• Journal of Surface Science and Engineering
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• v.57 no.2
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• pp.115-124
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• 2024

In advancing Li-ion battery (LIB) technology, the solid electrolyte interface (SEI) layer is critical for enhancing battery longevity and performance. Formed during the charging process, the SEI layer is essential for controlling ion transport and maintaining electrode stability. This research provides a detailed analysis of how vinylene carbonate (VC) influences SEI layer formation. The integration of VC into the electrolyte markedly improved SEI properties. Moreover, correlation analysis revealed a connection between electrolyte decomposition and battery degradation, linked to the EMC esterification and dicarboxylate formation processes. VC facilitated the formation of a more uniform and chemically stable SEI layer enriched with poly(VC), thereby enhancing mechanical resilience and electrochemical stability. These findings deepen our understanding of the role of electrolyte additives in SEI formation, offering a promising strategy to improve the efficiency and lifespan of LIBs.

• 한국전기화학회:학술대회논문집
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• 2000.10a
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• pp.27-27
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• 2000

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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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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• v.10 no.1
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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.

• Proceedings of the KAIS Fall Conference
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• 2007.11a
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• pp.356-358
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• 2007

본 논문에서는 농도가 다른 EC계의 전해질 용액 중에서 흑연의 Cyclic voltammetry(CV)를 측정하였다. CV후 전극표면에 생성된 SEI를 투과형 전자현미경으로 분석한 결과, PC계에서 얻어지는 결과와 유사하게 충 방전 반응 및 생성된 SEI의 성질이 전해질의 농도에 크게 의존하고 있음을 확인하였다.

• 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 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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• v.34 no.2
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• pp.384-388
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• 2013

Fluorine-doping on the $Li_{1+x}Mn_{1.9-x}Al_{0.1}O_4$ spinel cathode materials is found to alter crystal shape, and enhance initial interfacial reactivity and solid electrolyte interphase (SEI) formation, leading to improved initial coulombic efficiency in the voltage region of 3.3-4.3 V vs. Li/$Li^+$ in the room temperature electrolyte of 1 M $LiPF_6$/EC:EMC. SEM imaging reveals that the facetting on higher surface energy plane of (101) is additionally developed at the edges of an octahedron that is predominantly grown with the most thermodynamically stable (111) plane, which enhances interfacial reactivity. Fluorine-doping also increases the amount of interfacially reactive $Mn^{3+}$ on both bulk and surface for charge neutrality. Enhanced interfacial reactivity by fluorine-doping attributes instant formation of a stable SEI layer and improved initial cyclic efficiency. The data contribute to a basic understanding of the impacts of composition on material properties and cycling behavior of spinel-based cathode materials for lithium-ion batteries.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2017.05a
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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.

• 한국전기화학회:학술대회논문집
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• 2000.10a
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• pp.3-3
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• 2000

• Journal of the Korean Electrochemical Society
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• v.19 no.3
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• pp.69-79
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• 2016

Lithium ion battery with high energy density is expanding its application area to electric automobile and electricity storage field beyond existing portable electric devices. Such expansion of an application field is demanding higher characteristic and stable long life characteristic of an anode material, the natural graphite that became commercialized in lithium ion battery. This thesis produced cathode by using natural graphite anode material, analyzed creation of the cathode SEI film created due to initial reaction by using electrolyte additives, VC (vinylene carbonate), VEC (vinyl ethylene carbonate), and FEC (fluoroethylene carbonate), and considered correlation with the accompanying electrochemical transformation. This study compared and analyzed the SEI film variation of natural graphite cathode according to the electrolyte additive with SEI that is formed at the time of initial filling and cathode of $60^{\circ}C$ life characteristic. At the time of initial filling, the profile showed changes due to the SEI formation, and SEI was formed in No-Additive in approximately 0.9 V through EVS, but for VC, VEC, and FEC, the formation reaction was created above 1 V. In $60^{\circ}C$ lifespan characteristic evaluation, the initial efficiency was highest in No-Additive and showed high contents percentage, but when cycle was progressed, the capacity maintenance rate decreased more than VC and FEC as the capacity and efficiency at the time of filling decreased, and VEC showed lowest performance in efficiency and capacity maintenance rate. Changes of SEI could not be verified through SEM, but it was identified that as the cycle of SEI ingredients was progressed through FT-IR, ingredients of Alkyl carbonate ($RCO_2Li$) affiliation of the $2850-2900cm^{-1}$ was maintained more solidly and the resistance increased as cycle was progressed through EIS, and specially, it was identified that the resistance due to No-Additive and SEI of VEC became very significant. Continuous loss of additives was verified through GC-MS, and the loss of additives from partial decomposition and remodeling of SEI formed the non-uniform surface of SEI and is judged to be the increase of resistance.