• Journal of Electrochemical Science and Technology
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• v.4 no.1
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• pp.34-40
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• 2013

The structural and electrochemical properties of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ ($Fd{\bar{3}}m$, disordered spinel) cathode material were studied and compared with stoichiometric $LiNi_{0.5}Mn_{1.5}O_4$ ($P4_332$, ordered spinel). First cycle discharge capacity of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ was similar to that of $LiNi_{0.5}Mn_{1.5}O_4$ at C/3 and 1C rate, but cycling performance of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ was better than that of $LiNi_{0.5}Mn_{1.5}O_4$ especially at high rate of 1C. This can be explained by performing synchrotron based in-situ XRD and results of GITT measurements. It is considered that faster lithium ion diffusion in the $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ cathode results in the improvement of the rate capability. To study structural changes during cycling, synchrotron in-situ XRD patterns of both the samples were recorded at C/3 and 1C rate. Compared to stoichiometric $LiNi_{0.5}Mn_{1.5}O_4$, disordered $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ spinel sample has pseudo one phase behavior and one step phase transition between two cubic phases. So, $LiNi_{0.5}Mn_{1.5}O_4$ would experience a much greater strain and stress, originating from the two phase transitions between three cubic phases and suffer from capacity loss during cycling especially at high rate.

• Nuclear Engineering and Technology
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• v.53 no.5
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• pp.1511-1518
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• 2021

In most countries, the thermal criteria for the engineered barrier system (EBS) is set to below 100 ℃ due to the possible illitization in the buffer, which will likely be detrimental to the performance and safety of the repository. On the other hand, if the thermal criteria for the EBS increases, the disposal density and the cost-effectiveness for the high-level radioactive wastes will dramatically increase. Thus, fundamentals on the thermal behavior of the buffer under the elevated temperatures is of crucial importance. Yet, the behaviors at the elevated temperatures of the bentonite under groundwater-saturated conditions have not been reported to-date. Here, we have developed an in-situ synchrotron-based method for the thermal behavior study of the buffer under the elevated temperatures (25-250 ℃), investigated dspacings of the montmorillonite in the Korean bentonite (i.e., Ca-type) at dry and KURT (KAERI Underground Research Tunnel) groundwater-saturated conditions (KJ-ii-dry and KJ-ii-wet), and compared the behaviors with that of MX-80 (i.e., Na-type, MX-80-wet). The hydration states analyzed show tri-, bi-, and mono-hydrated at 25, 120, and 250 ℃, respectively for KJ-ii-wet, whereas tri-, mono-, and de-hydrated at 25, 150, and 250 ℃, respectively for MX-80-wet. The Korean bentonite starts losing the interlayered water at lower temperatures; however, holds them better at higher temperatures as compared with MX-80.

• Proceedings of the Korean Magnestics Society Conference
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• 2009.12a
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• pp.204-205
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• 2009

The magnetic properties and structure of FeRh thin film pitaxially grown onto MgO(001) substrate were studied by MPMS(Magnetic Properties Measure System) and in-situ temperature synchrotron XRD(X-ray Diffraction). The transition temperature of FeRh thin films was around 380K. Both M-T curve and d-spacing changes correspond to each other very closely.

• Proceedings of the Korean Ceranic Society Conference
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• 2000.10a
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• pp.204.2-204
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• 2000

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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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.

• Journal of Electrochemical Science and Technology
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• v.3 no.1
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• pp.29-34
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• 2012

The structural changes of $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material for lithium ion battery during the first charge was investigated in comparison with $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$ using a synchrotron based in situ X-ray diffraction technique. The structural changes of these two cathode materials show similar trend during first charge: an expansion along the c-axis of the unit cell with contractions along the a- and b-axis during the early stage of charge and a major contraction along the c-axis with slight expansions along the a- and b-axis near the end of charge at high voltage limit. In $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode, however, the initial unit cell volume of H2 phase is bigger than that of H1 phase since the c-axis undergo large expansion while a- and b- axis shrink slightly. The change in the unit cell volume for $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ during charge is smaller than that of $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$. This smaller change in unit cell volume may give the $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material a better structural reversibility for a long cycling life.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.05b
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• pp.79-83
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• 2001

In order to compare the barrier properties of Ta-N/Si(001) with those of Ta-N/Ta/Si(001), we studied structural properties of films grown by RF magnetron sputtering with various $Ar/N_2$ ratios. To evaluate the barrier properties, the samples were annealed in a vacuum chamber. Ex-situ x-ray scattering measurements were done using an in-house x-ray system. With increasing nitrogen ratio in Ta-N/Si(001), the barrier property of Ta-N/Si(001) was enhanced, finally failed at $750^{\circ}C$ due to the crystallization and silicide formation. Compared with Ta-N/Si(001), Ta-N/Ta/Si(001) forms silicides at $650^{\circ}C$. However it does not crystallize even at $750^{\circ}C$. With increasing nitrogen composition in Ta-N/Ta/Si(001), the formation of tantalum silicide was reduced and the surface roughness was improved. To observe the surface morphology of Ta-N/Ta/Si(001) during annealing, we performed an in-situ x-ray scattering experiment using synchrotron radiation of the 5C2 at Pohang Light Source(PLS). Addition of Ta layer between Ta-N and Si(001) improved the surface morphology and reduced the surface degradation at high temperatures. In addition, increasing $N_2/Ar$ flow ratio reduced the formation of tantalum silicide and enhanced the barrier properties.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.4
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• pp.459-467
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• 2021

In the majority of countries, the upper limit of buffer temperature in a repository is set to below 100℃ due to the possible illitization. This smectite-to-illite transformation is expected to be detrimental to the swelling functions of the buffer. However, if the upper limit is increased while preventing illitization, the disposal density and cost-effectiveness for the repository will dramatically increase. Thus, understanding the characteristics and creating a database related to the buffer under the elevated temperature conditions is crucial. In this study, a strategy to investigate the bentonite found in Korea under the elevated temperatures from a mineral transformation and radionuclides retardation perspective was proposed. Certain long-term hydrothermal reactions generated the bentonite samples that were utilized for the investigation of their mineral transformation and radionuclide retardation characteristics. The bentonite samples are expected to be studied using in-situ synchrotron-based X-Ray Diffraction (XRD) technique to determine the smectite-to-illite transformation. Simultaneously, the 'high-temperature and high-pressure mineral alteration measurement system' based on the Diamond Anvil Cell (DAC) will control and provide the elevated temperature and pressure conditions during the measurements. The kinetic models, including the Huang and Cuadros model, are expected to predict the time and manner in which the illitization will become detrimental to the performance and safety of the repository. The sorption reactions planned for the bentonite samples to evaluate the effects on retardation will provide the information required to expand the current knowledge of repository optimization.