• Title/Summary/Keyword: Jahn-Teller

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A study on the synthesis and improvement of electrochemical properties of olivine-type phosphate cathode materials for lithium rechargeable batteries by mechanical alloying (기계적 합금화법에 의한 리튬 이차전지용 phosphate계 양극물질의 제조 및 전기화학적 특성 향상에 관한 연구)

  • 김철우;권상준;정운태;이경섭
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2003.03a
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    • pp.216-216
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    • 2003
  • 현재 상용화되어 있는 리튬 이차전지용 양극재료로는 비교적 작동전압이 높은 층상 암염구조(LiCoO$_2$, LiNiO$_2$) 및 Spinet계(LiMn$_2$O$_4$) 전이금속 산화물이 대부분 이용되고 있다 하지만 LiCoO$_2$나 LiNiO$_2$ 같은 상용화 물질은 비교적 높은 비용과, 강한 독성 때문에 많은 문제점을 가지고 있다. 또 Spinel(LiMn$_2$O$_4$)는 낮은 비용과 환경친화적인 장점에도 불구하고 Jahn-Teller 변형과 관련된 구조적 변형이 심각하기 때문에 사이클시 비가역적인 용량의 감소가 심각하다. 이러한 관점에서 전이금속보다 그 양이 풍부하고 저렴할 뿐만 아니라 독성이 없는 Olivine 구조 (LiFePO$_4$)를 갖는 phosphate계 화합물에 관심을 가지게 되었다. LiFePO$_4$는 리튬 음극과 3.4V의 방전전압을 나타내며, 170mAh/g의 이론용량을 가지고 있어, Fe-base의 장점은 물론 안정적인 결정구조 및 현재 상용화된 재료들과 비슷한 에너지 밀도를 가진다. 따라서 본 연구에서는 양극물질의 기존 두 제조법인 고상반응법과 sol-gel법으로 대표되는 제조법의 단점을 상호 보완될 수 있다고 판단되는 기계적 합금화법(Mechanical Alloying, MA)공정을 도입하여 초미세립 분말 제조에 초점을 맞추어 Olivine phosphate계 양극물질의 제조 및 전기화학적 특성을 연구하였다.

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The study on Fabrication and Characterization of $LiMn_{2-x}Cu_{x}O_{4}$for cathode material of Lithium-ion Battery (리튬이온 이차전지 양극활물질 $LiMn_{2-x}Cu_{x}O_{4}$의 제작과 전극특성에 관한 연구)

  • 박종광;고건문;홍세은;윤기웅;안용호;한병성
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2001.07a
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    • pp.713-716
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    • 2001
  • In many papers, the electrochemical analysis of LiMn$_2$O$_4$shows the transition results of Mn$^{3+}$ ion. Charge ordering is accompanied by simultaneous orbital ordering due to the Jahn-Teller effect in Mnl$^{3+}$ ions. To analyze the cycle performance of LiMn$_{2-x}$Cu$_{x}$ O$_4$as the cathode of 4 V class lithium secondary batteries, XRD, TGA analysis were conducted. Although the cycle performance of the LiMn$_{2-x}$Cu$_{x}$ O$_4$was improved from pure LiMn$_2$O$_4$, the discharge capacity was significantly lower than LiCoO$_2$. In this paper, We study the Electrochemical characterization and enhanced stability of Cu-doped spinels in the LiMn$_{2-x}$Cu$_{x}$ O$_4$upon initial cycling.l cycling.

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A study on the Spinel phase cathode materials with high capacity for lithium secondary batteries (리튬 2차 전지용 고용량 스피넬계 양극물질 연구)

  • Hong, Ki-Joo;Sun, Yang-Kook
    • Proceedings of the KIEE Conference
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    • 2001.11b
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    • pp.106-108
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    • 2001
  • As 3V cathode material, a new doping spinel material, LiMn1.6Se0.4O4 powder with a phase-pure polycrystalline was synthesized by a sol-gel method. In spite of Jahn-teller distortion in 3V region($2.4{\sim}3.5V$), the LiMn1.6Se0.4O4 electrode shows no capacity loss. The material in the 3V region initially delivers a discharge capacity of 100mAh/g which increase with cycling to reach 105mAh/g after 90cycles. And 5V cathode material LiNi0.5-xMxMn1.5O4(M=Cr, V, Fe) compounds have been synthesized by sol-gel method. a series of electroactive spinel compounds, LiNi0.5-xMxMn1.5O4(M=Cr, V, Fe) has been studied by crystallographic and electrochemical methods. The material presents only one plateau at around 4.5 V vs. Li/Li+ with a large discharge capacity of 152mAh/g and fairly good cyclability.

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Magnetic Properties and Crystalline Transition for the NiCr1.7Fe0.3O4

  • Park, Seung-Iel;Choi, Kang-Ryong;Kouh, Tae-Joon;Kim, Chul-Sung
    • Journal of Magnetics
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    • v.12 no.4
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    • pp.137-140
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    • 2007
  • We have studied the temperature dependent magnetic properties and crystalline phase transitionn in small amount Fe doped nickel chromite. The Crystalline structure of $NiCr_{1.7}Fe_{0.3}O_4$ is spinel cubic (Fd-3m) structure with a lattice constant $a_0=8.317\AA$ at room temperature. The magnetic $N\acute{e}el$ temperature $(T_N)$ of the Fe doped nickel chromite sample is determined to be 250 K. The $M\ddot{o}ssbauer$ spectra exhibit that there are two magnetic phases with the two different sites for the $Cr^{3+}$ ions. The spectrum at 4.2 K is fitted to two magnetic components of the magnetic hyperfine fields $H_{hf}=496$ and 485 kOe. From the spectrum at 295 K, the electric quadrupole splittings are observed with large values of 0.49 and 0.50 mm/s, respectively. The values of the isomer shifts at all temperature ranges show that the Fe ions are ferric states. We are suggested that the dynamic Jahn-Teller distortion and anisotropic magnetic relaxation effects due to the crystalline phase transition.

1D-Coordination Polymer Formed by Structural Conversion of an Oxazolidine Ligand in Reaction with the Copper(II) Halides

  • Mardani, Zahra;Golsanamlou, Vali;Jabbarzadeh, Zahra;Moeini, Keyvan;Carpenter-Warren, Cameron;Slawin, Alexandra M.Z.;Woollins, J. Derek
    • Journal of the Korean Chemical Society
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    • v.62 no.5
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    • pp.372-376
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    • 2018
  • A 1D-coordination polymer of $1D-\{Cu({\mu}-picolinato)_2\}$ $\{Hakimi,\;2012\;\sharp73\}_n$ (1), was prepared by the reactions between 2-(2-(pyridin-2-yl)oxazolidin-3-yl)ethanol (AEPC) ligand and $CuCl_2$ or $CuBr_2$. The product was characterized by elemental analysis, UV-Vis, FT-IR spectroscopy and single-crystal X-ray diffraction. The X-ray analysis results revealed that the AEPC ligand, after reactions with the copper(II) chloride or bromide, gives the same product - $1D-\{Cu({\mu}-picolinato)_2\}_n$ (1). The coordination modes for various picolinate-based ligands were extracted from the Cambridge Structural Database (CSD). In the crystal structure of 1, the copper atom has a $CuN_2O_4$ environment and octahedral geometry, which is distorted by elongation of the axial bond lengths due to the Jahn-Teller effect.

Influences of A($Cu_{1/3}Nb_{2/3}$)$O_3$(A=Pb, Ba and Sr) on the Ferroelectric Paraelectric Phase Transition of $BaTiO_3$ Ceramics ($BaTiO_3$의 강유전-상유전 상전이에 미치는 A($Cu_{1/3}Nb_{2/3}$)$O_3$ (A=Pb, Ba 및 Sr)의 영향)

  • Park, Hyu-Bum;Kim, Jung;Kim, Si-Joong
    • Journal of the Korean Ceramic Society
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    • v.28 no.12
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    • pp.969-974
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    • 1991
  • The influences of A(Cu1/3Nb2/3)O3(A=Pb, Ba and Sr) on the ferroelectric-paraelectric phase transition of BaTiO3 ceramics has been investigated. The tetragonality of crystal structure decreased with increasing A(Cu1/3Nb2/3)O3 content at room temperature. A linear correlation between Curie point and the tetragonality of lattice was not observed. In all three systems the variation of Curie point with the mole fraction showed similar tendency that the Curie point decreased at lower mole fraction but gradually increased in the region of higher mole fractions, Diffuse phase transitions were observed at higher mole fractions. The variation of Curie points could be explained by internal stress and Jahn-Teller distortion of BO6 due to Cu2+, and it was thought that the diffuse character of phase transition was caused by compositional fluctuation.

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First-principles investigation of the monoclinic NaMnO2 cathode material for rechargeable Na-ion batteries

  • Zhang, Renhui;Lu, Zhibin;Yang, Yingchang;Shi, Wei
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1431-1435
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    • 2018
  • Using first-principles calculations, we successfully investigate the electrochemical performance of the monoclinic $NaMnO_2$ for the sodium ion batteries. $NaMnO_2$ possesses a voltage window of 3.54-2.52 V and theoretical reversible capacity of $136mAh\;g^{-1}$. Besides, we find that the metallicity of the monoclinic $NaMnO_2$ gradually increases during Na extraction. Moreover, the computational Na migration energy barrier in the monoclinic $NaMnO_2$ is 0.18 eV, ensuring ideal conductivity and reversible capacity. Although the Jahn-Teller distortion effects limit the enhancement of the reversible capacity of the monoclinic $NaMnO_2$, it is still a right cathode material for the sodium ion batteries. The computational results are well in consistent with the experimental investigations.

Magnetic and transport properties of $La_{0.8}Sr_{0.2}MnO_3/La_{0.8}Ca_{0.2}MnO_3$ bilayer

  • Li, S.F.;Kim, J.B.;Hyun, Y.H.;Lee, Y.P.;Prokhorov, V.G.;Komashko, V.A.
    • Journal of Korean Vacuum Science & Technology
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    • v.7 no.1
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    • pp.8-12
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    • 2003
  • The effects of lattice strain on the magnetic and the transport properties of La$_{0.8}$Sr$_{0.2}$MnO$_3$films grown on a LaAlO$_3$ (001) substrate and on a La$_{0.8}$Sr$_{0.2}$MnO$_3$ layer have been studied. It was observed that the metal-insulator and the ferromagnetic transitions turn out to be at higher temperatures for the film deposited on La$_{0.8}$Sr$_{0.2}$MnO$_3$ layer with respect to that on LaAlO$_3$. The dependence of Curie temperature on the bulk and the Jahn-Teller strains has also been determined. determined.

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Crystallographic and Magnetic Properties of Cu0.1Fe0.9Cr2S4 (Cu0.1Fe0.9Cr2S4의 결정학적 및 자기적 성질에 관한 연구)

  • Son, Bae-Soon;Kim, Sam-Jin;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.14 no.1
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    • pp.33-37
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    • 2004
  • Cu$_{0.1}$Fe$_{0.9}$Cr$_2$S$_4$ has been studied with Mossbauer spectroscopy, x-ray diffraction, vibrating sample magnetometer (VSM), and magnetoresistance (MR) measurement. The crystal structure was determined to be a cubic spinel with lattice parameter a$_{0}$=9.9880 $\AA$. The MR measurements show a semiconductor behavior below 110 K and metal behaved above 100 K. The temperature dependence of magnetization of Cu$_{0.1}$Fe$_{0.9}$Cr$_2$S$_4$ was reported. In addition to a large irreversibility between the zero-field-cooling (ZFC) and the field-cooling (FC) magnetization at applied field H=100 Oe, a cusp-like anomaly was observed in both the FC and ZFC curves. It shifted toward the lower temperature region with increasing magnetic field, and then showed convex type maximum at 110 K, under the applied field of 5 kOe. The Mossbauer spectra were measured from 15 K to room temperature. The asymmetric line broadening was observed for the sample Cu$_{0.1}$Fe$_{0.9}$Cr$_2$S$_4$, and it was considered to be dynamic Jahn-Teller relaxation. The charge state of Fe ions was ferrous in character. The unusual reduction of magnetic hyperfine field below 110 K was interpreted in terms of cancellation effect between the mutually opposite orbital current field (H$_{L}$) and Fermi contact field (H$_{C}$).

Small Polaron Hopping Conduction of n=3 Ruddlesden-Popper Compound La2.1Sr1.9Mn3O10 System (n=3인 Ruddlesden-Popper형 La2.1Sr1.9Mn3O10의 Small polaron Hopping 전도)

  • Jung, Woo-Hwan
    • Journal of the Korean Ceramic Society
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    • v.39 no.3
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    • pp.294-298
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    • 2002
  • Polycrystalline $La_{2.1}Sr_{1.9}Mn_3O_{10}$ with layered perovskite structure have been successfully synthesized and investigated with respect to their thermoelectric, electric and magnetic properties. The large magnetoresistance (MR) effect with $-{\Delta}{\rho}/{\rho}_0$ of ∼120% at 0.85T was observed in a wide temperature range below a cusp temperature in resistivity of about 120K, which is well below the magnetic $T_C$. At high temperature, a singnificant difference between the activation energy deduced from the electrical resistivity and thermoelectric power, a characteristic of small polaron, is observed. All of the experimental data can be well explained on the basis of the small polaron model.