• Membrane Journal
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• v.31 no.6
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• pp.417-425
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• 2021

As the demand for high-capacity batteries increases, there has been growing researches on the lithium metal anode with a capacity (3,860 mAh/g) of higher than that of conventional one and a low electrochemical potential (-3.040 V). In this study, using the anatase phased TiO₂ nanoparticles synthesized by hydrothermal synthesis, a PVdF-HFP/TiO₂ organic/inorganic composite material was designed and used as an interfacial protective layer for a Li metal anode. As-formed organic/inorganic-lithium composite thin film was confirmed through the crystalline structure and morphological analyses. In addition, the electrochemical test (cycle stability and voltage profile) confirmed that the protective layer of PVdF-HFP/TiO₂ composite (10 wt% TiO₂ and 1.1 ㎛ film thickness) contributed to the enhanced electrochemical performance of the lithium metal anode (Colombic efficiency retention: 90% for 77 cycles). Based on comparative test with the untreated lithium electrode, it was confirmed that our protective layer plays an important role to stabilize/improve the EC performance of the lithium metal negative electrode.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.2
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• pp.165-173
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• 2019

Lithium anodes (13, 15, 17, and 20 wt% Li) were fabricated by mixing molten lithium and iron powder, which was used as a binder to hold the molten lithium, at about $500^{\circ}C$ (discharge temp.). In this study, the effect of applied pressure and lithium content on the discharge properties of a thermal battery's single cell was investigated. A single cell using a Li anode with a lithium content of less than 15 wt% presented reliable performance without any abrupt voltage drop resulting from molten lithium leakage under an applied pressure of less than $6kgf/cm^2$. Furthermore, it was confirmed that even when the solid electrolyte is thinner, the Li anode of the single cell normally discharges well without a deterioration in performance. The Li anode of the single cell presented a significantly improved open-circuit voltage of 2.06 V, compared to that of a Li-Si anode (1.93 V). The cut-off voltage and specific capacity were 1.83 V and $1,380As\;g^{-1}$ (Li anode), and 1.72 V and $1,364As\;g^{-1}$ (Li-Si anode). Additionally, the Li anode exhibited a stable and flat discharge curve until 1.83 V because of the absence of phase change phenomena of Li metal and a subsequent rapid voltage drop below 1.83 V due to the complete depletion of Li at the end state of discharge. On the other hand, the voltage of the Li-Si anode cell decreased in steps, $1.93V{\rightarrow}1.72V(Li_{13}Si_4{\rightarrow}Li_7Si_3){\rightarrow}1.65V(Li_7Si_3{\rightarrow}Li_{12}Si_7)$, according to the Li-Si phase changes during the discharge reaction. The energy density of the Li anode cell was $807.1Wh\;l^{-1}$, which was about 50% higher than that of the Li-Si cell ($522.2Wh\;l^{-1}$).

• 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 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.

• Nano
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• v.13 no.12
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• pp.1850139.1-1850139.10
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• 2018

$Co_3O_4$ nanocrystals have been synthesized via an ordinary one-step calcination of a cobalt-based 2D coordination polymer [Co(tfbdc)(4,4'-bpy)$(H_2O)_2$]. As an anode material for lithium-ion batteries, the obtained $Co_3O_4$ nanocrystals exhibit high reversible capacity, excellent cyclic stability and better rate capability. The reversible capacity of the $Co_3O_4$ nanocrystals maintains $713mA\;h\;g^{-1}$ after 50 cycles at a current density of $50mA\;g^{-1}$. Our results confirm that searching for metal oxides nanomaterials used as anode materials of lithium ion batteries via the calcinations of 2D coordination polymer is a new route.

• 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.

• 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.10 no.1
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• pp.31-35
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• 2007

In this review article, we are going to explain the recent development of lithium secondary batteries for a cellular phone. There are three kinds of rechargeable batteries for cellular phones such as nickel-cadmium, nickel-metal hydride, and lithium ion or lithium ion polymer. The lithium secondary battery is one of the most excellent battery in the point of view of energy density. It means very small and light one among same capacity batteries is the lithium secondary battery. The market volume of lithium secondary batteries increases steeply about 15% annually. The trend of R&D is focused on novel cathode materials including $LiFePO_4$, novel anode materials such as lithium titanate, silicon, and tin, elecrolytes, and safety insurance.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.852-856
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• 2011

The lithium ion diffusion coefficients of bare, carbon-coated and Cr-doped $LiFePO_4$ were obtained by fitting the discharge curves of each half cell with Li metal anode. Diffusion losses at discharge curves were acquired with experiment data and fitted to equations. Theoretically fitted equations showed good agreement with experimental results. Moreover, theoretical equations are able to predict lithium diffusion coefficient and discharge curves at various discharge rates. The obtained diffusion coefficients were similar to the true diffusion coefficient of phase transformation electrodes. Lithium ion diffusion is one of main factors that determine voltage drop in a half cell with $LiFePO_4$ cathode and Li metal anode. The high diffusion coefficient of carbon-coated and Cr-doped $LiFePO_4$ resulted in better performance at the discharge process. The performance at high discharge rate was improved much as diffusion coefficient increased.

• Korean Journal of Materials Research
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• v.28 no.6
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• pp.337-342
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• 2018

Using a high pressure homonizer, we report on the electrochemical performance of $Li_4Ti_5O_{12}(LTO)$ particles manufactured as anode active material for lithium ion battery. High-pressure synthesis processing is performed under conditions in which the mole fraction of Li/Ti is 0.9, the synthesis pressure is 2,000 bar and the numbers of passings-through are 5, 7 and 10. The observed X-ray diffraction patterns show that pure LTO is manufactured when the number of passings-through is 10. It is found from scanning electron microscopy analysis that the average size of synthesized particles decreases as the number of passings-through increases. $LiCoO_2-based$ active cathode materials are used to fabricate several coin half/full cells and their battery characteristics such as lifetime, rate capability and charge transfer resistance are then estimated, revealing quite good electrochemical performance of the LTO particles as an effective anode active material for lithium secondary batteries.