• Proceedings of the Materials Research Society of Korea Conference
• /
• 2011.05a
• /
• pp.5-5
• /
• 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 the Korean Crystal Growth and Crystal Technology
• /
• v.6 no.3
• /
• pp.327-340
• /
• 1996

In this study, a series of $LiNbO_{3}$ crystals with different [Li]/[Nb] ratios, congruent $LiNbO_{3}$ crystals with doped Mg and with Mg and codoped with Mn were grown by the Czocharalski method. These were investigated by UV and IR spectrophotometry. Stoichiometry dependences of the UV absorption edge and the $OH^{-}$ absorption spectra were studied with different [Li]/[Nb] ratios. The position of the UV absorption edge adn the shape and peak point of the $OH^{-}$ absorption spectra changed monotonously upto a critical concentration of Mg ions. The mechanism of the incorporation of Mg ions changes at this concentration. The decomposition of the $OH^{-}$ absorption spectra using a Gaussian lineshape function showed that in Li-deficient crystals the absorption spectra consist of five components in contrast to more or less perfect stoichiometric crystals which reveal to three components. On the basis of these results, the intrinsic and the extrinsic defect structure models in $LiNbO_{3}$ crystals were examined. The behaviour of $\nu$ (OH) reflects the defect structure and supports the Li-site vacancy model as the intrinsic defect structure model and the corresponding extrinsic defect model. A brief discussion is also given of the behaviour of $\nu$ (OH) in $LiNbO_{3}$ crystals simultaneously doped with several kinds of impurity.

• Proceedings of the Korean Powder Metallurgy Institute Conference
• /
• 2006.09a
• /
• pp.694-695
• /
• 2006

As a candidate for lead-free piezoelectric materials, dense $95(Na_{0.5}K_{0.5})NbO_3-5LiTaO_3$ (NKN-5LT) ceramics were developed by conventional sintering process. Sintering temperature was lowered by adding $Li_2O$ as a sintering aid. The electrical properties of NKN-5LT ceramics were investigated as a function of $Li_2O$ concentration. At the addition of 1 mol% $Li_2O$, electromechanical coupling factor $(k_P)$ and piezoelectric coefficient $(d_{33})$ of NKN-5LT ceramics were found to reach the highest values of 0.37 and 250 pC/N, respectively.

• Transactions on Electrical and Electronic Materials
• /
• v.7 no.2
• /
• pp.76-80
• /
• 2006

Well-defined orthorhombic $LiMnO_2\;and\;LiCo_{0.1}Mn_{0.9}O_2$ were synthesized by a solid-state reaction and quenching process. X-ray diffraction (XRD) results revealed that the as-synthesized powders showed an orthorhombic phase of a space group with Pmnm. The $Li/LiMnO_2\;and\;Li/LiCo_{0.1}Mn_{0.9}O_2$ cells were constituted and cycled galvanostatically in the voltage range of 2.0-4.3 V vs. $Li/Li^+$ at a current density of $0.5\;mA\;cm^{-2}$ at room temperature and $50^{\circ}C$, respectively. The results demonstrated that the highest specific capacity of $Li/LiMnO_2$ cells at room temperature and $50^{\circ}C$ was 95 and $155\;mAh\;g^{-1}$, respectively. As for $Li/LiCo_{0.1}Mn_{0.9}O_2$ cells, the highest specific capacity at room temperature and $50^{\circ}C$ was 160 and $250\;mAh\;g^{-l}$, respectively. It could be seen that the performance of $Li/LiCo_{0.1}Mn_{0.9}O_2$ cells was better than that of $Li/LiMnO_2$ cells.

• Journal of the Korean Ceramic Society
• /
• v.48 no.5
• /
• pp.379-383
• /
• 2011

This paper presents the synthesis of one-dimensional spinel $LiMn_2O_4$ nanostructures using a facile and scalable two-step process. $LiMn_2O_4$ nanorods with average diameter of 100 nm and length of 1.5 ${\mu}m$ have been prepared by solid-state lithiation of hydrothermally synthesized ${\beta}$-$MnO_2$ nanorods. $LiMn_2O_4$ nanowires with diameter of 10 nm and length of several micrometers have been fabricated via solid-state lithiation of ${\beta}$-$MnO_2$ nanowires. The precursors have been lithiated with LiOH and reaction temperature and pressure have been controlled. The complete structural transformation to cubic phase and the maintenance of 1-D nanostructure morphology have been evaluated by XRD, SEM, and TEM analysis. The size distribution of the spinel $LiMn_2O_4$ nanorods/wires has been similar to the $MnO_2$ precursors. By control of reaction pressure, cubic 1-D spinel $LiMn_2O_4$ nanostructures have been fabricated from tetragonal $MnO_2$ precursors even below $500^{\circ}C$.

• Journal of the Korean Electrochemical Society
• /
• v.17 no.2
• /
• pp.103-110
• /
• 2014

In the study, a room temperature ionic liquids as a co-solvent was used to evaluate the feasibility with various electrodes in Li-ion batteries. 1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl) imide(PP12 TFSI) is an ionic liquid that melts at $85^{\circ}C$. Pure PP12 TFSI is not able to be used as an electrolyte because it is a solid salt at room temperature. PP12 TFSI is mixed with EC/DEC(1/1 vol.%) to prepare mixed solvents. The electrolyte 1.5M $LiPF_6$ in a mixed solvent having 44 wt.% PP12 TFSI is prepared to evaluated the various electrodes. The electrolytes provides good cycles life of cells with $LiNi_{0.5}Mn_{1.5}O_4(LNMO)$, $LiFePO_4(LFP)$, $Li_4Ti_5O_{12}(LTO)$ and artificial graphite. Further improvement of the cell performances can be accomplished by enhancing wettability of electrolytes to electrodes.

• Journal of the Korean Electrochemical Society
• /
• v.18 no.1
• /
• pp.17-23
• /
• 2015

$Li_4Ti_5O_{12}$ (LTO) have attracted much attention of researchers in the field of energy storage, because of their excellent stability for electric vehicle application. A main drawback of LTO is however their insulating nature due to the wide bandgap, which should be addressed to enhance the battery performance. In this study, we investigated the effect of water solubility of dopant precursor on the electrochemical characteristics of conducting LTO prepared by doping with $Cr^{3+}$ ions with the well-known wet-mixing method. The solubility of dopant precursor directly affected the morphology and the phase of doped LTO, and therefore their battery performance. In the case of employing the most soluble dopant precursor, $Cr(NO_3)_2$, the doped LTO demonstrated a markedly enhanced discharge capacity at high C-rate (130mAh/g @ 10C), which is about 2 times higher value than that of bare LTO.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 1997.05a
• /
• pp.90-90
• /
• 1997

• Korean Journal of Materials Research
• /
• v.15 no.5
• /
• pp.293-300
• /
• 2005

ZnO:Li epilayers were synthesized on sapphire substrates by the pulesd laser deposition (PLD) after the surface of the ZnO:Li sintered pellet was irradiated by the ArF (193 nm) excimer laser. The growth temperature was fixed at $400^{\circ}C$. The crystalline structure of epilayers was investigated by the photoluminescence (PL) and double crystal X-ray diffraction (DCXD). The carrier density and mobility of epilayers measured by van der Pauw-Hall method are $2.69\times10cm^{-3}$ and $52.137cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of epilayers obtained from the absorption spectra is well described by the Varshni's relation, $E_g(T)=3.5128eV{\cdot}(9.51\times10^{-4}eV/K)T^2/(T+280K)$. After the as-grown ZnO:Li epilayer was annealed in Zn atmospheres, oxygen and vaccum the origin of point defects of ZnO:Li has been investigated by PL at 10 K. The Peaks of native defects of $V_{zn},\;V_o,\;Zn_{int},\;and\;O_{int}$ showned on PL spectrum are classified as a donors or accepters type. We confirm that $ZnO:Li/Al_2O_3$ in vacuum do not form the native defects because ZnO:Li epilayers in vacuum existe in the form of stable bonds.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2003.11a
• /
• pp.209-209
• /
• 2003

The adventages of Li alloys have attracted the attention of many research groups, many of which have investigated tin-based alloys [1-2], Despite interesting performances of these, the irreversible capacity loss systematically observed on the first cycle for these compounds is a main drawback for their use as anode materials in lithium ion cells. Not only Sn is efficient in forming alloys with Li, Si can also react with Li to form alloys with a high Li/Si ratio, like Li$\_$22/Si$\_$5/ at 400$^{\circ}C$. It corresponds to a capacity of 4200mAh/g. Electrochemical Li-Si reaction occurs between 0 and 0.3 V against Li/Li$\^$+/, so that high-energy density battery can be realized. Despite the high theoretical capacity of elements like Si, however, particles of the alloys crack and fragment due to the repeated alloying and do-alloying which occurs as cell are charged and discharged. The research groups of Muggins [3] and Besenhard [4] have proposed that the volume expansion due to the insertion of Li can be reduced in micro- and submicro-structured matrix alloys. For this reason, the research group of J.R. Dahn investigated Sn/Mo sequential sputter deposition to prepare nanocomposites [5]. In this study, we investigated the characterization and the electrochemical characteristics of sequentially sputtered Si/Mo multilayer for microbattery anode.