• Title/Summary/Keyword: Li-doping

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One-Step β-Li2SnO3 Coating on High-nickel Layered Oxides via Thermal Phase Segregation for Li-ion Batteries

  • Seongmin Kim;Hanseul Kim;Sung Wook Doo;Hee-Jae Jeon;In Hye Kim;Hyun-seung Kim;Youngjin Kim
    • Journal of Electrochemical Science and Technology
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    • v.14 no.3
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    • pp.293-300
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    • 2023
  • The global energy storage markets have gravitated to high-energy-density and low cost of lithium-ion batteries (LIBs) as the predominant system for energy storage such as electric vehicles (EVs). High-Ni layered oxides are considered promising next-generation cathode materials for LIBs owing to their significant advantages in terms of high energy density. However, the practical application of high-Ni cathodes remains challenging, because of their structural and surface instability. Although extensive studies have been conducted to mitigate these inherent instabilities, a two-step process involving the synthesis of the cathode and a dry/wet coating is essential. This study evaluates a one-step β-Li2SnO3 layer coating on the surface of LiNi0.8Co0.2O2 (NC82) via the thermal segregation of Sn owing to the solubility limit with respect to the synthesis temperature. The doping, segregation, and phase transition of Sn were systematically revealed by structural analyses. Moreover, surface-engineered 5 mol% Sn-coated LiNi0.8Co0.2O2 (NC82_Sn5%) exhibited superior capacity retention compared to bare NC82 owing to the stable surface coating layer. Thus, the developed one-step coating method is suitable for improving the properties of high-Ni layered oxide cathode materials for application in LIBs.

2-Wavelength Organic Light-Emitting Diodes by selectively doping of RP-411 in the Host of $Bebq_2$ ($Bebq_2$ 호스트에 RP-411을 선택 도핑한 2-파장 유기발광 다이오드)

  • Kim, Min-Young;Jang, Ji-Geun
    • Journal of the Semiconductor & Display Technology
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    • v.10 no.1
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    • pp.23-26
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    • 2011
  • New organic light-emitting diodes with structure of ITO/DNTPD/TAPC/$Bebq_2/Bebq_2$:RP-411/ET-137/LiF/Al using the selective doping of 5% RP-411 in a single $Bebq_2$ host in the two wavelength(green, red) emitter formation were proposed and characterized. In the experiments, with a 300${\AA}$-thick undoped emitter of $Bebq_2$, three kinds of devices with different thicknesses of 30${\AA}$, 40${\AA}$ and 50${\AA}$ in the doped emitter of $Bebq_2$:RP-411 were fabricated. The electroluminescent spectra showed two peak emissions at the same wavelengths of 511 nm and 622 nm for the fabricated devices. When the device with a 30${\AA}$-thick doped emitter is referred as "D-1", the device with a 40${\AA}$-thick doped emitter is referred as "D-2" and the device with a 50${\AA}$-thick doped emitter is referred as "D-3", the relative intensity of 622 nm to 511 nm at two wavelength peaks was higher in the D-2 and the D-3 than in the D-1. The devices of D-1, D-2 and D-3 showed the color coordinates of (0.43, 0.46), (0.46, 0.44) and (0.48, 0.43) on the CIE chart, respectively.

Effect of Fe and BO3 Substitution in Li1+xFexTi2-x(PO4)3-y(BO3)y Glass Electrolytes (Li1+xFexTi2-x(PO4)3-y(BO3)y 계 유리 전해질에서 Fe 및 BO3 치환 효과)

  • Choi, Byung-Hyun;Jun, Hyung Tak;Yi, Eun Jeong;Hwang, Haejin
    • Journal of the Korean Electrochemical Society
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    • v.24 no.3
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    • pp.52-64
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    • 2021
  • The effect of Fe and BO3 doping on structure, thermal, and electrical properties of Li1+xFexTi2-x(PO4)3-y(BO3)y (x = 0.2, 0.5)-based glass and glass ceramics was investigated. In addition, their crystallization behavior during sintering and ionic conductivity were also investigated in terms of sintering temperature. FT-IR and XPS results indicated that Fe2+ and Fe3+ ions in Li1+xFexTi2-x(PO4)3-y(BO3)y glass worked as a network modifier (FeO6 octahedra) and also as a network former (FeO4 tetrahedra). In the case of the glass with low substitution of BO3, boron formed (PB)O4 network structure, while boron preferred BO3 triangles or B3O3 boroxol rings with increasing the BO3 content owing to boic oxide anomaly, which can result in an increased non-bridging oxygen. The glass transition temperature (GTT) and crystallization temperature (CT) was lowered as the BO3 substitution was increased, while Fe2+ lowered the GTT and raised the CT. The ionic conductivity of Li1+xFexTi2-x(PO4)3-y(BO3)y glass ceramics were 8.85×10-4 and 1.38×10-4S/cm for x = 0.2 and 0.5, respectively. The oxidation state of doped Fe and boric oxide anomaly were due to the enhanced lithium ion conductivity of glass ceramics.

Piezoelectric and Dielectric Properties of (Na,K,Li)(Nb,Sb,Ta)O3 Ceramics as a Function of Fe2O3 Addition (Fe2O3첨가에 따른 (Na,K,Li)(Nb,Sb,Ta)O3계 세라믹스의 압전 및 유전 특성)

  • Lee, Gwang-Min;Shin, Sang-Hoon;Yoo, Ju-Hyun
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.27 no.9
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    • pp.555-560
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    • 2014
  • In this paper, in order to develop outstanding Pb-free composition ceramics, the $Fe_2O_3$-doped ($Na_{0.525}K_{0.443}Li_{0.037}$)($Nb_{0.883}Sb_{0.08}Ta_{0.037}$)$O_3$ + 0.3 wt% $Bi_2O_3$ + x wt% $Fe_2O_3$ (x= 0~1.0 wt%)(abbreviated as NKL-NST) lead-free piezoelectric ceramics have been synthesized using the ordinary solid state reaction method. The effect of $Fe_2O_3$-doping on their microstructure and electrical properties were investigated. XRD diffraction pattern studies confirm that $Fe_2O_3$ completely diffused into the NKL-NST lattice to form a new stable soild solution with $Fe^{3+}$ entering the $Nb^{5+}$, $Sb^{5+}$ and $Ta^{5+}$ of B-site. And, phase structure of all the ceramics exhibited pure perovskite phase and no secondary phase was found in the ceramics. The ceramics doped with 0.6 wt% $Fe_2O_3$ have the optimum values of piezoelectric constant($d_{33}$), planar piezoelectric coupling coefficient($k_p$) and mechanical quality factor($Q_m$) : $d_{33}$ = 233 [pC/N], $k_p$= 0.44, $Q_m$= 95. These results indicate that the ($Na_{0.525}K_{0.443}Li_{0.037}$)($Nb_{0.883}Sb_{0.08}Ta_{0.037}$)$O_3$ +0.3 wt% $Bi_2O_3$ + 0.6 wt% $Fe_2O_3$ ceramic is a promising candidate for lead-free piezoelectric ceramics.

Synthesis and high Temperature properties of Li$_{1+x}$ Co$_{y}$ Mn$_{2-y}$ $O_4$spinel prepared by oxalate precipitation (Oxalate 침전법의 의한 Li$_{1+x}$ Co$_{y}$ Mn$_{2-y}$ $O_4$spinel의 합성 및 고온특성)

  • 김세호;이병우
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.10 no.3
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    • pp.239-244
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    • 2000
  • Synthesis and high temperature phase stability of $_{1+x}$ Co$_{y}$ Mn$_{2-y}$ $O_4$(0$\leq$x$\leq$0.2,y=0,1/9,1/6) spinel, both the excess lithium and cobalt added, have been studied. The spinel was prepared by oxalate precipitation method as the wet chemical process. Oxalate derived spinel was synthesized by heating of precipitates at temperature lower than $600^{\circ}C$. As a result of the TG-DTA and XRD analysis of prepared and quenched powders, it was found that reversible phase transitions started at temperatures $T_1$, $T_2$$T_{2'}$. The transitions involved weight (oxygen) loss and gain during heating and cooling. The effects of Li excess and Co doping on the spinel lattice constant, phase stability and transition temperatures of the prepared powders are investigated. This study would provide important data for determining the spinel preparation process such as synthesis temperature and cooling speed.

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Adipic Acid Assisted Sol-Gel Synthesis of Li1+x(Mn0.4Ni0.4Fe0.2)1-xO2 (0 < x < 0.3) as Cathode Materials for Lithium Ion Batteries

  • Karthikeyan, Kaliyappan;Amaresh, Samuthirapandian;Son, Ju-Nam;Kim, Shin-Ho;Kim, Min-Chul;Kim, Kwang-Jin;Lee, Sol-Nip;Lee, Yun-Sung
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.89-94
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    • 2013
  • Layered $Li_{1+x}(Mn_{0.4}Ni_{0.4}Fe_{0.2})_{1-x}O_2$ (0 < x < 0.3) solid solutions were synthesized using solgel method with adipic acid as chelating agent. Structural and electrochemical properties of the prepared powders were examined by means of X-ray diffraction, Scanning electron microscopy and galvanostatic charge/discharge cycling. All powders had a phase-pure layered structure with $R\bar{3}m$ space group. The morphological studies confirmed that the size of the particles increased at higher x content. The charge-discharge profiles of the solid solution against lithium using 1 M $LiPF_6$ in EC/DMC as electrolyte revealed that the discharge capacity increases with increasing lithium content at the 3a sites. Among the cells, $Li_{1.2}(Mn_{0.32}Ni_{0.32}Fe_{0.16})O_2$ (x = 0.2)/$Li^+$ exhibits a good electrochemical property with maximum initial capacity of 160 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ current density and the capacity retention after 25 cycles was 92%. Whereas, the cell fabricated with x = 0.3 sample showed continuous capacity fading due to the formation of spinel like structure during the subsequent cycling. The preparation of solid solutions based on $LiNiO_2-LiFeO_2-Li_2MnO_3$ has improved the properties of its end members.

Microstructure of Glass-ceramics Made from Bottom Ash Produced at a Thermal Power Plant (화력발전소 바닥재로 제조된 결정화 유리의 미세구조)

  • Kang, Seung-Gu
    • Korean Journal of Materials Research
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    • v.19 no.2
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    • pp.95-101
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    • 2009
  • Glass ceramics were made from coal bottom ash by adding CaO and $Li_2O$ as glass modifiers and $TiO_2$ as a nucleating agent in a process of melting and quenching followed by a thermal treatment. The surface of the glass ceramics has 1.6 times more $Li_2O$ compared to the inner matrix. When $TiO_2$ was not added or when only 2 wt% was added, the surface parts of the glass ceramics were crystalline with a thickness close to $130{\mu}m$. In addition, the matrixes showed only the glass phase and not the crystalline phase. However, doping of $TiO_2$ from 4 wt% to 10 wt% began to create small crystalline phases in the matrix with an increase in the quantity of the crystalline. The matrix microstructure of glass ceramics containing $TiO_2$ in excess of 8 wt% was a mixture of dark-gray crystalline and white crystalline parts. These two parts had no considerable difference in terms of composition. It was thought that the crystallization mechanism affects the crystal growth, direction and shape and rather than the existence of two types of crystals.

Kinetic Considerations on the Olivine Cathodes

  • Yamada Atsuo;Yonemura Masao;Takei Yuki;Sonoyama Noriyuki;Kanno Ryoji
    • 한국전기화학회:학술대회논문집
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    • 2003.11a
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    • pp.141-151
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    • 2003
  • The electrochemical activity of the olivine type $LiMPO_4$ (M=transition metals) cathodes strongly depends on various factors, e.g., the transition metal element M, perturbative doping of the supervalent cations into Li site, composite formation with conductive additives, state of charge/discharge, and particle size and its geometries, etc. This is, therefore, an important issue of interdisciplinary between electrochemistry and solid state science towards practical applications. In order to shed light on this interesting but complicated issue with the transport properties and crystallographic aspects, systematic discussion will be made with the review of our recent publications; (1) first principle derivation of the electronic structures, (2) crystallographic mapping of the selected solid solutions, (3) quantitative elucidation of the electron-lattice interaction, (4) spectroscopic detection of the local environment with Mossbauer and EXAFS, (5) synthetic optimization of the electrode composite, and (6) electrochemical evaluation of the reaction kinetics, particularly on M = Fe, Mn.

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Relationship between Particle Density and Electrochemical Properties of Spherical LiMn2-xMxO4 (M = Al, Mg, B) Spinel Cathode Materials (구형 스피넬계 LiMxMn2-xO4 (M = Al, Mg, B) 양극소재의 입자치밀도와 전지성능간의 상관관계에 대한 연구)

  • Kim, Kyoung-Hee;Jung, Tae-Gyu;Song, Jun-Ho;Kim, Young-Jun
    • Journal of the Korean Electrochemical Society
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    • v.15 no.2
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    • pp.67-73
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    • 2012
  • Spherical lithium manganese oxide spinel, $LiMn_{2-x}M_xO_4$ (M = Al, Mg, B) prepared by wet-milling, spray-drying, and sintering process has been investigated as a cathode material for lithium ion batteries. As-prepared powders exhibit various surface morphologies and internal density in terms of boron (B) doping level. It is found that the dopant B drives the growth of the primary particle and minimizes the surface area of the powder. As a result, the dopant enhances the internal density of the particles. Electrochemical tests demonstrated that the capacity of the synthesized material at 5 C could be maintained up to 90% of that at 0.2 C. The cycle performance of the material showed that the initial capacity was retained up to 80% even after 500 cycles under the high temperature of $60^{\circ}C$.

Effect of Particle Size and Doping on the Electrochemical Characteristics of Ca-doped LiCoO2 Cathodes

  • Hasan, Fuead;Kim, Jinhong;Song, Heewon;Lee, Seon Hwa;Sung, Jong Hun;Kim, Jisu;Yoo, Hyun Deog
    • Journal of Electrochemical Science and Technology
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    • v.11 no.4
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    • pp.352-360
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    • 2020
  • Lithium cobalt oxide (LiCoO2, LCO) has been widely used as a cathode material for Li-ion batteries (LIBs) owing to its excellent electrochemical performance and highly reproducible synthesis even with mass production. To improve the energy density of the LIBs for their deployment in electro-mobility, the full capacity and voltage of the cathode materials need to exploited, especially by operating them at a higher voltage. Herein, we doped LCO with divalent calcium-ion (Ca2+) to stabilize its layered structure during the batteries' operation. The Ca-doped LCO was synthesized by two different routes, namely solid-state and co-precipitation methods, which led to different average particle sizes and levels of dopant's homogeneity. Of these two, the solid-state synthesis resulted in smaller particles with a better homogeneity of the dopant, which led to better electrochemical performance, specifically when operated at a high voltage of 4.5 V. Electrochemical simulations based on a single particle model provided theoretical corroboration for the positive effects of the reduced particle size on the higher rate capability.