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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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A SOC Coefficient Factor Calibration Method to improve accuracy Of The Lithium Battery Equivalence Model (리튬 배터리 등가모델의 정확도 개선을 위한 SOC 계수 보정법)

  • Lee, Dae-Gun;Jung, Won-Jae;Jang, Jong-Eun;Park, Jun-Seok
    • Journal of the Institute of Electronics and Information Engineers
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    • v.54 no.4
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    • pp.99-107
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    • 2017
  • This paper proposes a battery model coefficient correction method for improving the accuracy of existing lithium battery equivalent models. BMS(battery management system) has been researched and developed to minimize shortening of battery life by keeping SOC(state of charge) and state of charge of lithium battery used in various industrial fields such as EV. However, the cell balancing operation based on the battery cell voltage can not follow the SOC change due to the internal resistance and the capacitor. Various battery equivalent models have been studied for estimation of battery SOC according to the internal resistance of the battery and capacitors. However, it is difficult to apply the same to all the batteries, and it tis difficult to estimate the battery state in the transient state. The existing battery electrical equivalent model study simulates charging and discharging dynamic characteristics of one kind of battery with error rate of 5~10% and it is not suitable to apply to actual battery having different electric characteristics. Therefore, this paper proposes a battery model coefficient correction algorithm that is suitable for real battery operating environments with different models and capacities, and can simulate dynamic characteristics with an error rate of less than 5%. To verify proposed battery model coefficient calibration method, a lithium battery of 3.7V rated voltage, 280 mAh, 1600 mAh capacity used, and a two stage RC tank model was used as an electrical equivalent model of a lithium battery. The battery charge/discharge test and model verification were performed using four C-rate of 0.25C, 0.5C, 0.75C, and 1C. The proposed battery model coefficient correction algorithm was applied to two battery models, The error rate of the discharge characteristics and the transient state characteristics is 2.13% at the maximum.

Effects of Pressure-shift Freezing on the Structural and Physical Properties of Gelatin Hydrogel Matrices

  • Kim, Byeongsoo;Gil, Hyung Bae;Min, Sang-Gi;Lee, Si-Kyung;Choi, Mi-Jung
    • Food Science of Animal Resources
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    • v.34 no.1
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    • pp.33-39
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    • 2014
  • This study investigates the effects of the gelatin concentration (10-40%, w/v), freezing temperatures (from $-20^{\circ}C$ to $-50^{\circ}C$) and freezing methods on the structural and physical properties of gelatin matrices. To freeze gelatin, the pressure-shift freezing (PSF) is being applied at 0.1 (under atmospheric control), 50 and 100 MPa, respectively. The freezing point of gelatin solutions decrease with increasing gelatin concentrations, from $-0.2^{\circ}C$ (10% gelatin) to $-6.7^{\circ}C$ (40% gelatin), while the extent of supercooling did not show any specific trends. The rheological properties of the gelatin indicate that both the storage (G') and loss (G") moduli were steady in the strain amplitude range of 0.1-10%. To characterize gelatin matrices formed by the various freezing methods, the ice crystal sizes which were being determined by the scanning electron microscopy (SEM) are affected by the gelatin concentrations. The ice crystal sizes are affected by gelatin concentrations and freezing temperature, while the size distributions of ice crystals depend on the freezing methods. Smaller ice crystals are being formed with PSF rather than under the atmospheric control where the freezing temperature is above $-40^{\circ}C$. Thus, the results of this study indicate that the PSF processing at a very low freezing temperature ($-50^{\circ}C$) offers a potential advantage over commercial atmospheric freezing points for the formation of small ice crystals.

Improvement of Positioning Performance for GPS Module(KGP9800C) (GPS모듈(KGP9800C)의 측위성능개선)

  • 신형일;김형석;김석재;배문기;박노선
    • Journal of the Korean Society of Fisheries and Ocean Technology
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    • v.37 no.3
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    • pp.181-189
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    • 2001
  • This paper describes the positioning accuracy of GPS moduls (KGP9800C, KiRyung) which need to record the operating position of fishing boat as realtime processing in order to develope auto recording system of fishing boat's operating information, and then it's positioning accuracy for DGPS receiver (MGP-100D, Shin-A) and DGPS beacon (GP-36, Furuno) were analyzed. Futhermore, it was examined the positioning error of the GPS module with processing algorithm to minimize the effect of the signal fluctuations. The results indicate that the positioning error is able to decrease 5m as 2drms, and such improvement of positioning performance for GPS module (KGP9800C) can be provide the basic design data in the development of the auto recording system of fishing boat's operating information.

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Thermal Effects on Stoichiometric LiTaO3 Single Crystal (정비조성 LiTaO3 단결정에 대한 열처리 효과)

  • Yeom, T.H.;Lee, S.H.
    • Journal of the Korean Magnetics Society
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    • v.15 no.3
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    • pp.177-180
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    • 2005
  • Ferroelectric $LiTaO_3$ single crystals, grown by the Czochralski method, were thermally treated at temperature $1000^{\circ}C\;and\;1100^{\circ}C$. Electron paramagnetic resonance (EPR) study of stoichiometric $LiTaO_3$ and thermally treated $LiTaO_3$ crystals has been investigated by employing an X-band spectrometer. From the $Fe^{3+}$ EPR spectra, it turned out that there is no change of site location and local site symmetry around $Fe^{3+}$ impurity ion between stoichiometric and thermally treated $LiTaO_3$ single crystals. We confirmed that the ionic state of $Fe^{3+}$ ion changed after thermal treatment. The EPR parameters of $Fe^{3+}$ ion in $LiTaO_3$ single crystals are determined with effective spin Hamiltonian.

Expression of c-Type Lysozyme from the Fleshy Shrimp Fenneropenaeus chinensis Is Upregulated Following Vibrio anguillarum and Lipopolysaccharide Injection

  • Qiao, Guo;Kim, Su-Kyoung;Cho, Yeong-Rok;Kim, Sukyoung;Jang, In-Kwon
    • Fisheries and Aquatic Sciences
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    • v.16 no.4
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    • pp.267-272
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    • 2013
  • Chicken-type lysozyme (c-lysozyme) is present in shrimp and is active against some bacteria. To further understand the regulation of c-lysozyme in the fleshy shrimp Fenneropenaeus chinensis, we determined the tissue-specific gene expression of c-lysozyme and the time-course of mRNA expression in response to Vibrio anguillarum and lipopolysaccharide (LPS) injection by quantitative reverse real-time polymerase chain reaction. The results showed that c-lysozyme was expressed in all tissues tested, including gill, eyestalk, eye, hemocytes, hepatopancreas, intestine, heart, and pleopod. It was most highly expressed in the intestine followed by the eyestalk, gill, hemocytes and hepatopancreas. The mRNA expression level began to decline in a short time after V. anguillarum challenge and was then upregulated by two fold or more at 24 h post injection (hpi) compared to that at 0 h. Expression was suppressed shortly after LPS injection and began to increase with higher levels of 5.8-, 5.2- and 8.4-fold at 24, 48, and 72 hpi, respectively. Higher expression was sustained and showed a gradual increasing trend until the end of the experiment (72 hpi). These results increase our understanding of the regulation of defense mechanisms and facilitate an evaluation of the effects of probiotics or immunostimulants in shrimp culture.

Preparation and Characterization of a Propofol-loaded Polymeric Micellar System: Nanoparticular Stability

  • Cho, Jae-Pyoung;Cho, Jin-Cheol;Oh, Eui-Chaul
    • Journal of Pharmaceutical Investigation
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    • v.38 no.6
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    • pp.393-398
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    • 2008
  • A propofol delivery system was prepared using two biocompatible polymeric surfactants, poloxamer 407 and PEG 400. The nanoparticular stability of the micellar system was evaluated in terms of temperature change, storage time and composition. The particle size of the system was slightly increased with elevating temperature from $4^{\circ}C$ to $25^{\circ}C$, but its distribution was unimodal. At $40^{\circ}C$, the system presented a bimodal particle size distribution and the increase in the fraction of particles larger than 15 nm. This result might be due to the expansion of the nanoparticles through micellar swelling at the high temperature. It was found that propofol was gradually come out of the system, stored for a month at three different temperatures (4, 25 and $40^{\circ}C$). The drug loss was apparently dependent on temperature and the system composition. Increasing temperature induced the acceleration of the drug loss of $7{\sim}10%$ at $4^{\circ}C$ and $14{\sim}16 %$ at $40^{\circ}C$. This may be owing to the high diffusivity resulting from the swelling of the hydrophilic surface of the nanoparticle at high temperature. However, the addition of PEG 400 to the system led to the reduction of the drug loss. This result is associated with the previous investigation that PEG coverage decreased diffusion coefficient because of the formation of the denser structure on the surface of nanoparticulate. Nevertheless, the limited amount of PEG, less than 2% (w/v), should be used to prevent the precipitation and discoloration of the system.

Effects of Light, Temperature, and Water Stress on the Photosynthesis and Respiration Rates of Leaves in Four Oak Species (4종(種)의 참나무엽(葉)의 광합성속도(光合成速度)와 호흡속도(呼吸速度)에 미치는 광(光), 온도(溫度), 수분(水分)의 영향(影響))

  • Han, Sang Sup;Kim, Ha Sun
    • Journal of Korean Society of Forest Science
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    • v.78 no.2
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    • pp.151-159
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    • 1989
  • The present study has been designed to define the effects of photosynthetically active radiation, leaf temperature, and water stress on photosynthesis and respiration of leaves of four oak species (Quercus mongolica, Quercus aliens, Quercus variabilis, and Quercus serrate). The results obtained are as follows : 1. The estimated light compensation points at which Pn approached zero were 38, 24, 20, and $18{\mu}Em^{-2}s^{-1}$ for Q. aliens, Q. variabilis, Q, mongolica, and Q. serrate, respectively. The light saturation points occurred at $500{\mu}Em^{-2}s^{-1}$ in three oak species except Q, aliens. 2. The maximum rates of Pn were 19.7, 15.2, 11.2, and 11.0 mg $CO_2$ $dm^{-2}h^{-1}$ for Q. variabilis, Q. serrate, Q. monglica, and Q. aliens leaves, respectively. 3. The transpiration rates of Q. variabilis and Q. serrate leaves were slightly higher than those of Q. mongolica and Q. aliens leaves at various photosynthetically active radiations(PAR), but cuticular transpiration rates at dark were similar in four oak species. 4. The optimum photosynthesis occurred at $25^{\circ}C$ in Q. aliens, Q. variabilis, and Q. serrate leaves, but $20^{\circ}C$ in Q. mongolica leaves. In four oak species, the net photosynthesis approached zero at about $40^{\circ}C$. 5. The dark respiration rates of leaves exhibited the following ranking of species : Q, variabilis > Q. mongolica > Q. aliens > Q. serrate. 6. The maximum productive efficiency (Pg/Rd) of leaves occurred highest in Q, serrate at $20^{\circ}C$, then in Q. mongolica at $20^{\circ}C$, then in Q, aliens at $25^{\circ}C$, and finally in Q. variabilis at $15^{\circ}C$. 7. The decrease of net photosynthesis in Q. serrate began at about -1.2 MPa, and then approached zero at -2.9 MPa of leaf water potential. The decrease of net photosynthesis began at 3% of water loss, and then approached zero at 17.5% of water loss. 8. As indicated by tissue-water relations parameters, it may be suggested that Q. aliens and Q. variabilis are more tolerant and favored on xeric forest soils than Q. mongolica and Q. serrate.

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Synthesis of m-Oxo and Bis( m-alkoxo) Bridged Diiron(III) Complexes Using a Tripodal Ligand, Bis(2-benzimidazolylmethy)ethanolamine

  • Gwak, Byeong Hun;Lee, Myeong Su
    • Bulletin of the Korean Chemical Society
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    • v.21 no.1
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    • pp.65-68
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    • 2000
  • A $\mu-oxo$ diiron(III) complex and two bis( $\mu-alkoxo)$ diiron(III) complexes with biomimetic tripodal ligand containing mixed N/O donor atoms were synthesized using a mononuclear iron(III) complex as starting material. Depending on the amounts and kinds of bases used, we obtained various kinds of diiron (III) complexes. The reaction of $[$Fe^{III}$(Hbbea)Cl_2]Cl$, 1, with an equivalent amount of $KO_2$ or NaOAc produced $[$Fe^{III}$_2O(Hb-bea)_2Cl_2]Cl_2$, 2. An additional equivalent amount of NaOBz or NaOAc converts complex 2 to complex 3 or complex 4 depending on the base used. The addition of two equivalent amounts of NaOBz orNaOAc directly converts complex 1 to $[$Fe^{III}$_2(bbea)_2(OBz)_2]Cl_2$, 3, or $[$Fe^{III}$_2(bbea)_2(OAc)_2]Cl_2$, 4, depending on the base used. Crystal data are as follows: [$Fe^{III}_2O(Hbbea)_2Cl_2]Cl_2$, 2: monoclinic space group $$P2_1/n$$, a = 8.421 (1) $\AA$, b = 18.416 (2) $\AA$, c = 13.736 (1) $\AA$, $\beta$ = 104.870 $(7)^{\circ}$, V = 2058.9 (4) $\AA^3$, Z = 2, R1 = 0.0469 and wR2 = 0.1201 for reflections with I > 2 ${\sigma}$(I).

The Scope and the Meaning of 'Time of Arrival' in Carriage of Passengers by Air : Focused on the Germanwings GmbH v. Ronny Henning, Case C-452/13 (2014). (항공여객운송에서의 지연보상과 도착시각의 의미 - EU 사법재판소 2014. 9. 14. 판결(ECLI:EU:C:2014:2141)을 중심으로 -)

  • Sur, Ji-Min
    • The Korean Journal of Air & Space Law and Policy
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    • v.33 no.2
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    • pp.267-290
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    • 2018
  • This paper reviews and criticizes the EU Case of C-452/13, Germanwings GmbH v. Ronny Henning. Under this case, Ronny Henning later sued Lufthansa's budget carrier Germanwings after it refused to pay him 250 euros compensation for a delay he said totalled more than three hours. Germanwings, however, maintained his flight had arrived only two hours and 58 minutes behind schedule. In those circumstances, the following question to the European Court of Justice (ECJ) for a preliminary ruling: What time is relevant for the term time of arrival used in Articles 2, 5 and 7 of Regulation [No 261/2004]: (a) the time that the aircraft lands on the runway (touchdown); (b) the time that the aircraft reaches its parking position and the parking brakes are engaged or the chocks have been applied (in-block time); (c) the time that the aircraft door is opened; (d) a time defined by the parties in the context of party autonomy? ECJ says that the situation of passengers on a flight does not change substantially when their aircraft touches down on the runway at the destination airport, when that aircraft reaches its parking position and the parking brakes are engaged or when the chocks are applied, as the passengers continue to be subject, in the enclosed space in which they are sitting, to various constraints. Therefore, it is only when the passengers are permitted to leave the aircraft and the order is given to that effect to open the doors of the aircraft that the passengers may in principle resume their normal activities without being subject to those constraints. ECJ rules that it is apparent that Articles 2, 5 and 7 of Regulation No 261/2004 must be interpreted as meaning that the concept of 'arrival time', which is used to determine the length of the delay to which passengers on a flight have been subject, corresponds to the time at which at least one of the doors of the aircraft is opened, the assumption being that, at that moment, the passengers are permitted to leave the aircraft.