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KR-20260067647-A - Method for manufacturing highly crystallized porous material and high voltage supercapacitor having the same porous material

KR20260067647AKR 20260067647 AKR20260067647 AKR 20260067647AKR-20260067647-A

Abstract

A method for manufacturing a highly crystalline porous carbon material that can be managed to a level of approximately < 10 ppm is provided, which requires the removal of heterogeneous elements or functional group impurities that may cause side reactions under high voltage conditions. The method is characterized by comprising: (a) a step of producing a graphitized polymer-deposited carbon substrate by depositing a graphitized polymer on the surface of a carbon substrate based on a wet process; (b) a step of manufacturing the graphitized polymer-deposited carbon substrate into a composite material having a surface-modified porous structure through physical and chemical processes; and (c) a step of manufacturing a highly crystalline porous carbon material with a carbon content of 80% or more by applying an ultra-high-speed power pulse to the composite material.

Inventors

  • 윤여흥
  • 박병준
  • 이영희
  • 김수빈

Assignees

  • 한국전력공사

Dates

Publication Date
20260513
Application Date
20241106

Claims (20)

  1. (a) A step of producing a graphitized polymer-deposited carbon substrate by depositing a graphitized polymer on the surface of a carbon substrate based on a wet process; (b) a step of manufacturing the graphitized polymer-deposited carbon substrate into a composite material having a surface-modified porous structure through physical and chemical processes; and (c) a step of manufacturing a highly crystalline porous carbon material with a carbon content of 80% or more by applying an ultra-high-speed power pulse to the above composite material; A method for manufacturing a highly crystalline porous carbon material characterized by including
  2. In Article 1, The above step (a) is, A step of dispersing the carbon substrate in a graphitizing polymer mixture dissolved in an organic solvent and reacting at room temperature to produce a reaction product; and A method for manufacturing a highly crystalline porous carbon material, characterized by comprising the step of increasing the temperature of the above reactants to a temperature of 40°C to 150°C to improve the bonding strength at the interface between the graphitized polymer and the carbon substrate to produce the graphitized polymer-deposited carbon substrate.
  3. In Article 2, The above step (b) is, A step of performing stirring on the above graphitized polymer-deposited carbon substrate; A step of removing the graphitized polymer that did not participate in the reaction through sequential filtration, washing, and drying; and A method for manufacturing a highly crystalline porous carbon material, characterized by comprising the step of heat-treating the above composite material in an inert gas atmosphere at a temperature of 150°C to 1,000°C for 1 hour to 48 hours.
  4. In Paragraph 3, A method for manufacturing a highly crystalline porous carbon material, characterized in that the surface modification above involves homogenizing and depositing the graphitized polymer on the surface of the carbon substrate.
  5. In Article 1, A method for manufacturing a highly crystalline porous carbon material characterized in that the graphitizing polymer is deposited on the surface and edge of the carbon substrate and graphitized in step (c).
  6. In Article 1, A method for manufacturing a highly crystalline porous carbon material, characterized in that the carbon matrix comprises an electrode of any one of the energy storage device materials selected from activated carbon, graphite , carbon nanotubes, graphene , and two-dimensional transition metal carbides ( Ti₂CTx , Ti₃C₂Tx , Mo₂CTx , Nb₂CTx ).
  7. In Article 1, A method for manufacturing a highly crystalline porous carbon material, characterized by graphitizing one of polyamic acid (PAA), polyimide, or coal using either physical graphitization energy via an optical reaction method or a thermal reaction method, or chemical reduction energy via a chemical reaction method.
  8. In Article 2, A method for manufacturing a highly crystalline porous carbon material, characterized in that, for dissolving the graphitized polymer, the organic solvent is one of acetone, ethanol, ethylene glycol, or N,NMP (N-methyl pyrolidone).
  9. In Article 1, A method for manufacturing a highly crystalline porous carbon material, characterized in that step (c) above applies an ultra-high-speed power pulse to the composite material at a voltage of 50V to 700V for a time of 10ms to 500ms.
  10. In Article 1, A method for manufacturing a highly crystalline porous carbon material characterized by the simultaneous progression of surface graphitization and internal graphitization using the Joule heating method.
  11. In Article 1, A method for manufacturing a highly crystalline porous carbon material, characterized by including the step of controlling the specific surface area by inducing thermal shock of the highly crystalline carbon material after the above step (c).
  12. In Article 1, A method for manufacturing a highly crystalline porous carbon material characterized by the fact that the highly crystalline porous carbon material does not undergo a change in shape after the application of the ultra-high-speed power pulse.
  13. In Article 1, A method for manufacturing a highly crystalline porous carbon material characterized in that, after step (c) above, the specific surface area of the highly crystalline porous carbon material is maintained or increased without decreasing.
  14. In Article 1, A method for manufacturing a highly crystalline porous carbon material, characterized in that, after step (c) above, the impurity content including hydrogen, oxygen, nitrogen, and sulfur of the highly crystalline porous carbon material is less than 1%.
  15. A highly crystalline porous carbon material manufactured according to a method for manufacturing a highly crystalline porous carbon material according to any one of claims 1 to 14.
  16. In Article 15, The above highly crystalline porous carbon material is characterized by having an sp² / sp³ ratio of 0.1 or less.
  17. In Article 16, The above highly crystalline porous carbon material is characterized by having a 2D/G ratio of 0.4 or higher.
  18. In Article 16, The above highly crystalline porous carbon material is characterized by having a specific surface area of 100 to 1,500 m² /g according to the BET evaluation method.
  19. In Article 16, The above highly crystalline porous carbon material is characterized by having an oxidation reaction voltage of 3.2V or higher in an electrochemical atmosphere.
  20. In Article 16, The above highly crystalline porous carbon material is characterized by having an operating voltage of 1V to 5V in a quaternary-ammonium-based organic electrolyte.

Description

Method for manufacturing highly crystallized porous carbon material and high voltage supercapacitor having the same porous material The present invention relates to a carbon material manufacturing technology, and more specifically to a method for manufacturing a highly crystalline porous carbon material and a high-voltage supercapacitor having the same. In general, supercapacitors exhibit higher energy density compared to conventional commercial electrolytic capacitors and also higher power density compared to lithium-ion batteries (LiB), a type of secondary battery, making them a focus of attention as next-generation energy storage devices. Among them, electric double-layer capacitors have a simpler cell configuration compared to secondary batteries due to their symmetrical positive/negative structure and exhibit high power density utilizing charge adsorption and desorption; however, their applications are limited due to low energy density. Since the charge amount is determined by the amount of charge adsorbed (Q), when a conductive carbon material with a large surface area is adopted as an electrode, activated carbon is typically used. The biggest problem is that despite about 30 to 40 years of research and development, the capacity of porous carbon electrodes has reached its limit (80-120 F/g), and it is technically very difficult to increase energy density through capacity increase. Therefore, increasing the relatively low operating voltage to a high voltage is considered the only alternative to improve energy density. Currently, the operating voltage limit of conventional supercapacitors is approximately 2.7 to 3.0 V (energy density: 1 to 5 Wh/kg), which is determined by the characteristics of the electrolyte, but under high voltage conditions above 3.0 V, it results in reduced lifespan due to adverse reactions between the electrolyte and the electrode. To overcome this, research and development are underway regarding various electrolyte salts, solvents, additives, and composition optimization, but it is difficult to control side reactions with the electrode at high voltages, so the operating voltage cannot exceed 3.0V. The fundamental reason for this is that while the electrolyte alone has a potential window of 4 to 7 V, the application of porous carbon material electrodes to secure capacity has a problem in that its stability is compromised. Therefore, to achieve high voltage in supercapacitor unit cells, not only must electrolytes be developed, but electrode materials capable of suppressing side reactions must also be developed simultaneously. In addition, to achieve high voltages for supercapacitor electrodes while using existing commercial electrolytes, it is necessary to suppress adverse reactions between the electrode and the electrolyte by stabilizing the electrode surface. In addition, it is necessary to secure a stable carbon structure (sp 3 → sp 2 ) on the surface of the porous carbon material. This is because the most vulnerable part to reaction is known to be the edge structure of the carbon structure. FIG. 1 is a process diagram showing a polymer deposition and heat treatment process according to an embodiment of the present invention. Figure 2 is a schematic diagram of the particle shape according to the manufacturing process illustrated in Figure 1. Figure 3 is a graph showing the X-ray diffraction (XRD) results of a supercapacitor electrode material according to the manufacturing process shown in Figure 1. Figure 4 is a graph showing the Raman spectroscopic results of the graphene electrode material according to the manufacturing process illustrated in Figure 1. FIG. 5 is a graph showing the results of elemental analysis of an example and a comparative example sample according to an embodiment of the present invention. FIG. 6 is an example screen showing the results of Scanning Electron Microscope (SEM) imaging of each sample according to an embodiment of the present invention. Figure 7 is a graph showing the results of comparing the specific surface area of each sample according to an embodiment of the present invention. FIG. 8 is a graph showing the linear scanning current curve results according to an embodiment of the present invention. FIG. 9 is a graph showing the charge and discharge results according to an embodiment of the present invention. FIG. 10 is a graph showing the results of electrochemical impedance spectroscopy (EIS) (Nyquist plot) according to an embodiment of the present invention. FIG. 11 is a graph showing the results of measuring the capacity and long-term life according to an embodiment of the present invention. Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, this is merely an example and the present invention is not limited thereto. Furthermore, in describing the present invention, if it is determined that a detailed description of known technology related to the present invention may unnece