• 한국자기학회지
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• 제21권6호
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• pp.198-203
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• 2011

연 x선 광흡수 분광법(soft x-ray absorption spectroscopy: XAS)과 연 x선 자기 원편광 이색성(soft x-ray magnetic circular dichroism: XMCD)을 이용하여 스피넬 준강자성 산화물인 $FeV_2O_4$의 전자 구조를 연구하였다. Fe 2p XAS와 V 2p XAS 측정으로 부터 $FeV_2O_4$에서 Fe 이온과 V이온의 고유한 원자가는 각각 약 $Fe^{2.3+}$의 혼합원자가 상태와 약 $V^{3+}$의 상태임을 알 수 있었다. 실험적으로 측정된 Fe 2p XMCD의 신호는 거의 $Fe^{2+}$ 상태에서 기인하였으며, $Fe^{3+}$ 상태는 Fe 2p XMCD의 신호에 거의 기여하지 않는다는 사실이 발견되었다. 그러므로 $FeV_2O_4$의 자성 특성을 결정함에 있어서 자기적으로 정렬된 $Fe^{2+}$ 상태 이온들이 중요한 역할을 한다고 생각된다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.5-5
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• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

• 한국자기학회지
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• 제26권4호
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• pp.124-128
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• 2016

이 연구에서는 연 X선 광흡수 분광법(soft X-ray absorption spectroscopy: XAS)과 연 X선 자기 원편광 이색성(soft X-ray magnetic circular dichroism: XMCD)을 이용하여 수직자기이방성을 보이는 [$Co(2{\AA})/Pd(x{\AA})$] 형의 다층박막의 전자구조를 연구하였다(x = $1{\AA}$, $3{\AA}$, $5{\AA}$, $7{\AA}$, $9{\AA}$). Co 2p XAS와 XMCD 스펙트럼은 Pd 층의 두께 변화에 상관없이 서로 매우 유사하였으며, 또한 Co 금속의 Co 2p XAS와 XMCD 스펙트럼과도 매우 유사함이 관찰되었는데, 이러한 결과는 [$Co(2{\AA})/Pd(x{\AA})$] 다층박막에서 Co 이온들이 금속 결합을 하고 있다는 사실을 보여 준다. Co 2p XMCD 스펙트럼을 분석하여 두께에 따른 궤도 자기모멘트(orbital magnetic moment)와 스핀 자기모멘트(spin magnetic moment) 의 크기를 결정하였다. 이 결과에 의하면 Pd 층의 두께(x)가 $1{\AA}$에서 $3{\AA}$으로 증가할 때, 궤도 자기모멘트가 가장 크게 증가하였으며, $x{\geq}3{\AA}$ 이상의 영역에서는 별 다른 변화가 없었다. 이러한 결과는 [$Co(2{\AA})/Pd(x{\AA})$] 다층박막의 계면에서의 스핀-궤도 상호작용이 수직자기 이방성에 매우 중요한 역할을 한다는 사실을 나타낸다.

• Macromolecular Research
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• 제16권7호
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• pp.575-585
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• 2008

There are two beamlines (BLs), 4C1 and 4C2, at the Pohang Accelerator Laboratory that are dedicated to small angle X-ray scattering (SAXS). The 4C1 BL was constructed in early 2000 and is open to public users, including both domestic and foreign researchers. In 2003, construction of the second SAXS BL, 4C2, was complete and commissioning and user support were started. The 4C2 BL uses the same bending magnet as its light source as the 4C1 BL. The 4C1 BL uses a synthetic double multilayer monochromator, whereas the 4C2 BL uses a Si(111) double crystal monochromator for both small angle and wide angle X-ray scattering. In the 4C2 BL, the collimating mirror is positioned behind the monochromator in order to enhance the beam flux and energy resolution. A toroidal focusing mirror is positioned in front of the monochromator to increase the beam flux and eliminate higher harmonics. The 4C2 BL also contains a digital cooled charge coupled detector, which has a wide dynamic range and good sensitivity to weak scattering, thereby making it suitable for a range of SAXS and wide angle X-ray scattering experiments. The general performance of the 4C2 BL was initially tested using standard samples and further confirmed by the experience of users during three years of operation. In addition, several grazing incidence X-ray scattering measurements were carried out at the 4C2 BL.

• 광물과 암석
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• 제35권4호
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• pp.447-455
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• 2022

Tl⁺ 이온으로 교환된 제올라이트 A (|Tl₁₂|[Si₁₂Al₁₂O₄₈]-LTA, Tl₁₂-A) 단결정을 진공 탈수시킨 후, 623 K에서 72시간 동안 ZrI₄ (g, 6.0 × 10³ Pa) 와 반응시켜, Zr,I,Tl-A (|Zr_0.25I_1.5Tl₁₂|[Si₁₂Al₁₂O₄₈]-LTA)를 제조하였다. 제조된 단결정의 구조는 294 K에서 단결정 X-선 회절 기술을 이용하여 Pm3m (a = 12.337(2) Å) 입방 공간군에 속함을 확인 하였고, F_o> 4σ(F_o)를 사용하여 최종 오차 인자를 R₁/wR₂= 0.055/0.189로 정밀화 하였다. 이 구조에서 Tl⁺ 이온은 6-ring 맞은편의 3-fold 축상의 서로 다른 3개의 결정학적 위치에서 단위세포당 7.5개가 발견되었고, 모든 8-ring 근처(단위세포당 3개)에서 3개의 결정학적 위치로 채워졌다. 그리고 단위세포당 1.5개의 Tl⁺ 이온은 ZrI₄(g)와 반응 후 sodalite cavity 안에서 3-fold 축상을 벗어난 자리에서 골격산소 O2 및 O3와 결합하면서 발견되었다. Zr⁴⁺ 이온은 6개의 I^- 이온과 함께 8면체의 ZrI₆^2- 형태로 large cavity 정중앙에 존재하였고, 이들은 8-ring 및 6-ring 근처에 존재하고 있던 Tl+ 양이온과 3차원적으로 연결하면서 ZrI₆Tl₁₁⁹⁺ cationic cluster을 형성하였다. 이러한 cationic cluster은 Zr,I,Tl-A의 large cavity 중에서 약 25%에만 존재하였다.