• 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.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.283-291
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• 2010

In this review, the studies on the electrochemical properties of $TiO_2$ nanotube as an anode material of lithium-ion battery, which was prepared by an alkaline hydrothermal reaction and anneling process, were investigated andanalyzed in terms of charge-dischage characteristics. Up to date, a maximum discharge capacity of $338mAh\;g^{-1}$(x=1.01) was achieved by the nanotube with $TiO_2(B)$ phase, whereas the theoretical capacity of $TiO_2$ anode was $335mAh\;g^{-1}$(x=1) in the basis of $Li_xTiO_2$ as a product of electrochemical reaction between $TiO_2$ and lithium. This was due to fast lithium transport by a shortened diffusion path provided by controlling the nanostructure of $TiO_2$, because the self-diffusion of lithium was slow in a basis of its activation energy as 0.48 eV. Due to an excellent ion storage capabilities in both the surface and the bulk phase, the $TiO_2$ nanotube could be a promising active material as both an anode of lithium-ion battery and an electrode of capacitor with high-rate performances.

• Applied Chemistry for Engineering
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• v.27 no.4
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• pp.415-420
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• 2016

To enhance electrochemical performances of anode materials, the surface of coal tar pitch (CTP) was modified by incorporating heteroatoms through chemical treatment with phosphoric acid ($H_3PO_4$). The prepared anode materials with modified CTP was analyzed by XRD, FE-SEM and XPS. The electrochemical performances of modified CTP were investigated by constant current charge/discharge test, rate performance, cyclic voltammetry and impedance tests using the electrolyte of $LiPF_6$ dissolved in the mixed organic solvents (ethylene carbonate : dimethyl carbonate = 1 : 1 vol% + vinylene carbonate 3 wt%). The coin cell using modified CTP ($H_3PO_4/CTP$ = 3 : 100 in weight) has better initial capacity and initial efficiency (489 mAh/g, 82%) than those of other composition coin cells. Also, it was found that the capacity retention was 86% after 30 cycles and the rate capability was 87% at 2 C/0.1 C.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.29 no.10
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• pp.652-658
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• 2016

Thermal batteries use inorganic salt as electrolyte, which is inactive at room temperature. As soon as heat pellets are fired by an igniter, all the solid electrolytes are instantly melted into excellent ionic conductors. However, the abnormal heat generation by the igniter flame or heat pellets causes the thermal decomposition of the electrode and the melting of the anode, eventually leading to a thermal runaway, which results in overheating or explosion. The thermal runaway can be significantly reduced by the adoption of $Zr/BaCrO_4$ heat papers. In this study, the heat papers with various ratios of fuel (Zr) and oxidizer ($BaCrO_4$) were prepared by the paper-making process. We have investigated the calorimetric value, burning rate, and ignition sensitivity. The ignition test of heat pellets and the discharge test of thermal batteries were also carried out. At the composition of 40 wt.% of Zr, the heat papers showed the highest specific calorimetric value and burning rate. As a result, $Zr/BaCrO_4$ heat paper made by the paper-making process has shown the applicability for thermal batteries.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.73-73
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• 2012

Modern technology-driven society largely relies on hybrid electric vehicles or electric vehicles for eco-friendly transportation and the use of high technology devices. Lithium rechargeable batteries are the most promising power sources because of its high energy density but still have a challenge. Graphite is the most widely used anode material in the field of lithium rechargeable batteries due to its many advantages such as good cyclic performances, and high charge/discharge efficiency in the initial cycle. However, it has an important safety issue associated with the dendritic lithium growth on the anode surface at high charging current because the conventional graphite approaches almost 0 V vs $Li/Li^+$ at the end of lithium insertion. Therefore, a fundamental solution is to use an electrochemical redox couple with higher equilibrium potentials, which suppresses lithium metal formation on the anode surface. Among the candidates, $Li_4Ti_5O_{12}$ is a very interesting intercalation compound with safe operation, high rate capability, no volume change, and excellent cycleability. But the insulating character of $Li_4Ti_5O_{12}$ has raised concerns about its electrochemical performance. The initial insulating character associated with Ti4+ in $Li_4Ti_5O_{12}$ limits the electronic transfer between particles and to the external circuit, thereby worsening its high rate performance. In order to overcome these weak points, several alternative synthetic methods are highly required. Hence, in this presentation, novel ways using a synergetic strategy based on 1D architecture and surface coating will be introduced to enhance the kinetic property of Ti-based electrode. In addition, first-principle calculation will prove its significance to design Ti-based electrode for the most optimized electrochemical performance.

• Journal of the Korean Electrochemical Society
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• v.24 no.4
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• pp.93-99
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• 2021

In order to decrease the weight of stretchable energy storage devices, interest in developing lightweight materials to replace metal current collectors is increasing. In this study, nanofibers prepared by electrospinning a conductive polymer, PEDOT:PSS, were used as current collectors for lithium ion batteries. The nanofiber showed improved electrical conductivity by using DMSO, a dopant, and indicated a stretch rate of 30% or more from the elasticity evaluation result. In addition, the use of the nanofiber current collector facilitates penetration of the liquid electrolyte and exhibits the effect of increasing the electronic conductivity through the nanofiber network. The lithium-ion battery using the DMSO-doped PEDOT:PSS@PAM nanofiber current collector indicated a high discharge capacity of 135mAh g^-1, and indicated a high capacity retention rate of 73.5% after 1000 cycles. Thus, the excellent electrochemical stability and mechanical properties of conductive nanofibers showed that they can be used as lightweight current collectors for stretchable energy storage devices.

• Journal of the Korean institute of surface engineering
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• v.56 no.1
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• pp.104-114
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• 2023

Three dimensional (3D) porous structures consisting of Cu@CoO core-shell-type nano-dendrites were synthesized and tested as the anode materials in lithium secondary batteries. For this purpose, first, the 3D porous films comprising Cu@Co core-shell-type nano-dendrites with various thicknesses were fabricated through the electrochemical co-deposition of Cu and Co. Then the Co shells were selectively anodized to form Co hydroxides, which was finally dehydrated to get Cu@CoO nanodendrites. The resulting electrodes exhibited very high reversible specific capacity almost 1.4~2.4 times the theoretical capacity of commercial graphite, and excellent capacity retention (~90%@50^th cycle) as compared with those of the existing transition metal oxides. From the analysis of the cumulative irreversible capacity and morphology change during charge/discharge cycling, it proved that the excellent capacity retention was attributed to the unique structural feature of our core-shell structure where only the thin CoO shell participates in the lithium storage. In addition, our electrodes showed a superb rate performance (70.5%@10.8 C-rate), most likely due to the open porous structure of 3D films, large surface area thanks to the dendritic structure, and fast electron transport through Cu core network.

• Korean Chemical Engineering Research
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• v.55 no.3
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• pp.307-312
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• 2017

In this study, the electrochemical performance of surface modified carbon using the PFO (pyrolyzed fuel oil) was investigated by chemical activation with KOH and $K_2CO_3$. PFO was heat treated at $390{\sim}400^{\circ}C$ for 1~3h to prepared the pitch. Three carbon precursors (pitch) prepared by the thermal reaction were 3903 (at $390^{\circ}C$ for 3h), 4001(at $400^{\circ}C$ for 1h) and 4002 (at $400^{\circ}C$ for 2h). Also, the effect of chemical activation catalysts and mixing time on the development of porosity during carbonization was investigated. The prepared carbon was analyzed by BET and FE-SEM. It was shown that chemical activation with KOH could be successfully used to develop carbon with specific surface area ($3.12m^2/g$) and mean pore size (22 nm). The electrochemical characteristics of modified carbon as the anode were investigated by constant current charge/discharge, cyclic voltammetry and electrochemical impedance tests. The coin cell using pitch (4002) modified by KOH has better initial capacity (318 mAh/g) than that of other pitch coin cells. Also, this prepared carbon anode appeared a high initial efficiency of 80% and the retention rate capability of 2C/0.1 C was 92%. It is found that modified carbon anode showed improved cycling and rate capacity performance.

• Journal of the Korean Electrochemical Society
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• v.15 no.3
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• pp.172-180
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• 2012

The $LiMn_2O_4$ cathodes for lithium ion battery were synthesized from various precursors of manganese oxides and manganese hydroxides. As the first step, nanosized precursors such as ${\alpha}-MnO_2$ (nano-sticks), ${\beta}-MnO_2$ (nano-rods), $Mn_3O_4$ (nano-octahedra), amorphous $MnO_2$(nano-spheres), and $Mn(OH)_2$ (nano-plates) were prepared by a hydrothermal or a precipitation method. Spinel $LiMn_2O_4$ with various sizes and shapes were finally synthesized by a solid-state reaction method from the manganese precursors and LiOH. Nano-sized (500 nm) octahedron $LiMn_2O_4$ showed high capacities of 107 mAh $g^{-1}$ and 99 mAh $g^{-1}$ at 1 C- and 50 C-rate, respectively. Three dimensional octahedral crystallites exhibit superior electrochemical characteristics to the other one-dimensional and two-dimensional shaped $LiMn_2O_4$ nanoparticles. After 500 consecutive charge discharge battery cycles at 10 C-rate with the nano-octahedron $LiMn_2O_4$ cathode, the capacity retention of 95% was observed, which is far better than any other morphologies studied in this work.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.868-873
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• 2019

In this study, the evaluation of performance of AORFB using methyl viologen and TEMPOL as organic active materials in neutral supporting electrolyte (NaCl) with various membrane types was performed. Using methyl viologen and TEMPOL as active materials in neutral electrolyte solution, the cell voltage is 1.37V which is relatively high value for AORFB. Two types of membranes were examined for performance comparison. First, when using Nafion 117 membrane which is commercial cation exchange membrane, only the charge process occurred in the first cycle and the single cell couldn't work because of its high resistance. However, when using Fumasep anion exchange membrane (FAA-3-50) instead of Nafion 117 membrane, the result was obtained as the totally different charge-discharge graphs. When current density was $40mA{\cdot}cm^{-2}$ and cut off voltage range was from 0.55 V to 1.7 V, the charge efficiency (CE) was 97% and voltage efficiency (VE) was 78%. In addition, the discharge capacity was $1.44Ah{\cdot}L^{-1}$ which was 54% of theoretical capacity ($2.68Ah{\cdot}L^{-1}$) at $10^{th}$ cycle and the capacity loss rate was $0.0015Ah{\cdot}L^{-1}$ per cycle during 50 cycles. Through cyclic voltammetry test, it seems that this difference in the performance between the full cell using Nafion 117 membrane and Fumasep anion exchange membrane came from increasing resistance due to chemical reaction between membrane and active material, not the capacity loss due to cross-over of active material through membrane.