• Carbon letters
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• v.12 no.3
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• pp.180-183
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• 2011

Li metal is accepted as a good counter electrode for electrochemical impedance spectroscopy (EIS) as the active material in Li-ion and Li-ion polymer batteries. We examined the existence of signal noise from a Li-metal counter quantitatively as a preliminary study. We suggest an electrochemical cell with one switchable electrode to obtain the exact impedance signal of active materials. To verify the effectiveness of the switchable electrode, EIS measurements of the solid electrolyte interphase (SEI) before severe $Li^+$ intercalation to SFG6 graphite (at > ca. 0.25 V vs. Li/$Li^+$) were taken. As a result, the EIS spectra without the signal of Li metal were obtained and analyzed successfully for the following parameters i) $Li^+$ conduction in the electrolyte, ii) the geometric resistance and constant phase element of the electrode (insensitive to the voltage), iii) the interfacial behavior of the SEI related to the $Li^+$ transfer and residence throughout the near-surface (sensitive to voltage), and iv) the term reflecting the differential limiting capacitance of $Li^+$ in the graphite lattice.

• Corrosion Science and Technology
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• v.22 no.4
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• pp.287-296
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• 2023

Li-ion batteries have been gaining increasing importance, driven by the growing utilization of renewable energy and the expansion of electric vehicles. To meet market demands, it is essential to ensure high energy density and battery safety. All-solid-state batteries (ASSBs) have attracted significant attention as a potential solution. Among the advantages, they operate with an ion-conductive solid electrolyte instead of a liquid electrolyte therefore significantly reducing the risk of fire. In addition, by using high-capacity alternative electrode materials, ASSBs offer a promising opportunity to enhance energy density, making them highly desirable in the automotive and secondary battery industries. In ASSBs, Li metal can be used as the anode, providing a high theoretical capacity (3860 mAh/g). However, challenges related to the high interfacial resistance between Li metal and solid electrolytes and those concerning material degradation during charge-discharge cycles need to be addressed for the successful commercialization of ASSBs. This review introduces and discusses the interfacial reactions between Li metal and solid electrolytes, along with research cases aiming to improve these interactions. Additionally, future development directions in this field are explored.

• Journal of Electrochemical Science and Technology
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• v.13 no.1
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• pp.78-89
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• 2022

ANODE-free Li-metal batteries (AFLMBs) operating with Li of cathode material have attracted enormous attention due to their exceptional energy density originating from anode-free structure in the confined cell volume. However, uncontrolled dendritic growth of lithium on a copper current collector can limit its practical application as it causes fatal issues for stable cycling such as dead Li formation, unstable solid electrolyte interphase, electrolyte exhaustion, and internal short-circuit. To overcome this limitation, here, we report a novel dual-salt electrolyte comprising of 0.2 M LiPF₆ + 3.8 M lithium bis(fluorosulfonyl)imide in a carbonate/ester co-solvent with 5 wt% fluoroethylene carbonate, 2 wt% vinylene carbonate, and 0.2 wt% LiNO₃ additives. Because the dual-salt electrolyte facilitates uniform/dense Li deposition on the current collector and can form robust/ionic conductive LiF-based SEI layer on the deposited Li, a Li/Li symmetrical cell exhibits improved cycling performance and low polarization for over 200 h operation. Furthermore, the anode-free LiFePO₄/Cu cells in the carbonate electrolyte shows significantly enhanced cycling stability compared to the counterparts consisting of different salt ratios. This study shows an importance of electrolyte design guiding uniform Li deposition and forming stable SEI layer for AFLMBs.

• Journal of Electrochemical Science and Technology
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• v.5 no.2
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• pp.37-44
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• 2014

The $Li-O_2$ battery has been attracting much attention recently, due to its very high theoretical capacity compared with Li-ion chemistries. Nevertheless, several studies within the last few years revealed that Li-ion derived electrolytes based on alkyl carbonate solvents, which have been commonly used in the last 27 years, are irreversibly consumed at the $O_2$ electrode. Accordingly, more stable electrolytes are required capable to operate with both the Li metal anode and the $O_2$ cathode. Thus, due to their favorable properties such as non volatility, chemical inertia, and favorable behavior toward the Li metal electrode, ionic liquid-based electrolytes have gathered increasing attention from the scientific community for its application in $Li-O_2$ batteries. However, the scale-up of Li-$O_2$ technology to real application requires solving the mass transport limitation, especially for supplying oxygen to the cathode. Hence, the 'LABOHR' project proposes the introduction of a flooded cathode configuration and the circulation of the electrolyte, which is then used as an oxygen carrier from an external $O_2$ harvesting device to the cathode for freeing the system from diffusion limitation.

• Journal of Electrochemical Science and Technology
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• v.14 no.1
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• pp.85-95
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• 2023

In recent years, solid-state Li metal batteries (SSLBs) have attracted significant attention as the next-generation batteries with high energy and power densities. However, uncontrolled dendrite growth and the resulting pulverization of Li during repeated plating/stripping processes must be addressed for practical applications. Herein, we report a plastic-crystal-based polymer/ceramic composite solid electrolyte (PCCE) to resolve these issues. To fabricate the one-side ceramic-incorporated PCCE (CI-PCCE) film, a mixed precursor solution comprising plastic-crystal-based polymer (succinonitrile, SN) with garnet-structured ceramic (Li₇La₃Zr₂O₁₂, LLZO) particles was infused into a thin cellulose membrane, which was used as a mechanical framework, and subsequently solidified by using UV-irradiation. The CI-PCCE exhibited good flexibility and a high room-temperature ionic conductivity of over 10^-3 S cm^-1. The Li symmetric cell assembled with CI-PCCE provided enhanced durability against Li dendrite penetration through the solid electrolyte (SE) layer than those with LLZO-free PCCEs and exhibited long-term cycling stability (over 200 h) for Li plating/stripping. The enhanced Li⁺ transference number and lower interfacial resistance of CI-PCCE indicate that the ceramic-polymer composite layer in contact with the Li anode enabled the uniform distribution of Li⁺ flux at the interface between the Li metal and CI-PCCE, thereby promoting uniform Li plating/stripping. Consequently, the Li//LiFePO₄ (LFP) full cell constructed with CI-PCCE demonstrated superior rate capability (~120 mAh g^-1 at 2 C) and stable cycle performance (80% after 100 cycles) than those with ceramic-free PCCE.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.161-167
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• 2018

In this study, transition metal coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. CNFs/Ni foam was immersed into 0.01 M transition metal solutions after growing CNFs on Ni foam via chemical vapor deposition (CVD) method. Transition metal coated CNFs/Ni foam was dried in an oven at $80^{\circ}C$. Morphologies, compositions, and crystal quality of CNFs-transition metal composites were characterized by scanning electron microscopy (SEM), Raman spectroscopy (Raman), and X-ray photoelectron spectroscopy (XPS), respectively. Electrochemical characteristics of CNFs-transition metal composites as anodes of Li secondary batteries were investigated using a three-electrode cell. Transition metal/CNFs/Ni foam was directly employed as a working electrode without any binder. Lithium foil was used as both counter and reference electrodes while 1 M $LiClO_4$ was employed as the electrolyte after it was dissolved in a mixture of propylene carbonate:ethylene carbonate (PC:EC) at 1:1 volume ratio. Galvanostatic charge/discharge cycling and cyclic voltammetry measurements were taken at room temperature using a battery tester. In particular, the capacity of the synthesized CNFs-Fe was improved compared to that of CNFs. After 30 cycles, the capacity of CNFs-Fe was increased by 78%. Among four transition metals of Fe, Cu, Co and Ni coated on carbon nanofibers, the retention rate of CNFs-Fe was the highest at 41%. The initial capacity of CNFs-Fe with 670 mAh/g was reduced to 275 mAh/g after 30 cycles.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.46-46
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• 2007

There has been rapid progress in the portable electronics industry. which has led to a great increase for a demand of portable, lightweight power sources. Lithium 2'nd batteries have met these demand. and many studies on the cahtod materials for the lithium 2,nd batteries have been reported during the last decade. Possible candidates for the cathode materials for lithium 2,nd batteries are $LiCoO_2$, $LiNiO_2$, and $LiMn_2O_4$. Currently $LiCoO_2$ is widely used. but $LiMn_2O_4$ is an excellent alternative material in view of its several advantages such a low cost as well as the wasy availability of raw materials and environmental benignity. In this study, find the most suitable synthesis method that satisfied high capacitor and stability cycle character, etc in Li-Mn oxide for 2'nd batteries. And also made an experiment on doping the $LiMn_2O_4$ spinel with a small amount of metal ions has a remarkable effect on the electrochemical properties and characterics of powder, BET, PSA, Porosity, etc.

• Journal of Electrochemical Science and Technology
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• v.2 no.3
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• pp.136-142
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• 2011

$Li_4Ti_5O_{12}$ is prepared through a solid-state reaction between $Li_2CO_3$ and anatase $TiO_2$ for applications in lithium-ion batteries. The rate capability is measured and the electrode polarization is analyzed through the galvanostatic intermittent titration technique (GITT). The rate characteristics and electrode polarization are highly sensitive to the amount of carbon loading. Polarization of the $Li_4Ti_5O_{12}$ electrode continuously increases as the reaction proceeds in both the charge and discharge processes. This relation indicates that both electron conduction and lithium diffusion are significant factors in the polarization of the electrode. The transition metal (Cu, Ni, Fe) ion added during the synthesis of $Li_4Ti_5O_{12}$ for improving the electrical conductivity also greatly enhances the rate capability.

• Electronics and Telecommunications Trends
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• v.36 no.3
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• pp.76-86
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• 2021

Technologies for lithium secondary batteries are now increasingly expanding to simultaneously improve the safety and higher energy and power densities of large-scale battery systems, such as electric vehicles and smart-grid energy storage systems. Next-generation lithium batteries, such as lithium-sulfur (Li-S) and lithium-air (Li-O₂) batteries by adopting solid electrolytes and lithium metal anode, can be a solution for the requirements. In this analysis of battery technology trends, solid electrolytes, including polymer (organic), inorganic (oxides and sulfides), and their hybrid (composite) are focused to describe the electrochemical performance achievable by adopting optimal components and discussing the interfacial behaviors that occurred by the contact of different ingredients for safe and high-energy lithium secondary battery systems. As next-generation rechargeable lithium batteries, Li-S and Li-O₂ battery systems are briefly discussed coupling with the possible use of solid electrolytes. In addition, Electronics and Telecommunications Research Institutes achievements in the field of solid electrolytes for lithium rechargeable batteries are finally introduced.

• Ceramist
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• v.21 no.4
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• pp.349-365
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• 2018

Since the electrification of vehicles has been extended, solid-state batteries have been attracting a lot of interest because of their superior safety. Especially, polymer, sulfide, and oxide based materials are being studied as solid electrolytes, and each type of materials has advantaged and disadvantages over others. Oxide electrolytes has higher chemical and electrochemical stability compared to the other types of electrolytes. However, ionic conductivity isn't high enough as much as that of organic liquid electrolytes. Also, there are many difficulties of fabricating solid-state batteries with oxide based electrolytes because they require a sintering process at very high temperature (above ${\sim}800^{\circ}C$). Herein, we review recent studies of solid-state batteries with oxide based electrolytes about the ionic conductivity, interfacial reactions with Li metal, and preparation of solid-state cell.