• Title/Summary/Keyword: Li$Co_{y}Ni_{1-y}O_{2}$.

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Synthesized and Characterization of high density cathode materials for Lithium Secondary Batteries (리튬이온이차전지용 고밀도 양극활물질의 합성 및 평가)

  • Kwon, Yong-Jin;Choi, Byung-Hyun;Ji, Mi-Jung;Sun, Yang-Kuk
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.429-429
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    • 2008
  • Li$[Ni_{1/2}Co_{1/2}]O_2$ powder were synthesized from co-precipitation spherical metal oxide, $[Ni_{1/2}Co_{1/2}](OH)_2$. The preparation of metal hydroxide was significantly dependent on synthetic conditions, such as pH, amount of chelating agent, stirring speed, etc. The optimized condition resulted in $[Ni_{1/2}Co_{1/2}](OH)_2$, of which the particle size distribution was uniform and the particle shape was spherical, as observed by scanning electron microscopy. Calcination of the uniform metal hydroxide with LiOH at higher temperature led to a well-ordered layer-structured Li$[Ni_{1/2}Co_{1/2}]O_2$, as confirmed by X-ray diffraction pattern. Also these materials have ${\alpha}-NaFeO_2$ ($R\bar{3}m$) structure. Due to the homogeneity of the metal hydroxide, $[Ni_{1/2}Co_{1/2}](OH)_2$, the final product, Li$[Ni_{1/2}Co_{1/2}]O_2$, was also significantly uniform, i.e., the average particle size was of about 10 to 15 ${\mu}m$ in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.41 $gcm^{-3}$, of which the value is comparable to that of commercialized $LiCoO_2$.

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Charge-discharge Properties by Cut-off Voltage Changes of Li(${Mn_{1-\delta}}{M_{\delta}$)$_2$$O_4$ and ${LiMn_2}{O_4}$in Li-ion Secondary Batteries (코발트와 니켈로 치환한 리튬이온 이차전지 Cathode, Li(${Mn_{1-\delta}}{M_{\delta}$)$_2$$O_4$${LiMn_2}{O_4}$의 Cut-off 전압 변화에 따른 충방전 특성)

  • 유광수;박재홍;이승원;조병원
    • Journal of the Korean Ceramic Society
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    • v.38 no.5
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    • pp.424-430
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    • 2001
  • Cut-off 전압 변화에 따른 충방전 특성을 알아보기 위하여 Mn을 다른 전이 금속이 Co와 Ni로 소량 치환시킨 Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$(M=Ni, Co, $\delta$=0, 0.05, 0.1, 0.2)를 고상 반응법으로 80$0^{\circ}C$에서 48시간 동안 유지하여 합성하였다. 충방전의 cut-off 전압은 2.5~4.4V, 3.0~4.5V, 3.5~4.5V, 3.5V~4.7V의 네 가지 전압범위고 하였다. 충방전 실험결과, Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$의 용량은 각각 Co와 Ni의 $\delta$=0.1에서 최대를 보였다. Co 치환 조성 재료와 순물질 모두에서 최대의 용량을 보인 cut-off 전압대는 3.5~4.5V 이었는데 이때의 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$와 LiM $n_2$ $O_4$의 초기 충전용량과 초기 방전용량은 각각 118, 119mAh/g과 114, 104mAh/g 이었다. 또한 모든 cut-off 전압대에서 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$는 순수한 LiM $n_2$ $O_4$보다 더 높은 용량과 우수한 싸이클 성능을 보였으며 그 결과는 밀착형 전지구성에서도 일치하였다.하였다.

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The Effect of Fabrication Process on the Characteristics of $LiCoO_2$ Cathode for Molten Carbonate Fuel Cell (용융탄산염 연료전지용 $LiCoO_2$ 산화전극의 제조방법에 따른 특성)

  • 임준혁;김태근
    • Journal of Environmental Science International
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    • v.5 no.4
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    • pp.535-544
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    • 1996
  • In the development of Molten Carbonate Fuel Cell, one of the serious problems is the dissolution of cathode material. Therefore, the development of the alternative cathode which is stable in molten carbonate is needed. In this research, the licoo, was chosen as alternative cathode material. $LiCoO_2$ powder was synthesized by high temperature calcination method and by citrate sol-gel method. And its structure and physical iharacteristics were analyzed by XRD, 1 R, TCA and porosimeter. The conductivity and solubility of $LiCoO_2$ electrode were also measured. Homogeneous $LiCoO_2$ Powder was obtained by citrate sol-Rel method at 445$^{\circ}C$, however, obtained above 75$0^{\circ}C$ by high temperature calcination method. Homogeneous particle size distribution and fine powder were obtained by the citrate sol-Rel method. $LiCoO_2$ electrode showed higher electric conductivity ($1.7 $\Omega$^{-1}cm^{-1}$) than NiO (0.1 $\Omega$^{-9} cm^{-1}) at $650^{\circ}C$. The solubilities of $LiCoO_2$ electrode in electrolyte were varies 0.6 to 1.0 ppm during 200 hours. So, the solubilities of $LiCoO_2$ were much lower than that of NiO.

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Effect of Calcination Temperature of Size Controlled Microstructure of LiNi0.8Co0.15Al0.05O2 Cathode for Rechargeable Lithium Battery

  • Park, Tae-Jun;Lim, Jung-Bin;Son, Jong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.357-364
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    • 2014
  • Size controlled, $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ cathode powders were prepared by co-precipitation method followed by heat treatment at temperatures between 750 and $850^{\circ}C$. The synthesized samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance. The synthesized $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ after calcined at $750^{\circ}C$ has a good electrochemical performance with an initial discharge capacity of $190mAhg^{-1}$ and good capacity retention of 100% after 30 cycles at 0.1C ($17mAg^{-1}$). The capacity retention of $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ after calcined at $750^{\circ}C$ is better than that at 800 and $850^{\circ}C$ without capacity loss at various high C rates. This is ascribed to the minimized cation disorder, a higher conductivity, and higher lithium ion diffusion coefficient ($D_{Li}$) observed in this material. In the differential scanning calorimetry DSC profile of the charged sample, the generation of heat by exothermic reaction was decreased by calcined at high temperature, and this decrease is especially at $850^{\circ}C$. This behavior implies that the high temperature calcinations of $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ prevent phase transitions with the release of oxygen.

Effects of Calcinations Temperature on the Electrochemical Properties of Li[Ni0.6Co0.2Mn0.2]O2 Lithium-ion Cathode Materials (리튬 이차전지용 양극활물질 Li[Ni0.6Co0.2Mn0.2]O2의 소성 온도가 전기화학적 특성에 미치는 영향)

  • Yoo, Gi-Won;Jeon, Hyo-Jin;Son, Jong-Tae
    • Journal of the Korean Electrochemical Society
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    • v.16 no.2
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    • pp.59-64
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    • 2013
  • Using $Na_2CO_3$ and $MeSO_4$ (Me = Ni, Co and Mn) as starting materials, the precursor of $[Ni_{0.6}Co_{0.2}Mn_{0.2}]CO_3$ has been synthesized by carbonate co-precipitation. The precursor was mixed with $Li_2CO_3$, and calcined at 750, 850, and$950^{\circ}C$ in air. Effect of calcinations temperature on characteristics of $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ cathode materials was investigated. The structure and characteristics of $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ were determined by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and electrochemical measurements. The X-ray diffraction (XRD) results show that the intensity ratio of $I_{(003)}/I_{(104)}$ increased and the R-factor ratio decreased with the increase of calcinations temperature. And Scanning electron microscopy (SEM) result show that the primary particle size increased. Especially, the $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ calcined at $950^{\circ}C$ for 24 H shows excellent electrochemical performances with reversible specific capacity of $165.3mAhg^{-1}$ [cut-off voltage 2.5~4.3 V, 0.1 C($17mAhg^{-1}$)] and good capacity retention of 95.4% after 50th charge/discharge cycles[cut-off voltage 2.5~4.3 V, 1 C($170mAhg^{-1}$)].

The Structural and Electrochemical Properties of Li[Ni0.6-xBaxCo0.1Mn0.3]O2 (x = 0, 0.01) by Barium Doping (Barium 도핑에 따른 Li[Ni0.6-xBaxCo0.1Mn0.3]O2(x=0, 0.01) 의 구조 분석 및 전기화학적 특성)

  • Jang, Byeong-Chan;Yoo, Gi-Won;Yang, Su-Bin;Min, Song-Gi;Son, Jong-Tae
    • Journal of the Korean Electrochemical Society
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    • v.17 no.4
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    • pp.222-228
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    • 2014
  • Ni-rich system $Li[Ni_{1-x-y}Co_xMn_y]O_2$ of lithium secondary battery cathode material keep a high discharge capacity. However, by the Ni content increases, there is a problem that the electrochemical properties and stability of the structure are reduced. In order to solve these problems, research for positive ion doping is performed. The one of the cathode material, barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01), was synthesized by the precursor, $Ni_{0.6}Co_{0.1}Mn_{0.3}(OH)_2$, from the co-precipitation method. The barium doped materials have studied the structural and electrochemical properties. The analysis of structural properties, results of X-ray diffraction analysis, and those results confirmed the change of the lattice from the binding energy in the structure by barium doping. Increased stability of the layered structure was observed by $I_{(006)}+I_{(102)}/I_{(101)}$(R-factor) ratio decrease. we expected that the electrochemical characteristics are improved. 23 mAh/g discharge capacity of barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01) electrode is higher than discharge capacity of $Li[Ni_{0.6}Co_{0.1}Mn_{0.3}]O_2$ due to decrease overvoltage. And, through the structural stability was confirmed that improved the cycle characteristics. We caused a reduction in charge transfer resistance between the electrolyte and the electrode was confirmed that the C-rate characteristics are improved.

Synthesis and Electrochemical Performance of Ni-rich NCM Cathode Materials for Lithium-Ion Batteries (리튬이온전지 양극활물질 Ni-rich NCM의 합성과 전기화학적 특성)

  • Kim, Soo Yeon;Choi, Seung-Hyun;Lee, Eun Joo;Kim, Jeom-Soo
    • Journal of the Korean Electrochemical Society
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    • v.20 no.4
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    • pp.67-74
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    • 2017
  • Layered Ni-rich NCM cathode materials $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$) have advantages of high energy density and cost competitive over $LiCoO_2$. The discharge capacity of NCM increases proportionally to the Ni contents. However, there is a problem that it is difficult to realize the stable electrochemical performance due to cation mixing. In this study, synthesis conditions for the layered Ni-rich NCMs are investigated to achieve deliver the ones having good electrochemical performances. Synthesis parameters are atmosphere, lithium source, synthesis time, synthesis temperature and Li/M (M=transition metal) ratio. The degree of cation mixing gets worse as the Ni content is increased from $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6) to $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8). It is confirmed that higher level of cation mixing affects negatively on the electrochemical performance of NCMs. Optimum synthesis conditions are explored for NCMx (x=6, 7, 8) in order to reduce the cation mixing. Under optimized conditions for three representative NCMx, a high initial discharge capacity and a good cycle life are obtained for $180mAh{\cdot}g^{-1}$, 96.2% (50 cycle) in NCM6, $187mAh{\cdot}g^{-1}$, 94.7% (50 cycle) in NCM7, and $201mAh{\cdot}g^{-1}$, 92.7% (50 cycle) in NCM8, respectively.

A Study on the Electrochemical Properties of LiNi0.8Co0.2-xMxO2[M=Al] Cathode Materials Prepared by Sol-Gel Method (졸-겔법에 의해 제조된 정극 활물질 LiNi0.8Co0.2-xMxO2[M=Al]의 전기화학적 특성)

  • Han, Chang-Joo;Cho, Won-Il;Cho, Byung-Won;Yun, Kyung-Suk;Jang, Ho
    • Journal of the Korean Electrochemical Society
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    • v.6 no.4
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    • pp.266-270
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    • 2003
  • The $LiN_{0.8}Co_{0.2}O_2$ has shown outstanding electrochemical properties. The microstructure of $LiN_{0.8}Co_{0.2}O_2$ cathode was investigated by using TEM (transmission electron microscopy) and X-ray diffraction techniques. The $LiN_{0.8}Co_{0.2}O_2$ was produced by sol-gel method to synthesize fine particles less than $1{\mu}m$ in the average diameter. In this study, emphasis was given to the examination and interpretation of the microstructural change during charge-discharge cycling experiments, which appeared to be one of the main causes of early degradation of rechargeable batteries. Results showed that the $1{\mu}m$ cathode produced by sol-gel method had high reversible capacity and excellent cycling stability due to its homogeneous distribution of Ni and Co cations on u atomic scale. In particular, the $1{\mu}m$ cathode did not show severe strain induced structural defects or cubic spinel disordering during cycling experiments, which had been observed in the conventional $LiCoO_2$ cathode. The $LiNi_{0.8}Co_{0.2-x}M_x[M=Al]$ compounds show good reversibility but low discharge capacity.

A Study on Optimization of Manufacturing Condition for LiNi1/3Mn1/3Co1/3O2-based Cathode Electrode (LiNi1/3Mn1/3Co1/3O2계 정극활물질을 적용한 전극 제조조건 최적화 연구)

  • Kim Hyun-Soo;Kim Sung-Il;Lee Chang-Woo;Moon Seong-In;Kim Woo-Seong
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.19 no.2
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    • pp.139-144
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    • 2006
  • A fabrication condition of the cathode electrode was optimized in a lithium secondary battery. The $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ powders were used as a cathode material. The $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$/Li cells were prepared with a certain formulation and their cycleability and rate-capability were evaluated. Optimum electrode composition simulated from the evaluated value was 86.3: 5.6: 8.1 in mass $\%$ of active material: binder: conducting material. Discharge capacity decreased markedly as the press ratio exceeded $30\%$ during preparation of the electrode. Discharge performance at a high current rate deteriorated abruptly as the electrode thickness was over $120{\mu}m$.

Improved Electrochemical Performance and Minimized Residual Li on LiNi0.6Co0.2Mn0.2O2 Active Material Using KCl (KCl을 사용한 LiNi0.6Co0.2Mn0.2O2계 양극활물질의 잔류리튬 저감 및 전기화학특성 개선)

  • Yoo, Gi-Won;Shin, Mi-Ra;Shin, Tae-Myung;Hong, Tae-Whan;Kim, Hong-kyeong
    • Journal of the Korean Electrochemical Society
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    • v.20 no.1
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    • pp.7-12
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    • 2017
  • Using a precursor of $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ as a starting material, a surface-modified cathode material was obtained by coating with KCl, where the added KCl reduces residual Li compounds such as $Li_2CO_3$ and LiOH, on the surface. The resulting electrochemical properties were investigated. The amounts of $Li_2CO_3$ and LiOH decreased from 8,464 ppm to 1,639 ppm and from 8,088 ppm to 6,287 ppm, respectively, with 1 wt% KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ that had been calcined at $800^{\circ}C$. X-ray diffraction results revealed that 1 wt% of KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ did not affect the parent structure but enhanced the development of hexagonal crystallites. Additionally, the charge transfer resistance ($R_{ct}$) decreased dramatically from $225{\Omega}$ to $99{\Omega}$, and the discharge capacity increased to 182.73mAh/g. Using atomic force microscopy, we observed that the surface area decreased by half because of the exothermic heat released by the Li residues. The reduced surface area protects the cathode material from reacting with the electrolyte and hinders the development of a solid electrolyte interphase (SEI) film on the surface of the oxide particles. Finally, we found that the introduction of KCl into $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ is a very effective method of enhancing the electrochemical properties of this active material by reducing the residual Li. To the best of our knowledge, this report is the first to demonstrate this phenomenon.