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Electrochemical Studies of Lithium Ion Battery Current Collector in the Aprotic Electrolytes: I. Al Current Collector (비수용성 전해질내 리튬이온전지용 집전체의 전기화학적 특성 연구: I. Al 집전체)

  • Park, Heai-Ku
    • Applied Chemistry for Engineering
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    • v.10 no.4
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    • pp.620-627
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    • 1999
  • Electrochemical properties of the Al current collector being used in lithium ion batteries have been studied in the 4 different aprotic electrolytes(1 M $LiBF_4$ EC : DMC, 1 M $LiBF_4$ EC : EMC. 1 M $LiPF_6$ EC : DMC. 1 M $LiPF_6$ EC : EMC) employing cyclic voltammetry and impedance measurement. Al electrode showed a wide range of the electrochemical window(0.5~4.1 V vs. $Li/Li^{+}$). However, solid interfacial materials has been formed on the Al surface due to reduction of impurities($H_2O$, $O_2$, etc), lithium salts, and electrolytes at low applied potentials, and aluminum oxides in the highly oxidizing potential as well. Especially, Al current collector was susceptible to localized in consequence of impurities in electrolytes.

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Li+ and Li+I-Li+ ions Solvated by 1,4-dioxane: An ion Mobility Spectrometry-Mass Spectrometry Study

  • Choi, Yunseop;Ji, Inyong;Seo, Jongcheol
    • Mass Spectrometry Letters
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    • v.12 no.4
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    • pp.152-158
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    • 2021
  • Electrospray ionization (ESI) and ion mobility spectrometry-mass spectrometry (IMS-MS) were employed to investigate the solvated structures of ionic species in the lithium iodide electrolyte solution in the gas phase. The Li+I-Li+ triple ion and single standalone Li+ ions solvated by 1,4-dioxane were successfully generated and observed by ESI-MS under the influence of dioxane vapor at the inlet region. Under the present experimental condition, (1,4-dioxane)m·Li+ complex ions (m = 1, 2, and 3) and a (1,4-dioxane)·Li+I-Li+ complex ion were observed, which were further examined by IMS to investigate their structures. The presence of multiple structural isomers was confirmed, which accounts for the endothermic conformational transition of 1,4-dioxane from a chair to a boat to achieve bidentate O-donor binding to Li+ and Li+I-Li+. Further structural details critical for the ion-solvent interactions were also examined and discussed with the help of density functional theory calculations.

Effects of Lithium Bis(Oxalate) Borate as an Electrolyte Additive on High-Temperature Performance of Li(Ni1/3Co1/3Mn1/3)O2/Graphite Cells (LiBOB 전해액 첨가제 도입에 따른 Li(Ni1/3Co1/3Mn1/3)O2/graphite 전지의 고온특성)

  • Jeong, Jiseon;Lee, Hyewon;Lee, Hoogil;Ryou, Myung-Hyun;Lee, Yong Min
    • 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.

Electrochemical Properties of LiMn2O4-LiNi1/3Mn1/3Co1/3O2 Cathode Materials in Lithium Secondary Batteries (리튬이차전지 양극활물질용 LiMn2O4-LiNi1/3Mn1/3Co1/3O2의 전기화학적 특성)

  • Kong, Ming Zhe;Nguyen, Van Hiep;Gu, Hal-Bon
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.29 no.5
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    • pp.298-302
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    • 2016
  • In this work, $LiMn_2O_4$ and $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ cathode materials are mixed by some specific ratios to enhance the practical capacity, energy density and cycle performance of battery. At present, the most used cathode material in lithium ion batteries for EVs is spinel structure-type $LiMn_2O_4$. $LiMn_2O_4$ has advantages of high average voltage, excellent safety, environmental friendliness, and low cost. However, due to the low rechargeable capacity (120 mAh/g), it can not meet the requirement of high energy density for the EVs, resulting in limiting its development. The battery of $LiMn_2O_4-LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ (50:50 wt%) mixed cathode delivers a energy density of 483.5 mWh/g at a current rate of 1.0 C. The accumulated capacity from $1^{st}$ to 150th cycles was 18.1 Ah/g when the battery is cycled at a current rate of 1.0 C in voltage range of 3.2~4.3 V.

Electrical Characteristics of Li(Mn$_{1-}$$\delta$Nb$\delta$)$_2$O$_4$ Cathode Materials for Li-Ion Secondary Batteries (리튬 이온 이차전지 Cathode용 Li(Mn$_{1-}$$\delta$Nb$\delta$)$_2$O$_4$의 전기적 특성)

  • 오용주;유광수
    • Journal of the Korean Ceramic Society
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    • v.35 no.9
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    • pp.995-1001
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    • 1998
  • As a basic study for cathode materials of {{{{ { {LiMn }_{2 }O }_{4 } }}-based lithium-ion secondary batteries Li({{{{ { { { {Mn }_{1-$\delta$ }Nb }_{$\delta$} )}_{2 }O }_{4 } }} ($\delta$=0.05, 0.1, 0.2) materials which Nb is substituted for Mn were synthesized by the solid state reaction at 80$0^{\circ}C$ and 110$0^{\circ}C$ respectively. The second phase {{{{ { LiNbO}_{3 } }} appeared above $\delta$=0.1 As the result of im-pedance analysis as the amount of substituted Nb increased the resistivity of grain boundary increased greatly. Compared to undoped-{{{{ { {LiMn }_{2 }O }_{4 } }} the electrical conductivity of Li({{{{ { { { {Mn }_{1-$\delta$ }Nb }_{$\delta$} )}_{2 }O }_{4 } }} decreased slightly but is charging capacity and potential plateau increased.

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Electrochemical Characteristics of $LiMn_{2}O_{4}$/Lithium Cells in Organic Electrolyte (유기전해액 $LiMn_{2}O_{4}$/Lithium 전지의 전기화학적 특성)

  • 임정환;도칠훈;문성인;윤문수
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2000.11a
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    • pp.371-374
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    • 2000
  • The electrochemical properties of LiM $n_2$ $O_4$as a cathode and an anode for the lithium secondary battery were evaluated. When LiM $n_2$ $O_4$ material was used as the cathode with the current collector of aluminum, the 1st specific capacity and the 1st Ah efficiency in LiM $n_2$ $O_4$/lithium cell were 123 mAh/g and 91.7%, respectively The anodic properties of LiM $n_2$ $O_4$ material was also evaluated in the LiM $n_2$ $O_4$/1ithium cell with the current collector of copper. It showed that the LiM $n_2$ $O_4$ was useful as the anode for the lithium secondary battery. During the 1st discharge, a potential plateau was observed at the potential of 0.3 $V_{Li}$ Li+/. The 1st specific charge capacity and the 1st specific discharge capacity were 790 mAh/s and 362 mAh/g, respectively. Therefore, the 1st Ah efficiency was 46%. The discharge capacity was gradually faded with the charge-discharge cycling to about 50th cycles. Thereafter, the discharge capacity was stabilized to about 110 mAh/g.

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A Study on Electrochemical Characteristics of LiCoO2/LiNi1/3Mn1/3Co1/3O2 Mixed Cathode for Li Secondary Battery (리튬2차전지용 LiCoO2/LiNi1/3Mn1/3Co1/3O2계 복합정극의 전기화학적 특성 연구)

  • Kim Hyun-Soo;Kim Sung-Il;Eom Seung-Wook;Kim Woo-Seong
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.19 no.1
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    • pp.64-70
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    • 2006
  • In this study, the $LiCoO_2/LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ mixed cathode electrodes were prepared and their electrochemical performances were measured in a high cut-off voltage. As the content of $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ increased in a mixed cathode, the reversible specific capacity and cycleability of the electrode enhanced, but the rate capability was deteriorated. On the contrary the rate capability of the cathode enhanced, but the reversible specific capacity and cycleability were deteriorated, increasing the content of $LiCoO_2$ in the mixed cathode. The cell of $LiCoO_2/LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ ($50:50 wt\%$) mixed cathode delivered a discharge capacity of ca. 168 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca. 152 mAh/g was obtained at a 2.0 C rate. However, the cell showed very stable cycleability: the discharge capacity of the cell after 20th charge/discharge cycling maintains ca. 163 mAh/g.

Single-Crystal Structure of |Li50Na25|[Si117Al75O384]-FAU

  • Kim, Hu Sik;Suh, Jeong Min;Kang, Jum Soon;Lim, Woo Taik
    • Journal of the Korean Chemical Society
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    • v.57 no.1
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    • pp.12-19
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    • 2013
  • The single-crystal structure of fully dehydrated partially $Li^+$-exchanged zeolite Y, ${\mid}Li_{50}Na_{25}{\mid}[Si_{117}Al_{75}O_{384}]$-FAU, was determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 100(1) K. Ion exchange was accomplished by flowing stream of 0.1 M aqueous $LiNO_3$ for 2 days at 293 K, followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. The structure was refined using all intensities to the final error indices (using only the 801 reflections with ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2=0.043/0.140$. The 50 $Li^+$ ions per unit cell are found at three different crystallographic sites. The 19 $Li^+$ ions occupy at site I' in the sodalite cavity: the $Li^+$ ions are recessed 0.30 ${\AA}$ into the sodalite cavity from their 3-oxygens plane (Li-O = 1.926(5) ${\AA}$ and $O-Li-O=117.7(3)^{\circ}$). The 20 $Li^+$ ions are found at site II in the supercage, being recessed 0.23 ${\AA}$ into the supercage (Li-O = 2.038(5) ${\AA}$ and $O-Li-O=118.7(3)^{\circ}$). Site III' positions are occupied by 11 $Li^+$ ions: these $Li^+$ ions bind strongly to one oxygen atom (Li-O = 2.00(8) ${\AA}$). About 25 $Na^+$ ions per unit cell are found at four different crystallographic sites: 4 $Na^+$ ions are at site I, 5 at site I', 12 at site II, and the remaining 4 at site III'.

Preparation and cation mixing phenomena of LiCo$O_2$and $LiCo_{1-x}$$Ni_x$$O_2$ solid solutions (LiCo$O_2$$LiCo_{1-x}$$Ni_x$$O_2$고용체의 제조 및 양이온 혼합 현상)

  • 임창성;안홍주;강승민;하정수;고영신
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.9 no.6
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    • pp.601-605
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    • 1999
  • $LiCoO_2$and $LiCo_{1-x}$$Ni_x$$O_2$ solid solutions were fabricated by the solid state reaction process. The structural cation mixing phenomena were investigated using XRD, SEM, particle size analysis and $^7$Li NMR,The synthesized LiCoO$_2$ and $LiCo_{1-x}Ni_XO_2$ microcrystallines showed the hexagonal layered structures. Mean particle sizes were increased with the increase of the amount of nickel in the solid solutions. The cation mixing effects were increased as increasing the fraction of nickel(x), x = 0.3, 0.5, 0.7. the peak frequency of $^7$Li NMR was shifted to the higher frequency and the line width increased as increasing the amount of nickel in the solid solutions.

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Preparation and Analysis of$LiMn_2O_4$ Cathode Material substituted Mg and Zn (Mg와 Zn이 치환된 $LiMn_2O_4$ 정극 활물질의 제조 및 특성 분석)

  • Jeong, In-Seong;Gu, Hal-Bon;Han, Kyoo-Seung
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2002.07b
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    • pp.707-710
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    • 2002
  • Spinel $LiMn_2O_4$ and $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4$ powders were synthesized by solid-state method at $800^{\circ}C$ for 36h. Crystal structure and electrochemical properties were analyzed by X-ray diffraction, charge-discharge test, cyclic voltammetry and ac impedance to $LiMn_2O_4$ and $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$. All cathode material showed spinel structure in X-ray diffraction. $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$ cell substituted $Mg^{2+}$ and $Zn^{2+}$ showed excellent discharge capacities than other cells, which it presented about 120mAh/g at the 1st cycle and about 73mAh/g at the 250th cycle, respectively. AC impedance of $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$ cells showed the similar resistance of about $65{\sim}110{\Omega}$ before cycling.

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