead-out side of the second graphene electrode 42A; the first conductive silver paint 45A is in contact with the first graphene electrode 41A and the first current collector substrate 43A, and the second conductive silver paint 46A is in contact with the second graphene electrode 42A and the second current collector substrate 44A. Here, the leading side of the first graphene electrode 41A and the leading side of the second graphene electrode 42A are sides directly subjected to laser engraving.
The first conductive silver paint 45A and the second conductive silver paint 46A are mainly used to improve charge collection characteristics and ensure good electrical contact between graphene and a current collector substrate. Since graphene itself has high conductivity, conductive silver paint can be optionally omitted according to circumstances.
Fig. 4B shows a schematic structural diagram of a graphene supercapacitor fabricated on a printed circuit board according to a preferred embodiment of the present invention, and as shown in fig. 4B, the first graphene electrode 41B and the second graphene electrode 42B have the same size and are both 4mm × 4mm, the first current collector substrate 43B and the second current collector substrate 44B have the size of 4mm × 6mm, and the distance between the first current collector substrate 43B and the second current collector substrate 44B is 0.4mm, it can be known that the formed graphene supercapacitor has the size of 4mm × 8.4 mm. Optionally, a first conductive silver paint 45B and a second conductive silver paint 46B are respectively manufactured on the first current collector substrate 43B and the second current collector substrate 44B, and the first conductive silver paint 45B connects the first graphene electrode 41B with an area of the first current collector substrate 43B where no graphene electrode is manufactured, so that the charge collection capability is further improved.
In the preferred embodiment, the capacitance of the graphene supercapacitor is 8mF, and the concentration of the graphite oxide solution is 5 mg/ml. It should be understood that the size of the graphene electrode and the current collector substrate is related to the concentration of the graphite oxide solution used, because the density and specific surface area of the prepared graphene are different when the concentration of the graphite oxide solution is changed. The sizes of the current collector substrate and the graphene electrode can be adjusted according to actual conditions.
The packaging structure of the graphene supercapacitor, the filled electrolyte and the like are not shown in fig. 4a and 4 b. Specifically, reference may be made to the encapsulation means in the prior art, for example, encapsulation with PDMS (polydimethylsiloxane). Optionally, the PET or PMMA mold, which is disposed prior to the drop coating of the graphite oxide solution, remains or partially remains as part of the encapsulation structure.
The electrolyte in this embodiment may be 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and nano-silica, 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and nano-silica, and 1-butyl-2, 3-methylimidazole bistrifluoromethylsulfonyl imide salt and nano-silica. Preferably, the electrolyte is a semi-solid mixture of 1-butyl 3-methylimidazole bistrifluoromethylsulfonyl imide salt ionic liquid and nano silicon dioxide, wherein the mass ratio of the 1-butyl 3-methylimidazole bistrifluoromethylsulfonyl imide salt ionic liquid to the nano silicon dioxide is 100: 3.
Fig. 5 is a schematic structural diagram of a graphene supercapacitor fabricated on a printed circuit board according to another embodiment of the present invention, and as shown in fig. 5, the graphene supercapacitor includes: the first graphene electrode 51 and the second graphene electrode 52 are interdigitated, and the first graphene electrode 51 and the second graphene electrode 52 are located on the printed circuit board between the first current collector substrate 53 and the second current collector substrate 54, that is, in this embodiment, the area to be dripped is the printed circuit board between the first current collector substrate 53 and the second current collector substrate 54; the first and second current collector substrates 53 and 54 are two pads with preset relative positions made on the printed circuit board; the relative position is determined according to the size of the required graphene super capacitor.
In one aspect of the present embodiment, the first graphene electrode 51 and the second graphene electrode 52 are respectively in contact with the first current collector substrate 53 and the second current collector substrate 54, and in this case, optionally, the graphene supercapacitor further includes: a first conductive silver paint 55 positioned on the leading-out side of the first graphene electrode 51 and a second conductive silver paint 56 positioned on the leading-out side of the second graphene electrode 52; the first conductive silver paint 55 is in contact with the first graphene electrode 51 and the first current collector substrate 53, and the second conductive silver paint 56 is in contact with the second graphene electrode 52 and the second current collector substrate 54.
The extraction side is the side corresponding to the graphite oxide film directly subjected to the laser engraving reduction treatment, i.e., the upper surfaces of the first and second graphene electrodes visible in fig. 5.
In another case of the embodiment of the present invention, the first graphene electrode 51 and the second graphene electrode 52 are not in contact with the first current collector substrate 53 and the second current collector substrate 54, and the graphene supercapacitor must include the above-mentioned first conductive silver paint 55 and the second conductive silver paint 56 to collect charges and establish an electrical connection between the graphene electrodes and the current collector substrates.
Of course, according to the embodiment shown in fig. 3, the first graphene electrode 51 and the second graphene electrode 52 in this example may also be in contact with the first current collector substrate 53 and the second current collector substrate 54, respectively, and at this time, the first conductive silver paint 55 and the second conductive silver paint 56 are optional parts, and the functions thereof are the same as the embodiment shown in fig. 3, and are not repeated here.
The package structure and the electrolyte selection are the same as those in the previous embodiment, and are not described herein again.
Compared with the previous embodiment, the interdigital first graphene electrode and the second graphene electrode can increase the electrochemical surface area of the graphene supercapacitor, and improve the storage capacity and the power density. Fig. 6 shows a charging curve diagram of a graphene supercapacitor according to the above embodiment of the present invention, the dimensions of the graphene supercapacitor are as follows: the length is 4mm, the width is 8mm, the height is 2mm, and the height is 2mm including the thickness of the electrolyte after solidification. In fig. 6, curves a and B represent charging curves of the graphene supercapacitor according to the present invention charged to 1V and 2V at a constant current of 50 μ a, respectively, and it can be seen that the charging curves have typical capacitance characteristics, the time required for charging to 1V is about 160s, and the capacitance can be calculated to be about 8.35 mF.
Therefore, the graphene supercapacitor provided by the invention has excellent charge and discharge characteristics.
The invention also provides an energy storage system comprising the graphene supercapacitor, which comprises: specifically, when the printed circuit board is designed, a reserved area for preparing the graphene super capacitor is arranged on the printed circuit board, and after the circuit board is manufactured, the graphene super capacitor is manufactured in the reserved area. Fig. 7 shows a block diagram of an energy storage system provided by an embodiment of the invention. As shown in fig. 7, the system includes:
a printed circuit board 71 with graphene supercapacitors 710; the printed circuit board 71 is further provided with: a rectifying element 711 and a filtering element 712; the input/output ends 712A and 712B of the filter element are correspondingly connected with the output ends 711B and 711D of the rectifying element respectively, and the input/output ends 712A and 712B of the filter element are connected with the first current collector substrate 710A and the second current collector substrate 710B of the graphene supercapacitor 710 respectively; the energy storage system further includes: a nano-generator 72; the output terminals 72A, 72B of the nanogenerator 72 are correspondingly connected to the input terminals 711A, 711C of the rectifying element 711 on the printed circuit board, respectively.
The energy storage system provided by the embodiment can be used for realizing an electronic system with a self-powered function, and takes a low-power consumption single chip microcomputer chip and a clock chip as examples, the two chips are small in energy density and power density of driving components, and are suitable for adopting a small super capacitor integrated by a printed circuit board and having the capacitance of about 5-10mF as an energy source, storing the electric quantity generated by a nano generator, and further combining a voltage conversion circuit and the like to continuously and stably provide the required power voltage for the single chip microcomputer chip.
According to the parallel strip graphene super capacitor designed by the method of the embodiment corresponding to fig. 2, the size range of the capacitor can be controlled between 3mm × 8mm and 10mm × 20mm, and specifically, the appropriate size of the capacitor is selected according to the different concentrations of the used graphite oxide.
The nano-generator 72 in this embodiment may be a friction generator and/or a zinc oxide nano-generator in the prior art, and those skilled in the art may select the nano-generator according to the needs, which is not limited herein. For example: the friction generator may be of a three-layer structure, a four-layer structure and a five-layer structure. The friction generator of each layer structure at least comprises two surfaces forming a friction interface, at least one of the two surfaces forming the friction interface is provided with a micro-nano structure, and the friction generator is provided with at least two output ends. The zinc oxide nano generator can be of a four-layer or five-layer structure and has two output ends.
In addition, the nano-generator 72 may be provided separately outside the printed circuit board 71, or may be provided on the printed circuit board 71, integrally integrated therewith. When the nano-generator 72 and the printed circuit board 71 are integrated, not only the working stability and reliability of the whole energy storage system can be improved, but also the space occupied by the energy storage system can be effectively reduced, and a person skilled in the art can select the nano-generator according to the requirement, and the selection is not limited here.
For the energy storage system shown in fig. 7, the working process is as follows: when external force acts on the nano generator, the nano generator is mechanically deformed, so that an alternating-current pulse electrical signal is generated. The alternating pulse electrical signal is firstly input to a rectifier element, and is rectified by the rectifier element to obtain unidirectional pulsating direct current. The unidirectional pulsating direct current is input to a filter element for filtering, and interference clutter in the unidirectional pulsating direct current is filtered to obtain a direct current signal. And finally, directly inputting the direct current signal to a graphene super capacitor for charging. Here, one graphene supercapacitor can be charged, and a plurality of parallel graphene supercapacitors can also be charged simultaneously.
According to the graphene supercapacitor manufactured on the printed circuit board provided by the embodiment of the invention, the energy storage circuit and the graphene supercapacitor are directly integrated internally, and the graphene supercapacitor is directly manufactured on the printed circuit board, so that the integration level of the energy storage system is improved. Because the bonding pad is directly connected with the wiring layer on the printed circuit board, the first current collector substrate and the second current collector substrate are used as leading-out ends of the graphene supercapacitor and are directly electrically connected with other elements on the printed circuit board through copper wires, welding procedures are saved, packaging cost is saved, the occupied space of the graphene supercapacitor is obviously reduced, and the high-integration energy storage system can be obtained by using the graphene supercapacitor.
Finally, it is noted that: the above-mentioned embodiments are only examples of the present invention, and it is a matter of course that those skilled in the art can make modifications and variations to the present invention, and it is considered that the present invention is protected by the modifications and variations if they are within the scope of the claims of the present invention and their equivalents.
Claims (15)
1. A preparation method of a graphene supercapacitor is characterized by comprising the following steps:
step S110: manufacturing two bonding pads on a printed circuit board to serve as a first current collector substrate and a second current collector substrate of the graphene supercapacitor;
step S120: dripping graphite oxide solution in a region to be dripped formed by the first current collector substrate and the second current collector substrate;
step S130: carrying out laser engraving reduction treatment on the graphite oxide film formed after the graphite oxide solution is dried and molded to obtain a first patterned graphene electrode and a second patterned graphene electrode;
step S140: and filling electrolyte and packaging the first graphene electrode and the second graphene electrode to form the graphene supercapacitor.
2. The method according to claim 1, wherein the step S110 specifically comprises: manufacturing two parallel bonding pads with preset sizes as a first current collector substrate and a second current collector substrate of the graphene supercapacitor;
the step S120 specifically includes: dripping graphite oxide solution on the surfaces of the first current collector substrate and the second current collector substrate;
the step S130 specifically includes: and carrying out laser engraving and reduction on the graphite oxide thin films formed after the graphite oxide solutions on the surfaces of the first current collector substrate and the second current collector substrate are dried and molded into first graphene electrodes and second graphene electrodes which are in parallel strips.
3. The method according to claim 1, wherein the step S110 specifically comprises: manufacturing two bonding pads with preset opposite positions on the printed circuit board to serve as a first current collector substrate and a second current collector substrate of the graphene supercapacitor;
the step S120 specifically includes: dripping graphite oxide solution on the surface of a printed circuit board between a first current collector substrate and a second current collector substrate or the surface formed by partial areas of the printed circuit board between the first current collector substrate and the second current collector substrate and the first current collector substrate and the second current collector substrate;
the step S130 specifically includes: and carrying out laser engraving and reduction on a graphite oxide film formed after the graphite oxide solution between the first current collector substrate and the second current collector substrate is dried and formed into interdigital first graphene electrodes and second graphene electrodes.
4. The method according to claim 1, 2 or 3, wherein before the step S120, further comprising:
and arranging a mold made of polyethylene terephthalate or polymethyl methacrylate around a region to be dripped, which is formed by the first current collector substrate and the second current collector substrate, wherein the thickness of the polyethylene terephthalate or the polymethyl methacrylate is 0.1mm-1 mm.
5. The method of claim 4, wherein the step S130 further comprises: and removing the polyethylene terephthalate mould or the polymethyl methacrylate mould.
6. The method according to claim 1, wherein before the step S140, further comprising:
the leading-out sides of the first graphene electrode and the second graphene electrode are respectively coated with first conductive silver paint and second conductive silver paint, the first conductive silver paint is in contact with the first graphene electrode and the first current collector substrate, and the second conductive silver paint is in contact with the second graphene electrode and the second current collector substrate.
7. The method of claim 1, wherein the step S140 further comprises:
placing a printed circuit board with a first graphene electrode and a second graphene electrode into a glove box, and filling electrolyte into the first graphene electrode and the second graphene electrode;
and packaging the first graphene electrode and the second graphene electrode filled with the electrolyte into the graphene supercapacitor.
8. The method according to claim 7, wherein the electrolyte is a semi-solid mixture of 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid and nano-silica, and the mass ratio of the 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid to the nano-silica is 100: 3.
9. A graphene supercapacitor, comprising:
two bonding pads manufactured on a printed circuit board are respectively used as a first current collector substrate and a second current collector substrate of the graphene supercapacitor;
the method comprises the steps that a first graphic graphene electrode and a second graphic graphene electrode which are made of graphite oxide films located in a region to be dripped and coated and formed by a first current collector substrate and a second current collector substrate are subjected to laser engraving reduction treatment, wherein the graphite oxide films are formed by drying and molding graphite oxide solution; and
and the first graphene electrode, the second graphene electrode and the electrolyte are packaged into the graphene supercapacitor by the packaging structure.
10. The graphene supercapacitor according to claim 9, wherein the first graphene electrode and the second graphene electrode are in the form of parallel strips and are respectively located on a first current collector substrate and a second current collector substrate; the first current collector substrate and the second current collector substrate are parallel and have a preset size.
11. The graphene supercapacitor according to claim 9, wherein the first graphene electrode and the second graphene electrode are interdigitated, and are located on a surface formed by a printed circuit board between the first current collector substrate and the second current collector substrate or a partial area of the printed circuit board between the first current collector substrate and the second current collector substrate and the first current collector substrate and the second current collector substrate, and the first current collector and the second current collector have a predetermined relative position.
12. The graphene supercapacitor according to claim 9, further comprising: the first conductive silver paint is positioned on the leading-out side of the first graphene electrode, and the second conductive silver paint is positioned on the leading-out side of the second graphene electrode; the first conductive silver paint is contacted with the first graphene electrode and the first current collector substrate, and the second conductive silver paint is contacted with the second graphene electrode and the second current collector substrate.
13. The graphene supercapacitor according to claim 9, wherein the electrolyte is a semi-solid mixture of 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt ionic liquid and nano-silica, and the mass ratio of the 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt ionic liquid to the nano-silica is 100: 3.
14. The graphene supercapacitor of claim 9, wherein the encapsulation structure further comprises: the mold is arranged around the region to be dripped and is made of polyethylene terephthalate or polymethyl methacrylate, wherein the thickness of the polyethylene terephthalate or the polymethyl methacrylate is 0.1mm-1 mm.
15. An energy storage system, comprising: a printed circuit board provided with a reserved area, wherein the reserved area is provided with the graphene supercapacitor of any one of claims 9 to 14;
the printed circuit board is further provided with: a rectifying element and a filter element; wherein,
the input/output end of the filter element is connected with the output end of the rectifying element, and the input/output end of the filter element is connected with the first current collector substrate and the second current collector substrate of the graphene supercapacitor;
the energy storage system further includes: a nano-generator;
and the output end of the nano generator is connected with the input end of the rectifying element on the printed circuit board.
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| CN115346804A (en) * | 2021-05-13 | 2022-11-15 | 中国科学院大连化学物理研究所 | Self-powered sensor circuit platform with embedded super capacitor and preparation method thereof |
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