• Title/Summary/Keyword: Si-Graphite Composite Anode

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Electrochemical Characteristics of Si/PC/CNF/PC Composite for Anode Material of Lithium ion Battery (이차전지 음극활물질 Si/PC/CNF/PC 복합 소재의 전기화학적 특성)

  • Jeon, Do-Man;Na, Byung-Ki;Rhee, Young-Woo
    • Korean Chemical Engineering Research
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    • v.56 no.6
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    • pp.798-803
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    • 2018
  • In order to use Si as an anode material for lithium-ion battery, the particle size was controlled to less than $0.5{\mu}m$ and carbon was coated on the surface with the thickness less than 10 nm. The carbon fiber was grown on the Si surface with 50~150 wt%, and the carbon coating was carried out once again. The Si composite material was mixed with dissimilar metals to increase the conductivity, and graphite was mixed to improve cyclic life characteristics. The physical and electrochemical characteristics of composite materials were measured with XRD, SEM, TEM and coin cell. The discharge capacity of Si/PC/CNF/PC was lower than that of Si/PC (Pyrolytic Carbon)/CNF (Carbon Nano Fiber). However, the cyclic life of Si/PC/CNF/PC was higher. Initial discharge capacity of 1512 mA h g-1 at 0.2 C rate and initial efficiency of 78% were shown. It also showed a capacity retention of 94% in 10 cycles.

Mitigating Metal-dissolution in a High-voltage 15 wt% Si-Graphite‖Li-rich Layered Oxide Full-Cell Utilizing Fluorinated Dual-Additives

  • Kim, Jaeram;Kwak, Sehyun;Pham, Hieu Quang;Jo, Hyuntak;Jeon, Do-Man;Yang, A-Reum;Song, Seung-Wan
    • Journal of Electrochemical Science and Technology
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    • v.13 no.2
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    • pp.269-278
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    • 2022
  • Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li1.13Mn0.463Ni0.203Co0.203O2 (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn2+-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

Pretreatment of SiO/C Composite Anode of Lithium ion Secondary Battery for High coulombic Efficiency and High Specific Capacity (리튬이차전지용 산화실리콘-흑연 복합체 고효율 음극의 전처리 특성)

  • Shin, Hye-Min;Veluchamy, Angathevar;Kim, Dong-Hun;Chung, Young-Dong;Kim, Hyo-Seok;Doh, Chil-Hoon;Jin, Bong-Soo;Kim, Hyun-Soo;Moon, Seong-In;Kim, Ki-Won;Oh, Dae-Hui
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.11a
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    • pp.43-44
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    • 2007
  • SiO and graphite composite has been prepared by adopting high energy ball milling technique. The anode material shows high initial discharge and charge capacity values of 1138 and 568 mAh/g, respectively. Since the materials formed during initial discharge process the nano silicon/$Li_4SiO_3\;and\;Li_2O$ remains as interdependent, it may be expected that the composite exhibiting higher amount of irreversible capacity$(Li_2O)$ will deliver higher reversible capacity. In this study, pretreatment method of constant current-constant voltage (CC-CV) Provided high coulombic efficiency of SiO/C composite electrode removing the greater part of irreversible capacity.

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High Coulombic Efficiency Negative Electrode(SiO-Graphite) for Lithium Ion Secondary Battery (리튬이온이차전지용 고효율 음극(SiO-Graphite))

  • Shin, Hye-Min;Doh, Chil-Hoon;Kim, Dong-Hun;Kim, Hyo-Seok;Ha, Kyung-Hwa;Jin, Bong-Soo;Kim, Hyun-Soo;Moon, Seong-In;Kim, Ki-Won;Oh, Dae-Hui
    • Journal of the Korean Electrochemical Society
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    • v.11 no.1
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    • pp.47-50
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    • 2008
  • A new anode composition material comprising of SiO and Graphite has been prepared by adopting High energy ball milling (HEBM) technique. The anode material shows high initial charge and discharge capacity values of 1139 and 568 mAh/g, respectively. The electrode sustains reversible discharge capacity value of 719 mAh/g at 30th cycle with a high coulombic efficiency${\sim}99%$. Since the materials formed during initial charge process the nano silicon/$Li_4SiO_3$ and $Li_2O$ remains as interdependent, it may be expected that the composite exhibiting higher amount of irreversibility$(Li_2O)$ will deliver higher reversible capacity. In this study, constant current-constant voltage (CC-CV) charge method was employed in place of usual constant current (CC) method in order to convert efficiently all the SiO particles which resulted high initial discharge capacity at the first cycle. We improved considerably the initial discharge specific capacity of SiO/G composite by pretreatment(CC-CV).

Evaluations of Si based ternary anode materials by using RF/DC magnetron sputtering for lithium ion batteries

  • Hwang, Chang-Muk;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.302-303
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    • 2010
  • Generally, the high energy lithium ion batteries depend intimately on the high capacity of electrode materials. For anode materials, the capacity of commercial graphite is unlike to increase much further due to its lower theoretical capacity of 372 mAhg-1. To improve upon graphite-based negative electrode materials for Li-ion rechargeable batteries, alternative anode materials with higher capacity are needed. Therefore, some metal anodes with high theoretic capacity, such as Si, Sn, Ge, Al, and Sb have been studied extensively. This work focuses on ternary Si-M1-M2 composite system, where M1 is Ge that alloys with Li, which has good cyclability and high specific capacity and M2 is Mo that does not alloy with Li. The Si shows the highest gravimetric capacity (up to 4000mAhg-1 for Li21Si5). Although Si is the most promising of the next generation anodes, it undergoes a large volume change during lithium insertion and extraction. It results in pulverization of the Si and loss of electrical contact between the Si and the current collector during the lithiation and delithiation. Thus, its capacity fades rapidly during cycling. Si thin film is more resistant to fracture than bulk Si because the film is firmly attached to the substrate. Thus, Si film could achieve good cycleability as well as high capacity. To improve the cycle performance of Si, Suzuki et al. prepared two components active (Si)-active(Sn, like Ge) elements film by vacuum deposition, where Sn particles dispersed homogeneously in the Si matrix. This film showed excellent rate capability than pure Si thin film. In this work, second element, Ge shows also high capacity (about 2500mAhg-1 for Li21Ge5) and has good cyclability although it undergoes a large volume change likewise Si. But only Ge does not use the anode due to its costs. Therefore, the electrode should be consisted of moderately Ge contents. Third element, Mo is an element that does not alloys with Li such as Co, Cr, Fe, Mn, Ni, V, Zr. In our previous research work, we have fabricated Si-Mo (active-inactive elements) composite negative electrodes by using RF/DC magnetron sputtering method. The electrodes showed excellent cycle characteristics. The Mo-silicide (inert matrix) dispersed homogeneously in the Si matrix and prevents the active material from aggregating. However, the thicker film than $3\;{\mu}m$ with high Mo contents showed poor cycling performance, which was attributed to the internal stress related to thickness. In order to deal with the large volume expansion of Si anode, great efforts were paid on material design. One of the effective ways is to find suitably three-elements (Si-Ge-Mo) contents. In this study, the Si based composites of 45~65 Si at.% and 23~43 Ge at.%, and 12~32 Mo at.% are evaluated the electrochemical characteristics and cycle performances as an anode. Results from six different compositions of Si-Ge-Mo are presented compared to only the Si and Ge negative electrodes.

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Preparation of Silicon-Carbon Composite via Magnesiothermic Reduction Method and Its Application to the Anode Material for Lithium Ion Battery (마그네슘열환원법을 이용한 실리콘-탄소 복합재 제조 및 리튬이차전지 음극재로의 이용)

  • Kim, Eudem;Kwon, Soon Hyung;Kim, Myung-Soo;Jung, Ji Chul
    • Korean Journal of Materials Research
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    • v.24 no.5
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    • pp.243-248
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    • 2014
  • Silicon-carbon composite was prepared by the magnesiothermic reduction of mesoporous silica and subsequent impregnation with a carbon precursor. This was applied for use as an anode material for high-performance lithium-ion batteries. Well-ordered mesoporous silica(SBA-15) was employed as a starting material for the mesoporous silicon, and sucrose was used as a carbon source. It was found that complete removal of by-products ($Mg_2Si$ and $Mg_2SiO_4$) formed by side reactions of silica and magnesium during the magnesiothermic reduction, was a crucial factor for successful formation of mesoporous silicon. Successful formation of the silicon-carbon composite was well confirmed by appropriate characterization tools (e.g., $N_2$ adsorption-desorption, small-angle X-ray scattering, X-ray diffraction, and thermogravimetric analyses). A lithium-ion battery was fabricated using the prepared silicon-carbon composite as the anode, and lithium foil as the counter-electrode. Electrochemical analysis revealed that the silicon-carbon composite showed better cycling stability than graphite, when used as the anode in the lithium-ion battery. This improvement could be due to the fact that carbon efficiently suppressed the change in volume of the silicon material caused by the charge-discharge cycle. This indicates that silicon-carbon composite, prepared via the magnesiothermic reduction and impregnation methods, could be an efficient anode material for lithium ion batteries.

Lithium Battery Anode Properties of Ball-Milled Graphite-Silicon Composites (볼밀링법으로 제조된 흑연-실리콘 복합체의 리튬전지 음전극 특성)

  • Kang, Kun-Young;Shin, Dong Ok;Lee, Young-Gi;Kim, Kwang Man
    • Korean Chemical Engineering Research
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    • v.51 no.4
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    • pp.411-417
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    • 2013
  • To use as an anode material of lithium secondary battery, graphite-silicon composite powders are prepared by ball-milling with silicon nanoparticles (average diameter 100 nm, 0~50 wt%) and graphite powder (average diameter $15{\mu}m$) and their electrochemical properties are examined. As the silicon content increases, the graphite becomes smaller by the ball-milling and amorphous phase appears whereas the silicon do not suffer the change of nanocrystalline phases and embeds within the amorphous phase of graphite. Cyclic voltammetry at low scan rate reveals that typical oxidation peaks of graphite and silicon appear at 0.2~0.35 and 0.55~0.6 V, respectively, with higher reversibility for repeated cycles. In contrast, the high-scan-rate redox behavior is very irreversible for repeated cycles. High irreversible capacity is exhibited in the initial charging-discharging cycles, but it diminishes as the cycle number increases. The saturated discharge capacity achieves about 485 mAh $g^{-1}$ at 50th cycle for the composite of Si 20 wt%. This is due to the formation of amorphous graphite morphology by the adequate composition (C:Si=8:2 w/w), which efficiently buffers the volume change during alloying/dealloying between silicon and lithium.

Silicon/Carbon Composites Having Bimodal Mesopores for High Capacity and Stable Li-Ion Battery Anodes (고용량 고안정성 리튬 이차전지 음극소재를 위한 이중 중공을 갖는 실리콘/탄소 복합체의 설계)

  • Park, Hongyeol;Lee, Jung Kyoo
    • Clean Technology
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    • v.27 no.3
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    • pp.223-231
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    • 2021
  • In order to address many issues associated with large volume changes of silicon, which has very low electrical conductivity but offers about 10 times higher theoretical capacity than graphite (Gr), a silicon nanoparticles/hollow carbon (SiNP/HC) composite having bimodal-mesopores was prepared using silica nanoparticles as a template. A control SiNP/C composite without a hollow structure was also prepared for comparison. The physico-chemical and electrochemical properties of SiNP/HC were analyzed by X-ray diffractometry, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements for surface area and pore size distribution, scanning electron microscopy, transmission electron microscopy, galvanostatic cycling, and cyclic voltammetry tests to compare them with those of the SiNP/C composite. The SiNP/HC composite showed significantly better cycle life and efficiency than the SiNP/C, with minimal increase in electrode thickness after long cycles. A hybrid composite, SiNP/HC@Gr, prepared by physical mixing of the SiNP/HC and Gr at a 50:50 weight ratio, exhibited even better cycle life and efficiency than the SiNP/HC at low capacity. Thus, silicon/carbon composites designed to have hollow spaces capable of accommodating volume expansion were found to be highly effective for long cycle life of silicon-based composites. However, further study is required to improve the low initial coulombic efficiency of SiNP/HC and SiNP/HC@Gr, which is possibly because of their high surface area causing excessive electrolyte decomposition for the formation of solid-electrolyte-interface layers.

Synthesis and Electrochemical Characteristics of Carbon Coated SiOx/ZnO Composites by Sol-gel Method (졸겔법으로 제조한 탄소피복된 SiOx/ZnO 복합체의 합성 및 전기화학적 특성)

  • Baek, Gwang-Yong;Jeong, Sang Mun;Na, Byung-Ki
    • Clean Technology
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    • v.22 no.4
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    • pp.308-315
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    • 2016
  • $SiO_x/ZnO$ composites were prepared from sol-gel method for excellent cycle life characteristics. The composites were coated by PVC as a carbon precursor. ZnO removal to create a void space therein was able to buffer the volume change during charge and discharge. To determine the crystal structure and the shape of the synthesized composite, XRD, SEM, TEM analysis was performed. The carbon contents in the composites were confirmed by TGA. The pore structure and pore size distribution of the composite was measured with the BET specific surface area analysis and BJH pore size distribution. Enhanced electric conductivity by carbon addition was determined from powder resistance measurement. Electrochemical properties were measured with the AC impedance and the charge and discharge cycle life characteristics. When carbon was coated on the $SiO_x/ZnO$ sample, the electrical conductivity and the discharge capacity were increased. After removal of ZnO with HCl the surface area of the sample was increased, but the discharge capacity was decreased. $SiO_x/ZnO$ sample without acarbon coating showed very low discharge capacity, and after carbon coating the sample showed high discharge capacity. For cycle life characteristics, $C-SiO_x/ZnO$ composite (Zn : Si : C = 1 : 1 : 8) with a capacity of $815mAh\;g^{-1}$ at 50 cycle and 0.2 C has higher capacity than existing graphite-based anode materials.