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SiOC Anode Material Derived from Poly(phenyl carbosilane) for Lithium Ion Batteries

  • Lee, Yoon Joo;Ryu, Ji Yeon;Roh, Kwang Chul;Kim, Soo Ryong;Kwon, Woo Teck;Shin, Dong-Geun;Kim, Younghee
    • Journal of the Korean Ceramic Society
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    • v.50 no.6
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    • pp.480-484
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    • 2013
  • Since SiOC was introduced as an anode material for lithium ion batteries, it has been studied with different chemical compositions and microstructures using various silicon based inorganic polymers. Poly(phenyl carbosilane) is a SiOC precursor with a high carbon supply in the form of the phenyl unit, and it has been investigated for film applications. Unlike any other siloxane-based polymers, oxygen atoms must be utilized in an oxidation process, and the amount of oxygen is controllable. In this study, SiOC anodes were prepared using poly(phenyl carbosilane) with different heat treatment conditions, and their electrochemical properties as an anode material for lithium ion batteries were studied. In detail, cyclic voltammetry and charge-discharge cycling behavior were evaluated using a half-cell. A SiOC anode which was prepared under a heat treatment condition at $1200^{\circ}C$ after an oxidation step showed stable cyclic performance with a reversible capacity of 360 mAh/g.

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

  • 이기령;정주영;문희수;이승원;이유기;박종완
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2003.11a
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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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Electrochemical Performance of Graphite/Silicon/Carbon Composites as Anode Materials for Lithium-ion Batteries (리튬이온배터리 Graphite/Silicon/Carbon 복합 음극소재의 전기화학적 성능)

  • Jo, Yoon Ji;Lee, Jong Dae
    • Korean Chemical Engineering Research
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    • v.56 no.3
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    • pp.320-326
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    • 2018
  • In this study, Graphite/Silicon/Carbon (G/Si/C) composites were synthesized to improve the electrochemical properties of Graphite as an anode material of lithium ion battery. The prepared G/Si/C composites were analyzed by XRD, TGA and SEM. Also the electrochemical performances of G/Si/C composites as the anode were performed by constant current charge/discharge, rate performance, cyclic voltammetry and impedance tests in the electrolyte of $LiPF_6$ dissolved inorganic solvents (EC:DMC:EMC=1:1:1 vol%). Lithium ion battery using G/Si/C electrode showed better characteristics than graphite electrode. It was confirmed that as the silicon content increased, the capacity increased but the capacity retention ratio decreased. Also, it was shown that both the capacity and the rate performances were improved when using the Silicon (${\leq}25{\mu}m$). It is found that in the case of 10 wt% of Silicon (${\leq}25{\mu}m$), G/Si/C composites have the initial discharge capacity of 495 mAh/g, the capacity retention ratio of 89% and the retention rate capability of 80% in 2 C/0.1 C.

Electrochemical Characteristics of Si/Mo Multilayer Anode for Lithium-Ion Batteries (리튬 이온 전지용 Si/Mo 다층박막 음극의 전기화학적 특성)

  • Park, Jong-Wan;Ascencio Jorge A.
    • Korean Journal of Materials Research
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    • v.16 no.5
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    • pp.297-301
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    • 2006
  • Si/Mo multilayer anode consisting of active/inactive material was prepared using rf/dc magnetron sputtering. Molybdenum acts as a buffer against the volume change of the Silicon. Multilayer deposited on RT (reversible treatment) copper foil current collector to enhance adhesion between Silicon and copper foil. Deposited Silicon was identified as an amorphous. Amorphous has a relatively open structure than crystal structure, thus prevents the lattice expansion and has many diffusion paths of Li ion. When deposited time of Silicon and Molybdenum is 30 second and 2 second respectably, electrode has more capacity and good cycle stability. A 3000 nm thick multilayer was maintained 99% of the initial capacity (1624 $mAhg^{-1}$) after 100 cycles. As the increase of the multilayer thickness (4500 nm, 6000 nm), Si/Mo mutilayer anodes show aggravation cycle stability.

Transmission Electron Microscope Specimen Preparation of Si-Based Anode Materials for Li-Ion Battery by Using Focused Ion Beam and Ultramicrotome

  • Chae, Jeong Eun;Yang, Jun Mo;Kim, Sung Soo;Park, Ju Cheol
    • Applied Microscopy
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    • v.48 no.2
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    • pp.49-53
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    • 2018
  • A successful transmission electron microscope (TEM) analysis is closely related to the preparation of the TEM specimen and should be followed by the suitable TEM specimen preparation depending on the purpose of analysis and the subject materials. In the case of the Si-based anode material, lithium atoms of formed Li silicide were removed due to ion beam and electron beam during TEM specimen preparation and TEM observation. To overcome the problem, we proposed a new technique to make a TEM specimen without the ion beam damage. In this study, two types of test specimens from the Si-based anode material of Li-ion battery were prepared by respectively adopting the only focused ion beam (FIB) method and the new FIB-ultramicrotome method. TEM analyses of two samples were conducted to compare the Ga ion damage of the test specimen.

Effect of Surface Area and Crystallinity of Amorphous Carbon Conductive Agent in SiOx Anode on the Performance of Lithium Ion Battery (리튬이온전지용 비정질 탄소 도전재의 표면적 및 흑연화도에 따른 SiOx 음극 활물질 특성 연구 )

  • Hyoung-Kyu Kang;Sung-Soo Kim
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.36 no.1
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    • pp.29-35
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    • 2023
  • Herein we investigated the effect of the conductive agent on the electrochemical performance of the SiOx anode. SiOx anodes have a relatively low volume expansion (~160%) compared to Pure-silicon, but have a problem in that they have a poor electrical conductivity characteristic. In this study, physical and electrochemical measurements were performed using two 0-dimensional amorphous carbon conductive agents with different crystallinity and surface area. The crystal structure of the conductive agents and the local graphitization degree were analyzed through XRD and Raman, and the surface area of the particles was observed through BET. In addition, the electrical performance according to the graphitization degree of the conductive agents was confirmed through a 4-point probe. As a result of the electrochemical cycle and rate performance, it was confirmed that the performance of SiOx using a conductive agent having a low graphitization degree and a high surface area was improved. The results in this study suggest that the graphitization degree and surface area of the amorphous carbon conductive agent may play an important role in the SiOx electrode.

Preparation and Characterization of Porous Silicon and Carbon Composite as an Anode Material for Lithium Rechargeable Batteries

  • Park, Junsoo;Lee, Jae-Won
    • Journal of Powder Materials
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    • v.22 no.1
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    • pp.15-20
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    • 2015
  • The composite of porous silicon (Si) and amorphous carbon (C) is prepared by pyrolysis of a nano-porous Si + pitch mixture. The nano-porous Si is prepared by mechanical milling of magnesium powder with silicon monoxide (SiO) followed by removal of MgO with hydrochloric acid (etching process). The Brunauer-Emmett-Teller (BET) surface area of porous Si ($64.52m^2g^{-1}$) is much higher than that before etching Si/MgO ($4.28m^2g^{-1}$) which indicates pores are formed in Si after the etching process. Cycling stability is examined for the nano-porous Si + C composite and the result is compared with the composite of nonporous Si + C. The capacity retention of the former composite is 59.6% after 50 charge/discharge cycles while the latter shows only 28.0%. The pores of Si formed after the etching process is believed to accommodate large volumetric change of Si during charging and discharging process.

Electrochemical Properties of Sub-micron Size Si Anode Materials Distributed by Wet Sedimentation Method (습식 분급으로 입도 조절된 서브 마이크론 크기의 Si 음극활물질의 전기화학적 특성 분석)

  • Jin-Seong Seo;Hyun-Su Kim;Byung-Ki Na
    • Korean Chemical Engineering Research
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    • v.61 no.1
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    • pp.39-44
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    • 2023
  • In this study, the particle size of Si polycrystals was controlled through wet-sedimentation method, and changes in the capacity and cyclic characteristics of the Si anode material according to the particle size were observed. After wet-sedimentation of Si particles pulverized by a vibration mill, the non-uniform particle distribution of Si was uniformly controlled. The d50 of a sample in which Si was sedimented for 24 hours decreased to 0.50 ㎛. As a result of the electrochemical characteristic analysis, the Rct value representing the resistance in the electrode was significantly reduced due to the decrease in particle size. The unclassified Si sample exhibited a discharge capacity of 2,869 mAh/g in the first cycle, and decreased to 85.7 mAh/g after 100 cycles. The sample in which Si was classified for 24 hours showed a capacity of 3,394 mAh/g initially, and maintained a capacity of 1,726 mAh/g after 100 cycles. As the size of the Si particles decreased, the discharge capacity increased and the cycle life was also increased.

Development of High Capacity Lithium Ion Battery Anode Material by Controlling Si Particle Size with Dry Milling Process (건식 분쇄 공정으로 Si 입도 제어를 통한 고용량 리튬이온전지 음극 소재의 개발)

  • Jeon, Do-Man;Na, Byung-Ki;Rhee, Young-Woo
    • Clean Technology
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    • v.24 no.4
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    • pp.332-338
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    • 2018
  • Currently graphite is used as an anode active material for lithium ion battery. However, since the maximum theoretical capacity of graphite is limited to $372mA\;h\;g^{-1}$, a new anode active material is required for the development of next generation high capacity and high energy density lithium ion battery. The maximum theoretical capacity of Si is $4200mA\;h\;g^{-1}$, which is about 10 times higher than the maximum theoretical capacity of graphite. However, since the volume expansion rate is almost 400%, the irreversible capacity increases as the cycle progresses and the discharge capacity relative to the charge is remarkably reduced. In order to solve these problems, it is possible to control the particle size of the Si anode active material to reduce the mechanical stress and the volume change of the reaction phase, thereby improving the cycle characteristics. Therefore, in order to minimize the decrease of the charge / discharge capacity according to the volume expansion rate of the Si particles, the improvement of the cycle characteristics was carried out by pulverizing Si by a dry method with excellent processing time and cost. In this paper, Si is controlled to nano size using vibrating mill and the physicochemical and electrochemical characteristics of the material are measured according to experimental variables.