• Corrosion Science and Technology
• /
• v.21 no.6
• /
• pp.445-453
• /
• 2022

SiO_x was prepared from a mixture of Si and SiO₂ via high-energy ball milling as a negative electrode material for Li-ion batteries. The molar ratio of Si to SiO₂ as precursors and the milling time were varied to identify the synthetic condition that could exhibit desirable anode performances. With an appropriate milling time, the material showed a unique microstructure in which amorphous Si nanoparticles were intimately embedded within the SiO₂ matrix. The interface between the Si and SiO₂ was composed of silicon suboxides with Si oxidation states from 0 to +4 as proven by X-ray photoelectron spectroscopy and electrochemical analysis. With the addition of a conductive carbon (Super P carbon black) as a coating material, the SiO_x/C manifested superior specific capacity to a commercial SiO_x/C composite without compromising its cycle-life performance. The simple mechanochemical method described in this study will shed light on cost-effective synthesis of high-capacity silicon oxides as promising anode materials.

• Applied Microscopy
• /
• v.48 no.2
• /
• pp.49-53
• /
• 2018

A successful transmission electron microscope (TEM) analysis is closely related to the preparation of the TEM specimen and should be followed by the suitable TEM specimen preparation depending on the purpose of analysis and the subject materials. In the case of the Si-based anode material, lithium atoms of formed Li silicide were removed due to ion beam and electron beam during TEM specimen preparation and TEM observation. To overcome the problem, we proposed a new technique to make a TEM specimen without the ion beam damage. In this study, two types of test specimens from the Si-based anode material of Li-ion battery were prepared by respectively adopting the only focused ion beam (FIB) method and the new FIB-ultramicrotome method. TEM analyses of two samples were conducted to compare the Ga ion damage of the test specimen.

• Journal of the Korean institute of surface engineering
• /
• v.56 no.1
• /
• pp.62-68
• /
• 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.

• Journal of Electrochemical Science and Technology
• /
• v.10 no.2
• /
• pp.131-138
• /
• 2019

To improve the performance of Si anodes in advanced Li-ion batteries, the design of the electrode plays a critical role, especially due to the large volumetric expansion in the Si anode during Li insertion. In our study, we used a simple fabrication method to prepare Si-based electrodes by grafting polyacrylic acid (PAA) to a carboxymethyl cellulose (CMC) binder (CMC-g-PAA). The procedure consists of first mixing nano-sized Si and the binders (CMC and PAA), and then coating the slurry on a Cu foil. The carbon network was formed via carbonization of the binders i.e., by a simple heat treatment of the electrode. The carbon network in the electrode is mechanically and electrically robust, which leads to higher electrical conductivity and better mechanical property. This explains its long cycle performance without the addition of a conducting agent (for example, carbon). Therefore, the partially carbonized CMC-g-PAA binder presented in this study represents a new feasible approach to produce Si anodes for use in advanced Li-ion batteries.

• Journal of the Korean Electrochemical Society
• /
• v.9 no.1
• /
• pp.34-39
• /
• 2006

Electrochemical properties of Cu foil current collector with a $Li_{0.5}La_{0.5}TiO_3$ Cu a Si thin film deposited by r.f sputtering as an anode for Li free battery were evaluated. The Cu foil current collectors were lied in and out of plasma during sputtering process. The X-ray diffraction results indicated that the as-deposited Si and $Li_{0.5}La_{0.5}TiO_3$ thin films in and out of plasma did not show any crystalline difference. The $Li_{0.5}La_{0.5}TiO_3$ film in plasma and Si film out of plasma showed better cyclability since crystalline $Li_{0.5}La_{0.5}TiO_3$ has much higher ionic conductivity and crystalline Si film is much sensitive far volume change during charge-discharge process. These results suggested that the deposition of amorphous Si on Cu foil current collector is much better for fabrication of Li free battery and it can be useful for the unique battery with a cycling number constraint of below 10.

• Journal of Electrochemical Science and Technology
• /
• v.10 no.1
• /
• pp.82-88
• /
• 2019

Here, we report on nanocrystalline Si-Al-M (M = Fe, Cu, Ni, Zr) alloys for use as an anode for lithium-ion batteries, which were fabricated via a melt-spinning method. Based on the XRD and TEM analyses, it was found that the Si-Al-M alloys consist of nanocrystalline Si grains surrounded by an amorphous matrix phase. Among the Si-Al-M alloys with different metal composition, Ni-incorporated Si-Al-M alloy electrode retained the high discharge capacity of 2492 mAh/g and exhibited improved cyclability. The superior $Li^+$ storage performance of Si-Al-M alloy with Ni component is mainly responsible for the incorporated Ni, which induces the formation of ductile and conductive inactive matrix with crystalline Al phase, in addition to the grain size reduction of active Si phase.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.2
• /
• pp.309-312
• /
• 2008

Two different anode composite materials comprising of Fe, Cu and Si prepared using high energy ball milling (HEBM) were explored for their capacity and cycling behaviors. Prepared powder composites in the ratio Cu:Fe:Si = 1:1:2.5 and 1:1:3.5 were characterized through X-Ray diffraction (XRD) and scanning electron microscope (SEM). Nevertheless, the XRD shows absence of any new alloy/compound formation upon ball milling, the elements present in Cu(1)Fe(1)Si(2.5)/Graphite composite along with insito generated Li2O demonstrate a superior anodic behavior and delivers a reversible capacity of 340 mAh/g with a high coulombic efficiency (98%). The higher silicon content Cu(1)Fe(1)Si(3.5) along with graphite could not sustain capacity with cycling possibly due to ineffective buffer action of the anode constituents.

• Journal of Electrochemical Science and Technology
• /
• v.12 no.3
• /
• pp.317-322
• /
• 2021

Silicon (Si) has been considered as a promising anode material because of its abundant reserves in nature, low lithium ion (Li⁺) intercalation/de-intercalation potential (below 0.5 V vs. Li/Li⁺) and high theoretical capacity of 4200 mA h/g. In this paper, we prepared a silicon-based (Si-based) anode material containing a small amount of silicon carbide by using magnesiothermic coreduction of silica and hexachlorobenzene. Because of good conductivity of silicon carbide, the cycle performance of the silicon-based anode materials containing few silicon carbide is greatly improved compared with pure silicon. The raw materials were formulated according to a silicon-carbon molar ratio of 10:0, 10:1, 10:2 and 10:3, and the obtained products were purified and tested for their electrochemical properties. After 1000 cycles, the specific capacities of the materials with silicon-carbon molar ratios of 10:0, 10:1, 10:2 and 10:3 were still up to 412.3 mA h/g, 970.3 mA h/g, 875.0 mA h/g and 788.6 mA h/g, respectively. Although most of the added carbon reacted with silicon to form silicon carbide, because of the good conductivity of silicon carbide, the cycle performance of silicon-based anode materials was significantly better than that of pure silicon.

• Korean Journal of Materials Research
• /
• v.16 no.5
• /
• pp.297-301
• /
• 2006

Si/Mo multilayer anode consisting of active/inactive material was prepared using rf/dc magnetron sputtering. Molybdenum acts as a buffer against the volume change of the Silicon. Multilayer deposited on RT (reversible treatment) copper foil current collector to enhance adhesion between Silicon and copper foil. Deposited Silicon was identified as an amorphous. Amorphous has a relatively open structure than crystal structure, thus prevents the lattice expansion and has many diffusion paths of Li ion. When deposited time of Silicon and Molybdenum is 30 second and 2 second respectably, electrode has more capacity and good cycle stability. A 3000 nm thick multilayer was maintained 99% of the initial capacity (1624 $mAhg^{-1}$) after 100 cycles. As the increase of the multilayer thickness (4500 nm, 6000 nm), Si/Mo mutilayer anodes show aggravation cycle stability.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.12
• /
• pp.2441-2444
• /
• 2008