• Journal of Electrochemical Science and Technology
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• v.13 no.2
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• pp.269-278
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• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

• 한국전기화학회:학술대회논문집
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• 2004.04a
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• pp.19-19
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• 2004

• Journal of Electrochemical Science and Technology
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• v.12 no.4
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• pp.377-386
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• 2021

The Li-rich oxides are promising cathode materials due to their high energy density. However, characteristics such as low rate capability, unstable cyclic performance, and rapid capacity fading during cycling prevent their commercialization. These characteristics are mainly attributed to the phase instability of the host structure and undesirable side reactions at the cathode/electrolyte interface. To suppress the phase transition during cycling and interfacial side reactions with the reactive electrolyte, K (potassium) doping and Nb oxide coating were simultaneously introduced to a Li-rich oxide (Li_1.2Ni_0.13Co_0.13Mn_0.54O₂). The capacity and rate capability of the Li-rich oxide were significantly enhanced by K doping. Considering the X-ray diffraction (XRD) analysis, the interslab thickness of LiO₂ increased and cation mixing decreased due to K doping, which facilitated Li migration during cycling and resulted in enhanced capacity and rate capability. The K-doped Li-rich oxide also exhibited considerably improved cyclic performance, probably because the large K⁺ ions disturb the migration of the transition metals causing the phase transition and act as a pillar stabilizing the host structure during cycling. The Nb oxide coating also considerably enhanced the capacity and rate capability of the samples, indicating that the undesirable interfacial layer formed from the side reaction was a major resistance factor that reduced the capacity of the cathode. This result confirms that the introduction of K doping and Nb oxide coating is an effective approach to enhance the electrochemical performance of Li-rich oxides.

• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.184-189
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• 2007

The importance of secondary battery industry is getting excited according to the development of battery industry as a high efficiency energy supplier of electronic machine of mobile information such as mobile phone, lap-top computer, PDA. It is rasing the interest about security of safety and high efficiency of cathode material for main part of secondary lithium battery. The cathode material which has been used like $LiCoO_2,\;LiMn_2O_4,\;LiNi_xCo_yMn_zO_2,\;LiNi_xCo_yM_zO_2$ (M=Al, Zr, Mg etc.,) the most typical material is $LiCoO_2$. But it is studying the development of substitute such as efficiency amelioration of $LiCoO_2$, thetiary element, olivine element because of the capacity of $LiCoO_2$, the matter of security; especially the betterment of efficiency, security research of safety has been actively processed in domestic and overseas about surface coating treatment of active cathode which is using oxide ($M_xO_3$). This study analyses side effect of battery according to increase of surface treatment, formation of precipitation for reagent condensation, non-reagent residue of oxide ($M_xO_3$) which is remains during the surface treatment of $LiCoO_2$; conducts study of new process, the consideration of the electrochemical property to improve oxide solution of mixing rate, mixture of surface treatment, dryness, calcinations conditionetc.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.460-464
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• 2013

A series of Mn compound were prepared by seed-assisted method. The seed used in this reaction was manufactured by calcination of $MnCO_3$ at various temperatures and effects of the calcination temperature on seed-assisted reaction were investigated. With increase of the calcination temperature, CMD (${\gamma}-MnO_2$) was recovered after seed-assisted reactions. LMO used as cathode active material in the Li-ion batteries were synthesized from Mn source obtained in the seed-assisted reaction and the electrochemical properties (rate capability, cycle life performance and specific capacity) of the LMO were investigated. The LMO synthesized from the CMD which is obtained by the reaction with seed prepared by calcination of $MnCO_3$ more than $350^{\circ}C$ shown good electrochemical properties.

• Journal of the Korean Electrochemical Society
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• v.19 no.1
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• pp.1-8
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• 2016

Capacity of layered lithium nickel-cobalt-manganese oxide ($LiNi_{1-x-y}Co_xMn_yO_2$) cathode material can increase by raising the charge cut-off voltage above 4.3 V vs. $Li/Li^+$, but it is limited due to anodic instability of conventional electrolyte. We have been screening and evaluating various sulfone-based compounds of dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS) as electrolyte additives for high-voltage applications. Here we report improved cycling performance of $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode by the use of dimethyl sulfone (DMS) additive under an aggressive charge condition of 4.6 V, compared to that in conventional electrolyte, and cathode-electrolyte interfacial reaction behavior. The cathode with DMS delivered discharge capacities of $198-173mAhg^{-1}$ over 50 cycles and capacity retention of 84%. Surface analysis results indicate that DMS induces to form a surface protective film at the cathode and inhibit metal-dissolution, which is correlated to improved high-voltage cycling performance.

• Nuclear Engineering and Technology
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• v.32 no.5
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• pp.514-520
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• 2000

The mechanism of corrosion behavior has to be understood clearly to select an optimum material for handling molten salts to be used in the oxide reduction process of PWR spent fuel. In this study, the oxidation states of corrosion products on the surface of Inconel 600 and 800H as well as their chemical compositions and structural informations were determined by using XPS, ICP-AES, AAS, EPMA and XRD after the corrosion experiment with lithium molten salts at 75$0^{\circ}C$ for 25 hours. Nickel and oxygen were detected from the corrosion products on the surface of Inconel plates and chromium was found to be dissolved out into lithium molten salts leaving cracks on the surface. The corrosion products were identified as metal oxides such as Fe$_2$O$_3$, Cr$_2$O$_3$, NiO, NiFe$_2$O$_4$and MnO by using XPS and XRD.

• Journal of the Korean Electrochemical Society
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• v.12 no.1
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• pp.81-87
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• 2009

An indium-tin oxide (ITO) coated spinel manganese oxide (${LiMn_2}{O_4}$, LMO) is prepared and its high-temperature ($55^{\circ}C$) cycle performance and rate capability are examined. A severe electrolyte decomposition and film deposition is observed on the un-coated ${LiMn_2}{O_4}$ cathode, which leads to a significant electrode polarization and capacity fading. Such an electrode polarization is, however, greatly reduced for the ITO-coated (> 2 mol%) LMO cathode, which leads to an improved cycle performance. This can be rationalized by a suppression of electrolyte decomposition, which is in turn indebted to a decrease in the direct contact area between LMO and electrolyte. The suppression of film deposition on the ITO-coated LMO cathode is confirmed by infra-red spectroscopy. The rate capability is also improved by the surface coating, which may be resulted from a suppression of resistive film deposition and high electric conductivity of ITO itself.

• Korean Journal of Materials Research
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• v.12 no.9
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• pp.712-717
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• 2002

New wet chemical method so called precipitation-evaporation method was suggested for preparing spinel structure lithium manganese oxide ($LiMn_2$$O_4$) for Li ion secondary battery. Using precipitation-evaporation method, $LiMn_2$$O_4$ cathode materials suitable for Li ion secondary batteries can be synthesized. Single spinel phase $LiMn_2$$O_4$ powder was synthesized at lower temperature compared to that of prepared by solid-state method. $LiMn_2$$O_4$ powder prepared by precipitation-evaporation method showed uniform, small size and well defined crystallinity particles. Li ion secondary battery using $LiMn_2$$O_4$ as cathode materials prepared by precipitation-evaporation method and calcined at $800^{\circ}C$ showed discharge capacity of 106.03mAh/g and discharge capacity of 95.60mAh/g at 10th cycle. Although Li ion secondary battery showed somewhat smaller initial capacity but good cyclic ability. It is suggested that electro-chemical properties can be improved by controlling particle characteristics by particle morphology modification during calcination and optimizing Li ion secondary battery assembly conditions.

• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.50-56
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• 2016

Spherical lithium manganese oxide spinel, $Li_{1.10}Mn_{1.86}Al_{0.02}Mg_{0.02}O_4$ was prepared by wet-milling, spray-drying, and sintering process. In the spray-drying process, solid content in slurry was varied from 20 to 30 wt%. In the sintering process, the precursors have been sintered under air or $O_2$ atmosphere. While the as-prepared samples exhibit excellent electrochemical properties at room temperature, the discharge voltage profiles at 5.0C are very different one from another. The origin for the difference especially at initial state of discharge is oxygen defect. The sample prepared in air has larger capacity related to the plateau at 3.3 V (vs. $Li/Li^+$) which is caused by the oxygen defects than the one prepared in $O_2$. The difference of discharge voltage profiles especially at the final state of discharge comes from different diffusion rate of $Li^+$ ions. The sample prepared from 30 wt% solid content of slurry shows twice higher diffusion rate than the samples prepared from 20 wt% solid content, which is attributed to better compactness between primary particles for the sample prepared from 30wt % solid content than the one prepared by 20 wt%.