Anodic Performances of Surface-Treated Natural Graphite for Lithium Ion Capacitors

박철민,Yong Nam Jo,박정우,유지상,Jeom-Soo Kim,최정규,김용준 대한화학회 2014 Bulletin of the Korean Chemical Society Vol.35 No.9

The surface of natural graphite was modified by the use of hydrogen peroxide and evaluated as an anode material for lithium ion capacitors (LICs). The surface treatment was carried out under various ultrasonic conditions of 200, 300, and 400W, which were applied to a mixture of natural graphite and hydrogen peroxide solution for 1 h. While the bulk structure was maintained, the hexagonal symmetry and physical properties of natural graphite, such as BET surface area, tap density, and particle size, were affected by the surface treatment. FT-IR and XPS measurements confirmed the signature of C=O on the surface of graphite samples after treatment. Both the pristine and surface-treated graphites showed a similar reversible capacity of 370 mAhg−1, and the coulombic efficiency of surface-treated graphite decreased with higher ultrasonic energies (89.1%, 89.0%, and 88.0% for 200, 300, and 400 W) comparing with pristine graphite (89.4%). The capacity retention of LICs was greatly improved with the treated natural graphite. The graphite treated under the ultrasonic energy of 300 W and pristine natural graphite showed capacity retention of 77.5% and 42.9%, implying that the surface treatment was an effective method for the improvement of natural graphite as an anode material for LICs.

Anodic Performances of Surface-Treated Natural Graphite for Lithium Ion Capacitors

Park, Chul Min,Jo, Yong Nam,Park, Jung Woo,Yu, Ji-Sang,Kim, Jeom-Soo,Choi, Jungkyu,Kim, Young-Jun Korean Chemical Society 2014 Bulletin of the Korean Chemical Society Vol.35 No.9

The surface of natural graphite was modified by the use of hydrogen peroxide and evaluated as an anode material for lithium ion capacitors (LICs). The surface treatment was carried out under various ultrasonic conditions of 200, 300, and 400W, which were applied to a mixture of natural graphite and hydrogen peroxide solution for 1 h. While the bulk structure was maintained, the hexagonal symmetry and physical properties of natural graphite, such as BET surface area, tap density, and particle size, were affected by the surface treatment. FT-IR and XPS measurements confirmed the signature of C=O on the surface of graphite samples after treatment. Both the pristine and surface-treated graphites showed a similar reversible capacity of $370mAhg^{-1}$, and the coulombic efficiency of surface-treated graphite decreased with higher ultrasonic energies (89.1%, 89.0%, and 88.0% for 200, 300, and 400 W) comparing with pristine graphite (89.4%). The capacity retention of LICs was greatly improved with the treated natural graphite. The graphite treated under the ultrasonic energy of 300 W and pristine natural graphite showed capacity retention of 77.5% and 42.9%, implying that the surface treatment was an effective method for the improvement of natural graphite as an anode material for LICs.

Electrical Conductivity of Chemically Reduced Graphene Powders under Compression

Adila Rani,Seung-Woong Nam,Kyoung-Ah Oh,Min Park 한국탄소학회 2010 Carbon Letters Vol.11 No.2

Carbon materials such as graphite and graphene exhibit high electrical conductivity. We examined the electrical conductivity of synthetic and natural graphene powders after the chemical reduction of synthetic and natural graphite oxide from synthetic and natural graphite. The trend of electrical conductivity of both graphene (synthetic and natural) was compared with different graphite materials (synthetic, natural, and expanded) and carbon nanotubes (CNTs) under compression from 0.3 to 60 MPa. We found that synthetic graphene showed a marked increment in electrical conductivity compared to natural graphene. Interestingly, the total increment in electrical conductivity was greater for denser graphite; however, an opposite behavior was observed in nanocarbon materials such as graphene and CNTs, probably due to the differing layer arrangement of nanocarbon materials.

Solid state electrochemical double layer capacitors with natural graphite and activated charcoal composite electrodes

Hansika, P.A.D.,Perera, K.S.,Vidanapathirana, K.P.,Zainudeen, U.L. Techno-Press 2019 Advances in materials research Vol.8 No.1

Electrochemical double layer capacitors (EDLCs) which are fabricated using carbon based electrodes have been emerging at an alarming rate to fulfill the energy demand in the present day world. Activated charcoal has been accepted as a very suitable candidate for electrodes but its cost is higher than natural graphite. Present study is about fabrication of EDLCs using composite electrodes with activated charcoal and Sri Lankan natural graphite as well as a gel polymer electrolyte which is identified as a suitable substitute for liquid electrolytes. Electrochemical Impedance Spectroscopy, Cyclic Voltammetry and Galvanostatic Charge Discharge test were done to evaluate the performance of the fabricated EDLCs. Amount of activated charcoal and natural graphite plays a noticeable role on the capacity. 50 graphite : 40 AC : 10 PVdF showed the optimum single electrode specific capacity value of 15 F/g. Capacity is determined by the cycling rate as well as the potential window within which cycling is being done. Continuous cycling resulted an average single electrode specific capacity variation of 48 F/g - 16 F/g. Capacity fading was higher at the beginning. Later, it dropped noticeably. Initial discharge capacity drop under Galvanostatic Charge Discharge test was slightly fast but reached near stable upon continuous charge discharge process. It can be concluded that initially some agitation is required to reach the maturity. However, the results can be considered as encouraging to initiate studies on EDLCs using Sri Lankan natural graphite.

리튬 이차전지의 음극재료인 천연흑연의 충방전 속도에 따른 충방전 용량

류지헌,오은영,오승모,Ryu Ji Heon,Oh Eun Young,Oh Seung M. 한국전기화학회 2004 한국전기화학회지 Vol.7 No.1

리튬 이차전지의 음극재료로서 천연흑연의 충방전 속도에 따른 용량특성을 조사하였다 정전류 조건에서 $0.0-2.0V(vs. Li/Li^+)$의 범위에서 충방전 하였을 때, 충전전류가 증가할수록 충전반응의 과전압이 증가하여 $Li^+$이온이 충분히 삽입되지 못한 상태에서 컷오프 전압(0.0 V)에 도달하기 때문에 충전용량은 충전전류의 크기가 클수록 감소하였다. 한편, 방전전류가 증가함에 따라 방전반응의 과전압도 증가하여 0.0-0.3V범위에서 방전반응이 일어나나 방전 컷오프 전압(2.0 V)과는 격차가 커서 $Li^+$이온이 탈리되지 못한 상태에서 방전 컷오프에 도달하는 현상은 없기 때문에 방전용량이 방전전류의 크기에 영향을 받지 않았다. 충전전류가 증가함에 따라 부반응인 리튬 전착반응의 과전압도 증가하므로 충전 컷오프 전압을 0.0V 이하로 낮출 수 있었다. 그러나 $Li^+$이온의 삽입반응에 비해 전착반응의 저항이 적어 충전전류에 따른 전착반응의 과전압 증가에는 한계가 있었다. 1C조건에서 -0.04V까지 충전 z컷오프 전압을 낮추었을 때 리튬의 전착반응은 없었고, 이로부터 약 $11\%$의 방전용량을 증가시킬 수 있었다. The charge/discharge capacity of natural graphite anode in lithium secondary batteries was examined as a function of charge/discharge rate. When the natural graphite anode was galvanostatically cycled in the range of 0.0-2.0V $(vs.\;Li/Li^+)$, the charging capacity decreased with an increase in the charging rate, which is caused by an earlier approach to the charging cut-off (0.0 V) before the complete charging that is in turn caused by an ever-increasing overpotential at higher rates. Even if the overpotential of discharging reaction also increased at higher discharge rates, the discharging reaction took place in the range of 0.0-0.3 V that is far below the discharge cut-off (2.0 V). As a result, the discharge capacity was not affected by the discharge rate because all the lithium ions once intercalated are fully discharged even at high current condition. As the overpotential of lithium deposition reaction also increased at high current condition, the charge capacity of natural graphite could be enlarged by lowering the charging cut-off voltage below 0.0 V, There is, however, a limitation for the lowering of cut-off voltage because the resistance for lithium deposition is smaller than that of lithium intercalation into graphite. When the charge cut-off voltage was lowered down to -0.04 V under IC condition, lithium ions were inserted into graphite without lithium deposition such that the discharge capacity could be raised up to $11\%$.

천연흑연 박리를 통한 그래핀 잉크 생산 및 프린팅

김규리,곽영원,전호영,최창호 한국청정기술학회 2022 청정기술 Vol.28 No.4

The remarkable mechanical, electrical, and thermal properties of graphene have recently sparked tremendous interest in various research fields. One of the most promising methods to produce large quantities of graphene dispersion is liquid-phase exfoliation (LPE) which utilizes ultrasonic waves or shear stresses to exfoliate bulk graphite into graphene flakes that are a few layers thick. Graphene dispersion produced via LPE can be transformed into graphene ink to further boost graphene’s applications, but producing high-quality graphene more economically remains a challenge. To overcome this shortcoming, an advanced LPE process should be developed that uses relatively cheap natural graphite as a graphene source. In this study, a flow-LPE process was used to exfoliate natural graphite to produce graphene that was three times cheaper and seven times larger than synthetic graphite. The optimal exfoliation conditions in the flow-LPE process were determined in order to produce high-quality graphene flakes. In addition, the structural and electrical properties of the flakes were characterized. The electrical properties of the exfoliated graphene were investigated by carrying out an ink formulation process to prepare graphene ink suitable for inkjet printing, and fabricating a printed graphene pattern. By utilizing natural graphite, this study offers a potential protocol for graphene production, ink formulation, and printed graphene devices in a more industrial-comparable manner. 그래핀의 우수한 기계적, 전기적, 열적 성질은 최근 몇 년 동안 여러 연구 분야에서 지대한 관심을 불러일으켰다. 그래핀을 생산하는 대표적인 방법인 습식공정 중 액상박리(liquid-phase exfoliation, LPE)는 초음파 및 높은 전단응력을 이용하여 벌크흑연을 그래핀으로 박리하는 기술이다. 액상박리에 의해 생산된 그래핀 분산액은 그래핀 잉크로 전환되어 그 활용폭을 더 넓힐 수 있는 장점이있지만 고품질의 그래핀을 생산하고 가격경쟁력을 확보해야 한다. 위 조건을 만족하기 위해서 그래핀을 효율적으로 박리할 수있는 공정 확보와 더불어 상대적으로 가격이 저렴한 천연흑연 기반의 그래핀 분산액 및 잉크를 생산해야 한다. 본 연구에서는합성흑연 보다 약 3배 정도 저렴하고 그 크기는7배 이상 큰 천연흑연을 흐름반응기 액상박리 공정을 이용하여 박리를 시도하고공정의 최적화와 박리된 그래핀의 구조적, 전기적 특성을 분석하였다. 천연흑연 기반 그래핀의 전기적 특성을 분석하기 위해잉크 정제화 공정을 거쳐 그래핀 잉크를 생산하고 인쇄 장비를 사용하여 그래핀 패턴을 제작하였다. 본 연구를 통해 보다 경제적인그래핀 분산액 및 잉크를 생산하고 그래핀 인쇄 소자를 개발할 수 있는 방법을 제시할 수 있을 것으로 기대된다.

Evaluation of low-purity natural graphite as a costeffective anode active material for lithium ion batteries

박윤태,이기태 한양대학교 세라믹연구소 2016 Journal of Ceramic Processing Research Vol.17 No.4

Low-purity natural graphite as an anode active material for lithium ion batteries was studied in order to reduce the cost oflithium ion batteries. The electrochemical performance of low-purity natural graphite was compared to that of high-puritycommercial grade graphite. No significant differences of the morphology or crystal structure were observed in the SEM, XRD,and Raman measurements. Based on the EDX and ICP-AES results, relatively larger amounts of Al and Fe than otherimpurities were found in the low-purity natural graphite powders. Although the LP18-99 sample contained various impurities,it showed good performance in comparison with the NG-R sample.

Preparation of the spheroidized graphite-derived multi-layered graphene via GIC (graphite intercalation compound) method

안정철,이은정,홍익표 한국공업화학회 2017 Journal of Industrial and Engineering Chemistry Vol.47 No.-

Artificially spheroidized natural graphite (SNG) was processed to obtain expanded graphite and graphenenanoplatelets using GIC (graphite intercalation compound)-assisted exfoliation process. Sulfuric acid andhydrogen peroxide were used as the intercalant and oxidant for the GIC formation, respectively. SNG wassuccessfully converted into both expanded graphite and graphene nanoplatelets. Degree of exfoliation ofthe produced graphene nanoplatelets was found to be proportional to the average diameter of startingmaterials. Graphene nanoplatelets prepared from SNG with average diameter of 50 mm were analyzed tohave the averaged lateral size of 45.4 mm at the thickness of ca. 5 nm.

코팅 피치의 물성제어를 통한 흑연 음극재의 전기화학 성능 향상 연구

김보라,김지홍,강석창,임지선,Kim, Bo Ra,Kim, Ji Hong,Kang, Seok Chang,Im, Ji Sun 한국공업화학회 2022 공업화학 Vol.33 No.5

A pitch coating method was proposed for the purpose of improving the electrochemical properties of natural graphite. The synthesis conditions of pitch coating were optimized via measuring electrochemical properties of pitch-coated graphite anodes. As the synthesis temperature increased, the thermal stability was improved in addition to an increase in the softening point and residual carbon weight. However, the synthesis temperature of 430 ℃ resulted in the synthesis of a large amount of NI (NMP Insoluble) due to excessive condensation reaction. As the surface uniformity and coating thickness increased due to high thermal stability, the initial coulombic efficiency and rate capability of the pitch-coated graphite were improved. However, the graphite coated with the pitch containing excessive NI showed lower electrochemical properties than the uncoated graphite. NI had low dispersibility and formed spheres after heat treatment, so it formed the heterogeneous and thicker SEI layer. The optimum conditions for forming a uniform surface and an appropriate coating layer were investigated.

Preparation of the spheroidized graphite-derived multi-layered graphene via GIC (graphite intercalation compound) method

An, Jung-Chul,Lee, Eun Jung,Hong, Ikpyo THE KOREAN SOCIETY OF INDUSTRIAL AND ENGINEERING 2017 JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY -S Vol.47 No.-

<P><B>Abstract</B></P> <P>Artificially spheroidized natural graphite (SNG) was processed to obtain expanded graphite and graphene nanoplatelets using GIC (graphite intercalation compound)-assisted exfoliation process. Sulfuric acid and hydrogen peroxide were used as the intercalant and oxidant for the GIC formation, respectively. SNG was successfully converted into both expanded graphite and graphene nanoplatelets. Degree of exfoliation of the produced graphene nanoplatelets was found to be proportional to the average diameter of starting materials. Graphene nanoplatelets prepared from SNG with average diameter of 50μm were analyzed to have the averaged lateral size of 45.4μm at the thickness of ca. 5nm.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>