• Title/Summary/Keyword: initial irreversible capacity

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Effective problem mitigation strategy of lithium secondary battery silicon anode utilized liquid precursor (에틸벤젠을 이용한 실리콘 산화물 음극재의 효과적인 카본 코팅 전략)

  • Sangryeol Lee;Seongsu Park;Sujong Chae
    • Journal of the Korean institute of surface engineering
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    • v.56 no.1
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    • pp.62-68
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    • 2023
  • Silicon (Si) is considered as a promising substitute for the conventional graphite due to its high theoretical specific capacity (3579 mAh/g, Li15Si4) and proper working voltage (~0.3V vs Li+/Li). However, the large volume change of Si during (de)lithiation brings about severe degradation of battery performances, rendering it difficult to be applied in the practical battery directly. As a one feasible candidate of industrial Si anode, silicon monoxide (SiOx) demonstrates great electrochemical stability with its specialized strategy, downsized Si nanocrystallites surrounded by Li+ inactive buffer phase (Li2O and Li4SiO4). Nevertheless, SiOx inherently has the initial irreversible capacity and poor electrical conductivity. To overcome those issues, conformal carbon coating has been performed on SiOx utilizing ethylbenzene as the carbon precursor of chemical vapor deposition (CVD). Through various characterizations, it is confirmed that the carbon is homogeneously coated on the surface of SiOx. Accordingly, the carbon-coated SiOx from CVD using ethylbenzene demonstrates 73% of the first cycle efficiency and great cycle life (88.1% capacity retention at 50th cycle). This work provides a promising synthetic route of the uniform and scalable carbon coating on Si anode for high-energy density.

Physical Properties of $LiPF_6/PC+EC+DEC$ Electrolyte by the Variation of PC Fraction and Initial Electrochemical Properties of Carbon Anode in the Electrolyte (PC 비율에 따른 $LiPF_6/PC+EC+DEC$ 전해액의 물리적 특성 및 탄소분극과의 초기 전기화학적 특성)

  • Doh Chil-Hoon;Moon Seong-In;Yun Mun-Soo
    • Journal of the Korean Electrochemical Society
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    • v.3 no.4
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    • pp.224-231
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    • 2000
  • The exfoliation of graphite (layer) was progressed due to the irreversible insertion of PC molecules between graphene layers, when propylene carbonate (PC) solvent was used as the organic solvents. The problem could be mitigated by the replacement of PC by ethylene carbonate (EC). But, the freezing point of EC-based electrolyte increased due to the high freezing point of $EC(36.2^{\circ}C)$. Therefore, EC+PC mixed electrolyte is expected as a good organic electrolyte for lithium ion battery. The EC-based organic electrolyte containing PC within pertinent quantity can be expected to have high molar conductivity and reduced exfoliation of graphite layer. The dielectric constant and molar conductivity of $LiPF_6/PC+EC+DEC$ electrolyte was investigated with a variation in the PC content. The electrochemical properties of carbon electrode in the electrolyte were also investigated. Molar conductivity and dielectric constant increased linearly by increasing the PC volume fraction in the electrolyte. The results of charge-discharge test for carbon/electrolyte/Li cell indicated that the initial irreversible specific capacity(IIC) of MCMB-6-28s and MPCF3000 decreased by the addition of $0.83 vol\%$ of PC, but increased with PC content over than $0.83 vol\%$. In the case of MPCF3000 and PCG100 having less than $10 vol\%$ PC, IIC was lower than 50 mAh/g. The discharge specific capacities varied with carbon material, but did not vary with PC content in the electrolyte.

Lithium Battery Anode Properties of Ball-Milled Graphite-Silicon Composites (볼밀링법으로 제조된 흑연-실리콘 복합체의 리튬전지 음전극 특성)

  • Kang, Kun-Young;Shin, Dong Ok;Lee, Young-Gi;Kim, Kwang Man
    • Korean Chemical Engineering Research
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    • v.51 no.4
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    • pp.411-417
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    • 2013
  • To use as an anode material of lithium secondary battery, graphite-silicon composite powders are prepared by ball-milling with silicon nanoparticles (average diameter 100 nm, 0~50 wt%) and graphite powder (average diameter $15{\mu}m$) and their electrochemical properties are examined. As the silicon content increases, the graphite becomes smaller by the ball-milling and amorphous phase appears whereas the silicon do not suffer the change of nanocrystalline phases and embeds within the amorphous phase of graphite. Cyclic voltammetry at low scan rate reveals that typical oxidation peaks of graphite and silicon appear at 0.2~0.35 and 0.55~0.6 V, respectively, with higher reversibility for repeated cycles. In contrast, the high-scan-rate redox behavior is very irreversible for repeated cycles. High irreversible capacity is exhibited in the initial charging-discharging cycles, but it diminishes as the cycle number increases. The saturated discharge capacity achieves about 485 mAh $g^{-1}$ at 50th cycle for the composite of Si 20 wt%. This is due to the formation of amorphous graphite morphology by the adequate composition (C:Si=8:2 w/w), which efficiently buffers the volume change during alloying/dealloying between silicon and lithium.

Initial Charge/Discharge of $LiCoO_2$ Composite Cathode with Various Content of Conductive Material for the Lithium ion Battery (리튬이온전지용 $LiCoO_2$정극의 도전재료에 따른 초기 충방전 특성)

  • Doh Chil-Hoon;Moon Seong-In;Yun Mun-Soo;Yun Suong-Kyu;Yum Duk-Hyung;Park Chun-Jun
    • Journal of the Korean Electrochemical Society
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    • v.2 no.3
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    • pp.123-129
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    • 1999
  • Initial electrochemical characteristics of $LiCoO_2$ electrode for lithium ion battery with various content of super s black as conductive material were evaluated through the charge/discharge with the potential range of 4.3V to 2.0V versus $Li^+/Li^+$. The rate of C/4 and C/2 by the 3 electrode test cell composed with an electrolytic solution of 1 mol/l $LiPF_6/EC+DEC(1:3\;by\; weight)$. Lithium was used as reference electrode. High impedance charge behavior was observed at early stage of charge. In the case of $3\%w/w$ of super s black as conductive material, the specific resistance of the high impedance releasing was $3.82\;{\Omega}\;{\cdot}\;g-LiCoCo_2$ at the current density of $0.5 mA/cm^2$, which corresponds 7 times of the specific resistance of electrode $(0.728 g-LiCoO_2)$. At second charge, the specific resistance of the high impedance releasing was 63 mn · g-Lico02, which corresponds 12eio of the specific resistance of electrode and only $1.7\%$ of that of the first charge. The first charge and discharge specific capacities at C/4 rate were 160-161 and $153\~155mAh/g-LiCoO_2$, respectively, to lead $95.4\~96.4\%$ of coulombic efficiencies and ca. $6 mAh/g-LiCoO_2$ of initial irreversible specific capacity. Specific resistance at the end of charge and rest showed low value at content of super s black between 2 and $7\%w/w$, which agreed with characteristics of irreversible specific capacity. Capacity densities were reduced by the increasing the content of conductive material. They were 447 and 431mAh/ml when 2 and $2.9\%w/w$ of super s black were used, respectively, at the rate of C/4.

Electrochemical Characteristics of Artificial Graphite Anode Coated with Petroleum Pitch treated by Solvent (용매 처리 석유계 피치로 코팅된 인조 흑연 음극소재의 전기화학적 특성)

  • Jo, Yoon Ji;Lee, Jong Dae
    • Korean Chemical Engineering Research
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    • v.57 no.1
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    • pp.5-10
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    • 2019
  • In this study, electrochemical characteristics of artificial graphite coated with petroleum pitch using solvent method as anode material of lithium ion battery were investigated. As the solvent, n-hexane, toluene, tetrahydrofuran and quinoline were used. The surface of the prepared anode material was analyzed by SEM and TEM. Also the electrochemical performances of the prepared anode materials were performed by constant current first charge/discharge, cycle, cyclic voltammetry and impedance tests in the electrolyte of $LiPF_6$ dissolved inorganic solvents (EC:DEC=1:1 vol%). The coating thickness of the prepared graphite was about 100-500 nm and the graphite coated with THF solvent had a smoother surface than that using other solvents. It was found that pitch-coated graphite (THF) show the low initial irreversible capacity (51 mAh/g), the high discharge capacity (360 mAh/g) and coulombic efficiency (99%).

Synthesis of Carbon Nano Silicon Composites for Secondary Battery Anode Materials Using RF Thermal Plasma (RF 열플라즈마를 이용한 이차전지 음극재용 탄소나노실리콘복합소재 합성)

  • Soon-Jik Lee;Dae-Shin Kim;Jeong-Mi Yeon;Won-Gyu Park;Myeong-Seon Shin;Seon-Yong Choi;Sung-Hoo Ju
    • Korean Journal of Materials Research
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    • v.33 no.6
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    • pp.257-264
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    • 2023
  • To develop a high capacity lithium secondary battery, a new approach to anode material synthesis is required, capable of producing an anode that exceeds the energy density limit of a carbon-based anode. This research synthesized carbon nano silicon composites as an anode material for a secondary battery using the RF thermal plasma method, which is an ecofriendly dry synthesis method. Prior to material synthesis, a silicon raw material was mixed at 10, 20, 30, 40, and 50 wt% based on the carbon raw material in a powder form, and the temperature change inside the reaction field depending on the applied plasma power was calculated. Information about the materials in the synthesized carbon nano silicon composites were confirmed through XRD analysis, showing carbon (86.7~52.6 %), silicon (7.2~36.2 %), and silicon carbide (6.1~11.2 %). Through FE-SEM analysis, it was confirmed that the silicon bonded to carbon was distributed at sizes of 100 nm or less. The bonding shape of the silicon nano particles bonded to carbon was observed through TEM analysis. The initial electrochemical charging/discharging test for the 40 wt% silicon mixture showed excellent electrical characteristics of 1,517 mAh/g (91.9 %) and an irreversible capacity of 133 mAh/g (8.1 %).

Synthesis of Silicon-Carbon by Polymer Coating and Electrochemical Properties of Si-C|Li Cell (고분자 도포를 이용한 실리콘-탄소의 합성 및 Si-C|Li Cell의 전기화학적 특성)

  • Doh, Chil-Hoon;Jeong, Ki-Young;Jin, Bong-Soo;An, Kay-Hyeok;Min, Byung-Chul;Choi, Im-Goo;Park, Chul-Wan;Lee, Kyeong-Jik;Moon, Seong-In;Yun, Mun-Soo
    • Journal of the Korean Electrochemical Society
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    • v.9 no.3
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    • pp.107-112
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    • 2006
  • Si-C composites were prepared by the carbonization of silicon powder covered by polyaniline(PAn). Physical and electrochemical properties of the Si-C composites were characterized by the particle size analysis, X-ray diffraction technique, scanning electron microscope, and electrochemical test of battery. The average particle size of the Si was increased by the coating of PAn and somewhat reduced by the carbonization to give silicone-carbon composites. XRD analysis' results were confirmed co-existence of crystalline silicon and amorphous-like carbon. SEM photos showed that the silicon particle were well covered with carbonacious materials depend on the PAn content. Si-C|Li cells were fabricated using the Si-C composites and were tested using the galvanostatic charge-discharge test. Si-C|Li cells gave better electrochemical properties than that of Si|Li cell. Si-C|Li cell using the Si-C from HCl undoped PAn Precursor showed better electrochemical properties than that from HCl doped PAn Precursor. Using the electrolyte containing FEC as an additive, the initial discharge capacity was increased. After that the galvanostatic charge-discharge test with the GISOC(gradual increasing of the state of charge) condition was carried out. Si-C(Si:PAn:50:50 wt. ratio)|Li cell showed 414 mAh/g of the reversible specific capacity, 75.7% of IIE(initial intercalation efficiency), 35.4 mAh/g of IICs(surface irreversible specific capacity).

Production of Activated Carbon from Waste Walnut Shell Using Phosphoric Acid and Its Adsorption Characteristics for Heavy Metal Ion (인산활성화제에 의한 폐호도껍질을 원료로 한 활성탄제조 및 이의 중금속 이온 흡착특성)

  • Lee Go-Eun;Ahn Ju-Hyun;Kim Dong-Su
    • Resources Recycling
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    • v.12 no.3
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    • pp.13-24
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    • 2003
  • The production characteristics of activated carbon from waste walnut shell have been investigated by taking activation temperature, activation time, amount of activating agent, and kind of activating agent as the major influential factors. The adsorption capacity of the activated carbon which was produced using phosphoric acid as the activating agent increased with activation temperature and showed its greatest value at about $550^{\circ}C$. Yield for activated carbon was observed to decrease continuously as the activation temperature was raised. The optimal activation time for the highest adsorption capacity was found to be about 2 hr, and as the activation time increased the yield for activated carbon was showed to decrease continuously. The increase in the amount of activating agent resulted in the increase of the yield for activated carbon, however, excessive amount of activating agent deteriorated its adsorption capacity reversely. The variations of the microstructure of activated carbon observed by SEM with several influential factors, correlated very well with its changes in the adsorbability with the same factors and the kind of activating agent was found to play an important role in the determination of the adsorption capacity of activated carbon. To investigate the adsorption characteristics of the produced activated carbon, the adsorption reactions of $Cu^{2+}$ ion were examined using the produced activated carbon as the adsorbent. In general, the kinetics of the adsorption of $Cu^{2+}$ ion was observed to follow a 2nd-order reaction and the rate constant for adsorption reaction increased as the initial concentration of adsorbate was diminished. The equilibrium adsorption of $Cu^{2+}$ was explained well with Freundlich model and its adsorption reaction was found to be endothermic. The activation energy for adsorption was calculated to be 13.07 kcal/mol, which implied that the adsorption reaction was very irreversible, and several thermodynamic parameters of adsorption reaction were estimated using van't. Hoff equation and thermodynamic relationships.

Evaluation of Adsorption Characteristics of 2-Picoline onto Sylopute (실로퓨트에 대한 2-피콜린의 흡착 특성 평가)

  • Yang, Ji-Won;Kim, Jin-Hyun
    • Korean Chemical Engineering Research
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    • v.57 no.2
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    • pp.210-218
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    • 2019
  • Batch experiment studies were carried out on the adsorption of the major tar compound, 2-picoline, derived from the plant cell cultures of Taxus chinensis, using Sylopute while varying parameters such as initial 2-picoline concentration, contact time and adsorption temperature. The experimental data were fitted to the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. Comparison of results revealed that the Langmuir isotherm model could account for the adsorption isotherm data with the highest accuracy among the four isotherm models considered. From the analysis of adsorption isotherms, it was found that adsorption capacity decreased with increasing temperature and the adsorption of 2-picoline onto Sylopute was favorable. The kinetic data were well described by the pseudo-second-order kinetic model, while intraparticle diffusion and boundary layer diffusion did not play a dominated role in 2-picoline adsorption according to the intraparticle diffusion model. Thermodynamic parameters revealed the exothermic, irreversible and non-spontaneous nature of adsorption. The isosteric heat of adsorption decreased as surface loading ($q_e$) increased, indicating a heterogeneous surface.

Analysis on Isotherm, Kinetic and Thermodynamic Properties for Adsorption of Acid Fuchsin Dye by Activated Carbon (활성탄에 의한 Acid Fuchsin 염료의 흡착에 대한 등온선, 동력학 및 열역학 특성치에 대한 해석)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.58 no.3
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    • pp.458-465
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    • 2020
  • Isotherms, kinetics and thermodynamic properties for adsorption of acid fuchsin (AF) dye by activated carbon were carried out using variables such as dose of adsorbent, pH, initial concentration and contact time and temperature. The effect of pH on adsorption of AF showed a bathtub with high adsorption percentage in acidic (pH 8). Isothermal adsorption data were fitted to the Freundlich, Langmuir, and Dubinin-Radushkevich isotherm models. Freundlich isothem model showed the highest agreement and confirmed that the adsorption mechanism was multilayer adsorption. It was found that adsorption capacity increased with increasing temperature. Freundlich's separation factor showed that this adsorption process was an favorable treatment process. Estimated adsorption energy by Dubinin-Radushkevich isotherm model indicated that the adsorption of AF by activated carbon is a physical adsorption. Adsorption kinetics was found to follow the pseudo-second-order kinetic model. Surface diffusion at adsorption site was evaluated as a rate controlling step by the intraparticle diffusion model. Thermodynamic parameters such as activation energy, Gibbs free energy, enthalpy entropy and isosteric heat of adsorption were investigated. The activation energy and enthalpy change of the adsorption process were 21.19 kJ / mol and 23.05 kJ / mol, respectively. Gibbs free energy was found that the adsorption reaction became more spontaneously with increasing temperature. Positive entropy was indicated that this process was irreversible. The isosteric heat of adsorption was indicated physical adsorption in nature.