• Title/Summary/Keyword: Lithium Metal Anode

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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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Three-dimensional porous films consisting of copper@cobalt oxide core-shell dendrites for high-capacity lithium secondary batteries (리튬이차전지용 고용량 음극을 위한 구리@코발트산화물 코어-쉘 수지상 기반 3차원 다공성 박막)

  • So-Young Joo;Yunju Choi;Woo-Sung Choi;Heon-Cheol Shin
    • Journal of the Korean institute of surface engineering
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    • v.56 no.1
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    • pp.104-114
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    • 2023
  • Three dimensional (3D) porous structures consisting of Cu@CoO core-shell-type nano-dendrites were synthesized and tested as the anode materials in lithium secondary batteries. For this purpose, first, the 3D porous films comprising Cu@Co core-shell-type nano-dendrites with various thicknesses were fabricated through the electrochemical co-deposition of Cu and Co. Then the Co shells were selectively anodized to form Co hydroxides, which was finally dehydrated to get Cu@CoO nanodendrites. The resulting electrodes exhibited very high reversible specific capacity almost 1.4~2.4 times the theoretical capacity of commercial graphite, and excellent capacity retention (~90%@50th cycle) as compared with those of the existing transition metal oxides. From the analysis of the cumulative irreversible capacity and morphology change during charge/discharge cycling, it proved that the excellent capacity retention was attributed to the unique structural feature of our core-shell structure where only the thin CoO shell participates in the lithium storage. In addition, our electrodes showed a superb rate performance (70.5%@10.8 C-rate), most likely due to the open porous structure of 3D films, large surface area thanks to the dendritic structure, and fast electron transport through Cu core network.

Properties and structure of Li-doped carbonized phenol resin electrode (Li-doped 탄화된 페놀레진 전극의 성질과 구조)

  • Kim, Han-Joo;Park, Jong-Eun;Lee, Hong-Ki;Park, Soo-Gil
    • Proceedings of the KIEE Conference
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    • 1999.11d
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    • pp.965-967
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    • 1999
  • In order to solve to instability in air and to format dentrite, we used carbonized phenol resin electrode which is amorphous carbon. The structure and properties of deeply Li-doped carbonized phenol resin have been investigated in association with their utilization as electrodes in rechargeable batteries. Resol type phenol resin used as starting material. The doped lithium was found neither in metallic nor in ionic states even in the most deeply doped state($C_{2.2}$Li stage). It has also been confirmed that the carbonized phenol resin electrode has a large capacity with good stability and reversibility. These results strongly suggest that the carbonized phenol resin can make an excellent anode material for secondary batteries. Finally, we discuss that the carbonized phenol resin doped up to the $C_2Li$ stage can exhibit an energy density per volume as high as lithium metal. We know that carbonized phenol resin can used as cathode as well as anode by cyclic voltammogram.

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Structuring of Bulk Silicon Particles for Lithium-Ion Battery Applications

  • Bang, Byoung-Man;Kim, Hyun-Jung;Park, Soo-Jin
    • Journal of Electrochemical Science and Technology
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    • v.2 no.3
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    • pp.157-162
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    • 2011
  • We report a simple route for synthesizing multi-dimensional structured silicon anode materials from commercially available bulk silicon powders via metal-assisted chemical etching process. In the first step, silver catalyst was deposited onto the surface of bulk silicon via a galvanic displacement reaction. Next, the silver-decorated silicon particles were chemically etched in a mixture of hydrofluoric acid and hydrogen peroxide to make multi-dimensional silicon consisting of one-dimensional silicon nanowires and micro-scale silicon cores. As-synthesized silicon particles were coated with a carbon via thermal decomposition of acetylene gas. The carbon-coated multi-dimensional silicon anodes exhibited excellent electrochemical properties, including a high specific capacity (1800 mAh/g), a stable cycling retention (cycling retention of 89% after 20 cycles), and a high rate capability (71% at 3 C rate, compared to 0.1 C rate). This process is a simple and mass-productive (yield of 40-50%), thus opens up an effective route to make a high-performance silicon anode materials for lithiumion batteries.

Characteristics of Lithium Metal Secondary Battery Using PAN Gel-electrolyte Mixed with TiO2 Ceramic Filler (TiO2 Ceramic Filler가 혼합된 젤상의 PAN 고분자 전해질을 이용한 리튬금속 이차전지의 특성)

  • Lim, Hyo-Sung;Kim, Hyung-Sun;Cho, Byung-Won;Lee, Tae-Hee
    • Journal of the Korean Electrochemical Society
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    • v.5 no.3
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    • pp.106-110
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    • 2002
  • Gel-type polyacrylonitrile(PAN) polymer electrolytes have been prepared using ethylene carbonate(EC), propylene carbonate(PC) and dimethyl carbonate(DMC) plasticizer, $LiPF_6$ salt and $TiO_2$ ceramic filler. Electrochemical properties, such as electrochemical stability, ionic conductivity and compatibility with lithium metal and mechanical properly of polymer electrolytes were investigated. Charge/discharge performance of lithium secondary battery using these polymer electrolytes were investigated. The maximum load that the polymer electrolyte resists increased about two times as a result of adding $TiO_2$ in the polymer electrolyte containing EC and PC. Polymer electrolyte containing EC, PC and $TiO_2$ also showed ionic conductivity of $2\times10^{-3} S/cm$ at room temperature and electrochemical stability window up to 와 4.5V. Polymer electrolyte containing EC, PC, and $TiO_2$ showed the most stable interfacial resistance of $130\Omega$ during 20 days in the impedance spectra of the cells which were constructed by lithium metals as electrodes. Lithium metal secondary battery which employed $LiCoO_2$ cathode, lithium metal anode and $TiO_2$-dispersed polymer electrolyte showed $90\%$ of charge/discharge efficiency at the 1C rate of discharge.

Electrochemical Properties of Additive-Free Nanostructured Cobalt Oxide (CoO) Lithium Ion Battery Electrode (첨가제 없이 제작된 나노구조 코발트 산화물 리튬이온 배터리 전극의 전기 화학적 특성)

  • Kim, Juyun;Park, Byoungnam
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.31 no.5
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    • pp.335-340
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    • 2018
  • Transition metal oxide materials have attracted widespread attention as Li-ion battery electrode materials owing to their high theoretical capacity and good Li storage capability, in addition to various nanostructured materials. Here, we fabricated a CoO Li-ion battery in which Co nanoparticles (NPs) are deposited into a current collector through electrophoretic deposition (EPD) without binding and conductive agents, enabling us to focus on the intrinsic electrochemical properties of CoO during the conversion reaction. Through optimized Co NP synthesis and electrophoretic deposition (EPD), CoO Li-ion battery with 630 mAh/g was fabricated with high cycle stability, which can potentially be used as a test platform for a fundamental understanding of conversion reaction.

Fabrication and electrochemical characterization of amorphous vanadium oxide thin films for thin film micro-battery by reactive r.f. sputtering (반응성 r.f. 스퍼터링에 의한 마이크로 박막 전지용 산화바나듐 박막의 제작 및 전기화학적 특성 평가)

  • 전은정;신영화;남상철;윤영수;조원일
    • Journal of the Korean Vacuum Society
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    • v.9 no.1
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    • pp.42-47
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    • 2000
  • The amorphous vanadium oxide thin films for thin-film rechargeable lithium batteries were fabricated by r.f. reactive sputtering at room temperature. As the experimental parameter, oxygen partial pressure was varied during sputtering. At high oxygen partial pressures(>30%), the as-deposited films, constant current charge/discharge characteristics were carried out in 1M $LiPF_6$, EC:DMC+1:1 liquid electrolyte using lithium metal as anode. The specific capacity of amorphous $V_2O_5$ after 200cycles of operation at room temperature was higher compared to crystalline $V_2O_5$. The amorphous vanadium oxide thin film and crystalline film showed about 60$\mu$Ah/$\textrm{cm}^2\mu\textrm{m}$ and about 38$\mu$Ah/$\textrm{cm}^2\mu\textrm{m}$, respectively. These results suggest that the battery capacity of the thin film vanadium oxide cathode strongly depends on the crystallinity.

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Effect of $ZnCl_2$ on Formation of Carbonized Phenol Resin Anode

  • Kim Han-Joo;Hong Ji-sook;Son Won-Ken;Park Soo-Gil;Oyama Noboru
    • Journal of the Korean Electrochemical Society
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    • v.3 no.2
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    • pp.85-89
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    • 2000
  • For replacing Li metal at Lithium ion Battery(LIB) system, we used carbon powder material which prepared by Pyrolysis of Phenol resin as starting material. It became amorphous carbon by Pyrolysis through it's self condensation by thermal treatment. Amorphous carbon can be doped with Li intercalation and deintercalation because it has wide interlayer. However, it has a problem with structural destroy due to weak carbon-carbon bond. So, we used $ZnCl_2$ as the pore-forming agent. This inorganic salt was used together with the resin serves not only as the pore-forming agent to form open pores, which grow into a three-dimensional network structure in the cured material, but also as the microstructure-controlling agent to form a loose structure doped with bulky dopants. We used SEM in order to find to difference of structure, and can calculate the distance of interlayer by XRD analysis. CV test showed oxidation and reduction.

Research on Risk Assessment of Lithium-ion Battery Manufacturing Process Considering Cell Materials (셀소재를 고려한 리튬2차전지 제조공정 위험성 평가 방법 연구)

  • Kim, Taehoon
    • Journal of the Korean Society of Safety
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    • v.37 no.2
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    • pp.76-87
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    • 2022
  • Lithium-ion batteries (LIBs) have attracted much interest for their high energy density (>150 mAh/g), high capacity, low self-discharge rate, and high coulombic efficiency. However, with the successful commercialization of LIBs, fire and explosion incidents are likely to increase. The thermal runaway is known as the major factor in battery-related accidents that can lead to a series of critical conditions. Considering this, recent studies have shown an increased interest in countering the safety issues associated with LIBs. Although safety standards for LIB use have recently been formulated, little attention has been paid to the safety around the manufacturing process for battery products. The present study introduces a risk assessment method suitable for assessing the safety of the LIB-manufacturing process. In the assessment method, a compensation parameter (Z-factor) is employed to correctly evaluate the process's safety on the basis of the type of material (e.g., metal anode, liquid electrolyte, solid-state electrolytes) utilized in a cell. The proposed method has been applied to an 18650 cell-manufacturing process, and three sub-processes have been identified as possibly vulnerable parts (risk index: >4). This study offers some crucial insights into the establishment of safety standards for battery-manufacturing processes.

Improving the Cycle Performance of Li Metal Secondary Batteries Using Three-Dimensional Porous Ag/VGCF-Coated Separators (3D 다공성 구조의 Ag-VGCF 코팅 분리막을 이용한 리튬금속 이차전지 수명향상)

  • Beom-Hui Lee;Dong-Wan Ham;Ssendagire Kennedy;Jeong-Tae Kim;Sun-Yul Ryou
    • Journal of the Korean Electrochemical Society
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    • v.27 no.3
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    • pp.88-96
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    • 2024
  • Lithium metal has garnered attention as a promising anode active material thanks to its high specific capacity, energy density, and the lowest reduction potential. However, the formation of dendrites, dendritic crystals that arise during the charge and discharge process, has posed safety and lifetime stability challenges. To resolve this, our study has introduced a novel separator design. This separator features a composite coating of vapor-grown carbon fiber, a conductive material in nanofibers, and silver. We have meticulously studied the impact of this innovative separator on the electrochemical properties of the lithium metal anode, unveiling promising results. To confirm the synergistic effect of VGCF and Ag, a separator with no surface treatment and a separator with only VGCF coated on one side were prepared and compared with the Ag-VGCF-separator. In the case of the bare separator, the Li metal surface is covered with dendrites during the initial charge and discharge process. In contrast, both the VGCF-separator and the Ag-VGCF-separator show Li precipitation inside the conductive coating layer coated on the separator surface. Additionally, the Ag-VGCF-separator showed a more uniform precipitate shape than the VGCF-separator. As a result, the Ag-VGCF-separators show improved electrochemical properties compared to the bare separators and the VGCF-separators.