• 제목/요약/키워드: Li(Si) anode

검색결과 87건 처리시간 0.023초

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

  • 임채남;안태영;유혜련;하상현;여재성;조장현;윤현기
    • 한국전기전자재료학회논문지
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    • 제32권2호
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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 ($522.2Wh\;l^{-1}$).

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

  • 류성수;김희식;김성원;김형태;정해원;이성민
    • 한국분말재료학회지
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    • 제21권5호
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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.

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

  • 임채남;윤현기;안태영;여재성;하상현;유혜련;백승수;조장현
    • 공업화학
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    • 제29권6호
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    • pp.696-702
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    • 2018
  • 최근 열전지는 우주 및 국방분야에서 활용하기 위하여 고출력 및 고에너지 밀도의 새로운 전극재료가 요구되는 실정이다. 본 논문에서는 성형성과 용량의 한계를 가지는 펠릿 타입의 리튬-실리콘 합금(Li(Si)) 음극을 대체하기 위하여 고밀도를 가지는 리튬음극을 제조하고, 단위전지 및 열전지의 전기화학적 성능에 미치는 영향을 고찰하였다. 리튬음극은 $500^{\circ}C$에서 안정적인 작동을 위하여 철 분말을 바인더로 사용하였고 리튬 중량별(17, 15, 13 wt%) 단위전지 성능평가를 통해 리튬 13 wt%에서 안정적인 성능을 확인하였다. 또한 리튬음극을 사용한 단위전지의 개회로전압이 2.06 V로 Li(Si) 음극 개회로전압 1.93 V에 비해 약 0.1 V 이상 높게 나타났고, first phase에서 리튬음극의 비용량은 $1,632As{\cdot}g^{-1}$로 Li(Si) 음극의 비용량 $1,181As{\cdot}g^{-1}$에 비해 약 1.4배 정도 성능이 향상됨을 확인하였다. 리튬음극을 적용한 열전지를 상온 및 고온 성능시험 결과를 통하여 Li(Si) 음극 열전지에 비해 전압 및 작동시간 등이 탁월하며, 출력특성 및 에너지밀도가 획기적으로 향상됨을 확인하였다.

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

  • 김민정;최남순;김성수
    • 전기화학회지
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    • 제17권2호
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    • pp.79-85
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    • 2014
  • 리튬2차전지용 음극활물질로 연구되고 있는 실리콘은 흑연에 비하여 높은 이론용량 (4200mAh/g for $Li_{4.4}Si$)을 가지기 때문에 고용량 음극소재로 각광받고 있다. 이러한 실리콘 음극은 반복적인 충방전에 의해 활물질 입자의 심각한 부피변화와 균열에 의한 새로운 표면이 전해액에 계속적으로 노출되는 문제로 인하여 두껍고 불안정한 피막생성을 유도한다. 불안정한 구조의 피막은 실리콘 음극의 전기화학적 성능뿐만 아니라 고온 열안정성을 저해할 수 있기 때문에 본 연구에서는 실리콘의 열안정성 향상을 위해 전해액 첨가제를 도입하여 피막구조를 변경하고자 한다. 전해액 첨가제인 lithium bis(oxalato)borate (LiBOB)가 실리콘 음극표면에 피막을 효과적으로 형성하였으며, 만충전 상태의 실리콘 음극의 $60^{\circ}C$ 저장시 용량유지 특성을 개선하였으며 고온에서의 열안정성 크게 향상시켰다.

박막전지용 Si/Mo 다층박막 음극의 전기화학적 특성 (Characterization of Si/Mo Multilayer Anode for Microbattery)

  • 이기령;정주영;문희수;이승원;이유기;박종완
    • 한국재료학회:학술대회논문집
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    • 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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    • pp.209-209
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    • 2003
  • The adventages of Li alloys have attracted the attention of many research groups, many of which have investigated tin-based alloys [1-2], Despite interesting performances of these, the irreversible capacity loss systematically observed on the first cycle for these compounds is a main drawback for their use as anode materials in lithium ion cells. Not only Sn is efficient in forming alloys with Li, Si can also react with Li to form alloys with a high Li/Si ratio, like Li$\_$22/Si$\_$5/ at 400$^{\circ}C$. It corresponds to a capacity of 4200mAh/g. Electrochemical Li-Si reaction occurs between 0 and 0.3 V against Li/Li$\^$+/, so that high-energy density battery can be realized. Despite the high theoretical capacity of elements like Si, however, particles of the alloys crack and fragment due to the repeated alloying and do-alloying which occurs as cell are charged and discharged. The research groups of Muggins [3] and Besenhard [4] have proposed that the volume expansion due to the insertion of Li can be reduced in micro- and submicro-structured matrix alloys. For this reason, the research group of J.R. Dahn investigated Sn/Mo sequential sputter deposition to prepare nanocomposites [5]. In this study, we investigated the characterization and the electrochemical characteristics of sequentially sputtered Si/Mo multilayer for microbattery anode.

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

  • 조충래;김명근;손근용;박원욱
    • 한국분말재료학회지
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    • 제24권1호
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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

  • 황창묵;박종완
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2010년도 제39회 하계학술대회 초록집
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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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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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    • 제30권7호
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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.

Fundamental Approach to Capacity Prediction of Si-Alloys as Anode Material for Li-ion Batteries

  • Kim, Jong Su;Umirov, Nurzhan;Kim, Hyang-Yeon;Kim, Sung-Soo
    • Journal of Electrochemical Science and Technology
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    • 제9권1호
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    • pp.51-59
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    • 2018
  • Various Si-Fe-Al ternary alloys were prepared with the same amount of Si by the melt spinning technique. The feasibility of the capacity prediction approach based on the estimation of the active amount of Si using the phase diagram was practically examined and reported. These predictions were verified by the electrochemical test of fabricated coin cells and other characterization methods. The capacity prediction approach using the phase diagram might be a fundamental and efficient method to accelerate the practical application of Si-based alloys as the anode material for Li-ion batteries. The details on the prediction procedure were discussed.

Thermally Crosslinked Polyimide Binders for Si-alloy Anodes in Li-ion Batteries

  • Chang, Hyeong-Seok;Ji, Sang-Gu;Rho, Miso;Lee, Byoung-Min;Kim, Sung-Soo;Choi, Jae-Hak
    • Journal of Electrochemical Science and Technology
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    • 제13권3호
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    • pp.339-346
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    • 2022
  • Silicon (Si) has attracted considerable attention due to its high theoretical capacity compared to conventional graphite anode materials. However, Si-based anode materials suffer from rapid capacity loss due to mechanical failure caused by large volume change during cycling. To alleviate this phenomenon, crosslinked polymeric binders with strong interactions are highly desirable to ensure the electrode integrity. In this study, thermally crosslinked polyimide binders were used for Si-alloy anodes in Li-ion batteries. The crosslinked polyimide binder was found to have high adhesion strength, resulting in enhanced electrode integrity during cycling. Therefore, the Si-alloy anodes with crosslinked polyimide binder provide enhanced electrochemical performance, such as Coulombic efficiency, capacity retention, and cycle stability.