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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.

Li Ion Diffusivity and Rate Performance of the LiFePO4 Modified by Cr Doping

  • Park, Chang-Kyoo;Park, Sung-Bin;Shin, Ho-Chul;Cho, Won-Il;Jang, Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.191-195
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    • 2011
  • This study reports the root cause of the improved rate performance of $LiFePO_4$ after Cr doping. By measuring the chemical diffusion coefficient of lithium ($D_{Li}$) using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the correlation between the electrochemical performance of $LiFePO_4$ and Li diffusion is acquired. The diffusion constants for $LiFePO_4$/C and $LiFe_{0.97}Cr_{0.03}PO_4$/C measured from CV are $2.48{\times}10^{-15}$ and $4.02{\times}10^{-15}cm^2s^{-1}$, respectively, indicating significant increases in diffusivity after the modification. The difference in diffusivity is also confirmed by EIS and the $D_{Li}$ values obtained as a function of the lithium content in the cathode. These results suggest that Cr doping facilitates Li ion diffusion during the charge-discharge cycles. The low diffusivity of the $LiFePO_4$/C leads to the considerable capacity decline at high discharge rates, while high diffusivity of the $LiFe_{0.97}Cr_{0.03}PO_4$/C maintains the initial capacity, even at high C-rates.

The Electrochemical Characterization of $LiMn_{2-y}M_{y}O_{4}$ Cathode Material. III. The Effect of Temperature on the Charge-discharge Property and AC Impedance of $LiMn_{2-y}M_{y}O_{4}$ ($LiMn_{2-y}M_{y}O_{4}$ 정극 활물질의 전기화학적 특성. III. $LiMn_{2-y}M_{y}O_{4}$의 충방전 특성과 AC 임피던스의 온도 의존성)

  • 정인성;구할본;김종욱;손명모;이헌수
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.14 no.8
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    • pp.663-669
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    • 2001
  • Spinel LiM $n_2$ $O_4$ and LiM $n_{1.9}$M $g_{0.1}$ $O_4$ power was synthesized with solid-state method by calcining the mixture of LiOH.$H_2O$, Mn $O_2$ and MgO at 80$0^{\circ}C$ for 36 h in an air atmosphere. To investigate the effect of temperature on he cycle performance of cathode material during cycling, charge-discharge experiments and ac impedance measurement were performed. Initial discharge capacity was gradually increased with the increase of charge-discharge temperature. Discharge capacity at high temperature was suddenly decreased during cycling. On the other hand, discharge capacity at low temperature was almost constant during cycling. It confirmed that Mn dissolution is serious at high temperature than at low temperature. LiM $n_2$ $O_4$ and LiM $n_{1.9}$M $g_{0.1}$ $O_4$ showed the best capacity and stability at room temperature.ure.ure.

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Properties of Al Doped LiMn2O4 Powders Prepared by Spray Pyrolysis Process (분무열분해 공정에 의해 합성된 Al이 치환된 LiMn2O4 분말의 특성)

  • Ju, Seo Hee;Jang, Hee Chan;Kang, Yun Chan
    • Korean Chemical Engineering Research
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    • v.47 no.1
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    • pp.84-88
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    • 2009
  • Al doped $LiMn_2O_4$ cathode powders with fine size were synthesized by an ultrasonic spray pyrolysis method from the spray solution with citric acid and ethylene glycol. The as-prepared powders with spherical shape, porous structure and micron size turned into $LiMn_{11/6}Al_{1/6}O_4$ powders with micron size and regular morphology after post-treatment above $800^{\circ}C$. The $LiMn_{11/6}Al_{1/6}O_4$ powders had low initial discharge capacity of 94 mAh/g at a post-treatment temperature of $700^{\circ}C$. As the post-temperature increased from $750^{\circ}C$ to $1,000^{\circ}C$, the initial discharge capacities of the $LiMn_{11/6}Al_{1/6}O_4$ powders changed from 103 to 117 mAh/g. The $LiMn_{11/6}Al_{1/6}O_4$ powders had the maximum discharge capacity at a post-treatment temperature of $750^{\circ}C$. However, the $LiMn_{11/6}Al_{1/6}O_4$ powders post-treated at a temperature of $900^{\circ}C$ had the good cycle properties. The discharge capacities of the $LiMn_{11/6}Al_{1/6}O_4$ powders dropped from 107 to 100 mAh/g (93% capacity retention) by the 70th cycle at a current density of 0.1 C.

Fabrication of LiMn2O4 Thin-Film Rechargeable Batteries by Sol-Gel Method and Their Electrochemical Properties (졸-겔 방법을 이용한 LiMn2O4 박막 이차 전지 제작 및 전기화학적 특성 조사)

  • Lee, J.H.;Kim, K.J.
    • Journal of the Korean Vacuum Society
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    • v.20 no.3
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    • pp.205-210
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    • 2011
  • Structural and electrochemical properties of spinel oxide $LiMn_2O_4$ thin films prepared by using a sol-gel method on Pt/Ti/$SiO_2$/Si substrates were investigated. When Li/Mn molar ratio of the film was smaller than 0.5, $Mn_2O_3$hase was found to coexist with $LiMn_2O_4$. Half-cell batteries fabricated using the $LiMn_2O_4$ films as the cathode were put into chargedischarge (C-D) cycles and the change in structural properties of the cathode after the cycles was examined by X-ray diffraction and Raman spectroscopy. As the C-D cycle number increases, the discharge capacity of pure $LiMn_2O_4$ battery gradually decreases, being reduced to 72% of the initial capacity at 300 cycles. Such capacity fading is attributable to the decrease in the number of $Li^+$ ions that return to the tetrahedral sites of the spinel structure during the discharge step and the resultant increase in $Mn^{4+}$ density in the film. Also, $Mn_2O_3$ phase gradually appeared in the film as the cycle number increases.

Synthesis of Defective-Structure Li4Mn5O12 by Combustion Method and Its Application to Hybrid Capacitor (연소합성법에 의한 결함구조 Li4Mn5O12제조와 하이브리드 커패시터 적용)

  • Kim, Hun-Uk;Sun, Yang-Kook;Lee, Bum-Suk;Jin, Chang-Soo;Shin, Kyoung-Hee
    • Journal of the Korean Electrochemical Society
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    • v.13 no.2
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    • pp.103-109
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    • 2010
  • $Li_4Mn_5O_{12}$ was synthesized by combustion method using $LiNO_3$, $Li(CH_3COO){\cdot}2H_2O$ and $Mn(CH_3COO)_2{\cdot}4H_2O$. $Li_4Mn_5O_{12}$ was obtained over $400^{\circ}C$, however, the sample calcined at $400^{\circ}C$ for any time was mixed phases of $Li_4Mn_5O_{12}$ and $Mn_2O_3$. $Li_4Mn_5O_{12}$ calcined at $400^{\circ}C$ for 5 h had larger first discharge capacity (41.5mAh/g) at 1C-rate for 3.7~4.4V than other calcined samples. Moreover, applying to hybrid capacitor, it had good discharge capacity (24.74 mAh/g or 10.46 mAh/cc) at 100 mA/g for 1~2.5 V and higher energy density (39Wh/kg or 16.49Wh/cc) at same condition.

Electrochemical Characteristics of Cr Added Li4Ti5O12 Prepared by Sol-gel Method (졸-겔법으로 합성한 Cr 첨가 Li4Ti5O12의 전기화학적 특성)

  • Kim, Sun-Ah;Cho, Woo-Ram;Jeong, Koo-Hyun;Cho, Byung-Won;Na, Byung-Ki
    • Journal of the Korean Electrochemical Society
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    • v.14 no.1
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    • pp.27-32
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    • 2011
  • The electorchemical properties of $Li_4Ti_5O_{12}$ added with Cr was tested. The addition or substitution of atoms to $Li_4Ti_5O_{12}$ are expected to modify the crystal structure, and therefore to change the electrochemical performances of $Li_4Ti_5O_{12}$. After the spinel structure $Li_4Ti_{5-x}Cr_xO_{12}$ (x = 0~0.2) were obtained via sol-gel method, the gel was heated in a muffle furnace at $800{\sim}850^{\circ}C$ for 12 h in air. The physical properties of the samples were characterized by TG-DTA, XRD, SEM, FT-IR, and the electrochemical properties were tested with battery cycler at 0.01~2.0 V range. The $Li_4Ti_5O_{12}$ exhibited 169.9 mAh/g at 1C and capacity recovery was 97.5% of the initial capacity at 0.1C. $Li_4Ti_{4.9}Cr_{0.1}O_{12}$ (Cr 1% added) showed best performance of 193.8 mAh/g at 1C and the capacity recovery was increased to 98.8% of the initial capacity at 0.1C.

The Effect of Y Doping on Electrochemical Behavior of Spherical $Li_4Ti_5O_{12}$ for Li-ion Batteries

  • Ji, Mi-Jeong;Choe, Byeong-Hyeon
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.10a
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    • pp.31.1-31.1
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    • 2011
  • $Li_4Ti_5O_{12}$ is emerging as a promising material with its good structure stability and little volume change during the electrochemical reaction. However, its electrochemical performance is significantly limited by low electronic or ionic conductivity. In addition, high tap density is needed forim proving its volumetric energy density and commercialization. To enhance these properties, the spherical-like $Li_4Ti_5O_{12}$ particles were synthesized and carried out doping with yttrium. Prepared Y-doped $Li_4Ti_5O_{12}$ as a anode material showed great capacity retention rate of 92% (5C/0.2C), compared with no dope done. Consequently, it was found that Y doping into $Li_4Ti_5O_{12}$ matrix reduces the polarization and resistance on SEI layer during the electrochemical reaction.

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Effects of Reaction Parameters on the Preparation of LiMn2O4 for Lithium-Ion Batteries by SHS (리튬이온전지용 LiMn2O4분말의 자전연소합성시 반응변수의 영향)

  • Jang, Chang-Hyun;Nersisyan Hayk;Won, Chang-Whan;Kwon, Hyuk-Sang
    • Journal of the Korean Ceramic Society
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    • v.43 no.9 s.292
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    • pp.588-593
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    • 2006
  • Spinel phase $LiMn_2O_4$ is of great interest as cathode materials for lithium-ion batteries. In this study, SHS (Self propagating High-temperature Synthesis) method to synthesize spinel $LiMn_2O_4$ directly from lithium nitrate, manganese oxide, manganese and sodium chloride were investigated. The influence of Li/Mn ratio, the heat-treated condition of product have been explored. The resultant $LiMn_2O_4$ synthesized under the optimum synthesis conditions shows perfect spinel structure, uniform particle size and excellent electrochemical performances.

The electrochemical properties of $LiFe_xMn_{1-x}PO_4$ cathode materials for lithium polymer batteries (리튬 폴리머 전지용 $LiFe_xMn_{1-x}PO_4$ 정극활물질의 전기화학적 특성)

  • Jun, Dae-Kyoo;Gu, Hal-Bon
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2005.07a
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    • pp.424-425
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    • 2005
  • The purpose of this study is to research and develop $LiFe_xMn_{1-x}PO_4$ cathode for lithium polymer batteries. $LiFe_xMn_{1-x}PO_4$ cathode active materials were prepared using a solid-state reaction by adding carbon black to the synthetic precursors. We investigated cyclic voltammetry and charge/discharge cycling of $LiFe_xMn_{1-x}PO_4$/SPE/Li cells. The discharge capacity of $LiFe_{0.5}Mn_{0.5}PO_4$ was l26mAh/g and 110mAh/g at 1st and 10th cycle.

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