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Application of Monte Carlo Simulation to Intercalation Electrochemistry I. Thermodynamic Approach to Lithium Intercalation into LiMn2O4 Electrode

  • Kim, Sung-Woo;Pyun, Su-Il
    • Journal of the Korean Electrochemical Society
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    • v.5 no.2
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    • pp.79-85
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    • 2002
  • The present article is concerned with the application of the Monte Carlo simulation to electrochemistry of lithium intercalation from the thermodynamic view point. This article first introduced the fundamental concepts of the ensembles, and Ising and lattice gas models in statistical thermodynamics for the Monte Carlo simulation in brief. Finally the Monte Carlo method based upon the lattice gas model was employed to analyse thermodynamics of the lithium intercalation into the transition metal oxides. Especially we dealt with the thermodynamic properties as the electrode potential curve and the partial molar internal energy and entropy of lithium ion in the case of the $LiMn_2O_4$ electrode, and consequently confirmed the utility of the Monte Carlo method in the field of electrochemistry of the lithium intercalation.

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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Improving the Electrochemical Properties of Lithium Terephthalate-based Lithium-Organic Battery with A Graphite Coated Current Collector (흑연 코팅 집전체를 이용한 Lithium Terephthalate 기반 리튬-유기 이차전지의 전기화학적 특성 개선)

  • Kwon, O Hyeon;Kim, Jong Bin;Kim, Jae-Kwang
    • Journal of the Korean Electrochemical Society
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    • v.22 no.3
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    • pp.122-127
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    • 2019
  • In this study, we investigate the electrochemical performance of lithium terephthalate (LTA) battery using graphite coated metal current collector to overcome the disadvantages of organic batteries which is high interfacial resistance between current collector and electrode. The LTA anode material is synthesized by acid-based ion exchange reaction without impurities. The contact properties between stick-type LTA-based electrode and graphite coated current collector are estimated by the cross-section SEM and EIS. The graphite coated current collector significantly reduced the interfacial resistance of the LTA battery. The second discharge capacities of bare current collector LTA and graphite coated current collector LTA batteries are 107.6 mAh/g and 148.8 mAh/g at 0.1C, respectively. The graphite coated current collector LTA batteries show higher cycle life, higher discharge capacity, and higher rate-capability than bare LTA batteries.

Synthetic Methods and Applications of Silicon Nanowire: A Review

  • Haque, Md Hasanul;Sohn, Honglae
    • Journal of Integrative Natural Science
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    • v.10 no.2
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    • pp.65-73
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    • 2017
  • In this review paper, we will discuss about the methods of synthesizing Si nanowires by Top-down and Bottom-up. Silicon nanowires have a lot of application on various fields such as Li ion batteries, solar cells, chemical and biological sensors. We will address some of the applications of silicon Nanowires.

Comparison of Characteristics of Electrodeposited Lithium Electrodes Under Various Electroplating Conditions (다양한 전착조건에서 제작된 리튬 전극의 특성 연구)

  • Lim, Rana;Lee, Minhee;Kim, Jeom-Soo
    • Journal of the Korean Electrochemical Society
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    • v.22 no.3
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    • pp.128-137
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    • 2019
  • A lithium is the lightest metal on the earth. It has some attractive characteristics as a negative electrode material such as a low reduction potential (-3.04 V vs. SHE) and a high theoretical capacity ($3,860mAh\;g^{-1}$). Therefore, it has been studied as a next generation anode material for high energy lithium batteries. The thin lithium electrode is required to maximize the efficiency and energy density of the battery, but the physical roll-press method has a limitation in manufacturing thin lithium. In this study, thin lithium electrode was fabricated by electrodeposition under various conditions such as compositions of electrolytes and the current density. Deposited lithium showed strong relationship between process condition and its characteristics. The concentration of electrolyte affects to the shape of deposited lithium particle. As the concentration increases, the shape of particle changes from a sharp edged long one to a rounded lump. The former shape is favorable for suppressing dendrite formation and the elec-trode shows good stripping efficiency of 92.68% (3M LiFSI in DME, $0.4mA\;cm^{-2}$). The shape of deposited particle also affected by the applied current density. When the amount of current applied gets larger the shape changes to the sharp edged long one like the case of the low concentration electrolyte. The combination of salts and solvents, 1.5M LiFSI + 1.5M LiTFSI in DME : DOL [1 : 1 vol%] (Du-Co), was applied to the electrolyte for the lithium deposition. The lithium electrode obtained from this electrolyte composition shows the best stripping efficiency (97.26%) and the stable reversibility. This is presumed to be due to the stability of the surface film induced by the Li-F component and the DOL effect of providing film flexibility.

Synthesized and Characterization of high density cathode materials for Lithium Secondary Batteries (리튬이온이차전지용 고밀도 양극활물질의 합성 및 평가)

  • Kwon, Yong-Jin;Choi, Byung-Hyun;Ji, Mi-Jung;Sun, Yang-Kuk
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.429-429
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    • 2008
  • Li$[Ni_{1/2}Co_{1/2}]O_2$ powder were synthesized from co-precipitation spherical metal oxide, $[Ni_{1/2}Co_{1/2}](OH)_2$. The preparation of metal hydroxide was significantly dependent on synthetic conditions, such as pH, amount of chelating agent, stirring speed, etc. The optimized condition resulted in $[Ni_{1/2}Co_{1/2}](OH)_2$, of which the particle size distribution was uniform and the particle shape was spherical, as observed by scanning electron microscopy. Calcination of the uniform metal hydroxide with LiOH at higher temperature led to a well-ordered layer-structured Li$[Ni_{1/2}Co_{1/2}]O_2$, as confirmed by X-ray diffraction pattern. Also these materials have ${\alpha}-NaFeO_2$ ($R\bar{3}m$) structure. Due to the homogeneity of the metal hydroxide, $[Ni_{1/2}Co_{1/2}](OH)_2$, the final product, Li$[Ni_{1/2}Co_{1/2}]O_2$, was also significantly uniform, i.e., the average particle size was of about 10 to 15 ${\mu}m$ in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.41 $gcm^{-3}$, of which the value is comparable to that of commercialized $LiCoO_2$.

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Recovery of Pure Ni(II) Compound by Precipitation from Hydrochloric Acid Solution Containing Si(IV) (규소(IV)가 함유된 염산용액으로부터 침전법에 의한 고순도 니켈(II)화합물의 회수)

  • Moon, Hyun Seung;Song, Si Jeong;Tran, Thanh Tuan;Lee, Man Seung
    • Resources Recycling
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    • v.30 no.6
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    • pp.36-42
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    • 2021
  • Spent lithium-ion batteries are treated by reduction-smelting at high temperatures to recover valuable metals. Solvent extraction and precipitation of the HCl leaching solution of reduction-smelted metallic alloys resulted in a filtrate containing Ni(II) and a small amount of Si(IV). Adsorption and precipitation experiments were conducted to recover pure Ni(II) compounds from the filtrate. Si(IV) was selectively loaded onto polyacrylamide, but this method did not efficiently filter the solution due to an increase in viscosity. The addition of Na2CO3 as a precipitant to the filtrate led to the simultaneous precipitation of Ni(II) and Si(IV). However, it was possible to recover nickel oxalate with a purity higher than 99.99% by selectively precipitating Ni(II) with the addition of Na2C2O4 as a precipitant.

Separation of Ni(II), Co(II), Mn(II), and Si(IV) from Synthetic Sulfate and Chloride Solutions by Ion Exchange (황산과 염산 합성용액에서 이온교환에 의한 니켈(II), 코발트(II), 망간(II) 및 실리케이트(IV)의 분리)

  • Nguyen, Thi Thu Huong;Wen, Jiangxian;Lee, Man Seung
    • Resources Recycling
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    • v.31 no.3
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    • pp.73-80
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    • 2022
  • Reduction smelting of spent lithium-ion batteries at high temperature produces metallic alloys. Following solvent extraction of the leaching solutions of these metallic alloys with either sulfuric or hydrochloric acid, the raffinate is found to contain Ni(II), Co(II), Mn(II), and Si(IV). In this study, two cationic exchange resins (Diphonix and P204) were employed to investigate the loading behavior of these ions from synthetic sulfate and chloride solutions. Experimental results showed that Ni(II), Co(II), and Mn(II) could be selectively loaded onto the Diphonix resin from a sulfate solution of pH 3.0. With a chloride solution of pH 6.0, Mn(II) was selectively loaded onto the P204 resin, leaving Ni(II) and Si(IV) in the effluent. Elution experiments with H2SO4 and/or HCl resulted in the complete recovery of metal ions from the loaded resin.

A Study on the Characteristics of Local Corrosion for Gas Absorption Refrigeration and Hot Water Systems in LiBr-$H_2O$ Working Fluids (LiBr작동유체 중에서 가스흡수식 냉온수기의 국부부식 특성에 관한 연구)

  • Uh- Joh Lim;Ki-Cheol Jeong;Byoung-Du Yun
    • Journal of Advanced Marine Engineering and Technology
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    • v.27 no.6
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    • pp.714-720
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    • 2003
  • Due to the electric power shortage in summer season and regulation of freon refrigerant, the application of gas absorption refrigeration and hot water systems are considerably increasing trend. But, this system consists of condenser, heat exchanger, supply pipe and radiator etc. which are easily corroded by acidity and dissolved oxygen and gases. In result, this system occurs scale attachment and corrosion damage like pitting and crevice corrosion. In this study, electrochemical polarization test of heat exchanger tubing material (copper, aluminium brass, 30% cupronickel(30% Cu-Ni)) was carried out in 60% lithium bromide solution at $95^{\circ}C$. As a result of polarization test, corrosion behavior by impressed potential and local corrosion. such as galvanic corrosion, pitting corrosion behavior, of tubing materials was investigated. The main results obtained are as follows: (1) The effect of pitting and crevice corrosion control of 30% cupronickel in 60% LiBr solution at $95^{\circ}C$ is very excellent. (2) Dissimilar metal corrosion of 30% cupronickel coupling to aluminium bronze is the most sensitive. (3) Current density behavior of tube materials by impressed potential is high in order of copper > aluminium brass > 30% cupronickel.