• Bulletin of the Korean Chemical Society
• /
• 제35권2호
• /
• pp.466-470
• /
• 2014

In this paper, organic solvent electrolytes were prepared by a mixture of propylene carbonate (PC), dimethyl carbonate (DMC), tetraethylammonium tetrafluoroborate ($TEABF_4$)s to evaluate the ionic properties of propylene carbonate (PC)/dimethyl carbonate (DMC) mixtures as solvents for a capacitor application, in view of improving the electrochemical performances. The bulk resistance and interfacial resistance of the mixture electrolytes were investigated using an AC impedance method. The morphology of carbon-based electrodes which were contained in different electrolytes was analyzed by scanning electron microscopy (SEM) method. From the experimental results, by increasing the FEC content, capacitance of electrodes was increased, and the interfacial resistance was decreased. In particular, by a content of 2 vol % FEC in 0.2 M $TEABF_4$ PC/DMC solvent, the electrolyte showed the superior capacitance. However, when FEC content exceeds 2 vol %, the capacitance was decreased and the interfacial resistance was increased.

• Bulletin of the Korean Chemical Society
• /
• 제32권1호
• /
• pp.105-108
• /
• 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
• /
• 제8권1호
• /
• pp.53-60
• /
• 2017

Fluoroethylene carbonate (FEC) was studied as an additive for the electrolyte in lithium ion batteries with the $LiNi_{0.5}Mn_{1.5}O_4$ (LNMO) spinel cathode operating at a high potential beyond 4.7 V (vs. $Li/Li^+$). It was found that the FEC additive was electrochemically active for the $1^{st}$ charge cycle on the LNMO cathode. The presence of a large amount of FEC (more than 40 vol%) in the electrolyte caused severe side reactions with abnormally long voltage plateaus. In contrast, when the electrolyte contained less than 30 vol% FEC, the surface of the LNMO cathode was stabilized by the formation of the solid-electrolyte interphase (SEI), leading to improved cyclability. However, the resistance from the SEI limited the rate capability because of sluggish lithium transportation through the SEI and electronic insulation between the particles in the electrode.

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

• 전기화학회지
• /
• 제18권2호
• /
• pp.58-67
• /
• 2015

음극 표면에 solid electrolyte interphase (SEI)를 형성하는 전해질 첨가제인 lithium bis(oxalate) borate (LiBOB), fluoroethylene carbonate (FEC), vinylene carbonate (VC), 2-(triphenylphosphoranylidene) succinic anhydride (TPSA)를 $Li(Ni_{1/3}Co_{1/3}Mn_{1/3})O_2$ (NCM)/graphite 전지에 도입하여 고온 저장 특성을 비교하였다. 각 전지를 50%의 충전상태(stage of charge, SOC)에서, 고온 저장($60^{\circ}C$, 20일) 시킨 이후의 용량 유지율을 확인한 결과, LiBOB 1 wt.%가 가장 우수한 용량 유지 특성(초기 방전용량 대비 86.7%)을 나타내었다. LiBOB 1 wt.%의 경우 고온 저장 전후의 전지 저항 증가 및 SEI 두께 변화가 가장 적었고, 이는 음극 SEI에 포함된 다량의 semi-carbonate 물질과 연관성이 높다고 판단된다. 또한, LiBOB 1 wt.%가 포함된 NCM/graphite 전지의 상온($25^{\circ}C$) 및 고온수명($60^{\circ}C$) 특성도 기준 전해액(1.15 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate/ethyl methyl carbonate (EC/EMC, 3/7 by volume))보다 각각 6%와 9% 향상된 결과를 보여주었다. 따라서, LiBOB이 상온 성능을 동등 이상으로 유지하면서도 고온 특성을 개선할 수 있는 우수한 전해액 첨가제로 판단된다.

• Bulletin of the Korean Chemical Society
• /
• 제34권6호
• /
• pp.1795-1799
• /
• 2013

The corrosion property of aluminum by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt is investigated in liquid and gel electrolytes consisting of ethylene carbonate/propylene carbonate/ethylmethyl carbonate/diethyl carbonate (20:5:55:20, vol %) with vinylene carbonate (2 wt %) and fluoroethylene carbonate (5 wt %) using conductivity measurement, cyclic voltammetry, scanning electron microscopy, and energy dispersive X-ray spectroscopy. All corrosion behaviors are attenuated remarkably by using three gel electrolytes containing 3 wt % of hydrophilic and hydrophobic fumed silica. The addition of silica particles contributes to the increase in the ionic conductivity of the electrolyte, indicating temporarily formed physical crosslinking among the silica particles to produce a gel state. Cyclic voltammetry also gives lower anodic current responses at higher potentials for repeating cycles, confirming further corrosion attenuation or electrochemical stability. In addition, the degree of corrosion attenuation can be affected mainly by the electrolytic constituents, not by the hydrophilicity or hydrophobicity of silica particles.

• 전기화학회지
• /
• 제17권1호
• /
• pp.49-56
• /
• 2014

탄소가 코팅된 일산화규소(C-coated SiO) 전극에서 전해질 첨가제로서 lithium bis(oxalato)borate(LiBOB)의 영향을 조사하였다. 전해질 조성은 1.3M $LiPF_6$/ethylene carbonate (EC), fluoroethylene carbonate (FEC), diethyl carbonate (DEC) (5:25:70 v/v/v)이며, 여기에 LiBOB을 0.5 wt.% 첨가한 것과 첨가하지 않은 2가지 전해질을 사용하였다. LiBOB을 첨가하지 않은 전해질에서 C-coated SiO 전극은 초기에 저항이 작은 피막이 형성되어 결정질의 $Li_{15}Si_4$를 형성할 때까지 합금화가 진행되며 동시에 큰 부피 변화를 보였다. 따라서 입자의 균열이 발생하고, 전극의 저항이 증가하여 충방전이 진행됨에 따라 용량이 빠르게 감소하였다. 반면에 LiBOB이 첨가된 전해질에서는 초기에 LiBOB의 환원분해에 의해 저항이 큰 피막이 형성되어, 합금화 반응이 원활히 진행되지 못하였다. 따라서 결정질 $Li_{15}Si_4$도 생성되지 못하였고, 결과적으로 부피변화도 적게 발생하므로 입자의 균열과 전극 저항의 증가도 적게 나타났다. 이러한 효과로 싸이클 후반부에서 용량감소가 적었고, 싸이클 성능도 좋은 결과를 보였다. 반면 피막 저항에 의한 영향이 줄어드는 $45^{\circ}C$ 에서는 LiBOB 첨가에 관계없이 합금화 반응이 유사하게 진행되며 비슷한 싸이클 성능을 나타내었다.

• Journal of Electrochemical Science and Technology
• /
• 제5권4호
• /
• pp.95-104
• /
• 2014

Electrochemical performance of Li-ion cells with $LiMn_2O_4$ cathodes and graphite anodes with carbonates electrolytes containing quaternary ammonium-based room temperature ionic liquids (ILs) is investigated. Eight different ILs based on tetraalkylammonium, pyrrolidinium or piperidinium cations paired with bis(trifluoromethylsulfonyl)imide or tris(pentafluoroethyl)trifluorophosphate anions are examined in combination with dimethyl carbonate as a main solvent and fluoroethylene carbonate as a solid electrolyte interface forming agent. It is shown that cycling properties of the cells are strongly affected by the content of ILs in the electrolyte mixtures and its increase corresponds to lower discharge capacity retention. Since viscosity and conductivity of ILs are of a great importance for the electrolytes formulation, some kind of combined parameter should be used for the assessment of IL applicability and calculated values of Walden products for neat ILs represent one of the possible options. Besides, positive effect of ILs on reduction of flammability and enhancement of thermal stability of electrolytes in contact with charged electrodes have been demonstrated by means of self-extinguishing time test and differential scanning calorimetry respectively.

• 전기화학회지
• /
• 제15권1호
• /
• pp.19-26
• /
• 2012

표준 전해액에 2중량%의 VC(vinylene carbonate)와 FEC(fluoroethylene carbonate)를 각각 첨가한 전해액으로부터 흑연 음극 표면에 SEI(solid electrolyte interphase) 층을 형성시키고, SEI 특성에 따른 흑연 음극의 저온($-30^{\circ}C$) 충방전 특성을 조사하였다. 흑연의 충 방전 용량은 FEC를 첨가한 전해액, 표준 전해액, 그리고 VC를 첨가한 전해액의 순서로 감소하였고, 충 방시 발생하는 과전압은 반대경향을 보이며 증가하였다. 이는 첨가제의 종류에 따라 생성된 SEI 층의 저항과 전하전달저항에 차이가 있음을 설명하는데, 이를 SEI 층의 화학 조성과 두께를 비교하여 확인하였다. 표준 전해액으로부터 생성된 SEI 층은 C-O 성분을 포함하는 고분자 형태의 화합물과 리튬 염의 환원분해로 생성된 $Li_xPF_yO_z$ 등으로 구성되었다. VC를 포함한 전해액으로부터 생성된 SEI 층은 C-O 화합물 비율이 높고 조밀하여 리튬 염의 분해가 억제되어 얇은 피막이 생성됨에도 불구하고 가장 큰 저항 값을 보였다. 반면에 FEC로부터 생성된 SEI 층은 C-O 성분의 비율이 VC를 첨가한 전해액의 경우보다는 작으면서도 리튬 염의 분해가 크지 않아서, 리튬 이온의 이동이 가장 용이한 피막을 형성하고 있어 가장 낮은 피막저항 및 전하전달 저항을 나타내었다. 결론적으로 FEC를 첨가제로 사용한 경우 생성된 SEI 층의 저항이 가장 작아서 흑연 음극의 저온특성이 가장 우수하였다.

• Journal of Electrochemical Science and Technology
• /
• 제13권1호
• /
• pp.78-89
• /
• 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.