• 제목/요약/키워드: $G_2$-M transition

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

  • 김수연;최승현;이은주;김점수
    • 전기화학회지
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    • 제20권4호
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    • pp.67-74
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    • 2017
  • 층상구조의 Ni-rich NCM계 양극활물질 $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$)은 $LiCoO_2$ 대비 높은 에너지밀도와 가격 경쟁력의 장점을 가진다. Ni 함량에 비례하여 가역 방전용량이 증가하는 장점이 있는 반면, 합성 중에 발생하는 양이온 혼합으로 인해 안정적인 전기화학성능을 구현하기 어려운 문제가 있다. 본 연구에서는 합성 분위기, 리튬 원료물질, 합성 시간, 합성 온도, Li/M (M=transition metal) 비율 등의 다양한 합성조건을 변수로 하여 Ni 함량 증가에 따라 최적의 층상구조 Ni-rich NCM을 각각 합성하고 이에 대한 전기화학성능을 보고하였다. $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6)을 기준으로 Ni 함량이 증가한 $Li[Ni_{0.7}Co_{0.15}Mn_{0.15}]O_2$ (NCM7)와 $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8)의 합성시 전이금속 중 Ni의 비율이 증가함에 따라 양이온 혼합이 증가하는 것이 관찰되었고, 이는 전기화학 성능에 부정적인 영향을 끼치는 것으로 확인되었다. Ni 비율별 NCM에 대한 연구결과 비율 내확인한 최적의 조건에서 NCM6은 $180mAh{\cdot}g^{-1}$, 96.2% (50회), NCM7은 $187mAh{\cdot}g^{-1}$, 94.7% (50회), NCM8은 $201mAh{\cdot}g^{-1}$, 92.7% (50회)의 초기 방전용량 및 수명평가 후 용량유지율 값을 각각 구현하였다.

Kinetic Considerations on the Olivine Cathodes

  • Yamada Atsuo;Yonemura Masao;Takei Yuki;Sonoyama Noriyuki;Kanno Ryoji
    • 한국전기화학회:학술대회논문집
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    • 한국전기화학회 2003년도 전지기술심포지움
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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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Polymerization of Hydrosilanes and Vinyl Monomers in the Presence of Transition Metal Complex

  • Kim, Myoung-Hee;Lee, Jun;Cha, Hyo Chang;Shin, Joong-Hyeok;Woo, Hee-Gweon
    • 통합자연과학논문집
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    • 제2권1호
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    • pp.18-23
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    • 2009
  • This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.

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The Importance of the Aging Time to Prepare Cu/ZnO/Al2O3 Catalyst with High Surface Area in Methanol Synthesis

  • Jung, Heon;Yang, Dae-Ryook;Joo, Oh-Shim;Jung, Kwang-Deog
    • Bulletin of the Korean Chemical Society
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    • 제31권5호
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    • pp.1241-1246
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    • 2010
  • Ternary Cu/ZnO/$Al_2O_3$ catalysts were prepared by a co-precipitation method. The precursor structures were monitored during the aging. The first precipitate structure was amorphous georgeite, which transformed into the unknown crystalline structure. The transition crystalline structure was assigned to the crystalline georgeite, which was suggested with elemental analysis, IR and XRD. The final structure of precursors was malachite. The Cu surface area of the resulting Cu/ZnO/$Al_2O_3$ was maximized to be 30.6 $m^2$/g at the aging time of 36 h. The further aging rapidly decreased Cu surface areas of Cu/ZnO/$Al_2O_3$. ZnO characteristic peaks in oxide samples almost disappeared after 24 h aging, indicating that ZnO was dispersed in around bulk CuO. TOF of the prepared catalysts of the Cu surface area ranges from 13.0 to 30.6 $m^2/g_{cat}$ was to be 2.67 ${\pm}$ 0.27 mmol/$m^2$.h in methanol synthesis at the condition of $250^{\circ}C$, 50 atm and 12,000 mL/$g_{cat}$. h irrespective of the XRD and TPR patterns of CuO and ZnO structure in CuO/ZnO/$Al_2O_3$. The pH of the precipitate solution during the aging time can be maintained at 7 by $CO_2$ bubbling into the precipitate solution. Then, the decrease of Cu surface area by a long aging time can be prevented and minimize the aging time to get the highest Cu surface area.

Ga$_2$O$_3$ 첨가에 따른 SiO$_2$-PbO-K$_2$O-Al$_2$O$_3$계 적외선 센서용 Glass fiber의 광학적 특성 (Optical properties of the glass fiber by adding Ga$_2$O$_3$ in the SiO$_2$-PbO-K$_2$O-Al$_2$O$_3$ system for Infrared sensor)

  • 윤상하;강월호
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 1996년도 춘계학술대회 논문집
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    • pp.68-71
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    • 1996
  • In the study, the thermal and optical properties of SiO$_2$-PbO-K$_2$O-Al$_2$O$_3$ g1asses were investigated. According to Ga$_2$O$_3$ addictions, the properties of bulk glass, transition temperature and softening temperature were increased, whereas thermal expansion coefficient was decreased; In the optical properties, refractive index was increased, and IR cut-off wavelength was enlarged from 4.64$\mu\textrm{m}$ to 5.22$\mu\textrm{m}$. But, the optical loss of fiber was decreased.

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AN ALGORITHMIC APPROACH TO THE MARKOV CHAIN WITH TRANSITION PROBABILITY MATRIX OF UPPER BLOCK-HESSENBERG FORM

  • Shin, Yang-Woo;Pearce, C.E.M.
    • Journal of applied mathematics & informatics
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    • 제5권2호
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    • pp.403-426
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    • 1998
  • We present an algorithm to find an approximation for the stationary distribution for the general ergodic spatially-inhomogeneous block-partitioned upper Hessenberg form. Our approximation makes use of an associated upper block-Hessenberg matrix which is spa-tially homogeneous except for a finite number of blocks. We treat the MAP/G/1 retrial queue and the retrial queue with two types of customer as specific instances and give some numerical examples. The numerical results suggest that our method is superior to the ordinary finite-truncation method.

Generic studies on thermo-solutal convection of mercurous chloride system of ${Hg_2}{Cl_2}$ and Ne during physical vapor transport

  • Choi, Jeong-Gil;Lee, Kyong-Hwan;Kim, Geug-Tae
    • 한국결정성장학회지
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    • 제19권1호
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    • pp.39-47
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    • 2009
  • The effects of thermo-solutal convection on mercurous chloride system of ${Hg_2}{Cl_2}$, and Ne during physical vapor transport are numerically investigated for further understanding and insight into essence of transport phenomena, For $10\;K{\le}{\Delta}T{\le}30\;K$, the growth rate slowly increases and, then is decreased gradually until ${\Delta}T$=50 K, The occurrence of this critical point near at ${\Delta}T$=30 K is likely to be due to the effects of thermo-physical properties stronger than the temperature gradient corresponding to driving force for thermal convection. For the range of $10\;Torr{\le}P_B{\le}300\;Torr$, the rate is second order-exponentially decayed with partial pressures of component B, $P_B$. For the range of $5{\le}M_B{\le}200$, the rate is second order-exponentially decayed with a function of molecular weight of component B, $M_B$. Like the case of a partial pressure of component B, the effects of a molecular weight arc: reflected through the binary diffusivity coefficients, which are intimately related with suppressing the convection flow inside the growth enclosure, i,e., transition from convection to diffusion-dominant flow mode as the molecular weight of B increases. The convective mode is near at a ground level, i,e., on earth (1 $g_0$), and the convection is switched to the diffusion mode for $0.1\;g_0{\le}g{\le}10^{-2}g_0$, whereas the diffusion region ranges from $10^{-2}g_0$ up to $10^{-5}g_0$.

Preparation of Thermo-Responsive and Injectable Hydrogels Based on Hyaluronic Acid and Poly(N-isopropylacrylamide) and Their Drug Release Behaviors

  • Ha Dong In;Lee Sang Bong;Chong Moo Sang;Lee Young Moo;Kim So Yeon;Park Young Hoon
    • Macromolecular Research
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    • 제14권1호
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    • pp.87-93
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    • 2006
  • Copolymers composed of hyaluronic acid (HA) and poly(N-isopropylacrylamide) (PNIPAAm) were prepared to create temperature-sensitive injectable gels for use in controlled drug delivery applications. Semi-telechelic PNIPAAm, with amino groups at the end of each main chain, was synthesized by radical polymerization using 2-aminoethanethiol hydrochloride (AESH) as the chain transfer agent, and was then grafted onto the carboxyl groups of HA using carbodiimide chemistry. The result of the thermo-optical analysis revealed that the phase transition of the PNIPAAm-grafted HA solution occurred at around 30$\∼$33$^{circ}C$. As the graft yield of PNIPAAm onto the HA backbone increased, the HA-g-PNIPAAm copolymer solution exhibited sharper phase transition. The short chain PNIPAAm-grafted HA ($M_{w}$=6,100) showed a narrower temperature range for optical turbidity changes than the long chain PNIPAAm-grafted HA ($M_{w}$=13,100). PNIPAAm-grafted HA exhibited an increase in viscosity above 35$^{circ}C$, thus allowing the gels to maintain their shape for 24 h after in vivo administration. From the in vitro riboflavin release study, the HA-g-PNIPAAm gel showed a more sustained release behavior when the grafting yield of PNIPAAm onto the HA backbone was increased. In addition, BSA released from the PNIPAAm-g-HA gels showed a maximum concentration in the blood 12 h after being injected into the dorsal surface of a rabbit, followed by a sustained release profile after 60 h.

Kinetic Study on Nucleophilic Substitution Reaction of 5-Nitro-8-quinolyl Benzoate, Picolinate, Nicotinate and Isonicotinate with Alkali Metal Ethoxide: Effect of Nonleaving Group on Reactivity and Transition State Structure

  • Lee, Jieun;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제35권6호
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    • pp.1789-1793
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    • 2014
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of 5-nitro-8-quinolyl nicotinate (4) and 5-nitro-8-quinolyl isonicotinate (5) with alkali metal ethoxides (EtOM; M = K, Na and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOM] curve slightly upward for the reactions with EtOK and EtONa but are linear for the reactions with EtOLi and for those with EtOK in the presence of 18-crown-6-ether. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $EtO^-{\approx}EtOLi$ < EtOK < EtONa for the reactions of 4 and EtOLi < $EtO^-$ < EtOK < EtONa for the reactions of 5. Comparison of the kinetic results for the reactions of 4 and 5 with those reported previously for the corresponding reactions of 5-nitro-8-quinolyl benzoate (2) and picolinate (3) has revealed that the esters possessing a pyridine ring (i.e., 3-5) are significantly more reactive than the benzoate ester 2 due to the presence of the electronegative N atom (e.g., 2 << 3 < 4 < 5). It has been concluded that $M^+$ ion catalyzes the reactions of 3-5 by increasing the electrophilicity of the reaction center through a five-membered cyclic transition state (TS) for the reaction of 3 and via a four-membered cyclic TS for the reactions of 4 and 5.

$Pb(Fe _{1/2}Ta_{1/2})O_3$의 합성, 유전특성 및 질서배열구조 (Syntheses, Dielectric Properties and Ordering Structures of $Pb(Fe _{1/2}Ta_{1/2})O_3$)

  • 우병철;김병국;김병호
    • 한국결정학회지
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    • 제13권3_4호
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    • pp.165-171
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    • 2002
  • 고상반응법에 의해 합성된 분말을 $1100^{\circ}C$에서 소결함으로써 밀도가 $9.3g/cm^3$이고 평균입경이 $5.1{\pm}1.2{\mu}$$Pb(Fe_{1/2}Ta_{1/2})O_3$를 단일상으로 합성하였다. (공간군: Pm3m) $-150{\sim}50^{\circ}C$에서 측정된 비유전율은 인가전압의 주파수가 1kHz일 때 $-41^{\circ}C$에서 비유전율이 3100으로 최대값을 가지고 유전완화(dielectric relaxation)현상 및 완만한 상전이(diffuse phase transition, DPT)가 뚜렷하게 관찰되는 전형적인 완화형 강유전특성을 보였으며 소결후 $1000^{\circ}C$에서의 열처리 시간이 증가함 에 따라 상전이의 완만화도는 감소하여 정상 강유전체화 하였다. 한편, 소결직후 $Fe^{3+}$$Ta^{5+}$ 이온은 투과전자현미경으로도 검출할 수 없는 정도의 단거리 영역에서 화학양론적으로 1 : 1 질서 배열하고 있으며 이러한 B자리 양이온의 질서배열은 열처리 시간이 증가함에 따라 강화됨을 라만분광법으로 확인하였다. 소결직후 $Pb(Fe^{12}Ta_{1/2})O_3$센서의 완화형 강유전특성은 B자리 양이온의 화학양론적 1:1 단거리 질서배열구조와, 열처리한 $Pb(Fe_{1/2}TA_{1/2})O_3$에서의 완화형 강유전특성 감소는 열처리에 따라 강화된 화학양론적 1:1 단거리 질서배열구조와 연관지을 수 있었다.