• 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.7 no.2
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• pp.179-184
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• 2016

The interface between the surface of a cathode material and the electrolyte gives rise to surface reactions such as solid electrolyte interface (SEI) and chemical side reactions. These reactions lead to increased surface resistance and charge transfer resistance. It is consequently necessary to improve the electrochemical characteristics by suppressing these reactions. In order to suppress unnecessary surface reactions, we coated cathode material using polypropylene (PP). The PP coating layer effectively reduced the SEI film that is generated after a 4.3 V initial charging process. By mitigating the formation of the SEI film, the PP-coated Li[(Ni_0.6Co_0.1Mn_0.3)_0.36(Ni_0.80Co_0.15Al0.05)_0.64)]O₂(NCS) electrode provided enhanced transport of Li⁺ ions due to reduced SEI resistance (R_SEI) and charge transfer resistance (R_ct). The initial charge and discharge efficiency of the PP-coated NCS electrode was 96.2 % at a current density of 17 mA/g in a voltage range of 3.0 ~ 4.3 V, whereas the efficiency of the NCS electrode was only 94.7 %. The presence of the protective PP layer on the cathode improved the thermal stability by reducing the generated heat, and this was confirmed via DSC analysis by an increased exothermic peak.

• Applied Chemistry for Engineering
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• v.16 no.4
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• pp.507-512
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• 2005

When carbon electrode is used as an anode in Li ion battery, passivation film forms on the electrode surface during the initial charge process due to so called Solid-Electrolyte Interphase (SEI). The passivation film formed by solvent decomposition during the initial charge process affects charge/discharge capacity. In this paper, 1 M $LiPF_6,EC:DEC$ (1 : 1, volume ratio) electrolyte with $Li_2CO_3$, at various temperatures, the electrochemical characteristics of passivation film formed on Kawasaki Mesophase Fine Carbon electrode surface were investigated by using chronopotentiometry, cyclic voltammetry, and impedance spectroscopy. Experimental observations indicated that as solvent decomposition occurred, the decomposition voltage was strongly dependent on ionic conductivity, which was low in the process at low temperature. The impedance of passivation film formed during the initial charge process, were dependent on the temperature.

• 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 Industrial and Engineering Chemistry
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• v.67
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• pp.266-275
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• 2018

Herein, a novel operating life (OL) test method was evaluated with 200 mAh pouch-type lithium-ion batteries. By combining the calendar life (CL) test with intermediate pulse power cycling, more realistic life prediction was possible, which encompassed real operation of batteries accompanying with thermal acceleration. Larger capacity decrease and resistance increase of pouch cell were observed in the OL test, which was well explained using the SEI film growth model. After dissemble of pouch cell, capacity loss and resistance increase mostly occurred within anode, reflecting that SEI film growth on anode surface was highly attributable to cell degradation.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11b
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• pp.545-549
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• 2001

We have produced electrolyte solution out of 1.15M $LiPF_6$ EC/EMC/DEC/PC(30/55/10/5 by vol%) as a reference, and at the same time, performed basic physical property test using a single solvent of 1.15M $LiPF_6$ DEC, DMC, EMC and a 2 component electrolyte solution of 1.15M $LiPF_6$ EC/DEC(1/2 by vol%) and PC/DEC(1/2 by vol%). Cyclic Voltammetry Analysis showed that, compared to existing carbonate organic solvent, the addition of DEC,DMC and EMC brought the de-decomposition peak of salt anion of $PF_6$ and the solvent at lower oxidization potential of 2.3V, 0.7V and 2.1V(vs. $Li/Li^+$). In addition, a kinetics current peak, in which intercalation of Lt is proceeded at 750mV, 450mV(vs. $Li/Li^+$), was confirmed. These findings suggest that the DEC solvent decomposition occurred at an electric potential lower than that of oxidization of existing carbonate organic solvent. Through the impedance analysis, we checked electric charge transfer resistance($R_{ct}$) according to the electric potential of $Li^+$ intercalation at 750mV(vs. $Li/Li^+$), which was the same as the resistance ($R_f$) and cyclic voltammetry of SEI film that was formed at Reference. By doing so, we found that the significant decrease of polarization resistance($R_p$) when Reference was played a part in the formation of compact SEI layer at the initial decomposition reaction.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11a
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• pp.545-549
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• 2001

We have produced electrolyte solution out of 1.15M LiPF$\sub$6/ EC/EMC/DEC/PC(30/55/10/5 by vol%) as a reference, and at the same time, performed basic physical property test using a single solvent of 1.15M LiPF$\sub$6/DEC, DMC, EMC and a 2 component electrolyte solution of 1.15M LiPF$\sub$6/ EC/DEC(1/2 by vo%%) and PC/DEC(1/2 by vol%). Cyclic Voltammetry Analysis showed that, compared to existing carbonate organic solvent, the addition of DEC, DMC and EMC brought the de-decomposition peak of salt anion of PF$\sub$6/$\^$-/ and the solvent at lower oxidization potential of 2.3V, 0.7V and 2.1V(vs. Li/Li$\^$+/\`). In addition, a kinetics current peak, in which intercalation of Li$\^$+/ is proceeded at 750mv, 450mv(vs. Li/Li$\^$+/), was confirmed. These findings suggest that the DEC solvent decomposition occurred at an electric potential lower than that of oxidization of existing carbonate organic solvent. Through the impedance analysis, we checked electric charge transfer resistance(R$\sub$ct/) according to the electric potential of Li$\^$+/ intercalation at 750mv(vs. Li/Li$\^$+/), which was the same as the resistance (R$\sub$f/) and cyclic voltammetry of SEI film that was formed at Reference. By doing so, we found that the significant decrease of polarization resistance(R$\sub$p/) when Reference was played a part in the formation of compact SEI layer at the initial decomposition reaction.

• 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.

• Journal of the Korean Chemical Society
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• v.10 no.4
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• pp.153-157
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• 1966

The measurement of Oxidation of nickel has been investigated using vacuum quartz microbalance in the temperature range of $500^{\circ}{\sim}800^{\circ}C$ at various oxygen pressure. The rate constants of nickel-oxidation were evaluated according to the parabolic rate law. From the Arrhenius equation, the activation energy in the range of experimental temperatures were found that $E_{act}$= 35.4 Kcal/mole. It was also found that the parabolic rate constants varied approximately as the one fifth power of the oxygen pressure for nickel-oxidation. The mechanism for the oxidation of this metal were seemed to be via cation vacancy produced by excess of oxygen dissolved in the oxide film.

• Bulletin of the Korean Chemical Society
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• v.30 no.4
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• pp.783-786
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• 2009

Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and ion chromatography(IC) were employed to analyze the thermal behavior of $Li_xCoO_2$ cathode material of lithium ion battery. The mass loss peaks appearing between 60 and 125 ${^{\circ}C}$ in TGA and the exothermic peaks with 4.9 and 7.0 J/g in DSC around 75 and 85 ${^{\circ}C}$ for the $Li_xCoO_2$ cathodes of 4.20 and 4.35 V cells are explained based on disruption of solid electrolyte interphase (SEI) film. Low temperature induced HF formation through weak interaction between organic electrolyte and LiF is supposed to cause carbonate film disruption reaction, $Li_2CO_3\;+\;2HF{\rightarrow}\;2LiF\;+\;CO_2\;+\;H_2O$. The different spectral DSC/TGA pattern for the cathode of 4.5 V cell has also been explained. Presence of ionic carbonate in the cathode has been identified by ion chromatography and LiF reported by early researchers has been used for explaining the film SEI disruption process. The absence of mass loss peak for the cathode washed with dimethyl carbonate (DMC) implies ionic nature of the film. The thermal behavior above 150 ${^{\circ}C}$ has also been analyzed and presented.