• Title/Summary/Keyword: Li-Si alloys

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Evaluations of Si based ternary anode materials by using RF/DC magnetron sputtering for lithium ion batteries

  • Hwang, Chang-Muk;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.302-303
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    • 2010
  • Generally, the high energy lithium ion batteries depend intimately on the high capacity of electrode materials. For anode materials, the capacity of commercial graphite is unlike to increase much further due to its lower theoretical capacity of 372 mAhg-1. To improve upon graphite-based negative electrode materials for Li-ion rechargeable batteries, alternative anode materials with higher capacity are needed. Therefore, some metal anodes with high theoretic capacity, such as Si, Sn, Ge, Al, and Sb have been studied extensively. This work focuses on ternary Si-M1-M2 composite system, where M1 is Ge that alloys with Li, which has good cyclability and high specific capacity and M2 is Mo that does not alloy with Li. The Si shows the highest gravimetric capacity (up to 4000mAhg-1 for Li21Si5). Although Si is the most promising of the next generation anodes, it undergoes a large volume change during lithium insertion and extraction. It results in pulverization of the Si and loss of electrical contact between the Si and the current collector during the lithiation and delithiation. Thus, its capacity fades rapidly during cycling. Si thin film is more resistant to fracture than bulk Si because the film is firmly attached to the substrate. Thus, Si film could achieve good cycleability as well as high capacity. To improve the cycle performance of Si, Suzuki et al. prepared two components active (Si)-active(Sn, like Ge) elements film by vacuum deposition, where Sn particles dispersed homogeneously in the Si matrix. This film showed excellent rate capability than pure Si thin film. In this work, second element, Ge shows also high capacity (about 2500mAhg-1 for Li21Ge5) and has good cyclability although it undergoes a large volume change likewise Si. But only Ge does not use the anode due to its costs. Therefore, the electrode should be consisted of moderately Ge contents. Third element, Mo is an element that does not alloys with Li such as Co, Cr, Fe, Mn, Ni, V, Zr. In our previous research work, we have fabricated Si-Mo (active-inactive elements) composite negative electrodes by using RF/DC magnetron sputtering method. The electrodes showed excellent cycle characteristics. The Mo-silicide (inert matrix) dispersed homogeneously in the Si matrix and prevents the active material from aggregating. However, the thicker film than $3\;{\mu}m$ with high Mo contents showed poor cycling performance, which was attributed to the internal stress related to thickness. In order to deal with the large volume expansion of Si anode, great efforts were paid on material design. One of the effective ways is to find suitably three-elements (Si-Ge-Mo) contents. In this study, the Si based composites of 45~65 Si at.% and 23~43 Ge at.%, and 12~32 Mo at.% are evaluated the electrochemical characteristics and cycle performances as an anode. Results from six different compositions of Si-Ge-Mo are presented compared to only the Si and Ge negative electrodes.

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Large Glass-forming Ability and Magnetocaloric Effect in Gd55Co20Al23Si2 Bulk Metallic Glass

  • Li, Qian;Cai, Pingping;Shen, Baolong;Akihiro, Makino;Akihisa, Inoue
    • Journal of Magnetics
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    • v.16 no.4
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    • pp.440-443
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    • 2011
  • In this study, we investigated the glass-forming ability (GFA) and magnetocaloric effect (MCE) of $Gd_{55}Co_{20}Al_{23}Si_2$ bulk glassy alloy. It is found that the addition of 2 at% Si is effective for extension of the supercooled liquid region (${\Delta}T_x$), the ${\Delta}T_x$ is 55 K for the $Gd_{55}Co_{20}Al_{25}$ glassy alloy, and increases to 79 K for the $Gd_{55}Co_{20}Al_{23}Si_2$ alloy. As a result, $Gd_{55}Co_{20}Al_{23}Si_2$ glassy alloys with diameters up to 5 mm were successfully synthesized. The alloys also exhibit large MCE, i.e., the magnetic entropy change (${\Delta}S_m$) of 8.9 J $kg^{-1}\;K^{-1}$, the full width at half maximum of the ${\Delta}S_m$ (${\delta}T_{FWHM}$) of 87 K, and the refrigerant capacity (RC) of 774 J $kg^{-1}$.

Microstructures and Electrochemical Properties of Si-M (M : Cr, Ni) as Alloy Anode for Li Secondary Batteries (리튬이차전지용 Si-M (M : Cr, Ni) 합금 음극의 미세구조와 전기화학적 특성)

  • Lee, Sung-Hyun;Sung, Jewook;Kim, Sung-Soo
    • Journal of the Korean Electrochemical Society
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    • v.18 no.2
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    • pp.68-74
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    • 2015
  • To compare the microstructure and electrochemical properties between two binary alloys (Cr-Si, Ni-Si), two composition of binary alloys with the same capacity were selected using phase-diagram and prepared by matrix-stabilization method to suppress the volume expansion of Si by inactive-matrix. Master alloys were made by Arc-melting followed by fine structured ribbon sample preparation by Rapid Solidification Process (RSP, Melt-spinning method) under the same conditions. Also powder samples were produced by wet grinding for X-Ray Diffraction (XRD) and electrochemical measurements. As predicted from the phase diagram, only active-Si and inactive-matrix ($CrSi_2$, $NiSi_2$) were detected. The results of Scanning Electron Microscope (SEM) and Transmission Electron Microscopy - Energy Dispersive X-ray Spectroscopy (TEM-EDS) show that Cr-Si alloy has finer microstructure than Ni-Si alloy, which was also predictable through phase diagram. The electrochemical properties related to microstructure were evaluated by coin type full- and half-cells. Separately, self-designed test-cells were used to measure the volume expansion of Si during reaction. Volume expansion of Cr-Si alloy electrode with finer microstructure was suppressed significantly and improved in cycle capability, in comparison Ni-Si alloy with coarse microstructure. From these, we could infer the correlation of microstructure, volume expansion and electrochemical degradation and these properties might be predicted by phase diagram.

Crystallization Behavior and Electrochemical Properties of Si50Al30Fe20 Amorphous Alloys as Anode for Lithium Secondary Batteries Prepared by Rapidly Solidification Process (액체급랭응고법으로 제조된 리튬 이차전지 음극활물질용 Si50Al30Fe20 비정질 합금의 결정화 거동 및 전기화학적 특성)

  • Seo, Deok-Ho;Kim, Hyang-Yeon;Kim, Sung-Soo
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.32 no.4
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    • pp.341-348
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    • 2019
  • This paper reports the microstructure and electrochemical properties of Si-Al-Fe ternary amorphous alloys prepared by rapid solidification as an anode for lithium secondary batteries. The microstructure was analyzed using XRD and HR-TEM with EDS mapping. In accordance with DSC analysis, annealing was performed to crystallize the active nano-Si in the amorphous alloy. Thus, nano-Si forms (~80 nm) embedded in the matrix alloy, such as $Fe_2Al_3Si_3$, $FeSi_2$, and $Fe_{0.42}Si_{2.67}$, were successfully synthesized. The electrode based on the Si-Al-Fe ternary alloy delivered an initial discharge capacity of approximately $700mAh^{g-1}$, and exhibited a high Coulombic efficiency of 99.0~99.6% from the $2^{nd}$ to $70^{th}$ cycles.

Pitting Characteristics and Electrochemical Polarization Behaviors in Al-Cu-Si-Mg-Ag-Zr Alloys with Ageing (Al-Cu-Li-Mg-Ag-Zr합금의 시효에 따른 전기화학적 분극 거동과 공식특성)

  • Min, B.C.;Chung, D.S.;Shon, T.W.;Cho, H.K.
    • Journal of the Korean Society for Heat Treatment
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    • v.9 no.2
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    • pp.103-111
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    • 1996
  • In this paper, we studied on both electrochemical polarization behaviors and pitting characteristics of ultra high strength Al-Cu-Li-Mg-Ag-Zr alloys(named C1 and C2) and 2090 alloy according to their treatments in the deaerated 3.5% NaCl, using by the potentiodynamic and the potentiostatic method, SEM micrograph and surface roughness including depth of pitting attack. With the cyclic polarization curves, the hysteresis of the C1 and C2 alloys appeared more remarkably than that of the 2090 alloy, because of precipitation microstructural difference between C1, C2 alloys and 2090 alloy. In the pitting experiments, the correlations between pitting growth and aging conditions were analyzed with the SEM micrograph and measurement of the pit depth.

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Electrochemical Characteristics of Cu3Si as Negative Electrode for Lithium Secondary Batteries at Elevated Temperatures (리튬 이차전지 음극용 Cu3Si의 고온에서의 전기화학적 특성)

  • Kwon, Ji-Y.;Ryu, Ji-Heon;Kim, Jun-Ho;Chae, Oh-B.;Oh, Seung-M.
    • Journal of the Korean Electrochemical Society
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    • v.13 no.2
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    • pp.116-122
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    • 2010
  • A $Cu_3Si$ film electrode is obtained by Si deposition on a Cu foil using DC magnetron sputtering, which is followed by annealing at $800^{\circ}C$ for 10 h. The Si component in $Cu_3Si$ is inactive for lithiation at ambient temperature. The linear sweep thermammetry (LSTA) and galvano-static charge/discharge cycling, however, consistently illustrate that $Cu_3Si$ becomes active for the conversion-type lithiation reaction at elevated temperatures (> $85^{\circ}C$). The $Cu_3Si$ electrode that is short-circuited with Li metal for one week is converted to a mixture of $Li_{21}Si_5$ and metallic Cu, implying that the Li-Si alloy phase generated at 0.0 V (vs. Li/$Li^+$) at the quasi-equilibrium condition is the most Li-rich $Li_{21}Si_5$. However, the lithiation is not extended to this phase in the constant-current charging (transient or dynamic condition). Upon de-lithiation, the metallic Cu and Si react to be restored back to $Cu_3Si$. The $Cu_3Si$ electrode shows a better cycle performance than an amorphous Si electrode at $120^{\circ}C$, which can be ascribed to the favorable roles provided by the Cu component in $Cu_3Si$. The inactive element (Cu) plays as a buffer against the volume change of Si component, which can minimize the electrode failure by suppressing the detachment of Si from the Cu substrate.

Electrochemical Performance of Ti-Si Alloy Anode using Nodule Type Current Collector

  • Shin, Min-Seon;Park, Jung-Bae;Lee, Sung-Man
    • Journal of the Korean Electrochemical Society
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    • v.20 no.4
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    • pp.61-66
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    • 2017
  • The cycle performance of Ti-Si alloy anode material for Li-ion batteries has been investigated as a function of loading level of electrode using a nodule type of substrate, in which the current collector of flat foil is also used for comparison. The Ti-Si alloy powders are prepared by mechanical alloying method. The electrodes with the nodule type of current collector exhibit enhanced cycling performance compared to those using the flat foil because the alloy particles are more strongly adhered to substrate and the stress caused by lithiation and delithiation reaction can be effectively relaxed by nodule-type morphology. It appears, however, that the cycle performance is critically dependent on the loading level of electrode, even when the nodule type of current collector is applied. With high loading level, cracks are initiated at surface of electrode due to a steep stress gradient through the electrode thickness during cycling, leading to capacity fading.

Mechanical Properties of Al-Si Composite Powders produced by Gas Atomization Process

  • Kim Jin-Chun;Wang Li-Fe;Chung In-Sang;Kim Yong-Jin
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2004.11a
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    • pp.46-47
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    • 2004
  • The microstructure and mechanical properties of the hypereutectic prealloyed Al-Si powders prepared by the gas atomization process were described in this paper. With increasing the gas pressure of the atomization, the average powder size was decreased from about $145{\mu}m\;to\;80{\mu}m$. The primary eutectic Si particles were uniformly distributed in the Al matrix and their size varied in the range of $8-10{\mu}m$. The high densified specimens with above 96% of the theoretical density were fabricated the hot pressing process. The UTS mechanical properties of VN1 specimens were much higher than that of conventional hypoeutectic Al-Si alloys.

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Use of Li-K-Cd Alloy to Remove MCl3 in LiCl-KCl Eutectic Salt (Li-K-Cd 합금을 이용한 LiCl-KCl 용융염에서 금속염화물의 제거)

  • Kim, Gha-Young;Kim, Tack-Jin;Jang, Junhyuk;Kim, Si-Hyung;Lee, Chang Hwa;Lee, Sung-Jai
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.16 no.3
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    • pp.309-313
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    • 2018
  • In this study, we prepared Li-K-Cd alloy, which meets the requirement of eutectic ratio of Li:K, to maintain the operating temperature of the drawdown process at $500^{\circ}C$ and to achieve the reuse of LiCl-KCl molten salt. The prepared Li-K-Cd alloys were added to LiCl-KCl salt bearing U and Nd at $500^{\circ}C$ to investigate the removal of $UCl_3$ in the salt. The reduction of $UCl_3$ in the salt was examined by measuring the OCP value of salt and analyzing the salt composition by ICP-OES. Reduction was also visually confirmed by change of salt color from dark purple to white. The experimental results reveal that the prepared Li-K-Cd alloy has reductive extractability for $UCl_3$ in salt. By improving the preparation method, the Li-K-Cd alloy can be applied to the drawdown process.

Application of Gamma Ray Densitometry in Powder Metallurgy

  • Schileper, Georg
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2002.07a
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    • pp.25-37
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    • 2002
  • The most important industrial application of gamma radiation in characterizing green compacts is the determination of the density. Examples are given where this method is applied in manufacturing technical components in powder metallurgy. The requirements imposed by modern quality management systems and operation by the workforce in industrial production are described. The accuracy of measurement achieved with this method is demonstrated and a comparison is given with other test methods to measure the density. The advantages and limitations of gamma ray densitometry are outlined. The gamma ray densitometer measures the attenuation of gamma radiation penetrating the test parts (Fig. 1). As the capability of compacts to absorb this type of radiation depends on their density, the attenuation of gamma radiation can serve as a measure of the density. The volume of the part being tested is defined by the size of the aperture screeniing out the radiation. It is a channel with the cross section of the aperture whose length is the height of the test part. The intensity of the radiation identified by the detector is the quantity used to determine the material density. Gamma ray densitometry can equally be performed on green compacts as well as on sintered components. Neither special preparation of test parts nor skilled personnel is required to perform the measurement; neither liquids nor other harmful substances are involved. When parts are exhibiting local density variations, which is normally the case in powder compaction, sectional densities can be determined in different parts of the sample without cutting it into pieces. The test is non-destructive, i.e. the parts can still be used after the measurement and do not have to be scrapped. The measurement is controlled by a special PC based software. All results are available for further processing by in-house quality documentation and supervision of measurements. Tool setting for multi-level components can be much improved by using this test method. When a densitometer is installed on the press shop floor, it can be operated by the tool setter himself. Then he can return to the press and immediately implement the corrections. Transfer of sample parts to the lab for density testing can be eliminated and results for the correction of tool settings are more readily available. This helps to reduce the time required for tool setting and clearly improves the productivity of powder presses. The range of materials where this method can be successfully applied covers almost the entire periodic system of the elements. It reaches from the light elements such as graphite via light metals (AI, Mg, Li, Ti) and their alloys, ceramics ($AI_20_3$, SiC, Si_3N_4, $Zr0_2$, ...), magnetic materials (hard and soft ferrites, AlNiCo, Nd-Fe-B, ...), metals including iron and alloy steels, Cu, Ni and Co based alloys to refractory and heavy metals (W, Mo, ...) as well as hardmetals. The gamma radiation required for the measurement is generated by radioactive sources which are produced by nuclear technology. These nuclear materials are safely encapsulated in stainless steel capsules so that no radioactive material can escape from the protective shielding container. The gamma ray densitometer is subject to the strict regulations for the use of radioactive materials. The radiation shield is so effective that there is no elevation of the natural radiation level outside the instrument. Personal dosimetry by the operating personnel is not required. Even in case of malfunction, loss of power and incorrect operation, the escape of gamma radiation from the instrument is positively prevented.

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