• Title/Summary/Keyword: $NiCo_2O_4$

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Li3PO4 Coated Li[Ni0.75Co0.1Mn0.15]O2 Cathode for All-Solid-State Batteries Based on Sulfide Electrolyte

  • Lee, Joo Young;Park, Yong Joon
    • Journal of Electrochemical Science and Technology
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    • v.13 no.3
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    • pp.407-415
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    • 2022
  • Surface coating of cathodes is an essential process for all-solid-state batteries (ASSBs) based on sulfide electrolytes as it efficiently suppresses interfacial reactions between oxide cathodes and sulfide electrolytes. Based on computational calculations, Li3PO4 has been suggested as a promising coating material because of its higher stability with sulfides and its optimal ionic conductivity. However, it has hardly been applied to the coating of ASSBs due to the absence of a suitable coating process, including the selection of source material that is compatible with ASSBs. In this study, polyphosphoric acid (PPA) and (NH4)2HPO4 were used as source materials for preparing a Li3PO4 coating for ASSBs, and the properties of the coating layer and coated cathodes were compared. The Li3PO4 layer fabricated using the (NH4)2HPO4 source was rough and inhomogeneous, which is not suitable for the protection of the cathodes. Moreover, the water-based coating solution with the (NH4)2HPO4 source can deteriorate the electrochemical performance of high-Ni cathodes that are vulnerable to water. In contrast, when an alcohol-based solvent was used, the PPA source enabled the formation of a thin and homogeneous coating layer on the cathode surface. As a consequence, the ASSBs containing the Li3PO4-coated cathode prepared by the PPA source exhibited significantly enhanced discharge and rate capabilities compared to ASSBs containing a pristine cathode or Li3PO4-coated cathode prepared by the (NH4)2HPO4 source.

Analysis for Atomic Structural Deterioration and Electrochemical Properties of Li-rich Cathode Materials for Lithium Ion Batteries (리튬이차전지용 리튬과잉계 양극 산화물의 충방전 과정 중 원자 구조 열화 과정과 전기화학 특성에 대한 분석)

  • Park, Seohyeon;Oh, Pilgun
    • Applied Chemistry for Engineering
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    • v.31 no.1
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    • pp.97-102
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    • 2020
  • Recently, various degradation mechanisms of lithium secondary battery cathode materials have been revealed. As a result, many studies on overcoming the limitation of cathode materials and realizing new electrochemical properties by controlling the degradation mechanism have been reported. Li-rich layered oxide is one of the most promising cathode materials due to its high reversible capacity. However, the utilization of Li-rich layered oxide has been restricted, because it undergoes a unique atomic structure change during the cycle, in turn resulting in unwanted electrochemical degradations. To understand an atomic structure deterioration mechanism and suggest a research direction of Li-rich layered oxide, we deeply evaluated the atomic structure of 0.4Li2MnO3_0.6LiNi1/3Co1/3Mn1/3O2 Li-rich layered oxide during electrochemical cycles, by using an atomic-resolution analysis tool. During a charge process, Li-rich materials undergo a cation migration of transition metal ions from transition metal slab to lithium slab due to the structural instability from lithium vacancies. As a result, the partial structural degradation leads to discharge voltage drop, which is the biggest drawback of Li-rich materials.

Synthesis and Structure of Nickel(II) Complex with N-Benzylisonitrosoacetylacetone Imine (N-Benzylisonitrosoacetylacetone Imine Ni(II) 착물의 합성 및 구조)

  • Byung Kyo Lee;Dae Sub O;Heung Lark Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.6
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    • pp.536-542
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    • 1988
  • A nickel(Ⅱ) complex, Ni(IAA-NBz) (IAA-NBz') with ligand, N-benzylisonitrosoacetyl acetone imine (H-IAA-NBz) has been synthesized. This complex is very stable at room temperature and has cis-form and trans-form isomers. The ratio of nickel (Ⅱ) ion and ligand combined is 1 : 2. The elemental analysis, ir, nmr. electronic spectra and mass spectra have been studied. It is suggested from these studies that the isonitroso group of one ligand, H-IAA-NBz coordinates to nickel(Ⅱ)ion through the nitrogen atom to form five-membered ring, while that of the other ligand, H-IAA-NBz coordinates to nickel (Ⅱ) ion through the oxygen atom to form six-membered ring in square-planar complex.

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Stabilization of High Nickel Cathode Materials with Core-Shell Structure via Co-precipitation Method (공침법을 통하여 합성된 코어-쉘 구조를 가지는 하이 니켈 양극 소재 안정화)

  • Kim, Minjeong;Hong, Soonhyun;Jeon, Heongkwon;Koo, Jahun;Lee, Heesang;Choi, Gyuseok;Kim, Chunjoong
    • Korean Journal of Materials Research
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    • v.32 no.4
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    • pp.216-222
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    • 2022
  • The capacity of high nickel Li(NixCoyMn1-x-y)O2 (NCM, x ≥ 0.8) cathodes is known to rapidly decline, a serious problem that needs to be solved in a timely manner. It was reported that cathode materials with the {010} plane exposed toward the outside, i.e., a radial structure, can provide facile Li+ diffusion paths and stress buffer during repeated cycles. In addition, cathodes with a core-shell composition gradient are of great interest. For example, a stable surface structure can be achieved using relatively low nickel content on the surface. In this study, precursors of the high-nickel NCM were synthesized by coprecipitation in ambient atmosphere. Then, a transition metal solution for coprecipitation was replaced with a low nickel content and the coprecipitation reaction proceeded for the desired time. The electrochemical analysis of the core-shell cathode showed a capacity retention of 94 % after 100 cycles, compared to the initial discharge capacity of 184.74 mA h/g. The rate capability test also confirmed that the core-shell cathode had enhanced kinetics during charging and discharging at 1 A/g.

Syntheses of Tetradentate Nitrogen-Oxygen(N2O2)) Ligands with Substituents and the Determination of Stability Constants of Their Heavy(II) Metal Complexes (치환기를 가진 질소-산소(N2O2)계 네 자리 리간드의 합성과 중금속(II)이온 착화합물의 안정도상수 결정)

  • Kim, Sun-Deuk;Seol, Jong-Min
    • Journal of Environmental Science International
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    • v.21 no.4
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    • pp.421-435
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    • 2012
  • Novel $N_2O_2$ tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the $para$ position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The proton dissociation constants ($logK_n{^H}$) of the phenol hydroxyl group and secondary amine of the synthesized $N_2O_2$ ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants ($log{\beta}_p$) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of $para$ Hammett substituent constants(${\delta}_p$). The stability constants($logK_{ML}$) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of $log{\beta}_p$ of the ligands. The order of the $logK_{ML}$ value of the each transition metal (II) ion was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II), which agreed well with that of Iriving-Williams series.

Reduction and Decomposition Characteristics of CaSO4 Based Oxygen Carrier Particles (CaSO4 기반 산소전달입자의 환원과 분해특성)

  • RYU, HOJUNG;KIM, HANA;LEE, DONGHO;JIN, GYOUNGTAE;BAEK, JEOMIN
    • Transactions of the Korean hydrogen and new energy society
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    • v.26 no.6
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    • pp.600-608
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    • 2015
  • As a candidate for cheap oxygen carrier, $CaSO_4$ based oxygen carriers have been developing. However, research on reaction characteristics and side reaction of $CaSO_4$ based oxygen carrier is very limited. There are many possible reactions for main components of syngas from coal. In this study, we prepared three $CaSO_4$ based oxygen carriers ($CaSO_4$-$Fe_2O_3$/bentonite, $CaSO_4$-$K_2CO_3$/bentonite, $CaSO_4$-CaO/bentonite) and performed reduction tests by hydrogen. Cyclic reduction-oxidation tests up to $5^{th}$ cycle are also conducted using hydrogen as fuel. Reduction reactivity of those $CaSO_4$ based oxygen carriers were compared with that of NiO based oxygen carrier (OCN703-1100). Real weight change fractions of $CaSO_4$ based oxygen carriers were higher than theoretical oxyen transfer capacity and reactivity of these particles decreased with the number of cycle increased. To check possible side reaction of $CaSO_4$ based oxygen carriers, $CaSO_4$ decomposition tests were carried out and $SO_2$ was detected even at $700^{\circ}C$. Consequently, we could conclude that $CaSO_4$ based oxygen carriers decompose and release $SO_2$ and this reaction lead reactivity decay of $CaSO_4$ based oxygen carries.

Piezoelectric and Dielectric Properties of Low Temperature Sintered Pb(Mn1/3Nb2/3)0.02(Ni1/3Nb2/30.12(ZrxTi1-x)0.86O3 System Ceramics

  • Yoo, Ju-Hyun;Lee, Sang-Ho
    • Transactions on Electrical and Electronic Materials
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    • v.10 no.4
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    • pp.121-124
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    • 2009
  • In this study, in order to develop compositions of ceramics suitable for piezoelectric actuator and ultrasonic vibrator applications using low temperature sintering, multilayer, PMN-PNN-PZT ceramics were fabricated using $Li_2CO_3$ and $Na_2CO_3$ as sintering aids. Their structural, piezoelectric and dielectric characteristics were investigated according to the Zr/Ti ratio. As the Zr/Ti ratio increased, the electromechanical coupling factor $k_p$, and piezoelectric constant $d_{33}$ and the mechanical quality factor $Q_m$ all increased with Zr/Ti ratio and then decreased after the ratio exceeded 50/50. At the ratio of Zr/Ti =49/51 and sintering temperature of $900^{\circ}C$; the density, electromechanical coupling factor $k_p$, dielectric constant ${\varepsilon}_r$ piezoelectric $d_{33}$ constant and mechanical quality factor $Q_m$ all showed the optimum values of 7.900 $g/cm^3$, 0.576, 856, 312 pC/N, 1,326, respectively. These property values are very suitable for multilayer ceramics actuator applications.

Mineralogy, Geochemistry, and Formation of Ferromanganese Nodules from the KONOD-1 Site, Northeastern Equatorial Pacific (북동(北東) 적도(赤道) 태평양(太平洋)(KONOD-1) 망간 단괴(団塊)의 은물조성(銀物組成), 화학분석(化學成分)과 성인(成因))

  • Kang, Jung-Keuk;Han, Sang-Joon
    • 한국해양학회지
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    • v.23 no.3
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    • pp.110-122
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    • 1988
  • Between the Clarion and Clipperton fracture zones of the Northeastern Pacific, nodules and crusts were collected from abyssal plain and hills by the Korea Ocean Research and Development Institute in December, 1983 aboard the R/V KANA KEOKI of the Hawaii Institute of Geophysics. Mineralogical and geochemical data of bulk nodules are obtained and compared with analyses of other studies. Mechanisms of nodule formation are discussed based on these data. Generally, the nodules of the KONOD-1 site are composed of todorokite and ${\delta}-MnO_2$. The contents of Mn, Fe, Ni, and Cu of the bulk nodules are variable and the average contents of metals are slightly lower (Mn, 21.40%; Ni, 0.9%; Cu, 0.8%) than those of nodules from other abyssal plains between the Clarion and Clipperton fracture zones. High Mn/Fe (average 3.9; maximum 5.9) and Cu/Ni (average 0.8; maximum 1.0) ratios are similar to the nodules that were formed diagenetically in the northeast Pacific. The chemical characteristics of the KONOD-1 nodules reflect their sedimentary environments; nodules with higher diagenetic signatures occur in areas of thin Quaternary siliceous ooze, and nodules of lower diagenetic influence occur in topographically irregular abyssal hill areas.

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Cathode side protection coating for Planar-type SOFC interconnect (평판형 SOFC 분리판 보호코팅 개발)

  • Lee, Jaemyung;Jun, Jaeho;Sung, ByungGeun;Kim, Dohyung;Jun, Junghwan
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.11a
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    • pp.83.2-83.2
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    • 2010
  • 평판형 고체산화물 연료전지(planar SOFC : Solid oxide Fuelcell)는 높은 전류 효율 및 출력밀도를 가지는 중,대형 발전용 전기소자이다. SOFC 스택을 600~800도에서 작동할 경우, 금속 분리판에서 휘발된 크롬에 의한 열화현상과 금속의 산화에 의한 표면 저항의 증가가 큰 문제점으로 알려져 있으며, 이를 개선하기 위한 많은 연구가 진행되고 있다. 본 연구에서는 금속 분리판의 열화를 억제하기 위한 여러 보호코팅의 특성을 밝히고, 특성차이의 원인을 분석하고자 하였다. 모재는 상용 STS444합금 (Nisshin steel 생산) 2.0mmt 박판을 사용하였으며, 표면 상태를 균일하게 하기 위하여 표면은 동일한 #1200 번 사포로 연마후 코팅하였다. 적용한 코팅은 전기도금 Ni 코팅, (MnCo)3O4 wet powder spray 코팅, (MnCo)3O4 ADM코팅 3종이었으며, 코팅층의 두께는 최적 공정조건에 따라 달리 하였다. 산화후 형성되는 표면 산화물의 전기적 특성을 평가하기 위하여 시험편의 비면적 저항 (ASR : area specific resistance)을 장시간 측정하였다. 측정편의 크기는 가로 4cm ${\times}$ 세로 4cm였으며, 100시간 공기중 산화후 측정하였다. 표면 접촉을 높이기 위하여 Pt paste를 40~50um도포하였으며, 1~0.1A인가된 전류에 대한 저항을 4전극법 (4-probe)으로 측정하였다. 표면 코팅층이 크롬 휘발을 억제하는 정도를 평가하기 위하여 크롬 휘발량을 측정하였다. 시편은 가로 1.5cm ${\times}$ 세로 1cm 였으며, 공급된 공기와 수분의 혼합가스와 응축기 표면에 흡착된 크롬의 양을 ICP-MASS법으로 측정하였다.

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Effect of $Ca^{++}$ Ionophore and $Ca^{++}$-Channel Blocker on the Mouse Oocyte Maturation (생쥐 난자성숙에 미치는 $Ca^{++}$ Ionophore와 $Ca^{++}$ Channel Blocker의 영향)

  • Bae, In-Ha;Kim, Hyun-Sook;Kim, Moon-Kyoo
    • Clinical and Experimental Reproductive Medicine
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    • v.19 no.2
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    • pp.105-116
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    • 1992
  • The present study was examined to clarify the role of calcium ion as a factor for the maturation of mouse oocytes. Follicles and cumulus-enclosed oocytes were isolated with two sharp needles under a stereomicroscope from female mouse (ICR) ovaries which were treated PMSG 5 IU 45-46 hours previously. Isolated follicles and cumulus-enclosed oocytes were cultured for 14-16 hours in an organ culture system at $37^{\circ}C$, 5% $CO_2$ in air and 100% humudified in incubator. MHBS was the basic medium used from which A23187, verapamil, $NiCl_{2.}$ $6H_2O$ and $LaCl_{3.}$ $7H_2O$ were added depending on the experimental groups. In follicle- or cumulus-enclosed oocytes wre cultured in these differently treated media. Following results were obtained from the present study. 1. The calcium ionophore A23187 directly or indirectly seems to stimulate GVBD of follicle-enclosed mouse oocytes. Increasing concentration of ionophore A23187 1ed to an increase in oocytes degeneration from the cumulus-enclosed mouse oocytes. 2. The organic $Ca^{++}$ channel blocker, verapamil does not induce GVBD of follicle-enclosed mouse oocytes. Specially, higher dose of 1 mM verapamil induced GVBD of follicle-enclosed mouse oocytes. However, cytoplasm of GVBD oocytes in 1 mM verapamil treated groups appeared shrunk. In the cumulus-enclosed oocytes, polar body formation was reduced in verapamil treated groups and degeneration increased. Verapamil inhibit oocyte maturation (polar body formation). 3. The $Ca^{++}$ inhibitor, Nickel ($NiCl_{2.}$ $6H_2O$) inhibits maturation of the follicle-enclosed oocytes. In the cumulus-enclosed oocytes the progression to MII (PB formation) was reduced and degeneration of mouse oocytes increased as the concentration of $Ni^{++}$ increase. The results indicates that nickel act as an inhibitor of calcium. 4. The $Ca^{++}$ inhibitors, Lanthanum ($LaCl_{3.}$ $7H_2O$) has shown different effect from that of nickel. In follicle-enclosed oocytes, 0.01mM lanthanum induced maturation of mouse oocytes. Polar body formation was reduced in the cumulus-enclosed oocytes all lanthanum treated group.

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