• 전기화학회지
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• 제15권3호
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• pp.154-159
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• 2012

Si계 음극소재는 리튬 삽입-탈착 중 일어나는 큰 구조적 부피변화와 입도변화로 인해 빠른 성능 퇴화가 일어나는 단점이 있다. 산화물 SiO 음극소재는 리튬과의 반응 중 비활성상인 $Li_2O$ 및 lithium silicate가 형성되어 Si의 부피변화를 완화시키는 버퍼 역할을 하므로 용량은 Si보다 적으나 개선된 용량 유지 특성을 보이는 것으로 알려져 있다. 본 연구에서는 Si의 부피변화 완화를 위하여 저가의 $SiO_2$와 입자간 전기전도성을 향상시키는 흑연을 구조안정화 기재로서 사용하여 Si-$SiO_2$-흑연 복합재 음극을 제작하였다. 구조안정화 뿐만 아니라 silane계 전해액 첨가제를 이용하여 Si-$SiO_2$-흑연 복합재 음극과 전해액간 계면을 안정화시킴으로써 용량 유지 특성이 개선되는 효과에 대해 보고하고자 한다.

• Korean Chemical Engineering Research
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• 제61권1호
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• pp.32-38
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• 2023

본 연구에서는 리튬 이온 배터리 용 음극활물질인 실리콘의 사이클 안정성 및 율속 특성을 개선하기 위해 도파민이 코팅된 실리콘/실리콘카바이드/카본(Si/SiC/C) 복합소재의 전기화학적 특성을 조사하였다. Stöber 법에 CTAB을 추가하여 CTAB/SiO₂를 합성한 후 열 흡수제로써 NaCl을 첨가한 마그네슘 열 환원법을 통해 Si/SiC 복합소재를 제조하였으며, 도파민의 중합반응을 통해 탄소코팅을 하여 Si/SiC/C 음극소재를 합성하였다. 제조된 Si/SiC/C 음극소재의 물리적 특성 분석을 위해 SEM, TEM, XRD와 BET를 사용하였으며, 1 M LiPF₆ (EC : DEC = 1 : 1 vol%) 전해액에서 리튬 이온 배터리의 사이클 안정성, 율속 특성, 순환전압전류 및 임피던스 테스트를 통해 전기화학적 특성을 조사하였다. 제조된 1-Si/SiC는 100사이클, 0.1 C에서 633 mAh/g의 방전용량을 나타냈으며, 도파민이 코팅된 1-Si/SiC/C는 877 mAh/g으로 사이클 안정성이 향상된 것을 확인할 수 있었다. 또한 5C에서 576 mAh/g의 높은 용량과 0.1 C/0.1 C 일 때 99.9%의 용량 회복 성능을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.145-148
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• 2011

The thermal behavior of lithiated Si anodes has been investigated using differential scanning calorimetry (DSC). In particular, the effect of Si particle size on the thermal stability of a fully lithiated Si electrode was investigated. For DSC measurements, a lithiated Si anode was heated in a hermetically sealed high-pressure pan with a polyvinylidene fluoride (PVDF) binder and a 1 M $LiPF_6$ solution in an ethylene carbonate (EC)-diethyl carbonate (DEC) mixture. The thermal evolution around $140^{\circ}C$ increases with lithiation and with decreasing particle size; this phenomenon is attributed to the thermal decomposition of the solid electrolyte interface (SEI) film. Exothermic peaks, following a broad peak at around $140^{\circ}C$, shift to a lower temperature with a decrease in particle size, indicating that the thermal stability of the lithiated Si electrode strongly depends on the Si particle size.

• 한국전기전자재료학회논문지
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• 제32권1호
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• pp.70-77
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• 2019

$SiO_x$ nanoparticles were granulated, and their microstructures and effects on electrochemical behaviors were investigated. In spite of the promising electrochemical performance of $SiO_x$, nanoparticles have limitations such as high surface area, low density, and difficulty in handling during slurry processing. Granulation can be one solution. In this study, pelletizing and annealing were conducted to create particles with sizes of several decades of micron. Decrease in surface area directly influences the initial charge and discharge process when granules are applied as anode materials for Li-ion batteries. Lower surface area is key to decreasing the amount of irreversible phase-formation, such as $Li_2Si_2O_5$, $Li_2SiO_3$ and $Li_4SiO_4$, as well as forming the solid electrolyte interface. Additionally, aggregation of nanoparticles is required to obtain further enhancement of the electrochemical behavior due to restrictions that there be no $Li_4SiO_4$-related reaction during the first discharge process.

• 공업화학
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• 제25권6호
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• pp.592-597
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• 2014

본 연구에서는 리튬이차전지의 음극활물질로 graphite의 전기화학적 특성을 향상시키기 위하여 졸-겔 법에 의한 graphite/$SiO_2$ 복합소재를 제조하였다. 제조된 graphite/$SiO_2$ 합성물은 XRD, FE-SEM과 EDX를 사용하여 분석하였다. $SiO_2$에 의해 표면 개질된 graphite는 SEI 층을 안정화시키는데 장점을 보여 주었다. Graphite/$SiO_2$ 전극을 작업 전극으로, 리튬메탈을 상대전극으로 하여 리튬이차전지의 전기화학 특성을 조사하였다. $LiPF_6$ 염과 EC/DMC 용매를 전해질로 사용하여 제조한 코인 셀의 전기화학적 거동은 충방전, 사이클, 순환전압전류, 임피던스 테스트를 진행하여 평가하였다. Graphite/$SiO_2$ 전극을 사용한 리튬이차전지는 graphite 전극을 사용한 전지보다 우수한 특성을 보여주었으며, 0.1 C rate에서 465 mAh/g의 용량을 보여주었다. 또한 개질된 graphite 전극은 0.8 C rate에서 99%의 용량 보존율을 보여주었다.

• 한국전기전자재료학회논문지
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• 제19권7호
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• pp.636-643
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• 2006

Si-C materials were synthesized by the heating the mixture of silicon and polyvinylidene fluoride (PVDF). The electrochemical properties of the Si-C materials as the high capacitive anode materials of lithium secondary batteries were evaluated by the galvanostatic charge-discharge test through 2032 type $Si-C{\mid}Li$ coin cells. Charge-discharge tests were performed at C/10 hour rate(C = 372 mAh/g). Initial discharge and charge capacities of $Si-C{\mid}Li$ cell using a Si-C material derived from PVDF(20wt.%) were found to be 1,830 and 526 mAh/g respectively. The initial discharge-charge characteristics of the developed Si-C electrode were analyzed by the electrochemical galvanostatic test adopting the capacity limited charge cut-off condition(GISOC). The range of reversible specific capacity IIE(intercalation efficiency at initial discharge-charge) and IICs(surface irreversible specific capacity) were 216 mAh/g, 68 % and 31 mAh/g, respectively.

• 대한화학회지
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• 제60권5호
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• pp.299-309
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• 2016

In this study, the physicochemical and electrochemical properties of carbon nanomaterials and synthesized nano-carbon/Si composites were studied. The nano-carbon/Si composites were ball-milled to a nano size and coated with pyrolytic carbon using Chemical Vapor Deposition (CVD). They were then finely mixed with respective nano-carbon materials. The physicochemical properties of samples were analyzed using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), Raman spectroscopy, X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and surface area analyzer. The electrochemical characteristics were investigated using the galvanostatic charge-discharge and cyclic voltammetry (CV) measurements. Three-electrode cells were fabricated using the carbon nanomaterials and nano-carbon/Si composites as anode materials and LiPF₆ and LiClO₄ as electrolytes of Li secondary batteries. Reversibility using LiClO₄ as an electrolyte was superior to that of LiPF₆ as the electrolyte. The initial discharge capacities of nano-carbon/Si composites were increased compared to the initial discharge capacities of nano-carbon materials.

• Korean Chemical Engineering Research
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• 제56권3호
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• pp.320-326
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• 2018

본 연구에서는리튬이온전지음극활물질로 Graphite의 전기화학적특성을향상시키기 위하여 Graphite/Silicon/Carbon (G/Si/C) 복합소재를 제조하였다. 제조된 G/Si/C 합성물은 XRD, TGA, SEM을 사용하여 물성을 분석하였다. 또한 $LiPF_6$ (EC:DMC:EMC=1:1:1 vol%) 전해액에서 리튬이차전지의 충 방전 사이클, 율속, 순환전압전류 및 임피던스 테스트를 통해 전기화학적 성능을 조사하였다. G/Si/C 전극을 사용한 리튬이온전지는 Graphite 전극을 사용한 전지보다 우수한 특성을 나타내었으며 Silicon 함량이 늘어날수록 용량은 높아지나 안정성이 저하됨을 확인하였다. 또한 $25{\mu}m$ 이하의 Silicon을 사용하였을 때 용량과 안정성 모두 향상되는 것을 나타내었다. Silicon (${\leq}25{\mu}m$) 10 wt%인 경우 G/Si/C 복합소재는 495 mAh/g의 초기 방전 용량, 89%의 용량 보존율과 2 C/0.1 C에서 80%의 속도 특성을 보였다.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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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 Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (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.

• 전기화학회지
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• 제20권4호
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• pp.61-66
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• 2017

The cycle performance of Ti-Si alloy anode material for Li-ion batteries has been investigated as a function of loading level of electrode using a nodule type of substrate, in which the current collector of flat foil is also used for comparison. The Ti-Si alloy powders are prepared by mechanical alloying method. The electrodes with the nodule type of current collector exhibit enhanced cycling performance compared to those using the flat foil because the alloy particles are more strongly adhered to substrate and the stress caused by lithiation and delithiation reaction can be effectively relaxed by nodule-type morphology. It appears, however, that the cycle performance is critically dependent on the loading level of electrode, even when the nodule type of current collector is applied. With high loading level, cracks are initiated at surface of electrode due to a steep stress gradient through the electrode thickness during cycling, leading to capacity fading.