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Structural Behavior of Mixed $LiMn_2O_4-LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ Cathode in Li-ion Cells during Electrochemical Cycling

  • Yun, Won-Seop;Lee, Sang-U
    • 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.

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Characteristics of Particle Flow and Heat Transfer in Liquid-Particle Swirling Fluidized Beds (액체-입자 Swirling 유동층에서 유동입자 흐름 및 열전달 특성)

  • Son, Sung-Mo;Kang, Suk-Hwan;Kang, Yong;Kim, Sang-Done
    • Korean Chemical Engineering Research
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    • v.44 no.5
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    • pp.505-512
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    • 2006
  • Characteristics of particle holdup and heat transfer were investigated in a liquid-particle swirling fluidized bed whose diameter was 0.102 m and 2.5 m in height. Effects of liquid velocity, particle size and swirling liquid ratio($R_s$) on the particle holdup and immersed heater-to-bed overall heat transfer coefficient were examined. The particle holdup increased with increasing particle size and swirling liquid ratio but decreased with increasing liquid velocity.The local particle holdup was relatively high in the region near the heater when the $R_s$ value was 0.1~0.3, but the radial particle holdup was almost uniform when the $R_s$ value was 0.5, whereas, when the $R_s$ value was 0.7, the local particle holdup was relatively low in the region near the heater. The heat transfer characteristics between the immersed heater and the bed was well analyzed by means of phase space portraits and Kolmogorov entropy(K) of the time series of temperature difference fluctuations. The phase space portraits of temperature difference fluctuations became stable and periodic and the value of Kolmogorov entropy tended to decrease with increasing the value of $R_s$ from 0.1 to 0.5. The Kolmogorov entropy exhibited its maximum value with increasing liquid velocity. The value of overall heat transfer coefficient(h) showed its maximum value with the variation of liquid velocity, bed porosity or swirling liquid ratio, but it increased with increasing particle size. The value of K exhibited its maximum at the liquid velocity at which the h value attained its maximum. The particle holdup and overall heat transfer coefficient were well correlated in terms of dimensionless groups of operating variables.

Standardization and unification of the terms and conditions used for diagnosis in oriental medicine III (한의진단명과 진단요건의 표준화 연구III - 3차년도 연구결과 보고 -)

  • Choi, Sun-Mi;Yang, Ki-Sang;Choi, Seung-Hoon;Park, Kyung-Mo;Park, Jong-Hyun;Shim, Bum-Sang;Kim, Sung-Woo;Roh, Seok-Seon;Lee, In-Seon;Cheong, Jin-Hong;Lee, Jin-Yong;Kim, Dal-Rae;Im, Hyeong-Ho;Kim, Yun-Beom;Park, Seong-Sik;Song, Tae-Won;Kim, Jong-U;Lee, Seung-Gi;Choe, Yun-Jeong;Sin, Sun-Sik
    • Korean Journal of Oriental Medicine
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    • v.3 no.1
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    • pp.41-65
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    • 1997
  • The diagnostic requirements were suggested and explained regarding the systems of differentiation of symptoms and signs in the third year study of standardization and unification of the terms and conditions used for diagnosis in oriental medicine. The systems were as follows : - analysing and differentiating of epidemic febrile disease - analysing and differentiating in accordance with the Sasang constitutional medicine baced on four-type recognition - differentiation of diease according to pathological changes of Chong and Ren channels - standards for diagnosis of women's disease - standards for diagnosis of children's disease - standards for diagnosis of motor and sensor disturbance(-muscle born joint etc.) - standards for diagnosis of neuropsychiatric diease - standards for diagnosis of five sense organ diease - standards for diagnosis of external disease. The indivisual diagnosis pattern was arranged by the diagnostic requirments in the following odor : another name, notion of diagnosis pattern, index of differentiation of symptoms and signs, the main point of diagnosis, analysis of diagnosis pattern, discrimination of diagnosis pattrrn, prognosis, a way of curing a diseases, prescription, herbs in common use, dieases appearing the diagnosis pattern, documents. The standards for diagnosis of each disease was arranged by the diagnostic requirments in the following odor. another name, notion of diease, the main point of diagnosis, analysing and differentiating of disease, analysis of diease, discrimination of disease, prognosis, a way of curing and prescription of disease, dieases In western medicine appearing the disease in oriental medicine, documents.

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What Do Female Jobs Do for Women's Job Continuity? : Occupational Sex Segregation and Women's Job Exits in the U.S.

  • Min, Hyeon-Ju
    • Korea journal of population studies
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    • v.29 no.1
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    • pp.185-207
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    • 2006
  • Predominant explanations of the persistence of sex segregation ill occupations link job choices to profoundly gendered responses to childbearing and other family demands, arguing that women are more likely to seek jobs which are in some sense compatible with motherhood, either because they are family friendly (flexible, low intensity work) or because they are easy to exit and re-enter. In this paper, I examine the effect of occupational sex segregation on job exits into the labor market among women, with a special attention to the role of childbearing and child rearing. I use data from detailed employment histories gathered from the National Longitudinal Survey of Youth (NLSY) in continuous time event history models. My results indicate that women in female dominated jobs are less likely to exit their jobs than women in other types of occupations. Further this relationship is not shaped by motherhood. While mothers or pregnant women are more likely to leave work, mothers in female-dominated occupations are slightly less likely to leave employment than mothers in other occupations. These results are not consistent with the ideas that women's choice of female-dominated occupations expresses a gendered identity and women strategically seek jobs which accommodate maternal roles. Taken together, my findings do not provide support to the idea that women choose female-dominated occupations because they are easier to integrate with motherhood (except for the pregnancy period).

Myelin Content in Mild Traumatic Brain Injury Patients with Post-Concussion Syndrome: Quantitative Assessment with a Multidynamic Multiecho Sequence

  • Roh-Eul Yoo;Seung Hong Choi;Sung-Won Youn;Moonjung Hwang;Eunkyung Kim;Byung-Mo Oh;Ji Ye Lee;Inpyeong Hwang;Koung Mi Kang;Tae Jin Yun;Ji-hoon Kim;Chul-Ho Sohn
    • Korean Journal of Radiology
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    • v.23 no.2
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    • pp.226-236
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    • 2022
  • Objective: This study aimed to explore the myelin volume change in patients with mild traumatic brain injury (mTBI) with post-concussion syndrome (PCS) using a multidynamic multiecho (MDME) sequence and automatic whole-brain segmentation. Materials and Methods: Forty-one consecutive mTBI patients with PCS and 29 controls, who had undergone MRI including the MDME sequence between October 2016 and April 2018, were included. Myelin volume fraction (MVF) maps were derived from the MDME sequence. After three dimensional T1-based brain segmentation, the average MVF was analyzed at the bilateral cerebral white matter (WM), bilateral cerebral gray matter (GM), corpus callosum, and brainstem. The Mann-Whitney U-test was performed to compare MVF and myelin volume between patients with mTBI and controls. Myelin volume was correlated with neuropsychological test scores using the Spearman rank correlation test. Results: The average MVF at the bilateral cerebral WM was lower in mTBI patients with PCS (median [interquartile range], 25.2% [22.6%-26.4%]) than that in controls (26.8% [25.6%-27.8%]) (p = 0.004). The region-of-interest myelin volume was lower in mTBI patients with PCS than that in controls at the corpus callosum (1.87 cm3 [1.70-2.05 cm3] vs. 2.21 cm3 [1.86-3.46 cm3]; p = 0.003) and brainstem (9.98 cm3 [9.45-11.00 cm3] vs. 11.05 cm3 [10.10-11.53 cm3]; p = 0.015). The total myelin volume was lower in mTBI patients with PCS than that in controls at the corpus callosum (0.45 cm3 [0.39-0.48 cm3] vs. 0.48 cm3 [0.45-0.54 cm3]; p = 0.004) and brainstem (1.45 cm3 [1.28-1.59 cm3] vs. 1.54 cm3 [1.42-1.67 cm3]; p = 0.042). No significant correlation was observed between myelin volume parameters and neuropsychological test scores, except for the total myelin volume at the bilateral cerebral WM and verbal learning test (delayed recall) (r = 0.425; p = 0.048). Conclusion: MVF quantified from the MDME sequence was decreased at the bilateral cerebral WM in mTBI patients with PCS. The total myelin volumes at the corpus callosum and brainstem were decreased in mTBI patients with PCS due to atrophic changes.

Combined Modality Therapy with Selective Bladder Preservation for Muscle Invading Bladder Cancer (침윤성 방광암 환자에서 방광 보존 치료)

  • Youn Seon Min;Yang Kwang Mo;Lee Hyung Sik;Hur Won Joo;Oh Sin Geun;Lee Jong Cheol;Yoon Jin Han;Kwon Heon Young;Jung Kyung Woo;Jung Se Il
    • Radiation Oncology Journal
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    • v.19 no.3
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    • pp.237-244
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    • 2001
  • Purpose : To assess the tolerance, complete response rate, bladder preservation rate and survival rate in patients with muscle-invading bladder cancer treated with selective bladder preservation protocol. Method and Materials : From October 1990 to June 1998, twenty six patients with muscle-invading bladder cancer (clinical stage T2-4, N0-3, M0) were enrolled for the treatment protocol of bladder preservation. They were treated with maximal TURBT (transurethral resection of bladder tumor) and 2 cycles of MCV chemotherapy (methotrexate, crisplatin, and vinblastine) followed by $39.6\~45\;Gy$ pelvic irradiation with concomitant cisplatin. After complete urologic evaluation (biopsy or cytology), the patients who achieved complete response were planed for bladder preservation treatment and treated with consolidation cisplatin and radiotherapy (19.8 Gy). The patients who had incomplete response were planed to immediate radical cystectomy. If they refused radical cystectomy, they were treated either with TURBT followed by MCV or cisplatin chemotherapy and radiotherapy. The median follow-up duration is 49.5 months. Results : The Patients with stage T2-3a and T3b-4a underwent complete removal of tumor or gross tumor removal by TURBT, respectively. Twenty one out of 26 patients $(81\%)$ successfully completed the protocol of the planned chemo-radiotherapy. Seven patients had documented complete response. Six of them were treated with additional consolidation cisplatin and radiotherapy. One patient was treated with 2 cycles of MCV chemotherapy due to refusal of chemo-radiotherapy. Five of 7 complete responders had functioning tumor-free bladder. Fourteen patients of incomplete responders were further treated with one of the followings : radical cystectomy (1 patient), or TURBT and 2 cycles of MCV chemotherapy (3 patients), or cisplatin and radiotherapy (10 patients). Thirteen patients of them were not treated with planned radical cystectomy due to patients' refusal (9 patients) or underlying medical problems (4 patients). Among twenty one patients, 12 patients $(58\%)$ were alive with their preserved bladder, 8 patients died with the disease, 1 patient died of intercurrent disease. The 5 years actuarial survival rates according to CR and PR after MCV chemotherapy and cisplatin chemoradiotherapy were $80\%\;and\;14\%$, respectively (u=0.001). Conclusion : In selected patients with muscle-invading bladder cancer, the bladder preservation could be achieved by MCV chemotherapy and cisplatin chemo-radiotherapy. All patients tolerated well this bladder preservation protoco. The availability of complete TURBT and the responsibility of neoadjuvant chemotherapy and chemoradiotherapy were important predictors for bladder preservation and survival. The patients who had not achieved complete response after neoadjuvant chemotherapy and chemoradiotherapy should be immediate radical cystectomy. A randomized prospective trial might be essential to determine more accurate indications between cystectomy or bladder preservation.

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