• 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.

• Proceedings of the Korean Ceranic Society Conference
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• 2003.10a
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• pp.121.2-121
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• 2003

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.413-413
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• 2011

최근 전기, 전자, 반도체 산업의 발전으로 전 고상 박막리튬전지는 초소형, 초경량의 마이크로 소자의 구현을 위한 고밀도 에너지원으로 각광받고 있다. 현재 양극박막은 대부분LCO(LiCoO2)계열이 이용되고 있으나, 코발트는 높은 가격과 인체 유해성 뿐만 아니라 상대적으로 낮은 용량(~140 mAh/g)등의 단점을 갖고 있어 향후 보다 고용량의 양극박막이 요구된다. 3원계 양극활물질 LiMO2(M=Co,Ni,Mn,etc.)은 우수한 충방전 효율 과 열적 안정성 뿐 아니라 277mAh/g의 높은 이론용량을 갖고 있어 고용량 양극박막으로의 적용시 고용량 박막이차전지 제작이 가능하다. 본 연구에서는 전 고상 박막 전지의 구현을 위하여 RF 스퍼터링법을 사용하여 Li[Li0.2Mn0.54Co0.13Ni0.13]O2 박막을 증착하였다. Li/MnCoNi의 몰 비율을 변화시켜 높은 전기화학적 특성을 갖는 분말을 합성하여 제조한 타겟으로 Pt/TiO2/SiO2/Si 기판위에 RF 스퍼터법을 이용하여 박막을 성장시켰다. 박막 증착 시 가스의 비율은 Ar:O2=3:1로 하고 증착 압력의 조절(0.005~0.02 torr)을 통하여 박막의 두께와 표면 특성을 조절하며 성장시켰다. 또한 박막을 다양한 온도에서($400{\sim}550^{\circ}C$) 열처리하여 결정화도와 전기화학적 특성을 측정하였다. 증착 된 박막의 구조적 특성은 X-ray diffraction(XRD) 과 scanning electron microscopy(SEM)로 관찰되었다. 박막의 전기화학적 특성 평가를 위하여 Cyclic voltammatry를 측정하여 가역성의 정도를 확인하고 WBC3000 battery cycler를 이용한 half-cell 테스트를 통하여 박막의 용량을 평가하였다.

• 한국전기화학회:학술대회논문집
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• 2004.04a
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• pp.59-59
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• 2004

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.242-246
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• 2017

The application of composite cathode materials including $LiFePO_4$ (lithium iron phosphate) of olivine crystal structure, which has high thermal stability, were investigated as alternatives for hybrid battery-capacitors with a $LiMn_2O_4$ (spinel crystal structure) cathode, which exhibits decreased performance at high temperatures due to Mn-dissolution. However, these composite cathode materials have been shown to have a reduction in capacity by conducting life cycle experiments in which a $LiFePO_4$/activated carbon cell was charged and discharged between 1.0 V and 2.3 V at two temperatures, $25^{\circ}C$ and $60^{\circ}C$, which caused a degradation of the anode due to the lowered voltage in the anode. To avoid the degradation of the anode, composite cathodes of $LiFePO_4/LiMn_2O_4$ (50:50 wt%), $LiFePO_4$/activated carbon (50:50 wt%) and $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (50:50 wt%) were prepared and the life cycle experiments were conducted on these cells. The composite cathode including $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ of layered crystal structure showed stable voltage behavior. The discharge capacity retention ratio of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ was about twice as high as that of a $LiFePO_4/LiMn_2O_4$ cell at thermal stability experiment for a duration of 1,000 hours charged at 2.3 V and a temperature of $80^{\circ}C$.

• Journal of Electrochemical Science and Technology
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• v.7 no.4
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• pp.245-250
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• 2016

The layered $Na_{0.6}Li_{0.6}[Mn_{0.72}Ni_{0.18}Co_{0.10}]O_2$ composite with well crystalized and high specific capacity is prepared by molten-salt method and using the substitution of Na for Li-ion battery. The effects of annealing temperature, time, Na contents, and electrochemical performance are investigated. In XRD analysis, the substitution of Na-ion resulted in the P2-$Na_{2/3}MO_2$ structure ($Na_{0.70}MO_{2.05}$), which co-exists in the $Na_{0.6}Li_{0.6}[Mn_{0.72}Ni_{0.18}Co_{0.10}]O_2$ composites. The discharge capacities of cathode materials exhibited $284mAhg^{-1}$ with higher initial coulombic efficiency.

• Journal of the Korean Ceramic Society
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• v.45 no.2
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• pp.112-118
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• 2008

To prepare the high-capacity cathode material with improved electrochemical performances, nanoparticles of $C0_3(PO_4)_2$ were coated on the powder surface of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$, which was already synthesized by simple combustion method. The coated powders after the heat treatment at >$700^{\circ}C$ surely showed well-structured crystalline property with nanoscale surface coating layer, which was consisted of $LiCOPO_4$ phase formed from the reaction bwtween $CO_3(PO_4)_2$ and lithium impurities. In addition, cycle performance was particularly improved by the $CO_3(PO_4)_2$-coating for the cathode material for lithium rechargeable batteries.

• 한국전기화학회:학술대회논문집
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• 2003.10a
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• pp.23-23
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• 2003

• Journal of the Korean Electrochemical Society
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• v.2 no.1
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• pp.5-12
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• 1999

By the PVA-precursor method, polycrystalline powder of $Li_xNi_{1-y}Co_yO_2$, cathode material for lithium battery, was synthesized. Using the powder as the cathode material, lithium ion batteries were fabricated, whose electrochemical properties were measured. The effect of changing synthetic conditions, such as PvA/metal mole ratio, concentration of PVA, degree of polymerization of PVA, pyrolysis condition, and metal stoichiometry, on the battery performance was investigated. Considering the initial performance of the cell, the optimum stoichiometry of the $Li_xNi_{1-y}Co_yO_2$, synthesized by the PVA-precursor method was observed to be x: 1.0 and y=0.26. A minor phase of $Li_2CO_3$, which was generated by the residual carbon in the powder precursor, deteriorated the performance of the cell. In order to eliminate the minor phase, the precursor had to be pyrolyzed under the flow of dry air. Annealing the powder at $500^{\circ}C$ under the flow of dry air also eliminated the minor phase, and the performance of the cell was largely improved by the treatment.

• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1695-1698
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• 2008