• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.1
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• pp.78-85
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• 2019

The effect of various lithium sources such as LiCl, LiOH, and Li-metal on the microstructure and electrochemical properties of granulated $SiO_x$ powders were investigated. Various lithium sources were metallurgically added for a passive pre-lithiation of $SiO_x$ to improve its low initial coulombic efficiency. In spite of using the same amount of Li in various sources, as well as the same process conditions, different lithium silicates were obtained. Moreover, irreversible phases were formed without reduction of $SiO_x$, which might be from additional oxygen incorporation during the process. Accordingly, there were no noticeable electrochemical enhancements. Nevertheless, the $Li_4SiO_4$ phase changes the initial electrochemical reaction, and consequently the relationship between the microstructure and electrochemical properties of metallurgically pre-lithiated $SiO_x$ could provide a guideline for the optimization of the performance of lithium ion batteries.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.160.2-160.2
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• 2014

Recently silicon has attracted intense interest as a promising anode material of lithium-ion batteries due to its extremely high capacity of 4200 mA/g (for Li4.2Si) that is much higher than 372 mAh/g (for LiC6) of graphite. However, it seriously suffers from large volume change (even up to 300%) of the electrode upon lithiation, leading to its pulverization or mechanical failure during lithiation/delithiation processes and the rapid capacity fading. To overcome this problem, Si nanowires have been considered. Use of such Si nanowires provides their facile relaxation during lithiation/delithiation without mechanical breaking. To design better Si electrodes, a study to unveil atomic-scale mechanisms involving the volume expansion and the phase transformation upon lithiation is critical. In order to investigate the lithiation mechanism in Si nanowires, we have developed a reactive force field (ReaxFF) for Si-Li systems based on density functional theory calculations. The ReaxFF method provides a highly transferable simulation method for atomistic scale simulation on chemical reactions at the nanosecond and nanometer scale. Molecular dynamics (MD) simulations with the ReaxFF reproduces well experimental anisotropic volume expansion of Si nanowires during lithiation and diffusion behaviors of lithium atoms, indicating that it would be definitely helpful to investigate lithiation mechanism of Si electrodes and then design new Si electrodes.

• Bulletin of the Korean Chemical Society
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• v.27 no.8
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• pp.1175-1180
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• 2006

Si-C composites were prepared by the carbonization of polyaniline (PAn) coated on silicone powder. The physical and electrochemical properties of the Si-C composites were characterized by particle-size analysis, X-ray diffraction, scanning electron microscopy, and battery electrochemical tests. The average particle size of Si was increased by the coating of Pan but somewhat reduced by the carbonization to give silicone-carbon composites. The co-existence of crystalline silicone and amorphous-like carbon was confirmed by XRD analyses. SEM photos showed that the silicone particles were well covered with carbonaceous materials, depending on the PAn content. Si-C$\mid$Li cells were fabricated using the Si-C composites and tested using galvanostatic charge-discharge. Si-C$\mid$Li cells gave better electrochemical properties than Si|Li cells. Si-C$\mid$Li cells using Si-C from HCl-undoped precursor PAn showed better electrochemical properties than precursor PAn doped in HCl. The addition of an electrolyte containing 4-fluoroethylene carbonate (FEC) increased the initial discharge capacity. Also, another electrochemical test, the galvanostatic charge-discharge test with GISOC (gradual increasing of the state of charge) was carried out. Si-C(Si:PAn = 50:50 wt. ratio)|Li cell showed 414 mAh/g of reversible specific capacity, 75.7% of IIE (initial intercalation efficiency), 35.4 mAh/g of IICs (surface irreversible specific capacity).

• Journal of the Korean Ceramic Society
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• v.41 no.8
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• pp.593-598
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• 2004

To make the all-solid-state lithium thin film battery having less than 1 fm in thickness, LiCoO$_2$ thin films were deposited on Pt/TiO$_2$/SiO$_2$/Si substrate as a function of Li/Co mole ratio and the deposition temperature by Pulsed Laser Deposition (PLD). Especially, LiCoO$_2$ thin films deposited at 50$0^{\circ}C$ with target of Li/Co=1.2 mole ratio show an initial discharge capacity of 53 $\mu$Ah/cm$^2$-$\mu$m and capacity retention of 67.6％. The microstructural and electrochemical properies of (Li, La)TiO3 thin films grown on LiCoO$_2$Pt/TiO$_2$/SiO$_2$/Si structures by Pulsed Laser Deposition (PLD) were investigated at various deposition temperatures. The thin films grown at 10$0^{\circ}C$ show an initial discharge capacity of approximately 51 $\mu$Ah/cm$^2$-$\mu$m and moreover show excellent discharge capacity retention of 90％ after 100 cycles. An amorphous (Li, La)TiO$_3$ solid electrolyte is possible for application to solid electrolyte for all-solid-state lithium thin film battery below 1 $\mu$m.

• Journal of the Korean Electrochemical Society
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• v.9 no.3
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• pp.107-112
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• 2006

Si-C composites were prepared by the carbonization of silicon powder covered by polyaniline(PAn). Physical and electrochemical properties of the Si-C composites were characterized by the particle size analysis, X-ray diffraction technique, scanning electron microscope, and electrochemical test of battery. The average particle size of the Si was increased by the coating of PAn and somewhat reduced by the carbonization to give silicone-carbon composites. XRD analysis' results were confirmed co-existence of crystalline silicon and amorphous-like carbon. SEM photos showed that the silicon particle were well covered with carbonacious materials depend on the PAn content. Si-C|Li cells were fabricated using the Si-C composites and were tested using the galvanostatic charge-discharge test. Si-C|Li cells gave better electrochemical properties than that of Si|Li cell. Si-C|Li cell using the Si-C from HCl undoped PAn Precursor showed better electrochemical properties than that from HCl doped PAn Precursor. Using the electrolyte containing FEC as an additive, the initial discharge capacity was increased. After that the galvanostatic charge-discharge test with the GISOC(gradual increasing of the state of charge) condition was carried out. Si-C(Si:PAn:50:50 wt. ratio)|Li cell showed 414 mAh/g of the reversible specific capacity, 75.7% of IIE(initial intercalation efficiency), 35.4 mAh/g of IICs(surface irreversible specific capacity).

• Korean Chemical Engineering Research
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• v.54 no.1
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• pp.16-21
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• 2016

Silicon/Carbon/CNT composites as anode materials for lithium-ion batteries were synthesized to overcome the large volume change during lithium alloying-de alloying process and low electrical conductivity. Silicon/Carbon/CNT composites were prepared by the fabrication processes including the synthesis of SBA-15, magnesiothermic reduction of SBA-15 to obtain Si/MgO by ball milling, carbonization of phenolic resin with CNT and HCl etching. The prepared Silicon/Carbon/CNT composites were analysed by XRD, SEM, BET and EDS. In this study, the electrochemical effect of CNT content to improve the capacity and cycle performance was investigated by charge/discharge, cycle, cyclic voltammetry and impedance tests. The coin cell using Silicon/Carbon/CNT composite (Si:CNT=93:7 in weight) in the electrolyte of $LiPF_6$ dissolved in organic solvents (EC:DMC:EMC=1:1:1 vol%) has better capacity (1718 mAh/g) than those of other composition coin cells. The cycle performance of coin cell was improved as CNT content was increased. It is found that the coin cell (Si:CNT=89:11 in weight) has best capacity retension (83%) after 2nd cycle.

• Journal of Electrochemical Science and Technology
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• v.2 no.4
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• pp.193-197
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• 2011

The influences of the thickness and microstructure of Fe layer on the electrochemical performances of Fe/Si multilayer thin film anodes were investigated. The Fe/Si multilayer films were prepared by electron beam evaporation, in which Fe layer was deposited with/without simultaneous bombardment of Ar ion. The kinetics of Li insertion/extraction reactions in the early stage are slowed down with increasing the thickness of Fe layer, but such a slowdown seems to be negligible for thin Fe layers less than about $500{\AA}$. When the Fe layer was deposited with ion bombardment, even the $300{\AA}$ thick Fe layer significantly suppress Li diffusion through the Fe layer. This is attributed to the dense microstructure of Fe layer, induced by ion beam assisted deposition (IBAD). It appears that the Fe/Si multilayer films prepared with IBAD show good cyclability compared to the film deposited without IBAD.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.17 no.9
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• pp.930-935
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• 2004

$({Li}_{0.5}0{La}_{0.5}){TiO}_3$ (LLTO) solid electrolyte was grown on LiCo{O}_2 (LCO) cathode films deposited on $Pt/Ti{O}-2/Si{O}_2/Si$ substrate using pulsed laser deposition for all-solid-state lithium microbattery. LLTO solid electrolyte exhibits an amorphous phase at various deposition temperatures. LLTO films deposited at 10$0^{\circ}C$ showed a clear interrace without any chemical reaction with LCO, and showed an initial discharge capacity of 50 $\mu$Ah/cm$^2$-$\mu$m and capacity retention of 90 % after 100 cycles with Li anode in 1mol$ LiCl{O}_4$ in propylene carbonate (PC). The increase of capacity retention in LLTO/LCO structure than LCO itself was attributed to the structural stability of LCO cathode films by the stacked LLTO. The cells of LLTO/LCO with LLTO grown at $100^{\circ}C$ showed a good cyclic property of 63.6 % after 300 cycles. An amorphous LLTO solid electrolyte is possible for application to solid electrolyte for all-solid-state lithium microbattery.

• Journal of the Korean Chemical Society
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• v.50 no.3
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• pp.243-246
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• 2006

The LiCoO2 thin films were prepared on the Pt/Ti/SiO2/Si substrate by spin coating using citrate sol. The citrate sol was spin-coated on substrate and dried at 380oC for 15 min. to evaporate the solvents and remove the organic materials. The as-deposited films were annealed at 750oC for 10 min. in air for crystallization. The X-ray diffraction patterns for the film have been indexed hexagonal system with space group R3m. The active area of LiCoO2 films for electrochemical test was about 11cm2. A Li foil and 1M LiClO4 in propylene carbonate(PC) and ethylene carbonate(EC) (1:1)were used as an anode and an electrolyte, respectively. The galvanostatic charge-discharge test was carried out at constant current density ranging from 5 A/cm2 in the voltage window between 4.2 and 3.0 V. The first discharge capacity of the film is 0.35Ah/cm2-m. The cycling behavior of the LiCoO2 film is also reported.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.11a
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• pp.350-351
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• 2005

The electrochemical behavior of Si-C material synthesized by heating the mixture of silicon and polyvinylidene fluoride (PVDF). Coin cells of the type 2025 were made using the synthesized material and the electrochemical studies were performed. Si-C/Li cells were made by using the developed Si-C material. Charge/discharge test was performed at 0.1C hour rate. Initial charge and discharge capacities at Si-C material derived from 20 wt.% of PVDF was found to be 1,830 and 526 mAh/g respectively. Initial charge/discharge characteristics of the electrode were analyzed. The level of reversible specific capacity was about 216 mAh/g at Si-C material derived from 20 wt.% of PVDF, IIE, intercalation efficiency at initial charge/discharge, was 68 %. Surface irreversible specific capacity was 31 mAh/g, and average specific resistance was 2.6 ohm*g.