WO2022045551A1 - Procédé de production de charbon actif dérivé de kénaf - Google Patents

Procédé de production de charbon actif dérivé de kénaf Download PDF

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WO2022045551A1
WO2022045551A1 PCT/KR2021/007782 KR2021007782W WO2022045551A1 WO 2022045551 A1 WO2022045551 A1 WO 2022045551A1 KR 2021007782 W KR2021007782 W KR 2021007782W WO 2022045551 A1 WO2022045551 A1 WO 2022045551A1
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kenaf
kac
carbon
koh
activated carbon
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PCT/KR2021/007782
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Korean (ko)
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정용석
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제주대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Definitions

  • the present invention relates to kenaf-derived activated carbon and a method for preparing the same.
  • Electric supercapacitors that can store electric charges through physical adsorption/desorption processes are attracting attention as the most promising energy storage equipment in various fields such as portable electronic devices and electric vehicles because of their high electric capacity and long-term cycle stability.
  • the electrochemical performance of a supercapacitor depends on the properties of the electrode material used in its manufacture. In particular, since the capacitance of supercapacitors is proportional to the surface of the active material and inversely proportional to the thickness of electric double-layers (EDLs), an improved electrode design with high surface area and appropriate nanoporous structure EDLs is needed.
  • Activated carbon has a high specific surface area, low price, excellent electrical conductivity and well-defined pore structure, so it is widely used as an electrode material for supercapacitors.
  • nanostructured carbon materials containing redoxactive heteroatoms are attracting attention as cathode materials for the storage of lithium and/or sodium ions.
  • Several heteroatom functional groups in nanostructured carbon materials can act as redox hosts for fast and highly stable pseudocapacitive charge charging. Therefore, increasing the energy density of supercapacitors has been proposed as a strategy that can be used for both EDL capacitance and pseudocapacitance.
  • the inventors of the present invention completed the present invention by confirming that the nanostructure and pore structure can be controlled by adjusting the KOH ratio in the preparation of kenaf-derived nanoporous activated carbon by chemical activation with KOH.
  • the present invention includes the steps of pre-carbonizing kenaf to 400 °C at a heating rate of 1 to 5 °C min -1 ; and a chemical activation step of treating the pre-carbonized kenaf with KOH in a weight ratio of 1:1 to 6 while heating to 800°C at a heating rate of 1 to 10°C min -1 ; It provides a manufacturing method of
  • the present invention also provides a kenaf-derived activated carbon prepared by the manufacturing method according to the present invention.
  • the kenaf-derived activated carbon of the present invention is an amorphous carbon structure composed of a nanometer hexagonal carbon layer with well-developed micropores and multiple O- and N-containing species, and a plurality of redox-activated heterogeneous carbons such as oxygen and nitrogen. It has atoms and shows a high specific surface area of 2,150.1 m 2 g -1 . Due to these unique material properties, it exhibits high long-term cycle stability and specific capacitance of ⁇ 132.5 W hkg -1 , thereby exhibiting high electrochemical performance corresponding to a Na-ion storage cathode, and thus can be used as an excellent electrode material for supercapacitors.
  • Figure 3 shows (a) nitrogen adsorption and desorption isotherms of kACs nitrogen adsorption and desorption isotherms and (b) its pore size distribution results.
  • the present invention relates to kenaf-derived activated carbon and a method for preparing the same.
  • the kenaf-derived activated carbon may be prepared by the following preparation method:
  • the heating rate in the pre-carbonizing step may be 2° C. min ⁇ 1 , but is not limited thereto.
  • the pre-carbonizing step can heat the kenaf to 400° C. at a slow heating rate of 2° C. min ⁇ 1 to form more conjugated structures that are converted to carbon structures.
  • the heating rate may be 5° C. min ⁇ 1 , but is not limited thereto.
  • the nanostructure and pore structure of the activated carbon can be controlled by treating the pre-carbonized kenaf with KOH in a weight ratio of 1:1 to 6, for example, 1:4 by weight, but is limited thereto. doesn't happen
  • the kenaf may be a fine powder of kenaf stems, but is not limited thereto.
  • the kenaf may be used by grinding the kenaf stem into a fine powder and then drying the kenaf, but is not limited thereto.
  • Heating in the pre-carbonizing step and the chemical activation step may be carried out under an Ar flow, for example, may be carried out under a constant Ar flow of 100 cm 3 min ⁇ 1 , but is not limited thereto.
  • the kenaf-derived activated carbon prepared by the above manufacturing method may be used as an electrode material for a supercapacitor, but is not limited thereto.
  • the stems of kenaf were crushed into fine powder using a grinder and dried in a convection oven for one day. Then, about 4.0 g of kenaf powder was pre-carbonized to 400° C. without dwelling time. The heating rate was 2° C. min ⁇ 1 under a constant Ar flow of 100 cm 3 min ⁇ 1 . The pre-carbonized kenaf powder was washed several times until neutralized with 0.1 M HCl solution and deionized water. After drying at 80° C. for 2 days in a convention oven, a chemical activation process was performed using KOH at a weight ratio of 1:1, 1:2, 1:4, and 1:6 until 800°C.
  • KOH powder was stirred and mixed with the pre-carbonized kenaf in the above weight ratio, and then activation was performed.
  • the prepared kenaf-derived activated carbons (kACs) were named kAC-0.5, kAC-1, kAC-2, and kAC-4, respectively.
  • the heating rate was 5° C. min ⁇ 1 under a constant Ar flow of 100 cm 3 min ⁇ 1 .
  • the thermal behavior of the kenaf stems was analyzed by thermogravimetric analysis (TGA; TG 209 F3, NETZSCH, Germany) from room temperature to 1,000°C at a heating rate of 10°C min ⁇ 1 under inactivated argon gas.
  • TGA thermogravimetric analysis
  • the morphology of the kAC sample was field-emission. It was confirmed using scanning electron microscopy (FE-SEM, S-4300, Hitachi, Japan).
  • Raman spectra were recorded using a linearly polarized continuous-wave laser (514.5 nm, 2.41 eV, 16 mW). The laser beam was focused using a ⁇ 100 objective lens to make a spot with a diameter of ⁇ 1 ⁇ m.
  • XPS X-ray photoelectron spectroscopy
  • the pore structure of the sample was analyzed using an N2 adsorption/desorption isotherm obtained at -196°C using a surface area and porosimetry analyzer (Tristar, Micromeritics, USA).
  • kAC electrochemical properties of kAC were confirmed using Wonatech automatic battery cycler and CR2032 type coin cell. After the coin cells were assembled in an argon-filled glove box, the samples were tested as working electrodes with metallic Na foils as reference and counter electrodes.
  • a working electrode a slurry was prepared in N-methyl-2-pyrrolidone (OCI Co., 99.9%, USA) in conductive carbon (10 wt.%; Alfa Aesar Co., purity: >99%, England) and polyvinylidene fluoride (10 wt. .%; Sigma-Aldrich, USA) and an active material (80 wt.%) were mixed.
  • N-methyl-2-pyrrolidone OCI Co., 99.9%, USA
  • conductive carbon 10 wt.%; Alfa Aesar Co., purity: >99%, England
  • polyvinylidene fluoride 10 wt. .%; Sigma-Aldrich, USA
  • the prepared slurry was uniformly coated on Al foil (Wellcos Co., Korea), dried at 80° C. for 1 hour, and then roll pressed.
  • the mass loading of the active material was ⁇ 1 mg cm ⁇ 2 and the total electrode weight was about 1-2 mg.
  • a glass microfiber filter (GF/F, Whatman, Germany) was used as a separator.
  • the thermal stability of kenaf was confirmed by TGA and DTA as shown in FIG. 1a . Below 150°C, a slight weight loss ( ⁇ 2wt.%) was observed due to the removal of adsorbed moisture. The weight was kept constant up to about 200 °C, but in the temperature range between 250 and 350 °C, thermal decomposition of the kenaf started and a rapid weight loss of ⁇ 67 wt.% ( ⁇ 78 wt. of the total weight of the kenaf was observed. 350 °C In the above, the weight steadily decreased, and a residual weight of about 14% was measured after pyrolysis to 1,000° C.
  • kAC-1 and Kac-2 The morphology of kAC was observed using FE-SEM and shown in Fig. 1b. Activated samples with low KOH ratios (kAC-1 and Kac-2) showed random micro-scale bulk particle morphology, whereas high KOH ratios were observed. With kAC-4 and kAC-6, they showed collapsed structures with rough surfaces.
  • the chemical activation mechanism using KOH is as follows: 1) creation of pore structure through redox reaction between potassium compound and carbon atom, 2) development of pore structure through gasification of carbon, and 3) activation into carbon matrix Further development of the pore structure through extension of the carbon lattice caused by intercalation of metallic potassium generated during That is, the structural difference between kACs is caused by the different activation effects according to the KOH ratio, the amount of etched carbon, and the exfoliated carbon layer.
  • the carbon microstructure of kAC was analyzed through XRD and Raman spectroscopy, and the results are shown in FIG. 2a.
  • the XRD pattern of kAC-0 shows two broad peaks centered at approximately 23° and 43°, which correspond to the (002) and (100) reflective surfaces of the hexagonal graphite structure, respectively, indicating that a typical amorphous carbon structure exists.
  • the graphite (002) peaks of kACs were shifted to small angles and broadened, indicating that the average interlayer distance increased and the number of stacked layers decreased, respectively.
  • the trend of (002) peak extinction becomes more evident as the KOH ratio increases.
  • the XRD patterns of kAC-4 and kAC-6 show little (002) reflection, confirming the low stacking structure of the carbon layer caused by the consumption of carbon by oxygen and the passage of metallic potassium between the graphitic carbon layers. it will do
  • the Raman spectrum of the kAC sample shows two representative carbon bands, an E 2g vibration model of a graphite layer with sp 2 carbon at a frequency of ⁇ 1580 cm ⁇ 1 (referred to as G band) and a structural defect at a frequency of ⁇ 1,350 cm ⁇ 1 .
  • G band an E 2g vibration model of a graphite layer with sp 2 carbon at a frequency of ⁇ 1580 cm ⁇ 1
  • a structural defect at a frequency of ⁇ 1,350 cm ⁇ 1 showed a model of A 1g breathing (known as the D-band) of sp 2 bonded carbons near the basal edge corresponding to .
  • the D-band A 1g breathing
  • all kAC samples showed almost similar Raman spectra even after activation with a high KOH ratio (kAC-4).
  • the ID/IG intensity ratios of kAC-0, kAC-1, kAC-2, kAC-4, and kAC-6 were estimated to be 0.89, 0.92, 0.86, 0.89, and 0.87, respectively, which are hexagonal with a few nanometers. This indicates that the carbon structure was not significantly destroyed through the activation process. That is, after the chemical activation process, the kAC sample still contains a hexagonal carbon crystal structure.
  • the surface properties of kAC were confirmed using XPS and are shown in Table 1.
  • the heteroatom content nitrogen + oxygen
  • a number of heteroatoms are mainly introduced into topological defect sites such as mono- and di-vacancies, Stone-Wales defects, adatoms, and edge defects.
  • the pore structure and surface area of kACs were investigated using a nitrogen adsorption/desorption isothermal curve, and are shown in FIG. 3 and Table 2. As the KOH ratio increased, it was observed that the amount of nitrogen adsorption significantly increased at a relative pressure of 0.1 or less, indicating that the amount of monolayer adsorption increased. This result suggests that the adsorption of nitrogen molecules on the surface of the carbon layer increases with the increase of the insufficient stacking hindered hexagonal structure induced by chemical activation.
  • the isothermal curves of kAC-1 and kAC-2 are representative International Union of Pure and Applied Chemistry (IUPAC) type-I shape, which represents the micropore structure.
  • the specific surface areas calculated using the Brunauer-Emmett-Teller (BET) theory were 1,350 and 1,941 m 2 g ⁇ 1 , respectively, and the micropore surface areas corresponded to 1,048 and 1,523 m 2 g ⁇ 1 , respectively.
  • the isothermal curves of kAC-4 and kAC-6 showed IUPAC type-I and type-II hybrid isotherms, indicating micropore and macropore structures.
  • the specific surface areas of kAC-4 and kAC-6 were 2,128 and 2,719 m 2 g ⁇ 1 , respectively.
  • kAC-4 and kAC-6 have more meso- and macropores, indicating that they have advantages for fast charge charging as well as high specific surface area for capacitive EDL charge charging.
  • the electrochemical performance of kAC was investigated in a voltage range of 1.5-4.5 V vs Na + /Na at a current rate of 01 A g -1 and shown in FIG. 4 .
  • the second-order galvanostatic charge/discharge curves of all samples showed a linear profile without plateaus, leading to a surface-driven capacitive charge behavior.
  • the profiles of the electrodes except for the kAC-6 electrode showed no voltage hysteresis, indicating a reversible charge mechanism based on the electric double layer phenomenon.
  • the reversible capacitance is about 150 mA hg -1 at a charge/discharge rate of 0.1 A g -1
  • the kAC-6 electrode has an irreversible electricity of ⁇ 110 mA hg -1 capacity, which means low reversibility due to the relatively large mesopores causing the cylinder effect.
  • the rate characteristic of the kAC-4 electrode demonstrates a significantly faster charge-charge kinetics, showing a clear difference with increased charge-discharge rate compared to other samples.
  • the specific capacity of the kAC-4 electrode was 150, 145, 141, 123, 113, 95, and 83 mA hg -1 at charge/discharge rates of 0.1, 0.2, 0.5, 1, 2, 5, and 10 A g -1 , respectively. , and a reversible specific capacity of ⁇ 149 mA hg ⁇ 1 was recovered, which is noteworthy reversibility.
  • S EXT values >2 nm) excluding the micropore regions of kAC-4 and kAC-6 were 554 and 1,113 m 2 g ⁇ 1 , respectively.

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  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

La présente invention concerne du charbon actif dérivé de kénaf pouvant être utilisé en tant que matériau d'électrode pour supercondensateur et un procédé de fabrication correspondant et peut présenter une stabilité de cycle à long terme et une capacité spécifique élevée grâce à un procédé de précarbonisation et à un procédé d'activation chimique.
PCT/KR2021/007782 2020-08-25 2021-06-22 Procédé de production de charbon actif dérivé de kénaf WO2022045551A1 (fr)

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KR20200025804A (ko) * 2018-08-31 2020-03-10 주식회사 티씨케이 활성탄 및 이의 제조방법

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ABDUL RAZAK MUHAMMAD NIZAM, AHMAD NOORDEN ZULKARNAIN, ANI FARID NASIR, ABDUL MALEK ZULKURNAIN, JAMIAN JASRUL JAMANI, BASHIR NOURUD: "Electrochemical properties of kenaf-derived activated carbon electrodes under different activation time durations for supercapacitor application", INDONESIAN JOURNAL OF ELECTRICAL ENGINEERING AND COMPUTER SCIENCE, vol. 19, no. 2, pages 1105, XP055904273, ISSN: 2502-4752, DOI: 10.11591/ijeecs.v19.i2.pp1105-1112 *
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