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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.

Silicon-Based Anode with High Capacity and Performance Produced by Magnesiothermic Coreduction of Silicon Dioxide and Hexachlorobenzene

  • Ma, Kai
    • Journal of Electrochemical Science and Technology
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    • v.12 no.3
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    • pp.317-322
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    • 2021
  • Silicon (Si) has been considered as a promising anode material because of its abundant reserves in nature, low lithium ion (Li+) intercalation/de-intercalation potential (below 0.5 V vs. Li/Li+) and high theoretical capacity of 4200 mA h/g. In this paper, we prepared a silicon-based (Si-based) anode material containing a small amount of silicon carbide by using magnesiothermic coreduction of silica and hexachlorobenzene. Because of good conductivity of silicon carbide, the cycle performance of the silicon-based anode materials containing few silicon carbide is greatly improved compared with pure silicon. The raw materials were formulated according to a silicon-carbon molar ratio of 10:0, 10:1, 10:2 and 10:3, and the obtained products were purified and tested for their electrochemical properties. After 1000 cycles, the specific capacities of the materials with silicon-carbon molar ratios of 10:0, 10:1, 10:2 and 10:3 were still up to 412.3 mA h/g, 970.3 mA h/g, 875.0 mA h/g and 788.6 mA h/g, respectively. Although most of the added carbon reacted with silicon to form silicon carbide, because of the good conductivity of silicon carbide, the cycle performance of silicon-based anode materials was significantly better than that of pure silicon.

Recent Developments in Anode Materials for Li Secondary Batteries (리튬이차전지용 음극 소재 기술 개발 동향)

  • Kim, Sung-Soo
    • Journal of the Korean Electrochemical Society
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    • v.11 no.3
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    • pp.211-222
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    • 2008
  • Li secondary batteries, which have been in successful commercialization, are becoming important technology as power sources in non-IT application like HEV(Hybrid Electric Vehicle) as well as in portable electronics. It is not the overstatement that the commercialization of Li secondary battery was a result of the development of carbonaceous anode material and safety mechanisms. The R&D of electrode materials of Li secondary batteries is one of the core technologies in the development and it has enormous influences on various fields as well as on the battery industry. Here, the current research of anode materials is described and the underlying problems associated with development, advantages and drawbacks is analyzed.

Novel Synthesis Method and Electrochemical Characteristics of Lithium Titanium Oxide as Anode Material for Lithium Secondary Battery

  • Kim Han-Joo;Park Soo-Gil
    • KIEE International Transactions on Electrophysics and Applications
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    • v.5C no.3
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    • pp.119-123
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    • 2005
  • Lithium titanium oxide as anode material for energy storage prepared by novel synthesis method. Li$_{4}$Ti$_{5}$O$_{12}$ based spinel-framework structures are of great interest material for lithium-ion batteries. We describe here Li$_{4}$Ti$_{5}$O$_{12}$ a zero-strain insertion material was prepared by novel sol-gel method and by high energy ball milling (HEBM) of precursor to from nanocrystalline phases. According to the X-ray diffraction and scanning electron microscopy analysis, uniformly distributed Li$_{4}$ Ti$_{5}$O$_{12}$ particles with grain sizes of 100nm were synthesized. Lithium cells, consisting of Li$_{4}$ Ti$_{5}$O$_{12}$ anode and lithium cathode showed the 173 mAh/g in the range of 1.0 $\~$ 3.0 V. Furthermore, the crystalline structure of Li$_{4}$ Ti$_{5}$O$_{12}$ didn't transform during the lithium intercalation and deintercalation process.

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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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.

Enhancing Electrochemical Performance of Co(OH)2 Anode Materials by Introducing Graphene for Next-Generation Li-ion Batteries

  • Kim, Hyunwoo;Kim, Dong In;Yoon, Won-Sub
    • Journal of Electrochemical Science and Technology
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    • v.13 no.3
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    • pp.398-406
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    • 2022
  • To satisfy the growing demand for high-performance batteries, diverse novel anode materials with high specific capacities have been developed to replace commercial graphite. Among them, cobalt hydroxides have received considerable attention as promising anode materials for lithium-ion batteries as they exhibit a high reversible capacity owing to the additional reaction of LiOH, followed by conversion reaction. In this study, we introduced graphene in the fabrication of Co(OH)2-based anode materials to further improve electrochemical performance. The resultant Co(OH)2/graphene composite exhibited a larger reversible capacity of ~1090 mAh g-1, compared with ~705 mAh g-1 for bare Co(OH)2. Synchrotron-based analyses were conducted to explore the beneficial effects of graphene on the composite material. The experimental results demonstrate that introducing graphene into Co(OH)2 facilitates both the conversion and reaction of the LiOH phase and provides additional lithium storage sites. In addition to insights into how the electrochemical performance of composite materials can be improved, this study also provides an effective strategy for designing composite materials.

Performance of Expanded Graphite as Anode Materials for High Power Li-ion Secondary Batteries

  • Park, Do-Youn;Lim, Yun-Soo;Kim, Myung-Soo
    • Carbon letters
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    • v.11 no.4
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    • pp.343-346
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    • 2010
  • The various expanded graphites (EGs) was prepared and applied as anode material for high power Li-ion secondary battery (LIB). By changing the processing conditions of EG, a series of EG with different structure were produced, showing the changed electrochemical properties. The charge-discharge test showed that the initial reversible capacity of EG anodes prepared at the suitable conditions was over 400 mAh/g and the charge capacity at 5 C-rate was 83.2 mAh/g. These values demonstrated the much improved electrochemical properties as compared with those for the graphite anode of 360 mAh/g and 19.4 mAh/g, respectively, showing the possibility of EG anode materials for high power LIB.

Strategic design for oxide-based anode materials and the dependence of their electrochemical properties on morphology and architecture

  • Gang, Yong-Muk
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.73-73
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    • 2012
  • Modern technology-driven society largely relies on hybrid electric vehicles or electric vehicles for eco-friendly transportation and the use of high technology devices. Lithium rechargeable batteries are the most promising power sources because of its high energy density but still have a challenge. Graphite is the most widely used anode material in the field of lithium rechargeable batteries due to its many advantages such as good cyclic performances, and high charge/discharge efficiency in the initial cycle. However, it has an important safety issue associated with the dendritic lithium growth on the anode surface at high charging current because the conventional graphite approaches almost 0 V vs $Li/Li^+$ at the end of lithium insertion. Therefore, a fundamental solution is to use an electrochemical redox couple with higher equilibrium potentials, which suppresses lithium metal formation on the anode surface. Among the candidates, $Li_4Ti_5O_{12}$ is a very interesting intercalation compound with safe operation, high rate capability, no volume change, and excellent cycleability. But the insulating character of $Li_4Ti_5O_{12}$ has raised concerns about its electrochemical performance. The initial insulating character associated with Ti4+ in $Li_4Ti_5O_{12}$ limits the electronic transfer between particles and to the external circuit, thereby worsening its high rate performance. In order to overcome these weak points, several alternative synthetic methods are highly required. Hence, in this presentation, novel ways using a synergetic strategy based on 1D architecture and surface coating will be introduced to enhance the kinetic property of Ti-based electrode. In addition, first-principle calculation will prove its significance to design Ti-based electrode for the most optimized electrochemical performance.

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Built-in voltage in organic light-emitting diodes from the measurement of modulated photocurrent (변조 광전류 측정법을 이용하여 전극 변화에 따른 유기발광소자의 내장 전압)

  • Lee, Eun-Hye;Yoon, Hee-Myoung;Han, Wone-Keun;Kim, Tae-Wan;Ahn, Joon-Ho;Oh, Hyun-Seok;Jang, Kyung-Uk;Chung, Dong-Hoe
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.06a
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    • pp.51-52
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    • 2007
  • Built-in voltage in organic light-emitting diodes was studied using modulated photocurrent technique ambient conditions. From the bias voltage-dependent photocurrent, built-in voltage of the device is determined. The applied bias voltage when the magnitude of modulated photo current is zero corresponds to a built-in voltage. Built-in voltage in the device is generated due to a difference of work function of the anode and cathode. A device was made with a structure of anode/$Alq_3$/cathode to study a built-in voltage. ITO and ITO/PEDOT:PSS were used as an anode, and Al and LiF/AI were used as a cathode. It was found that an incorporation of PEDOT:PSS layer between the ITO and $Alq_3$ increases a built-in voltage by about 0.4V. This is consistent to a difference of a highest occupied energy states of ITO and PEDOT:PSS. This implies that a use of PEDOT:PSS layer in anode improves the efficiency of the device because of a lowering of anode barrier height. With a use bilayer cathode system LiF/Al, it was found that the built-in voltage increases as the LiF layer thickness increases in the thickness range of 0~1nm. For 1nm thick LiF layer, there is a lowering of electron barrier by about 0.2eV with respect to an Al-only device. It indicates that a very thin alkaline metal compound LiF lowers an electron barrier height.

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