• Korean Chemical Engineering Research
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• v.61 no.1
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• pp.32-38
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• 2023

In this study, the electrochemical properties of dopamine coated silicon/silicon carbide/carbon(Si/SiC/C) composite materials were investigated to improve cycle stability and rate performance of silicon-based anode active material for lithium-ion batteries. After synthesizing CTAB/SiO₂ using the Stöber method, the Si/SiC composites were prepared through the magnesium thermal reduction method with NaCl as heat absorbent. Then, carbon coated Si/SiC anode materials were synthesized through polymerization of dopamine. The physical properties of the prepared Si/SiC/C anode materials were analyzed by SEM, TEM, XRD and BET. Also the electrochemical performance were investigated by cycle stability, rate performance, cyclic voltammetry and EIS test of lithium-ion batteries in 1 M LiPF₆ (EC: DEC = 1:1 vol%) electrolyte. The prepared 1-Si/SiC showed a discharge capacity of 633 mAh/g and 1-Si/SiC/C had a discharge capacity of 877 mAh/g at 0.1 C after 100 cycles. Therefore, it was confirmed that cycle stability was improved through dopamine coating. In addition, the anode materials were obtain a high capacity of 576 mAh/g at 5 C and a capacity recovery of 99.9% at 0.1 C/0.1 C.

• Journal of Surface Science and Engineering
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• v.56 no.1
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• pp.62-68
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• 2023

Silicon (Si) is considered as a promising substitute for the conventional graphite due to its high theoretical specific capacity (3579 mAh/g, Li₁₅Si₄) and proper working voltage (~0.3V vs Li⁺/Li). However, the large volume change of Si during (de)lithiation brings about severe degradation of battery performances, rendering it difficult to be applied in the practical battery directly. As a one feasible candidate of industrial Si anode, silicon monoxide (SiO_x) demonstrates great electrochemical stability with its specialized strategy, downsized Si nanocrystallites surrounded by Li⁺ inactive buffer phase (Li₂O and Li₄SiO₄). Nevertheless, SiO_x inherently has the initial irreversible capacity and poor electrical conductivity. To overcome those issues, conformal carbon coating has been performed on SiO_x utilizing ethylbenzene as the carbon precursor of chemical vapor deposition (CVD). Through various characterizations, it is confirmed that the carbon is homogeneously coated on the surface of SiO_x. Accordingly, the carbon-coated SiOx from CVD using ethylbenzene demonstrates 73% of the first cycle efficiency and great cycle life (88.1% capacity retention at 50th cycle). This work provides a promising synthetic route of the uniform and scalable carbon coating on Si anode for high-energy density.

• Korean Journal of Materials Research
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• v.33 no.6
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• pp.257-264
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• 2023

To develop a high capacity lithium secondary battery, a new approach to anode material synthesis is required, capable of producing an anode that exceeds the energy density limit of a carbon-based anode. This research synthesized carbon nano silicon composites as an anode material for a secondary battery using the RF thermal plasma method, which is an ecofriendly dry synthesis method. Prior to material synthesis, a silicon raw material was mixed at 10, 20, 30, 40, and 50 wt% based on the carbon raw material in a powder form, and the temperature change inside the reaction field depending on the applied plasma power was calculated. Information about the materials in the synthesized carbon nano silicon composites were confirmed through XRD analysis, showing carbon (86.7~52.6 %), silicon (7.2~36.2 %), and silicon carbide (6.1~11.2 %). Through FE-SEM analysis, it was confirmed that the silicon bonded to carbon was distributed at sizes of 100 nm or less. The bonding shape of the silicon nano particles bonded to carbon was observed through TEM analysis. The initial electrochemical charging/discharging test for the 40 wt% silicon mixture showed excellent electrical characteristics of 1,517 mAh/g (91.9 %) and an irreversible capacity of 133 mAh/g (8.1 %).

• Journal of the Korean Electrochemical Society
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• v.14 no.4
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• pp.239-244
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• 2011

In this study, $Fe_3O_4$/graphene and CuO/graphene composites were synthesized by the polyol reduction method using ethylene glycol, and their performances as the anodes of lithium ion batteries were evaluated. The physical characteristics of the synthesized composites were analyzed by SEM, XRD, and TGA. In addition, their electrochemical properties were examined by the electrochemical analysis techniques such as charge/discharge performance, cyclic voltammetry, and AC impedance spectroscopy. The cells composed of $Fe_3O_4$/graphene and CuO/graphene composites showed better performance than the graphene electrode, due to the dispersion of nanosized $Fe_3O_4$ or CuO on the surface of graphene and the formation of good electrical network in the electrode. Their composites kept the reversible capacity more than 600 mAh/g even after the charging/discharging of 30 cycles.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.108-109
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• 2012

This talk will begin with the demonstration of facile synthesis of silicon nanostructures using the magnesiothermic reduction on silica nanostructures prepared via self-assembly, which will be followed by the characterization results of their performance for energy storage. This talk will also report the fabrication and characterization of highly porous, stretchable, and conductive polymer nanocomposites embedded with carbon nanotubes (CNTs) for application in flexible lithium-ion batteries. It will be presented that the porous CNT-embedded PDMS nanocomposites are capable of good electrochemical performance with mechanical flexibility, suggesting these nanocomposites could be outstanding anode candidates for use in flexible lithium-ion batteries. Directed self-assembly (DSA) of block copolymers (BCPs) can generate uniform and periodic patterns within guiding templates, and has been one of the promising nanofabrication methodologies for resolving the resolution limit of optical lithography. BCP self-assembly processing is scalable and of low cost, and is well-suited for integration with existing semiconductor manufacturing techniques. This talk will introduce recent research results (of my research group) on the self-assembly of Si-containing block copolymers for the achievement of sub-10 nm resolution, fast pattern generation, transfer-printing capability onto nonplanar substrates, and device applications for nonvolatile memories. An extraordinarily facile nanofabrication approach that enables sub-10 nm resolutions through the synergic combination of nanotransfer printing (nTP) and DSA of block copolymers is also introduced. This simple printing method can be applied on oxides, metals, polymers, and non-planar substrates without pretreatments. This talk will also report the direct formation of ordered memristor nanostructures on metal and graphene electrodes by the self-assembly of Si-containing BCPs. This approach offers a practical pathway to fabricate high-density resistive memory devices without using high-cost lithography and pattern-transfer processes. Finally, this talk will present a novel approach that can relieve the power consumption issue of phase-change memories by incorporating a thin $SiO_x$ layer formed by BCP self-assembly, which locally blocks the contact between a heater electrode and a phase-change material and reduces the phase-change volume. The writing current decreases by 5 times (corresponding to a power reduction of 1/20) as the occupying area fraction of $SiO_x$ nanostructures varies.

• Journal of Electrochemical Science and Technology
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• v.11 no.1
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• pp.92-98
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• 2020

SnO₂-based high-capacity anode materials are attractive candidate for the next-generation high-performance lithium-ion batteries since the theoretical capacity of SnO₂ can be ideally extended from 781 to 1494 mAh g^-1. Here 3D etched Cu foam is applied as a current collector for electron path and simultaneously a substrate for the SnO₂ coating, for developing an integrated electrode structure. We fabricate the 3D etched Cu foam through an auto-catalytic electroless plating method, and then coat the SnO₂ onto the self-supporting substrate through a simple sol-gel method. The catalytic dissolution of Cu metal makes secondary pores of both several micrometers and several tens of micrometers at the surface of Cu foam strut, besides main channel-like interconnected pores. Especially, the additional surface pores on etched Cu foam are intended for penetrating the individual strut of Cu foam, and thereby increasing the surface area for SnO₂ coating by using even the internal of Cu foam. The increased areal capacity with high structural integrity upon cycling is demonstrated in the SnO₂-coated 3D etched Cu foam. This study not only prepares the etched Cu foam using the spontaneous chemical reactions but also demonstrates the potential for electroless plating method about surface modification on various metal substrates.

• Journal of Electrochemical Science and Technology
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• v.7 no.4
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• pp.306-315
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• 2016

Amorphous vanadium titanates (aVTOs) are examined for use as a negative electrode in lithium-ion batteries. These amorphous mixed oxides are synthesized in nanosized particles (<100 nm) and flocculated to form secondary particles. The $V^{5+}$ ions in aVTO are found to occupy tetrahedral sites, whereas the $Ti^{4+}$ ions show fivefold coordination. Both are uniformly dispersed at the atomic scale in the amorphous oxide matrix, which has abundant structural defects. The first reversible capacity of an aVTO electrode ($295mAhg^{-1}$) is larger than that observed for a physically mixed electrode (1:2 $aV_2O_5$ | $aTiO_2$, $245mAhg^{-1}$). The discrepancy seems to be due to the unique four-coordinated $V^{5+}$ ions in aVTO, which either are more electron-accepting or generate more structural defects that serve as $Li^+$ storage sites. Coin-type Li/aVTO cells show a large irreversible capacity in the first cycle. When they are prepared under nitrogen (aVTO-N), the population of surface hydroxyl groups is greatly reduced. These groups irreversibly produce highly resistive inorganic compounds (LiOH and $Li_2O$), leading to increased irreversible capacity and electrode resistance. As a result, the material prepared under nitrogen shows higher Coulombic efficiency and rate capability.

• Journal of the Korean Electrochemical Society
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• v.16 no.3
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• pp.177-183
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• 2013

As the development of available binder in the harsh conditions is needed, we propose the proper binder for high-voltage lithium-ion secondary batteries based on the quantum chemistry modeling. The optimized structures, HOMO (Highest Occupied Molecular Orbital) energies and ionization potentials of 4 binders, which were considered from monomer to tetramer, were investigated by the semi-empirical and DFT (Density Functional Theory) calculations. The results show that the ionization potential values by calculation tend to be close to the oxidation potentials from the measurement of linear sweep voltametry (LSV). The order of oxidative resistance from high value to low value is following: poly(hexafluropropylene), poly(vinylidene fluoride), poly(methyl acrylate) and poly(acryl amide). Also these results correspond with the experimental values. Thus, we find the reason why HOMO (Highest Occupied Molecular Orbital) energy of PHFP has the highest value than other binders by analysis of HOMO orbital structures.

• Journal of the Korean Electrochemical Society
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• v.20 no.3
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• pp.49-54
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• 2017

We develop a ceramic composite separator prepared by coating $ZrO_2$ nanoparticles with a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) copolymer on a polyvinyl alcohol (PVA) mechanical support prepared by electrospinning technique to improve thermal properties. The gurley number of the ceramic composite separator shows much lower value than that of a PE separator even though it possesses the polymeric coating layer with ceramic nanoparticles. In addition, the proposed sample shows higher electrolyte uptake than PE separator, leading to enhancing the ionic conductivity of the proposed sample and, by extension, the rate discharge properties of lithium ion batteries. Thermal stability of the ceramic composite separator is dramatically improved without any degradation in electrochemical performance compared to the performance of conventional PE separators.

• Resources Recycling
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• v.31 no.1
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• pp.12-20
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• 2022

The smelting reduction of spent lithium-ion batteries results in metallic alloys containing Co, Cu, Fe, Mn, Ni, and Si. A process to separate metal ions from the sulfuric acid leaching solution of these metallic alloys has been reported. In this process, ionic liquids are employed to separate Fe(III) and Cu(II). In this study, D2EHPA and Cyanex 301 were employed to replace these ionic liquids. Fe(III) and Cu(II) from the sulfate solution were sequentially extracted using 0.5 M D2EHPA with three stages of cross-current and 0.3 M Cyanex 301. The stripping of Fe(III) and Cu(II) from the loaded phases was performed using 50% (v/v) and 60% (v/v) aqua regia solutions, respectively. The mass balance results from this process indicated that the recovery and purity percentages of the metals were greater than 99%.