• Title/Summary/Keyword: spinel phase

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Phase Evolution in LiMO2(M=Co,Ni) Cathode Materials for Secondary Lithium Ion Batteries : Effect of Temperature and Oxygen Partial Pressure (리튬 2차 전지용 양극활물질 LiMO2(M=Co,Ni)의 온도와 산소 분압에 따른 상전이 거동)

  • Huang, Cheng-Zhu;Kim, Ho-Jin;Jeong, Yeon-Uk;Lee, Joon-Hyung;Kim, Jeong-Joo
    • Journal of the Korean Ceramic Society
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    • v.42 no.4
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    • pp.292-297
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    • 2005
  • $LiMO_{2}(M=Co,Ni)$ samples were synthesized with $Li_{2}CO_{3},\;Co_{3}O_{4}$, and NiO by the solid-state reaction method. In the case of $LiCoO_{2}$, at low temperature$(T=400^{\circ}C)$ spinel structure was synthesized and the obtained spinel phase was transformed to layered phase at high temperature$(T\ge600^{\circ}C)$. The phase transition behaviors of $LiCoO_{2}$ were investigated with various heating temperature and time. The rate of transition was directly proportional to the concentrations of reactant, and activation energy of reaction was around 6.76 kcal/mol. When CoO(rock salt structure) was used as a starting material instead of $Co_{3}O_{4}$(spinel structure), layered structure of $LiCoO_{2}$ was obtained at low temperature. In the case of $LiNiO_{2}$ the transition from layered structure to rock salt structure occurred easily by disordering/ordering reaction, but did not occur in $LiCoO_{2}$. The difference in metal ion radii in $LiCoO_{2}$ and $LiNiO_{2}$ results in different behaviors of phase transitions.

Microstructure of ZnO Varistors with Various Additives (다양한 첨가 성분을 함유한 ZnO 바리스터의 미세구조)

  • Lee, Hoon;Cho, Sung-Gurl;Kim, Chang-Jo;Kim, Hyung-Sik
    • Journal of the Korean Ceramic Society
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    • v.32 no.12
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    • pp.1323-1330
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    • 1995
  • The effects of various additives on the microstructures of sintered ZnO varistors were examined. Bi2O3, Sb2O3 and Cr2O3 were added to ZnO step by step to identify the effect of each component. The specimens were prepared by sintering at 110$0^{\circ}C$ and 120$0^{\circ}C$ in ambient atmosphere. In ZnO-Bi2O3-Sb2O3 ternary system, decrease of averge grain size due to antimony oxide addition depends on sintering temperature as well as Bi2O3 content. When Sb2O3 was partly or completely replaced by Cr2O3, grain size was further reduced. A significant amount of pyrochlore phase which was not transformed to spinel and Bi2O3-rich liquid phase seemed to remain during sintering at 110$0^{\circ}C$. Unlike ZnO-Bi2O3-Sb2O3 system, the $\alpha$-spinel phase containing significant amount of Cr did not transform to pyrochlore during furnace cooling. Fine spinel particles around 1${\mu}{\textrm}{m}$ size were ovserved within ZnO grains and grain boundaries, which were believed to be responsible for grain-growth inhibition in ZnO-Bi2O3-Sb2O3.

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Effects of Co/Fe Sulfate Pigments on the Colour and Phase of Porcelain (Co/Fe 황화물의 혼합안료에 의한 도자기 표면의 상형성과 색변화)

  • Kim, Nam-Heun;Shin, Dae-Yong;Kim, Kyung-Nam
    • Korean Journal of Materials Research
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    • v.32 no.8
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    • pp.354-360
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    • 2022
  • In this study, an Co/Fe coated porcelain using a cobalt and ferrous sulfate was sintered at 1,250 ℃. The specimens were investigated by HR-XRD, FE-SEM (EDS), Dilatometer, and UV-vis spectrophotometer. The surface of the porcelain was uniformly fused with the pigment, and white ware and celadon body specimens were densely fused to a certain thickness from the surface. Other new compounds were produced by the chemical reaction of cobalt/ferrous sulfate with the porcelain body during the sintering process. These compounds were identified as cobalt ferrite spinel phases for white ware and white mixed ware, and an andradite phase for the celadon body, and the amorphous phase, respectively. As for the color of the specimens coated with cobalt and ferrous mixed pigments, it was found that the L* value was greatly affected by the white ware, and the a* and b* values were significantly changed in the celadon body. The L* values of the specimens fired with pure white ware, celadon body, and white mix ware were 72.1, 60.92, 82.34, respectively. The C7F3 pigment coated porcelain fired at 1,250 ℃ had L* values of 39.91, 50.17, and 40.53 for the white ware, celadon body, and white mixed ware, respectively; with a* values of -1.07, -2.04, and -0.19, and at b* values of 0.46 and 6.01, it was found to be 4.03. As a new cobalt ferrite spinel phase was formed, it seemed to have had a great influence on the color change of the ceramic surface.

Electrical Properties and Structures of Spinel Type LiMn$_{2-y}$M$_y$O$_4$(M=Cr$^{3+}$) Doped with Transition Metal (전이금속으로 치환된 Spinel형 LiMn$_{2-y}$M$_y$O$_4$(M=Cr$^{3+}$)의 구조 및 전기적 성질)

  • 형경우;김중헌;권태윤
    • Journal of the Korean Ceramic Society
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    • v.36 no.9
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    • pp.930-936
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    • 1999
  • For LiMn2O4 based spinel structures the stoichiometric reaction conditions need be considered carefully because the electrical properties depend on the structural stability. In order to obtain the homogeneous compound the Pechini process was chosen which could obtain a stoichiometry phase even low temperature and dependency of the synthetic condition on structural stability and electrochemical performance was investigated. X-ray diffraction studies showed that the compounds doped with transition metal have smaller lattice constants than those un doped. The dc conductivity was evaluated by a four probe method in the low and high temperature region respectively. The variations of basal spacings for the cathode were detected to be dependent on the extent of current flows (under dc)

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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.

Characterization of Spinel Lithium Manganite Prepared by Citrate Sol-Gel Method

  • 홍영식;박휴범;이지은;한치환;김시중
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1153-1158
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    • 1997
  • The powder characteristics of LiMn2O4 prepared by the citrate sol-gel method have been investigated. The optimum pH for the preparation of homogeneous citrate gel was calculated by the theoretical consideration of thermodynamic equilibrium constants for metal-citrate complexes and metal salts. The obtained citrate gel was prefired at 300 ℃ and calcined at 300-700 ℃ for 1 h. The obtained powders were characterized by TG/DSC, FT-IR spectrometer, X-ray diffractometer, SQUID magnetometer, SEM, and particle size analyzer. It was observed that the mixed phases of spinel LiMn2O4 and Mn3O4 were transformed into spinel LiMn2O4 phase and the vibrational bands due to the carbonate and nitrate were also disappeared over 400 ℃. At temperatures below 150 K, inverse molar susceptibilities of every sample began to show an antiferromagnetic ordering of Mn magnetic moments.

Growth of Spinel CoMn2O4 Thin Films and Post-growth Annealing Effects on Their Physical Properties (CoMn2O4 스피넬 박막의 합성과 후열처리가 박막의 물리적 특성에 미치는 영향)

  • Kim, D.R.;Kim, J.K.;Yoon, S.W.;Song, J.H.
    • Journal of the Korean Magnetics Society
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    • v.25 no.5
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    • pp.144-148
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    • 2015
  • We grew spinel structured $CoMn_2O_4$ thin films and have studied post-growth annealing effects on their physical properties. After post-growth annealing at $700^{\circ}C$ that is lower than the growth temperature ($720^{\circ}C$), crystal structure became cleared accompanying a change of surface structure. In the temperature dependences of magnetization, phase transitions were observed at ~100 K for both before and after post-growth treated samples which were not observed for the bulk. For both samples, ferromagnetic behaviors were observed above 100 K while it turned to ferrimagnetism at low temperature below 100 K. In particular, the ferrimagnetic behavior became strong after the post-growth treatment. These results indicate that the post-growth annealing process plays an important role in determining the physical properties of spinel $CoMn_2O_4$ thin film.

Variation of Li Diffusion Coefficient during Delithiation of Spinel LiNi0.5Mn1.5O4

  • Rahim, Ahmad Syahmi Abdul;Kufian, Mohd Zieauddin;Arof, Abdul Kariem Mohd;Osman, Zurina
    • Journal of Electrochemical Science and Technology
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    • v.13 no.1
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    • pp.128-137
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    • 2022
  • For this study, the sol gel method was used to synthesize the spinel LiNi0.5Mn1.5O4 (LNMO) electrode material. Structural, morphological, electrochemical, and kinetic aspects of the LNMO have been characterized. The synthesized LNMO was indexed with the Fd3m cubic space group. The excellent capacity retention indicates that the spinel framework of LNMO has the ability to withstand high rate charge-discharge throughout long cycle tests. The Li diffusion coefficient (DLi) changes non-monotonically across three orders of magnitude, from 10-9 to 10-12 cm2 s-1 determined from GITT method. The variation of DLi seemed to be related to three oxidation reactions that happened throughout the charging process. A small dip in DLi at the beginning stage of Li deintercalation is correlated with the oxidation of Mn3+ to Mn4+. While two pronounced DLi minima at 4.7 V and 4.75 V are due to the oxidation of Ni2+/Ni3+ and Ni3+/Ni4+ respectively. The depletion of DLi at the high voltage region is attributed to the occurrence of two successive phase transformation phenomena.

Preparation and Characterization of Black Zirconia Ceramics by Black Color Spinel Pigment (스피넬계 흑색 안료를 이용한 흑색 지르코니아 세라믹스의 제조 및 특성분석)

  • Lee, Kwang-Ho;Lee, Yong-Seok;Park, Joo-Seok;Lee, Byung-Ha
    • Journal of the Korean Ceramic Society
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    • v.45 no.4
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    • pp.214-219
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    • 2008
  • The zirconia ceramics are widely used because of their excellent mechanical properties. Recently, many researches to make a colored zirconia was achieved to satisfy the individual aesthetic requirements. In this study, the synthesis of black-color spinel-based inorganic pigments which are stable above $1400^{\circ}C$ and the fabrication of black-colored zirconia using the synthesized pigments are investigated. Inorganic pigments which have spinel structure and near black color were synthesized by a solid state reaction method using a $Fe_2O_3,\;Cr_2O_3$, CoO and NiO powder as a starting materials at $1600^{\circ}C$. Most of synthesized pigments were black colored spinel phases and single spinel phase was successfully synthesized at the composition range of $Cr_2O_3:25{\sim}35%,\;Fe_2O_3:45{\sim}55%$, CoO:20% and NiO:$6{\sim}10%$. The black-colored zirconia was fabricated at $1410^{\circ}C$ with the 5 wt% synthesized pigments and their properties were evaluated. The results showed that the strength value was more than 848 MPa, absorption rate was 0.1%, the brightness of color was $L^*:40{\sim}42$, the tone of color is $a^*:0.2{\sim}0.8$ and $b^*:-1.1{\sim}2.4$. As a result, the black-colored zirconia was suitable for a artificial jewelry or decoration zirconia goods.

Synthesis of One-dimensional Spinel LiMn2O4 Nanostructures as a Positive Electrode in Lithium Ion Battery

  • Lee, Hyun-Wook;Muralidharan, P.;Kim, Do-Kyung
    • Journal of the Korean Ceramic Society
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    • v.48 no.5
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    • pp.379-383
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    • 2011
  • This paper presents the synthesis of one-dimensional spinel $LiMn_2O_4$ nanostructures using a facile and scalable two-step process. $LiMn_2O_4$ nanorods with average diameter of 100 nm and length of 1.5 ${\mu}m$ have been prepared by solid-state lithiation of hydrothermally synthesized ${\beta}$-$MnO_2$ nanorods. $LiMn_2O_4$ nanowires with diameter of 10 nm and length of several micrometers have been fabricated via solid-state lithiation of ${\beta}$-$MnO_2$ nanowires. The precursors have been lithiated with LiOH and reaction temperature and pressure have been controlled. The complete structural transformation to cubic phase and the maintenance of 1-D nanostructure morphology have been evaluated by XRD, SEM, and TEM analysis. The size distribution of the spinel $LiMn_2O_4$ nanorods/wires has been similar to the $MnO_2$ precursors. By control of reaction pressure, cubic 1-D spinel $LiMn_2O_4$ nanostructures have been fabricated from tetragonal $MnO_2$ precursors even below $500^{\circ}C$.