Method for manufacturing a micro 3D current collector using a laser direct energy deposition method and method for manufacturing a 3D electrode for a supercapacitor

Abstract

Manufacture a micro metal wire using a laser-based direct energy deposition method. 【Solution means】The present invention relates to a method for manufacturing a micro 3D current collector and a method for manufacturing a 3D electrode for a supercapacitor using a laser direct energy deposition method. More specifically, a micro metal structure is directly printed on a substrate using a laser-based direct energy deposition process, and this can be utilized as a current collector for a micro supercapacitor. The current collector having the printed micro metal wire not only has high electrical conductivity, but also can have a larger area for depositing an energy storage active material due to the large surface area of the wire. The present invention relates to a method for manufacturing a micro 3D current collector using a laser direct energy deposition method.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a micro 3D current collector using a laser direct energy deposition method and a method for manufacturing a 3D electrode for a supercapacitor.

Background Art

[0002] Electrochemical capacitors represent an intermediate energy storage system between dielectric capacitors and batteries, and have attracted much attention because they have a higher energy density than ordinary dielectric capacitors and a higher power density than batteries.

[0003] In particular, micro-supercapacitors are suitable as portable and lightweight power sources applicable to small electronic devices such as MEMS (micro-electromechanical systems), small robots, wearable electronic fibers, and implantable medical devices.

[0004] Generally, a supercapacitor is composed of an electrode material, an electrolyte, a separator, and a current collector. Among them, the electrode material is the most important component and dominates the overall electrochemical performance of the supercapacitor.

[0005] Ideal supercapacitor electrode materials require various characteristics such as a high surface area, well-controlled porosity, high electrical conductivity, desirable electroactive sites, high thermal and chemical stability, and low manufacturing cost and process.

[0006] Micro metal structures with high electrical conductivity have various application fields such as electrochemical electrodes, MEMS, 3D interconnects, thermal management devices, and biomedical implants.

[0007] In the fields of medical, biological, and environmental applications, micro power sources (micro energy storage devices) are used in portable and wearable electronic products and there is a great demand. Micro-supercapacitors are one of the promising micro power sources.

[0008] Since the 3D electrode can overcome the geometric limitations of the conventional 2D electrode, it can have higher energy storage performance.

[0009] The metal current collector is suitable for micro-supercapacitors due to its high conductivity, flexibility, and excellent mechanical properties.

[0010] Conventional multi-layer coating technology can restrictively realize a 3D microelectrode structure, but it is not practical because the production time and cost are very high.

[0011] Therefore, methods of manufacturing current collectors using laminated manufacturing (3D printing) with cost-effective materials have also been attempted.

[0012] Typically, SLA or SLM methods, which are metal printing technologies, can fabricate 3D microstructures in a powder bed, but they have the drawback of being difficult to print directly on various types of substrates.

Summary of the Invention

Problems to be Solved by the Invention

[0013] Therefore, the present invention was devised to solve the above-mentioned conventional problems, and the object of the present invention is to manufacture micro metal wires using a laser-based direct energy deposition method.

[0014] Another object of the present invention is to manufacture a 3D current collector for a micro-supercapacitor having a high aspect ratio using a laser-based direct energy deposition method.

[0015] Also, another object of the present invention is to manufacture a micro-supercapacitor with a current collector processed by direct energy deposition and an electrodeposited active material.

[0016] According to an embodiment of the present invention, it is an object to directly print a micro metal structure on a substrate using a laser-based direct energy deposition process and utilize this as a current collector of a microsupercapacitor.

[0017] In addition, according to an embodiment of the present invention, an object is to provide a method for manufacturing a micro 3D current collector using a laser direct energy deposition method, in which a current collector having a printed micro metal wire has not only high electrical conductivity and aspect ratio, but also a larger area for depositing an energy storage active material due to the large surface area of the wire.

[0018] According to an embodiment of the present invention, an object is to provide a method for manufacturing a micro 3D current collector using a laser direct energy deposition method and a method for manufacturing a 3D electrode for a supercapacitor, in which reduced graphene oxide and polyaniline are electrodeposited on a micro wire to provide a large active area and cause a rapid reversible redox reaction, thereby further improving the capacitance of the microsupercapacitor.

[0019] On the other hand, the technical problems to be achieved by the present invention are not limited to the technical problems described above, and other technical problems not mentioned will be clearly understood by those having ordinary knowledge in the technical field to which the present invention belongs from the following description.

Means for Solving the Problems

[0020] A first object of the present invention can be achieved by a method for manufacturing a micro 3D metal structure, which includes a step of printing a plurality of micro wires on a substrate using a laser direct energy deposition method on the substrate.

[0021] And, before the printing step, it can be further characterized by further including a step of laser cutting the substrate into an interdigital pattern or a Comb structure.

[0022] Also, the laser direct energy deposition irradiates a laser while supplying metal powder onto the substrate through a nozzle of a laser direct energy deposition system, and prints such that the longitudinal direction of the micro wire is perpendicular to the plane direction of the substrate. It can be characterized by this.

[0023] And, the laser direct energy deposition system can be characterized by including a jig for fixing the substrate, a moving stage for moving the jig in the X, Y, and Z axis directions, a nozzle for supplying metal powder to the substrate, and a laser irradiation module for irradiating a laser to the metal powder supplied onto the substrate for printing.

[0024] Also, the diameter of the micro wire can be characterized by being 80 to 150 μm and the height being 1 to 2 mm.

[0025] And, the metal powder can be characterized by being a nickel-based alloy powder having a particle size distribution of 15 to 45 μm.

[0026] A second object of the present invention can be achieved as a micro 3D metal structure characterized by being manufactured by the manufacturing method according to the aforementioned first object.

[0027] A third object of the present invention can be achieved as a micro 3D current collector characterized by having the micro 3D metal structure according to the aforementioned second object.

[0028] A fourth object of the present invention is a method for manufacturing a micro 3D electrode, which includes a step of fabricating a current collector by a method for manufacturing a micro 3D metal structure using a laser direct energy deposition method according to the aforementioned first object, and a step of depositing an active material on the surface of a micro wire of the current collector, and can be achieved as a method for manufacturing a 3D electrode for a micro supercapacitor.

[0029] And the step of depositing the active material can be characterized by including a step of depositing reduced graphene oxide and a step of depositing polyaniline.

[0030] Also, the step of depositing the reduced graphene oxide can be characterized by electrochemically depositing the reduced graphene oxide in a three-electrode system using an aqueous graphene oxide suspension.

[0031] And in the above three-electrode system, the current collector can be used as a working electrode, the Pt mesh can be used as a counter electrode, and the saturated calomel electrode can be used as a reference electrode.

[0032] Also, the step of depositing the polyaniline can be characterized by polymerizing aniline in a three-electrode system using a mixed solution of sulfuric acid and aniline and electrochemically depositing the polyaniline.

[0033] And in the above three-electrode system, the electrode on which the graphene oxide is deposited can be used as a working electrode, the Pt mesh can be used as a counter electrode, and Ag / AgCl can be used as a reference electrode.

[0034] A fifth object of the present invention can be achieved as a 3D electrode for a micro supercapacitor, which is characterized by being manufactured by the manufacturing method according to the aforementioned fourth object.

[0035] A sixth object of the present invention can be achieved as a micro supercapacitor, which includes the 3D electrode according to the aforementioned fifth object and an electrolytic solution.

Advantages of the Invention

[0036] According to the embodiments of the present invention, by using a laser-based direct energy deposition method, there is an effect that a micro-supercapacitor can be manufactured with a micro metal wire, a 3D current collector for a micro-supercapacitor, a current collector processed by direct energy deposition, and an electrodeposited active material.

[0037] And, according to the embodiments of the present invention, by using a laser-based direct energy deposition (Direct Energy Deposition) process, a micro metal structure can be directly printed on a substrate and utilized as a current collector of a micro-supercapacitor having a high aspect ratio.

[0038] Also, according to the method for manufacturing a micro 3D current collector using the laser direct energy deposition method according to the embodiments of the present invention, the current collector having the printed micro metal wire not only has high electrical conductivity and aspect ratio, but also has a large surface area of the wire, so that there is an effect of having a larger area for depositing an energy storage active material.

[0039] According to the method for manufacturing a micro 3D current collector and the method for manufacturing a 3D electrode for a supercapacitor using the laser direct energy deposition method according to the embodiments of the present invention, reduced graphene oxide and polyaniline are electrodeposited on the micro wire, providing a large active area and causing a rapid reversible redox reaction, thereby further improving the capacitance of the micro-supercapacitor.

[0040] On the other hand, the effects that can be obtained by the present invention are not limited to the effects described above, and other effects not mentioned will be clearly understood by those with ordinary knowledge in the technical field to which the present invention pertains from the following description.

Brief Description of the Drawings

[0041] The attached drawings in this specification illustrate preferred embodiments of the present invention and serve to help understand the technical idea of the present invention together with the detailed description of the invention. Therefore, the present invention should not be analyzed by being limited to the matters described in such drawings.

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Modes for Carrying Out the Invention

[0043] Hereinafter, a method for manufacturing a supercapacitor having a micro 3D current collector using a laser direct energy deposition method according to an embodiment of the present invention will be described. FIG. 1 is a diagram showing a flowchart of a method for manufacturing a supercapacitor having a micro 3D current collector using a laser direct energy deposition method according to an embodiment of the present invention.

[0044] First, a method for manufacturing a 3D current collector having a 3D metal structure (10) on which a plurality of micro wires (2) are printed will be described.

[0045] In an embodiment of the present invention, the prepared substrate (1) is laser cut into an interdigital pattern or a Comb structure (S10). In a specific embodiment, a stainless steel SS316L substrate (1) is cut into an interdigital pattern or a Comb structure using a nanosecond pulsed fiber laser.

[0046] FIG. 2 is a schematic diagram of a substrate pattern manufacturing process according to an embodiment of the present invention. As shown in FIG. 2, it can be cut in an interdigital pattern, and each electrode can be designed in the shape of two fingers.

[0047] Then, with respect to the substrate (1, electrode layer) on which these patterns are formed, a plurality of micro wires (2) are printed and deposited on the substrate (1) using a laser direct energy deposition method (S20).

[0048] FIGS. 3 and 4 are schematic diagrams of a laser direct energy deposition system for manufacturing micro wires according to an embodiment of the present invention.

[0049] Then, FIGS. 5 to 7 show a perspective view, an enlarged view, and a micro wire SEM of a micro current collector on which a plurality of micro wires are printed according to an embodiment of the present invention.

[0050] As shown in FIG. 4, in laser direct energy deposition, while supplying metal powder onto a substrate (1) through a nozzle (131) of a laser direct energy deposition system (100), a laser is irradiated, and it can be seen that printing is performed such that the longitudinal direction of the micro wire (2) is perpendicular to the plane direction of the substrate (1).

[0051] Such a laser direct energy deposition system 100 utilizes a small beam spot diameter (~22 μm) and laser modulation. The metal powder according to an embodiment of the present invention may be nickel-based alloy powder having a spherical particle size distribution of 15 to 45 μm. However, all metal powders capable of laser direct energy deposition are targeted.

[0052] As shown in FIG. 4, a laser direct energy deposition system (100) includes a jig for fixing a substrate (1) and a moving stage (110) for moving such a jig in the X, Y, and Z axis directions. And it includes a powder supply module (130) for supplying metal powder to the substrate (1), and such a powder supply module (130) can be configured to include a powder supply unit (133), a pressure sensor (132) for measuring the supply pressure, and a nozzle (131) for injecting the metal powder.

[0053] And the laser irradiation module (120) is configured to irradiate a laser onto the metal powder supplied onto the substrate (1) to print the micro wire (2), and can be configured to include a laser oscillation unit (121), a PBS (122), a lens (123), and the like.

[0054] By applying such a laser direct energy deposition method, for example, 150 micro wires (diameter 110 μm, height 1.5 mm) (2) are printed on a substrate (1) to form a 3D metal interdigital current collector. Nitrogen gas is supplied through a protective gas supply unit 140 to protect the powder flow and the printing area.

[0055] As shown in Fig. 6, according to the embodiment of the present invention, it can be seen that 150 micro-wires with a diameter of 110 μm and a height of 1.5 mm (75 micro-wires (2) for each electrode) are printed in the interdigital pattern of the substrate (1). Each electrode is designed in two finger shapes, and three rows of micro-wires (2) are evenly printed on each finger-shaped electrode.

[0056] In the embodiment of the present invention, an active material can be electrodeposited on the micro 3D current collector using the aforementioned laser direct energy deposition method.

[0057] Fig. 8 is a diagram showing a 3D electrode on which reduced graphene oxide and polyaniline according to the embodiment of the present invention are deposited.

[0058] And Fig. 9 is an SEM of the state where reduced graphene oxide is deposited on the micro-wire according to the embodiment of the present invention, and Fig. 10 is a diagram showing an SEM of the state where polyaniline is deposited on the micro-wire on which reduced graphene oxide is deposited according to the embodiment of the present invention.

[0059] As shown in Fig. 8, it can be seen that the deposition of the active material according to the embodiment of the present invention includes a step (S30) of depositing reduced graphene oxide (20) and a step (S40) of depositing polyaniline (30).

[0060] Reduced graphene oxide (20) and polyaniline (30) are deposited on the micro-wire (2) of the current collector (10), increasing the active surface area and providing similar capacitor performance.

[0061] For the deposition of reduced graphene oxide 20 according to the embodiment of the present invention, first, an aqueous suspension of graphene oxide (5 mg / ml) with 0.1 M LiClO4 was used, and reduced graphene oxide 20 was deposited in a three-electrode system at a potential of -1.2 V for 8 minutes.

[0062] At this time, in the three-electrode system, the 3D printed current collector (10) is used as the working electrode, the Pt mesh as the counter electrode, and the saturated calomel electrode as the reference electrode. After the deposition process of reduced graphene (20), it is washed with DI water and then dried in a convection oven at 50 °C for 2 hours.

[0063] Then, for the deposition of polyaniline (30) according to the embodiment of the present invention, a solution obtained by mixing 0.5 M of H2SO4 and 0.01 M of aniline is used, and aniline is polymerized for 10 minutes in a three-electrode system with a potential of 0.75 V to deposit polyaniline (30).

[0064] In the three-electrode system, the electrode on which the graphene oxide (20) of the previous step is deposited is used as the working electrode, the Pt mesh as the counter electrode, and Ag / AgCl (sat. KCL) as the reference electrode. After the polyaniline (30) vapor deposition process, it is washed with DI water for 30 minutes and then dried.

[0065] Then, a microsupercapacitor (200) is fabricated by including the fabricated 3D electrode (40) in the electrolyte (S50). FIG. 11 is a diagram showing a schematic view of a supercapacitor using the micro 3D electrode according to the embodiment of the present invention.

[0066] That is, the fabricated 3D electrode 40 is filled with a 1 M H2SO4 electrolyte to form a microsupercapacitor element 200 and characterize its electrochemical performance.

[0067] The electrochemical performance of the microsupercapacitor (200) according to the embodiment of the present invention was experimented within a potential window of 0 to 0.8 V.

[0068] FIG. 12 is a diagram showing a CV test graph of the supercapacitor according to the embodiment of the present invention, and FIG. 13 is a diagram showing a charge-discharge curve graph of the supercapacitor according to the embodiment of the present invention.

[0069] As shown in Fig. 12, it can be seen that the 3D printed microsupercapacitor manufactured according to the embodiment of the present invention shows a wide CV graph region in the CV (Cyclic voltametry) test.

[0070] And, as shown in Fig. 13, the microsupercapacitor element manufactured according to the embodiment of the present invention has a cost amount performance of 2.77 F / cm 3 when it is 1 mA / cm in 1M H2SO4 electrolyte. 3 It can be seen that it shows.

[0071] Also, the devices and methods described above are not limited to the configurations and methods of the embodiments described above, and the above embodiments can be selectively combined with all or part of each embodiment so that various modifications can be made.

Claims

1. A method for manufacturing a micro 3D metal structure, comprising the steps of: A method for manufacturing a micro 3D metal structure using a laser direct energy deposition method, comprising the step of printing a plurality of microwires on a substrate using a laser direct energy deposition method.

2. In claim 1, Prior to the printing step The method for manufacturing a micro 3D metal structure using a laser direct energy deposition method further comprises a step of laser cutting the substrate into an interdigital pattern or a comb structure.

3. In claim 2, The laser direct energy deposition A method for manufacturing a micro 3D metal structure using a laser direct energy deposition method, comprising: supplying metal powder onto the substrate through a nozzle of a laser direct energy deposition system and irradiating a laser to print the microwires so that the length direction of the microwires is perpendicular to the planar direction of the substrate.

4. In claim 3, The laser direct energy deposition system includes a jig for fixing the substrate, a moving stage for moving the jig in the X-, Y-, and Z-axis directions, a nozzle for supplying metal powder to the substrate, and a laser irradiation module for irradiating a laser onto the metal powder supplied onto the substrate to print it.

5. 4. The method according to claim 3, The microwire has a diameter of 80 to 150 um and a height of 1 to 2 mm.

6. In claim 3, The method for manufacturing a micro 3D metal structure using a laser direct energy deposition method, wherein the metal powder is a nickel-based alloy powder having a particle size distribution of 15 to 45 um.

7. A micro 3D metal structure manufactured by the manufacturing method according to any one of claims 1 to 6.

8. A micro 3D current collector comprising the micro 3D metal structure according to claim 7.

9. A method for manufacturing a micro 3D electrode A method for manufacturing a micro 3D metal structure using the laser direct energy deposition method according to any one of claims 1 to 6, comprising the steps of: A method for manufacturing a 3D electrode for a micro-supercapacitor, comprising depositing an active material on a surface of the microwire of the current collector.

10. In claim 9, The step of depositing active material comprises: A method for fabricating a 3D electrode for a micro-supercapacitor, comprising the steps of depositing reduced graphene oxide and depositing polyaniline.

11. In claim 10, The step of depositing reduced graphene oxide comprises: A method for fabricating 3D electrodes for micro-supercapacitors, characterized by electrochemical deposition of reduced graphene oxide in a three-electrode system using an aqueous graphene oxide suspension.

12. 12. The micro-supercapacitor of claim 11 . In the three-electrode system, the current collector is used as a working electrode, the Pt mesh is used as a counter electrode, and the saturated calomel electrode is used as a reference electrode.

13. In claim 10, The step of depositing polyaniline includes: A method for fabricating 3D electrodes for micro-supercapacitors, characterized by polymerizing aniline in a three-electrode system using a mixed solution of sulfuric acid and aniline, and electrochemically depositing polyaniline.

14. 14. The micro-supercapacitor of claim 13 . In the three-electrode system, the electrode on which the graphene oxide is deposited is used as a working electrode, the Pt mesh is used as a counter electrode, and Ag / AgCl is used as a reference electrode.

15. A 3D electrode for a micro-supercapacitor, produced by the method according to claim 9.

16. A micro-supercapacitor comprising the three-dimensional electrode of claim 15 and an electrolyte.

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