• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.466-470
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• 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
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• v.32 no.1
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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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• v.8 no.1
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• pp.53-60
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• 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
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• v.14 no.4
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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 the Korean Electrochemical Society
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• v.18 no.2
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• pp.58-67
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• 2015

The effects of electrolyte additives, lithium bis(oxalate)borate (LiBOB), fluoroethylene carbonate (FEC), vinylene carbonate (VC), 2-(triphenylphosphoranylidene) succinic anhydride (TPSA), on high-temperature storage properties of $Li(Ni_{1/3}Co_{1/3}Mn_{1/3})O_2$/graphite are investigated with coin-type full cells. The 1 wt.% LiBOB-containing electrolyte showed the highest capacity retention after high temperature ($60^{\circ}C$) storage for 20 days, 86.7%, which is about 5% higher than the reference electrolyte, 1.15M lithium hexafluorophosphate ($LiPF_6$) in ethylene carbonate/ethyl methyl carbonate (EC/EMC, 3/7 by volume). This enhancement is closely related to the formation of semi-carbonate compounds originated from $BOB^-$ anions, thereby resulting in lower SEI thickness and interfacial resistance after storage. In addition, the 1 wt.% LiBOB-containing electrolyte also exhibited better cycle performance at 25 and $60^{\circ}C$ than the reference electrolyte, which indicates that LiBOB is an effective additive for high-temperature performance of $Li(Ni_{1/3}Co_{1/3}Mn_{1/3})O_2$/graphite chemistry.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1795-1799
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• 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.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.49-56
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• 2014

As an electrolyte additive, the effects of lithium bis(oxalate)borate (LiBOB) on the electrochemical properties of a carbon-coated silicon monoxide (C-coated SiO) negative electrode are investigated. The used electrolyte is 1.3M $LiPF_6$ that is dissolved in ethylene carbonate (EC), fluoroethylene carbonate (FEC), and diethyl carbonate (DEC) (5:25:70 v/v/v) with or without 0.5 wt. % LiBOB. In the LiBOB-free electrolyte, the film resistance is not so high in the initial period of cycling that lithiation is facilitated to generate the crystalline $Li_{15}Si_4$ phase. Due to repeated volume change that is caused by such a deep charge/discharge, cracks form in the active material to cause a resistance increase, which eventually leads to capacity fading. When LiBOB is added into the electrolyte, however, more resistive surface film is generated by decomposition of LiBOB in the initial period. The crystalline $Li_{15}Si_4$ phase does not form, such that the volume change and crack formation are greatly mitigated. Consequently, the C-coated SiO electrode exhibits a better cycle performance in the later cycles. At an elevated temperature ($45^{\circ}C$), wherein the effect of film resistance is less critical, the alloy ($Li_{15}Si_4$ phase) formation is comparable for the LiBOB-free and added cell to give a similar cycle performance.

• Journal of Electrochemical Science and Technology
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• v.5 no.4
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• pp.95-104
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• 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.

• Journal of the Korean Electrochemical Society
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• v.15 no.1
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• pp.19-26
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• 2012

SEI (solid electrolyte interphase) layers are generated on a graphite negative electrode from three different electrolytes and low-temperature ($-30^{\circ}C$) charge/discharge performance of the graphite electrode is examined. The electrolytes are prepared by adding 2 wt% of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) into a standard electrolyte solution. The charge-discharge capacity of graphite electrode shows the following decreasing order; FEC-added one>standard>VC-added one. The polarization during a constant-current charging shows the reverse order. These observations illustrate that the SEI film resistance and charge transfer resistance differ according to the used additives. This feature has been confirmed by analyzing the chemical composition and thickness of three SEI layers. The SEI layer generated from the standard electrolyte is composed of polymeric carbon-oxygen species and the decomposition products ($Li_xPF_yO_z$) of lithium salt. The VC-derived surface film shows the largest resistance value even if the salt decomposition is not severe due to the presence of dense film comprising C-O species. The FEC-derived SEI layer shows the lowest resistance value as the C-O species are less populated and salt decomposition is not serious. In short, the FEC-added electrolyte generates the SEI layer of the smallest resistance to give the best low-temperature performance for the graphite negative electrode.

• 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.