• Ceramist
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• v.22 no.4
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• pp.381-392
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• 2019

Recently, demands for lithium-ion batteries (LIB) in various fields are increasing. In particular, understanding of the reaction mechanism occurring at the electrode-electrolyte surface/interface is significant for the development of advanced LIBs. Meanwhile, research and development of LIBs highly requires a new specific characterization approach. For example, atomic force microscopy (AFM) has been utilized to the LIB research field for various purposes such as investigation of topography, electrochemical reactions, ion transport phenomena, and measurement of surface potential at high resolution. Advances in the AFM analysis have made it possible to inspect various material properties such as surface friction and Young's modulus. Therefore, this technique is expected to be a powerful method in the LIB research field. Here, we review and discuss ways to apply AFM to LIB studies.

• Journal of Electrochemical Science and Technology
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• v.12 no.4
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• pp.424-430
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• 2021

The element iron (Fe) is affordable and abundantly available, and thus, it finds use in a wide range of applications. As regards its application in rechargeable lithium-ion batteries (LIBs), the electrochemical reactions of Fe must be clearly understood during battery charging and discharging with the LIB electrolyte. In this study, we conducted systematic electrochemical analyses under various voltage conditions to determine the voltage at which Fe corrosion begins in general lithium salts and organic solvents used in LIBs. During cyclic voltammetry (CV) experiments, we observed a large corrosion current above 4.0 V (vs. Li/Li⁺). When a constant voltage of 3.7 V (vs. Li/Li⁺), was applied, the current did not increase significantly at the beginning, similar to the CV scenario; on the other hand, at a voltage of 3.8 V (vs. Li/Li⁺), the current increased rapidly. The impact of this difference was visually confirmed via scanning electron microscopy and optical microscopy. Our X-ray photoelectron spectroscopy measurements showed that at 3.7 V, a thick organic solid electrolyte interphase (SEI) was formed atop a thin fluoride SEI, which means that at ≥3.8 V, the SEI cannot prevent Fe corrosion. This result confirms that Fe corrosion begins at 3.7 V, beyond which Fe is easily corrodible.

• Applied Chemistry for Engineering
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• v.17 no.2
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• pp.183-187
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• 2006

The choice of solvents for electrolytes solutions is very important to improve the characteristics of charge/discharge in the Li-ion battery system. Such solvent systems have been widely investigated as electrolytes for Li-ion batteries. In this paper, the electrochemical properties of the solid electrolyte interphase film formed on carbon anode surface and the solvent decomposition voltage in 1 M LiPF6/EC:MA(x:y) electrolyte solutions prepared from the various mixing volume ratios are investigated by chronopotentiometry, cyclic voltammetry, and impedance spectroscopy. As a result, the solvent decomposition voltages are varied with the ionic conductivity of the electrolyte. Electrochemical properties of the passivation film were different, which are dependent on the mixture ratio of the solvents. Therefore, the most appropriate mixing ratio of EC and MA as a solvent in 1 M $LiPF_6/(EC+MA)$ system for Li-ion battery is approximately 1:3 (EC:MA, volume ratio).

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2029-2035
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• 2013

The impact of phosphorous (P)-doping on the electrochemical performance and surface chemistry of soft carbon is investigated by means of galvanostatic cycling and ex situ X-ray photoelectron spectroscopy (XPS). P-doping plays an important role in storing more Li ions and discernibly improves reversible capacity. However, the discharge capacity retention of P-doped soft carbon electrodes deteriorated at $60^{\circ}C$ compared to non-doped soft carbon. This poor capacity retention could be improved by vinylene carbonate (VC) participating in forming a protective interfacial chemistry on soft carbon. In addition, the effect of P-doping on exothermic thermal reactions of lithiated soft carbon with electrolyte solution is discussed on the basis of differential scanning calorimetry (DSC) results.

• Journal of Electrochemical Science and Technology
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• v.13 no.1
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• pp.78-89
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• 2022

ANODE-free Li-metal batteries (AFLMBs) operating with Li of cathode material have attracted enormous attention due to their exceptional energy density originating from anode-free structure in the confined cell volume. However, uncontrolled dendritic growth of lithium on a copper current collector can limit its practical application as it causes fatal issues for stable cycling such as dead Li formation, unstable solid electrolyte interphase, electrolyte exhaustion, and internal short-circuit. To overcome this limitation, here, we report a novel dual-salt electrolyte comprising of 0.2 M LiPF₆ + 3.8 M lithium bis(fluorosulfonyl)imide in a carbonate/ester co-solvent with 5 wt% fluoroethylene carbonate, 2 wt% vinylene carbonate, and 0.2 wt% LiNO₃ additives. Because the dual-salt electrolyte facilitates uniform/dense Li deposition on the current collector and can form robust/ionic conductive LiF-based SEI layer on the deposited Li, a Li/Li symmetrical cell exhibits improved cycling performance and low polarization for over 200 h operation. Furthermore, the anode-free LiFePO₄/Cu cells in the carbonate electrolyte shows significantly enhanced cycling stability compared to the counterparts consisting of different salt ratios. This study shows an importance of electrolyte design guiding uniform Li deposition and forming stable SEI layer for AFLMBs.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2519-2526
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• 2010

Silane-based self-assembly was employed for the surface modification of carbon-coated Si electrodes and their surface chemistry and electrochemical performance in battery electrolyte depending on the molecular structure of silanes was studied. IR spectroscopic analyses revealed that siloxane formed from silane-based self-assembly possessed Si-O-Si network on the electrode surface and high surface coverage siloxane induced the formation of a stable solid-electrolyte interphase (SEI) layer that was mainly composed of organic compounds with alkyl and carboxylate metal salt functionalities, and PF-containing inorganic species. Scanning electron microscopy imaging showed that particle cracking were effectively reduced on the carbon-coated Si when having high coverage siloxane and thickened SEI layer, delivering > 1480 mAh/g over 200 cycles with enhanced capacity retention 74% of the maximum discharge capacity, in contrast to a rapid capacity fade with low coverage siloxane.

• Journal of Applied Reliability
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• v.13 no.2
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• pp.129-140
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• 2013

As a fundamental experimental study for reliability improvement of lithium ion secondary battery, degradation mechanism was investigated by microscopic observation and acoustic emission monitoring. Microstructural observation of the decomposed battery after cycle test revealed mechanical and chemical damages such as interface delamination, microcrack of the electrodes, and solid electrolyte interphase (SEI). Acoustic emission (AE) signal was detected during charge and discharge of lithium ion battery to investigate relationships among cumulative count, discharge capacity, and microdamages. With increasing number of cycle, discharge capacity was decreased and AE cumulative count was observed to increase. Observed damages were attributed to sources of the detected AE signals.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.137-137
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• 2018

이 연구에서는 리튬이온전지용 음극 활물질의 리튬이온 저장 용량을 최적화시키기 위한 새로운 방법이 제안되었다. 그 방법은 솔루션 플라즈마 프로세스를 사용하여 원자 단위의 리튬을 탄소 기반 물질의 내부에 도핑 시키고, 열처리를 통해 그 내부를 재설계하는 것이다. 리튬이온전지용 음극 활물질로 리튬금속 자체를 사용하려는 시도는 있었으나, 이는 충전 및 방전 사이클이 반복됨에 따라 리튬이 수지상으로 석출되어 내부를 단락시키거나, 리튬금속 자체의 폭발성에 의한 취급상의 제약이 있었다. 한편, 원자 단위로 탄소 내부에 도핑 된 리튬은 열처리 과정 동안 탄소 내부에서 확산함으로써 더 많은 리튬이 저장될 수 있는 공간을 만들었고, 사이클이 반복됨에 따라 서서히 충전 및 방전 반응에 참여함으로써 전지의 성능을 개선시켰다. 리튬이 도핑 된 탄소의 전기화학적 테스트 결과를 Fig. 1에 나타내었다. 실험 결과에서 보여진 초기 고용량 및 장기 사이클 특성은 탄소 내부에 도핑 된 리튬이 전지 성능의 향상에 중요한 역할을 한다는 것을 시사한다. 또한, 사이클이 반복됨에 따라 점차 증가하는 용량은 첫 사이클에서 형성된 solid electrolyte interphase의 비가역 용량을 보상할 수 있을 것으로 생각된다. 이상의 결과를 통해, 탄소 내부에 원자단위의 리튬을 도핑시키는 새로운 접근은 리튬이온전지의 성능 개선을 위한 효과적인 방법이 될 수 있을 것으로 보이며, 향후 리튬 이외의 다른 원소들, 즉 소듐과 같은 물질에 대하여 도핑을 시도한다면 새로운 분야에서 이와 같은 접근법이 유용하게 적용될 수 있을 것으로 사료된다.

• Journal of the Korean Electrochemical Society
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• v.16 no.3
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• pp.169-176
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• 2013

Solid state lithium oxide compounds of layered structure, which has high stability of structure, are mainly used as the cathode materials in lithium-ion batteries (LIBs). Recently, the investigation of Solid Electrolyte Interphase (SEI) between active materials and electrolyte has been focusing to improve the performance of lithium-ion batteries. For the investigation of the SEI, the study of surface properties of cathode materials and anode materials is also required in advance. $LiNiO_2$ and $LiCoO_2$ are very similar layered structure of cathode active materials and representative solid state lithium oxide compounds in LIBs. Various experimental and theoretical studies have been doing for $LiCoO_2$. The theoretical investigation of $LiNiO_2$ is not sufficient, however, even if experimental studies of $LiNiO_2$ are enough. In this study, the surface energies of nine facets of $LiNiO_2$ crystal facets were calculated by Density Functional Theory. In XRD data of $LiNiO_2$, (003), (104), (101), et al. facets are main surfaces in order. However, the results of calculation are different with XRD data. Thus, both (104) and (101) facets, which are energetically stable and measured in XRD, are mainly exposed in the surface of $LiNiO_2$ and it is expected that intercalation and de-intercalation of Li-ion will be affected by them.

• 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.