• 제목/요약/키워드: jahn-teller effect

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이중 층 La1.4(Sr0.2Ca1.4)Mn2O7 세라믹스의 저온에서의 Small Polaron Hopping 전도 (Low-Temperature Small Polaron Hopping Conduction in Bilayer La1.4(Sr0.2Ca1.4)Mn2O7 Ceramics)

  • 정우환
    • 한국재료학회지
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    • 제18권1호
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    • pp.26-31
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    • 2008
  • The dc resistivity and thermoelectric power of bilayered perovskite $La_{1.4}(Sr_{0.2}Ca_{1.4})Mn_2O_7$ were measured as a function of the temperature. In the ferromagnetic phase, ${\rho}(T)$ was accurately predicted by $a_0+a_2T^2+a_{4.5}T^{4.5}$ with and without an applied field. At high temperatures, a significant difference between the activation energy deduced from the electrical resistivity and thermoelectric power, a characteristic of small polarons, was observed. All of the experimental data can be feasibly explained on the basis of the small polaron.

Polarization of the A-Band Emission from RbCl : Pb$^{2+}$

  • Kang, Jun-Gill
    • Bulletin of the Korean Chemical Society
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    • 제8권2호
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    • pp.115-118
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    • 1987
  • The angular dependence of polarization of the A-band emission from RbCl:$Pb^{2+}$ is measured at 13.4 K to determine the symmetry axes of the $Pb^{2+}-v^-_c$ dipoles. The results indicate that these centers posess tetragonal symmetry. This implies that $v^-_c$ is situated in the next-nearest-neighbor (nnn) position to the $Pb^{2+}$ ion. The polarization ratio of the A-band emission measured at various temperatures is found to be independent of the temperature. The temperature independence of polarization confirms that, for the ion, the Jahn-Teller effect reduced by strong spin-orbit interaction does not give rise to thermal depolarization.

Structure and Bonding of Perovskites A($Cu_{1/3}Nb_{2/3}$)$O_3$ (A=Sr, Ba and Pb) and their Series of Mixed Perovskites

  • Park Hyu-Bum;Huh Hwang;Kim Si-Joong
    • Bulletin of the Korean Chemical Society
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    • 제13권2호
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    • pp.122-127
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    • 1992
  • Some perovskites $A($Cu_{1}3}Nb_{2}3}$)O_3(A=$Sr^{2+}$$, $Ba^{2+}$ and $Pb^{2+}$) and their series of mixed perovskites have been prepared by solid state reaction. Single perovskite phase was obtained in Sr or Ba rich samples, but pyrochlore phase was found in Pb rich samples. The stability of perovskite phase is dependent on the ionicity of bonding as well as the tolerance factor. All the obtained perovskites have tetragonal symmetry distorted by Jahn-Teller effect of $Cu^{2+}$. In the case of $Sr(Cu_{1}3}Nb_{2}3})O_3$, some superlattice lines caused by threefold enlarging of fundamental unit cell were observed. And, the symmetry of B site octahedron and the bonding character of B-O bond have been studied by IR, ESR and diffuse reflection spectroscopy. It appeared that the symmetry and the bonding character are influenced by such factors as the size and the basicity of A cation.

소성법에 의한 LiMn2O4의 제조시 반응 온도의 영향과 전기화학적 특성 (The Effect of Reaction Temperature for Synthesis of LiMn2O4 by Calcination Process and the Electrochemical Characteristics)

  • 이철태;이진식;김현중
    • 공업화학
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    • 제9권2호
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    • pp.220-225
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    • 1998
  • 스피넬 구조의 $LiMn_2O_4$$Li_2CO_3$$MnO_2$를 사용하여 $750{\sim}900^{\circ}C$에서 소성해서 합성하였다. 이 때 $850^{\circ}C$에서 12시간 동안 소성할 경우 입방정 구조의 $LiMn_2O_4$가 얻어졌다. 그러나 $900^{\circ}C$에서 소성해서 합성할 경우 산소의 발생으로 인해서 0.06M의 $Mn^{+4}$$Mn^{+3}$로 전이되면서 $LiMn_2O_{3.97}$이 얻어졌다. 이것은 스피넬 구조의 $LiMn_2O_4$에서 octahedral site의 $Mn^{+3}$ 이온의 증가로 인해서 Jahn-Teller distortion이 발생되며, 이로 인해 $3.6{\sim}4.3V_{Li/Li}+$의 전위범위에서 $0.25mA/cm^2$으로 15 cycle 동안 충 방전 실험한 결과 $900^{\circ}C$에서 합성된 스피넬 구조의 $LiMn_2O_4$는 82 mAh/g에서 50 mAh/g으로 용량 감소가 나타났으나 $850^{\circ}C$에서 합성한 $LiMn_2O_4$는 102~64 mAh/g을 유지했다.

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전이금속 치환 리튬이온 이차전지 정극 Li($Mn_{1-\delta}$$M_{\delta}$)$_2$$O_4$의 전기적 특성 (Electrical Characteristics of Cathode Li($Mn_{1-\delta}$$M_{\delta}$)$_2$$O_4$ Substituted by Transition Metals in Li-Ion Secondary Batteries)

  • 박재홍;김정식;유광수
    • 한국세라믹학회지
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    • 제37권5호
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    • pp.466-472
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    • 2000
  • As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

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Enhanced Electrochemical Properties of Surface Modified LiMn2O4 by Li-Fe Composites for Rechargeable Lithium Ion Batteries

  • Shi, Jin-Yi;Yi, Cheol-Woo;Liang, Lianhua;Kim, Keon
    • Bulletin of the Korean Chemical Society
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    • 제31권2호
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    • pp.309-314
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    • 2010
  • The surface modified $LiMn_2O_4$ materials with Li-Fe composites were prepared by a sol-gel method to improve the electrochemical performance of $LiMn_2O_4$ and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and transmission electron microscopy (TEM)-EDS. XRD results indicate that all the samples (modified and pristine samples) have cubic spinel structures, and XRD, XPS, and TEM-EDS data reveal the formation of $Li(Li_xFe_xMn_{2-2x})O_4$ solid solution on the surface of particles. For the electrochemical properties, the modified material demonstrated dramatically enhanced reversibility and stability even at elevated temperature. These improvements are attributed to the formation of the solid solution, and thus-formed solid solution phase on the surface of $LiMn_2O_4$ particle reduces the dissolution of Mn ion and suppresses the Jahn-Teller effect.

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

  • 박종광;고건문;홍세은;윤기웅;안용호;한병성
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2001년도 하계학술대회 논문집
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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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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
    • 대한화학회지
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    • 제62권5호
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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.

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

  • 정우환
    • 한국세라믹학회지
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    • 제39권3호
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    • pp.294-298
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    • 2002
  • 다결정 층상 페로브스카이트형 $La_{2.1}Sr_{1.9}Mn_3O_{10}$를 성공적으로 합성하였으며, $La_{2.1}Sr_{1.9}Mn_3O_{10}$의 열기전력, 전기전도 및 자기적 특성을 조사하였다. 0.85T의 자장의 인가 시 자기전이 온도 $T_c$보다 매우 낮은 120K에서 금속-비금속전이 및 약 120%의 음의 $MR(-{\Delta}{\rho}/{\rho}_0)$이 관측되었다. 고온영역에서 small polaron의 특징중의 하나인 매우 큰 전기적 저항 및 열기전력의 활성화 에너지 차가 관측되었다. 전체적인 실험 결과는 small polaron hopping 모델로 설명가능 하였다.

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

  • 손배순;김삼진;김철성
    • 한국자기학회지
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    • 제14권1호
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    • pp.33-37
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    • 2004
  • Cu$_{0.1}$Fe$_{0.9}$Cr$_2$S$_4$에 대하여 x-선 회절기(XRD), 진동 시료 자화율 측정기(VSM), Mossbauer 분광기, 자기저항(Magnetoresistance;MR)법을 이용하여 시료의 결정학적 및 자기적 특성을 연구하였다. 결정구조는 cubic spinel 구조이며, 격자 상수는 a$_{0}$=9.9880 $\AA$이었다. 자기저항(MR)실험 결과 110 K 이하에서는 반도체적 거동을, 100 K 이상에서는 도체적인 거동을 보인다. VSM 실험결과 100 Oe 인가 자장 하에서 zero-field-cooling(ZFC)와 field-cooling(FC) 사이에 커다란 비가역적 첨점 형태가 관측되었다. 5 kOe인가 자장 하에서 포화자화값이 온도 상승과 더불어 110 K 까지 증가되는 현상이 관측되었다. 15 K∼300 K의 온도 범위에 걸쳐서 Mossbauer스펙트럼을 분석한 결과 전기사중극자 분열치가 Neel온도 이하에서 나타나기 시작하여 온도가 하강하면서 점차 증가하고 공명선의 선폭이 비대칭적으로 굵어짐을 볼 수 있었다. 이것은 동적 Jahn-Teller뒤틀림이 일어나고 있는 것으로 해석된다. Fe 이온의 전하상태는 +2이며, 초미세 자기장은 온도가 상승함에 따라 극저온에서 100 K 부근까지 증가하다가 감소하는 현상이 나타났다. 이것은 반대방향의 orbital current field(H$_{L}$)와 Fermi contact field(H$_{C}$) 사이의 상쇄효과로 해석된다.