• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2017년도 춘계학술대회 논문집
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• pp.169-169
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• 2017

Due to key roles for the electrochemical stability and charge capacity the solid-electrolyte interphase (SEI) has been extensively studied in anodes of a Li-ion battery cell. There is, however, few of investigation for cathodes. Using first-principles based calculations we describe atomic-level process of the SEI layer formation at the interface of a carbonate electrolyte and $LiMn_2O_4$ spinel cathode. Furthermore, using beyond the conventional density functional theory (DFT+U) calculations we examine the work function of the cathode and frontier orbitals of the electrolyte. Based on the results we propose that proton transfer at the interface is an essential mechanism initiating the SEI layer formation in the $LiMn_2O_4$. Our results can guide a design concept for stable and high capacity Li-ion battery cell through screening an optimum electrolyte fine-tuned energy band alignment for a given cathode.

• 전기화학회지
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• 제17권3호
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• pp.156-163
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• 2014

본 연구에서는 불소계 실란을 첨가제로 사용하여 전해액의 열화 반응을 억제함으로써 리튬이온전지의 싸이클 특성을 향상시키고자 하였다. 첨가제로 사용된 trifluoropropyltrimethoxysilane은 리튬염과 카보네이트계 유기 용매로 이루어진 액체 전해질보다 전기화학적 산화, 환원 분해반응이 먼저 일어나 음극 및 양극 표면에서 안정적인 고체전해질계면 (solid electrolyte interphase, SEI) 막을 형성하며, 5 wt.%의 첨가제를 포함하는 경우 가장 우수한 전기화학적 특성을 나타내었다. SEM 및 XPS 분석을 통해 전극 표면에 생성된 피막의 화학 성분을 분석하였으며, 이들 결과로부터 새로운 SEI 형성 첨가제로서 불소계 실란의 가능성을 확인하였다.

• Journal of Electrical Engineering and Technology
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• 제10권3호
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• pp.1102-1106
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• 2015

A hybrid supercapacitor (HS) is an energy storage device used to enhance the low weight energy density (Wh/kg) of a supercapacitor. On the other hand, a sudden decrease in capacity has been pointed out as a reliability problem after many charge/discharge cycles. The reliability problem of a HS affects the early aging process. In this study, the capacity performance of a HS was observed after charge/discharge. For detailed analysis of the initial charge/discharge cycles, the charge and discharge curve was measured at a low current density. In addition, a solid electrolyte interphase (SEI) layer was confirmed after the charge/discharge. A HC composed of a lithium titanate (LTO) anode and active carbon cathode was used. The charge/discharge efficiency of the first cycle was lower than the late cycles and the charge/discharge rate was also lower. This behavior was induced by SEI layer formation, which consumed Li ions in the LTO lattice. The formation of a SEI layer after the charge/discharge cycles was confirmed using a range of analysis techniques.

• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.105-108
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• 2011

The cycling behavior of $Li_4Ti_5O_{12}$ electrode in the ionic liquid (IL)-based electrolytes containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide and a small amount of additive (vinylene carbonate, ethylene carbonate, fluoroethylene carbonate) was investigated. The $Li_4Ti_5O_{12}$ electrode in the IL electrolyte with an additive exhibited reversible cycling behavior with good capacity retention. Electrochemical impedance spectroscopy and FTIR studies revealed that an electrochemically stable solid electrolyte interphase was formed on the $Li_4Ti_5O_{12}$ electrode in the presence of vinylene carbonate and ethylene carbonate during cycling.

• Journal of Electrochemical Science and Technology
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• 제10권1호
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• pp.55-60
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• 2019

Herein, the effect of counter anions on the formation of a solid electrolyte interphase (SEI) in a propylene carbonate (PC)-based electrolyte solution was investigated. Although the reversible capacities were different, reversible intercalation and de-intercalation of lithium ions occurred in the graphite negative electrode in the PC-based electrolyte solutions containing 1 M $LiClO_4$, $LiPF_6$, $LiBF_4$, and $LiCF_3SO_3$ at low temperature ($-15^{\circ}C$). This indicated that the surface films acted as an effective SEI to suppress further co-intercalation and decomposition reactions at low temperature. However, the SEIs formed at the low temperature were unstable in 1 M $LiPF_6$ and $LiBF_4/PC$ at room temperature ($25^{\circ}C$). On the other hand, increasing reversible capacity was confirmed in the case of $LiCF_3SO_3/PC$ at room temperature, because the SEI formed at the low temperature was still maintained. These results suggest that counter anions are an important factor to consider for the formation of effective SEIs in PC-based electrolyte solutions.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2016년도 추계학술대회 논문집
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• pp.97-97
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• 2016

Development of advanced Li-ion battery cells with high durability is critical for safe operation, especially in applications to electric vehicles and portable electronic devices. Understanding fundamental mechanism on the formation of a solid-electrolyte interphase (SEI) layer, which plays a substantial role in the electrochemical stability of the Li-ion battery, in a cathode was rarely reported unlike in an anode. Using first-principles density functional theory (DFT) calculations and ab-initio molecular dynamic (AIMD) simulations we demonstrate atomic-level process on the generation of the SEI layer at the interface of a carbonate-based electrolyte and a spinel $LiMn_2O_4$ cathode. To accomplish the object we calculate the energy band alignment between the work function of the cathode and frontier orbitals of the electrolyte. We figure out that a proton abstraction from the carbonate-based electrolyte is a critical step for the initiation of an SEI layer formation. Our results can provide a design concept for stable Li-ion batteries by optimizing electrolytes to form proper SEI layers.

• Journal of Electrochemical Science and Technology
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• 제14권4호
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• pp.369-376
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• 2023

The quick-charging performance of SiO electrodes is evaluated with a focus on solid electrolyte interphase (SEI)-reinforcing effects. The study reveals that the incorporation of fluoroethylene carbonate (FEC) into the SiO electrode significantly reduced the electrode fatigue, which is from the the viscoelastic properties of the FEC-derived SEI film. The impact of FEC is attributed to its ability to minimize the mechanical failure of the electrode caused by additional electrolyte decomposition. This beneficial outcome arises from volumetric stain-tolerant characteristics of the FEC-derived SEI film, which limited exposure of the bare SiO surface during 0.5 C-rate cycling. Notably, FEC greatly improves Li deposition during quick-charge cycles following aging at 0.5 C-rate cycling due to its ability to maintain a strong electrical connection between active materials and the current collector, even after extended cycling. Given these findings, we assert that mitigating SEI layer deterioration, which compromises the electrode structure, is vital. Hence, enhancing the interfacial attributes of the SiO electrode becomes crucial for maintaining kinetic efficiency of battery system.

• 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.

• Bulletin of the Korean Chemical Society
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• 제30권4호
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• pp.783-786
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• 2009

Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and ion chromatography(IC) were employed to analyze the thermal behavior of $Li_xCoO_2$ cathode material of lithium ion battery. The mass loss peaks appearing between 60 and 125 ${^{\circ}C}$ in TGA and the exothermic peaks with 4.9 and 7.0 J/g in DSC around 75 and 85 ${^{\circ}C}$ for the $Li_xCoO_2$ cathodes of 4.20 and 4.35 V cells are explained based on disruption of solid electrolyte interphase (SEI) film. Low temperature induced HF formation through weak interaction between organic electrolyte and LiF is supposed to cause carbonate film disruption reaction, $Li_2CO_3\;+\;2HF{\rightarrow}\;2LiF\;+\;CO_2\;+\;H_2O$. The different spectral DSC/TGA pattern for the cathode of 4.5 V cell has also been explained. Presence of ionic carbonate in the cathode has been identified by ion chromatography and LiF reported by early researchers has been used for explaining the film SEI disruption process. The absence of mass loss peak for the cathode washed with dimethyl carbonate (DMC) implies ionic nature of the film. The thermal behavior above 150 ${^{\circ}C}$ has also been analyzed and presented.

• 폴리머
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• 제34권4호
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• pp.357-362
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• 2010

Poly(ethyleneglycol diacrylate)(PEGDA) 혹은 2-ethylhexyl acrylate(2EHA)를 기반으로 하는 고체함 량 8~54 wt%의 젤 고분자 전해질(GPE)을 합성하여 상온 이온전도도 및 전기화학적 특성을 평가하였다. 그 결과 투명하고 균일한 젤을 형성하는 21 wt%의 PEGDA계에서 $1\times10^{-3}$ S/cm 이상의 높은 상온 이온전도도를 얻을 수 있었다. 하지만 GPE는 액체전해액에 비해 낮은 전압안정성을 보여주었는데, 고분자 합성과정에서 개시제인 AIBN 에 원인이 있음을 제안하였다. 그 결과 BPO를 개시제로 사용하여 전압안정성이 향상된 GPE를 확보할 수 있었다. 또한 음극에서 리튬이온의 삽입과 탈리가 용이하면서 환원분해전위에 안정한 계면피막이 형성되었음을 확인하였다.