• 한국표면공학회지
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• 제57권2호
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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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• 한국전기화학회 2000년도 추계총회 및 학술발표회
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• pp.27-27
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• 2000

• 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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• 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.

• 한국산학기술학회:학술대회논문집
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• 한국산학기술학회 2007년도 추계학술발표논문집
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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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• 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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• 제34권2호
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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.

• 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.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2000년도 추계총회 및 학술발표회
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• pp.3-3
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• 2000

• 전기화학회지
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• 제19권3호
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• pp.69-79
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• 2016

높은 에너지 밀도를 지닌 리튬 이온 전지는 현재 리튬 이온 전지에 상용화된 음극 활물질인 천연 흑연의 보다 높은 율 별 특성과 안정한 장수 명 특성을 요구하고 있다. 천연 흑연계 음극 활물질을 이용하여 리튬 전지 음극을 제작하여, SEI 피막의 형성 및 제어의 대표적인 전해질 첨가제인 VC (vinylene carbonate), VEC (vinyl ethylene carbonate), FEC (fluoroethylene carbonate)등의 다양한 첨가제를 사용하여 초기 반응에 의해 생성되는 SEI 피막을 분석하고 이에 따른 전기 화학 특성 변화를 측정하기 위하여 SEM, EVS (electorochemical voltage spectroscopy), 피막 분석, EIS (electrochemical impedance spectroscopy), FT-IR (Fourier transform infrared spectroscopy)등을 측정하여, 고온 수명 평가, 용량 유지율 및 성능 평가를 실시하여, $0^{\circ}C$ 수명특성 이후의 음극에 대한 분석을 비교 및 분석 평가 하였다. 초기 충전 시 profile에서 SEI의 형성에 의한 변화를 나타냈으며, EVS를 통하여 No-Additive가 약 0.9 V에서 SEI의 형성이 이루어지지만, VC, VEC, FEC의 경우 1 V 이상에서 형성반응이 이루어졌다. $60^{\circ}C$ 수명특성평가에서 초기 효율은 No-Additive가 가장 높게 나타나며 용량 유지율이 높게 나타났으나, cycle이 진행 될수록 충전 시 용량과 효율이 감소하여 VC, FEC보다 용량 유지율이 낮아졌고, VEC는 효율 및 용량 유지율 모두 성능이 가장 낮게 나타났다. SEM을 통하여 SEI의 변화를 확인할 수 없었지만, FT-IR을 통하여 SEI의 성분이 cycle이 진행이 될수록 첨가제에 의해 $2850-2900cm^{-1}$영역의 Alkyl carbonate ($RCO_2Li$) 계열의 성분이 더욱 견고하게 유지되는 것을 확인하였으며, EIS를 통하여 cycle이 진행될수록 저항은 증가하는 것으로 나타났고, 특히 No-Additive 및 VEC의 SEI에 의한 저항이 매우 커졌다는 것을 알 수 있었다.