• Title/Summary/Keyword: Si anode

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Electrochemical Behavior of Si/Cu/Graphite Composite Anode for Lithium Secondary Battery (리튬이차전지용 Si/Cu/Graphite 복합체 음극의 전기화학적 거동)

  • Kim, Hyung-Sun;Chung, Kyung-Yoon;Cho, Won-Il;Cho, Byung-Won
    • Journal of the Korean Electrochemical Society
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    • v.12 no.2
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    • pp.162-166
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    • 2009
  • The carbon-coated Si/Cu powders were synthesized by mechanical ball-milling and hydrocarbon gas decomposition methods at high temperature. The carbon-coated Si/Cu powder was used as anode for lithium secondary battery and its electrochemical behavior was investigated. In addition, the carbon-coated Si/Cu/graphite composite anode material was prepared using natural graphite powder and their electrochemical characteristics were compared with natural graphite anode. The specific capacity of carbon-coated Si/Cu anode increased to the initial 10 cycles. The carbon-coated Si/Cu/graphite composite anode exhibited the reversible specific capacity of 450mAh/g and the first cycle efficiency of 81.3% at $0.25mA/cm^2$. The cycling performance of the composite anode was similar to that of pure graphite anode except the reversible specific capacity value.

Electrochemical Characteristics of Carbon-coated Si/Cu/graphite Composite Anode

  • Kim, Hyung-Sun;Chung, Kyung-Yoon;Cho, Won-Il;Cho, Byung-Won
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1607-1610
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    • 2009
  • The carbon-coated Si/Cu powder has been prepared by mechanical ball milling and hydrocarbon gas decomposition methods. The phase of Si/Cu powder was analyzed using X-ray diffraction (XRD), dispersive Raman spectroscopy, electron probe microanalysis (EPMA) and transmission electron microscope (TEM). The carbon-coated Si/Cu powders were used as anode active material for lithium-ion batteries. Their electrochemical properties were investigated by charge/discharge test using commercial LiCo$O_2$ cathode and lithium foil electrode, respectively. The surface phase of Si/Cu powders consisted of carbon phase like the carbon nanotubes (CNTs) with a spacing layer of 0.35 nm. The carbon-coated Si/Cu/graphite composite anode exhibited a higher capacity than commercial graphite anode. However, the cyclic efficiency and the capacity retention of the composite anode were lower compared with graphite anode as cycling proceeds. This effect may be attributed to some mass limitations in LiCo$O_2$ cathode materials during the cycling.

The Research on Aluminum and Silcon Nanoparticles as Anode Materials for Lithium Ion Batteries (알루미늄 실리콘 나노분말을 이용한 리튬이온전지 음극재료에 관한 연구)

  • Kim, Hyeong-Jo;Tulugan, Kelimu;Kim, Hyung-Jin;Park, Won-Jo
    • Journal of Power System Engineering
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    • v.17 no.1
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    • pp.110-115
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    • 2013
  • The electrochemical performance and microstructure of Al-Si, Al-Si/C was investigated as anode for lithium ion battery. The Al-Si nano composite with 5 : 1 at% ratio was prepared by arc-discharge nano powder process. However, some of problem is occurred, when Al nano composite was synthesized by this manufacturing. The oxidation film is generated around Al-Si particles for passivating processing in the manufacture. The oxidation film interrupts electrical chemistry reaction during lithium ion insertion/extraction for charge and discharge. Because of the existence the oxidation film, Al-Si first cycle capacity is very lower than other examples. Therefore, carbon synthsized by glucose ($C_6H_{12}O_6$) was conducted to remove the oxidation film covered on the composite. The results showed that the first discharge cycle capacity of Al-Si/C is improved to 113mAh/g comparing with Al-Si (18.6mAh/g). Furthermore, XRD data and TEM images indicate that $Al_4C_3$ crystalline exist in Al-Si/C composite. In addition the Si-Al anode material, in which silicon is more contained was tested by same method as above, it was investigated to check the anode capacity and morphology properties in accordance with changing content of silicon, Si-Al anode has much higher initial discharge capacity(about 500mAh/g) than anode materials based on Aluminum as well as the morphology properties is also very different with the anode based Aluminum.

Effect of Lithium Contents and Applied Pressure on Discharge Characteristics of Single Cell with Lithium Anode for Thermal Batteries (리튬 함량 및 단위 셀 압력이 열전지용 리튬 음극의 방전 성능에 미치는 영향)

  • Im, Chae-Nam;Ahn, Tae-Young;Yu, Hye-Ryeon;Ha, Sang Hyeon;Yeo, Jae Seong;Cho, Jang-Hyeon;Yoon, Hyun-Ki
    • 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 ($522.2Wh\;l^{-1}$).

Electrochemical Properties of Lithium Anode for Thermal Batteries (열전지용 리튬음극의 전기화학적 특성)

  • Im, Chae-Nam;Yoon, Hyun Ki;Ahn, Tae-Young;Yeo, Jae Seong;Ha, Sang Hyeon;Yu, Hye-Ryeon;Baek, Seungsu;Cho, Jang Hyeon
    • Applied Chemistry for Engineering
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    • v.29 no.6
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    • pp.696-702
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    • 2018
  • Recently, the current thermal battery technology needs new materials for electrodes in the power and energy density to meet various space and defense requirements. In this paper, to replace the pellet type Li(Si) anode having limitations of the formability and capacity, electrochemical properties of the lithium anode with high density for thermal batteries were investigated. The lithium anode (Li 17, 15, 13 wt%) was fabricated by mixing the molten lithium and iron powder used as a binder to hold the molten lithium at $500^{\circ}C$. The single cell with 13 wt% lithium showed a stable performance. The 2.06 V (OCV) of the lithium anode was significantly improved compared to 1.93 V (OCV) of the Li(Si) anode. Specific capacities during the first phase of the lithium anode and Li(Si) were 1,632 and $1,181As{\cdot}g^{-1}$, respectively. As a result of the thermal battery performance test at both room and high temperatures, the voltage and operating time of lithium anode thermal batteries were superior to those of using Li(Si) anode thermal batteries. The power and energy densities of Li anode thermal batteries were also remarkably improved.

Effects of Particle Size and Binder Phase Addition on Formability of Li-Si Alloy Powder for Thermal Battery Anode (열전지 음극재용 Li-Si 원료의 성형성에 미치는 입자크기와 바인더첨가 효과)

  • Ryu, Sung-Soo;Kim, Hui-Sik;Kim, Seongwon;Kim, Hyung-Tae;Cheong, Hae-Won;Lee, Sung-Min
    • Journal of Powder Materials
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    • v.21 no.5
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    • pp.331-337
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    • 2014
  • The effects of particle size of Li-Si alloy and LiCl-KCl addition as a binder phase for raw material of anode were investigated on the formability of the thermal battery anode. The formability was evaluated with respect to filling density, tap density, compaction density, spring-back and compressive strength. With increasing particle size of Li-Si alloy powder, densities increased while spring-back and compressive strength decreased. Since the small spring-back is beneficial to avoiding breakage of pressed compacts, larger particles might be more suitable for anode forming. The increasing amount of LiCl-KCl binder phase contributed to reducing spring-back, improving the formability of anode powder too. The control of particle size also seems to be helpful to get double pressed pellets, which consisted of two layer of anode and electrolyte.

Effect of Lithium Bis(Oxalato)Borate Additive on Thermal Stability of Si Nanoparticle-based Anode (리튬 이차 전지용 실리콘 나노입자 음극의 고온 열안정성에 대한 Lithium bis(oxalato)borate첨가제의 효과)

  • Kim, Min-Jeong;Choi, Nam-Soon;Kim, Sung-Soo
    • Journal of the Korean Electrochemical Society
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    • v.17 no.2
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    • pp.79-85
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    • 2014
  • Silicon (Si) has been investigated as promising negative-electrode (anode) materials because its theoretical specific capacity of 4200 mAh/g for $Li_{4.4}Si$ is far higher than that of carbonaceous anodes in current commercial products. However, in practice, the application of Si to Li-ion batteries is still quite challenging because Si suffers from severe volume expansion and contraction and lead to a continuous solid electrolyte interphase (SEI)-filming process by cracking of Si. This process consumes the limited $Li^+$ source, builds up thick and unstable SEI layer on the Si active materials, and will eventually disable the cell. Since unstable SEI reduces electrochemical performance and thermal stability of the Si anode, the surface chemistry of the anode should be modified by using a functional additive. It is found that lithium bis(oxalato)borate (LiBOB) as an additive effectively protected the Si anode surface, improved capacity retention when stored at $60^{\circ}C$, and alleviated exothermic thermal reactions of fully lithiated Si anode.

Effects of Porous Microstructure on the Electrochemical Properties of Si-Ge-Al Base Anode Materials for Li-ion Rechargeable Batteries (리튬이차전지용 다공성 Si-Ge-Al계 음극활물질의 전기화학적 특성)

  • Cho, Chung Rae;Kim, Myeong Geun;Sohn, Keun Yong;Park, Won-Wook
    • Journal of Powder Materials
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    • v.24 no.1
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    • pp.24-28
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    • 2017
  • Silicon alloys are considered promising anode active materials to replace Li-ion batteries by graphite powder, because they have a relatively high capacity of up to 4200 mAh/g, and are environmentally friendly and inexpensive ECO-materials. However, its poor charge/discharge properties, induced by cracking during cycles, constitute their most serious problem as anode electrode. In order to solve these problems, Si-Ge-Al alloys with porous structure are designed as anode alloy powders, to improve cycling stability. The alloys are melt-spun to obtain the rapidly solidified ribbons, and then ball-milled to make fine powders. The powders are etched using 1 M HCl solution, which gives the powders a porous structure by removing the element Al. Subsequently, in this study, the microstructures and the characteristics of the etched powders are evaluated for application as anode materials. As a result, the etched porous powder shows better electrochemical properties than as-milled Si-Ge-Al powder.

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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The Effect of the Ratio of C45 Carbon to Graphene on the Si/C Composite Materials Used as Anode for Lithium-ion Batteries

  • Hoang Anh Nguyen;Thi Nam Pham;Le Thanh Nguyen Huynh;Tran Ha Trang Nguyen;Viet Hai Le;Nguyen Thai Hoang;Thi Thom Nguyen;Thi Thu Trang Nguyen;Dai Lam Tran;Thi Mai Thanh Dinh
    • Journal of Electrochemical Science and Technology
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    • v.15 no.2
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    • pp.291-298
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    • 2024
  • Due to its high theoretical capacity, Silicon (Si) has shown great potential as an anode material for lithium-ion batteries (LIBs). However, the large volume change of Si during cycling leads to poor cycling stability and low Coulombic efficiency. In this study, we synthesized Si/Carbon C45:Graphene composites using a ball-milling method with a fixed Si content (20%) and investigated the influence of the C45/Gr ratio on the electrochemical performance of the composites. The results showed that carbon C45 networks can provide good conductivity, but tend to break at Si locations, resulting in poor conductivity. However, the addition of graphene helps to reconnect the broken C45 networks, improving the conductivity of the composite. Moreover, the C45 can also act as a protective coating around Si particles, reducing the volume expansion of Si during charging/discharging cycles. The Si/C45:Gr (70:10 wt%) composite exhibits improved electrochemical performance with high capacity (~1660 mAh g-1 at 0.1 C) and cycling stability (~1370 mAh g-1 after 100 cycles). This work highlights the effective role of carbon C45 and graphene in Si/C composites for enhancing the performance of Si-based anode materials for LIBs.