• Title/Summary/Keyword: Li diffusivity

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Li Ion Diffusivity and Improved Electrochemical Performances of the Carbon Coated LiFePO4

  • Park, Chang-Kyoo;Park, Sung-Bin;Oh, Si-Hyung;Jang, Ho;Cho, Won-Il
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.836-840
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    • 2011
  • This study examines the effects of a carbon coating on the electrochemical performances of $LiFePO_4$. The results show that the capacity of bare $LiFePO_4$ decreased sharply, whereas the $LiFePO_4$/C shows a well maintained initial capacity. The Li ion diffusivity of the bare and carbon coated $LiFePO_4$ is calculated using cyclic voltammetry (CV) to determine the correlation between the electrochemical performance of $LiFePO_4$ and Li diffusion. The diffusion constants for $LiFePO_4$ and $LiFePO_4$/C measured from CV are $6.56{\times}10^{-16}$ and $2.48{\times}10^{-15}\;cm^2\;s^{-1}$, respectively, indicating considerable increases in diffusivity after modifications. The Li ion diffusivity (DLi) values as a function of the lithium content in the cathode are estimated by electrochemical impedance spectroscopy (EIS). The effects of the carbon coating as well as the mechanisms for the improved electrochemical performances after modification are discussed based on the diffusivity data.

The Evaluation of Diffusivity of Lithium for Coarsening of δ' Precipitate in AI-Li-Cu-Mg-Zr Alloy (Al-Li-Cu-Mg-Zr 합금에 있어서 δ'상 조대화를 위한 Lithium의 확산계수 평가)

  • Chung, D.S.;Kim, E.S.;Cho, H.K.
    • Journal of the Korean Society for Heat Treatment
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    • v.7 no.1
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    • pp.17-24
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    • 1994
  • The evaluation and analysis of diffusivity of lithium for coarsening and coarsening kinetics of ${\delta}^{\prime}$ precipitate in Al-Li-Cu-Mg-Zr alloy aged at $170^{\circ}C$ have been investigated by transmission electron microscopy. With ageing time, ${\delta}^{\prime}$ precipitate coaesened to followed $\bar{\gamma}{\propto}t^{1/3}$ and coarsening kinetics was found to be obeyed to the Lifshitz-Slyozov-Wagner(LSW) theory and diffusivity of lithium for coarsening of ${\delta}^{\prime}$ precipitate in Al-Li-Cu-Mg-Zr alloy was obtained to be $5.85{\times}10^{-17}{\sim}1.53{\times}10^{-16}$ by experimental coarsening rate constant and various coarsening kinetic theory. Diffusivity of lithium measured by using various model but MLSW and Tsumuraya (VI) et al. model in Al-Li-Cu-Mg-Zr alloy is similar to that calculated by the Costas's diffusivity equation. It was, therefore, suggested that additing to the Cu, Mg and Zr element in Al-Li system have no great effect on diiffusivity of lithium for coarsening of ${\delta}^{\prime}$ This suggest that in matrix.

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Li Ion Diffusivity and Rate Performance of the LiFePO4 Modified by Cr Doping

  • Park, Chang-Kyoo;Park, Sung-Bin;Shin, Ho-Chul;Cho, Won-Il;Jang, Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.191-195
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    • 2011
  • This study reports the root cause of the improved rate performance of $LiFePO_4$ after Cr doping. By measuring the chemical diffusion coefficient of lithium ($D_{Li}$) using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the correlation between the electrochemical performance of $LiFePO_4$ and Li diffusion is acquired. The diffusion constants for $LiFePO_4$/C and $LiFe_{0.97}Cr_{0.03}PO_4$/C measured from CV are $2.48{\times}10^{-15}$ and $4.02{\times}10^{-15}cm^2s^{-1}$, respectively, indicating significant increases in diffusivity after the modification. The difference in diffusivity is also confirmed by EIS and the $D_{Li}$ values obtained as a function of the lithium content in the cathode. These results suggest that Cr doping facilitates Li ion diffusion during the charge-discharge cycles. The low diffusivity of the $LiFePO_4$/C leads to the considerable capacity decline at high discharge rates, while high diffusivity of the $LiFe_{0.97}Cr_{0.03}PO_4$/C maintains the initial capacity, even at high C-rates.

Characterization of Brain Microstructural Abnormalities in High Myopia Patients: A Preliminary Diffusion Kurtosis Imaging Study

  • Huihui Wang;Hongwei Wen;Jing Li;Qian Chen;Shanshan Li;Yanling Wang;Zhenchang Wang
    • Korean Journal of Radiology
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    • v.22 no.7
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    • pp.1142-1151
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    • 2021
  • Objective: To evaluate microstructural damage in high myopia (HM) patients using 3T diffusion kurtosis imaging (DKI). Materials and Methods: This prospective study included 30 HM patients and 33 age- and sex-matched healthy controls (HCs) with DKI. Kurtosis parameters including kurtosis fractional anisotropy (FA), mean kurtosis (MK), axial kurtosis (AK), and radial kurtosis (RK) as well as diffusion metrics including FA, mean diffusivity, axial diffusivity (AD), and radial diffusivity derived from DKI were obtained. Group differences in these metrics were compared using tract-based spatial statistics. Partial correlation analysis was used to evaluate correlations between microstructural changes and disease duration. Results: Compared to HCs, HM patients showed significantly reduced AK, RK, MK, and FA and significantly increased AD, predominately in the bilateral corticospinal tract, right inferior longitudinal fasciculus, superior longitudinal fasciculus, inferior fronto-occipital fasciculus, and left thalamus (all p < 0.05, threshold-free cluster enhancement corrected). In addition, DKI-derived kurtosis parameters (AK, RK, and MK) had negative correlations (r = -0.448 to -0.376, all p < 0.05) and diffusion parameter (AD) had positive correlations (r = 0.372 to 0.409, all p < 0.05) with disease duration. Conclusion: HM patients showed microstructural alterations in the brain regions responsible for motor conduction and vision-related functions. DKI is useful for detecting white matter abnormalities in HM patients, which might be helpful for exploring and monitoring the pathogenesis of the disease.

Application of Diffusion Models to Anomalous Sorption in Fluoropolymer-aromatic Solvent Systems (불소고분자-방향족 용매계의 비이상적 흡수에 대한 확산 모델식의 적용)

  • 이상화
    • Membrane Journal
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    • v.10 no.3
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    • pp.139-147
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    • 2000
  • Non-Fickian (or anomalous) diffusion was observed in transient sorption of aromatic solvents(such as benzene, toluene, and chlorobenzene) in fluoropolymers (such as ETFE, ECTFE and PVDF). In this study, five other transient sorption models (Crank, Long & Richman, Berens & Hopfenberg, Neogi, Li) based on Fick's law were employed to fit the anomalous sorption data for aromatic solvents. The adjustable parameters were determined by least square analysis of the measured and predicted fractional uptake. For ETFE sorption data slightly deviating from Fickian behavior, all the models exhibited satisfactory results in fitting the anomalous sorption data. In particular, Neogj model predicted intrinsic diffusivity (0.4~0.8$\times$10$^{-5}$ $\textrm{cm}^2$/day) and equilibrium diffusivity (0.13~0.31$\times$10$^{-4}$ $\textrm{cm}^2$/day) as well as relaxation kinetics related to non-Fickain diffusion. For a typical sigmoidal sorption behavior in PVDF, only Crank's model could give the reasonable evaluation on transport properties. The ratio of intial diffusivity (D$_{i}$) to final equilibrium diffusivity (D$_{\infty}$) was ranged from 80 to 200. For the final stage of uptake In ECTFE with drastic acceleration, all the models exhibited significant deviations from the sorption data. New diffusion models based on thermodynamics and continuum mechanics should be employed to get valuable information on transport properties as well as relaxation kinetics coupled with non-Fickian diffusion.

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The Root Cause of the Rate Performance Improvement After Metal Doping: A Case Study of LiFePO4

  • Park, Chang-Kyoo;Park, Sung-Bin;Park, Ji-Hun;Shin, Ho-Chul;Cho, Won-Il;Jang, Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.921-926
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    • 2011
  • This study investigates a root cause of the improved rate performance of $LiFePO_4$ after metal doping to Fesites. This is because the metal doped $LiFePO_4$/C maintains its initial capacity at higher C-rates than undoped one. Using $LiFePO_4$/C and doped $LiFe_{0.97}M_{0.03}PO_4$/C (M=$Al^{3+}$, $Cr^{3+}$, $Zr^{4+}$), which are synthesized by a mechanochemical process followed by one-step heat treatment, the Li content before and after chemical delithiation in the $LiFePO_4$/C and the binding energy are compared using atomic absorption spectroscopy (AAS) and X-ray photoelectron spectroscopy (XPS). The results from AAS and XPS indicate that the low Li content of the metal doped $LiFePO_4$/C after chemical delithiation is attributed to the low binding energy induced by weak Li-O interactions. The improved capacity retention of the doped $LiFePO_4$/C at high discharge rates is, therefore, achieved by relatively low binding energy between Li and O ions, which leads to fast Li diffusivity.

The Synthesis and Electrochemical Performance of Microspherical Porous LiFePO4/C with High Tap Density

  • Cho, Min-Young;Park, Sun-Min;Kim, Kwang-Bum;Lee, Jae-Won;Roh, Kwang Chul
    • Journal of Electrochemical Science and Technology
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    • v.3 no.3
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    • pp.135-142
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    • 2012
  • Over the past few years, $LiFePO_4$ has been actively studied as a cathode material for lithium-ion batteries because of its advantageous properties such as high theoretical capacity, good cycle life, and high thermal stability. However, it does not have a very good power capability owing to the low lithium-ion diffusivity and poor electronic conductivity. Reduction in particle size of $LiFePO_4$ to the scale of nanometers has been found to dramatically enhance the above properties, according to many earlier reports. However, because of the intrinsically low tap density of nanomaterials, it is difficult to commercialize this method. Many studies are being carried out to improve the volumetric energy density of this material and many methods have been reported so far. This paper provides a brief summary of the synthesis methods and electrochemical performances of micro-spherical $LiFePO_4$ having high volumetric energy density.

Transport Behaviour of Electroactive Species in Ionic Compounds: A Focus on Li Diffusion through Transition Metal Oxide in Current Flowing Condition

  • Lee, Sung-Jai;Pyun, Su-Il
    • Journal of the Korean Electrochemical Society
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    • v.12 no.1
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    • pp.1-10
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    • 2009
  • This article reviewed transport behaviours of electroactive species in ionic compounds, focusing on chemical diffusion of Li through the transition metal oxide in a current flowing condition. For this purpose, a distinction has been first briefly made between migration and diffusion with respect to current, driving force and charge of electroactive species considered. Then, the equations for chemical diffusion are derived theoretically in open-circuit and current flowing conditions. Finally, the experimental methods such as ac impedance spectroscopy and current (potential) transient techniques are described in details for characterising chemical diffusion. In addition, the role of the thermodynamic enhancement factor in chemical diffusion is discussed.

Applications of Voltammetry in Lithium Ion Battery Research

  • Kim, Taewhan;Choi, Woosung;Shin, Heon-Cheol;Choi, Jae-Young;Kim, Ji Man;Park, Min-Sik;Yoon, Won-Sub
    • Journal of Electrochemical Science and Technology
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    • v.11 no.1
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    • pp.14-25
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    • 2020
  • Li ion battery (LIB) is one of the most remarkable energy storage devices currently available in various applications. With a growing demand for high-performance batteries, the role of electrochemical analysis for batteries, especially, electrode reactions are becoming very important and crucial. Among various analytical methods, cyclic voltammetry (CV) is very versatile and widely used in many fields of electrochemistry. Through CV, it is possible to know electrochemical factors affecting the reaction voltage and reversibility, and furthermore, quantitative analysis on Li+ diffusivity as well as intercalation and capacitive reactions, and also anionic redox reaction. However, the explanation or interpretation of the results of CV is often deficient or controversial. In this mini-review, we briefly introduce the principle of cyclic voltammetry and its applications in LIB to bring a better understanding of the electrochemical reaction mechanisms involved in LIB.

Assessment on Recovery of Cesium, Strontium, and Barium From Eutectic LiCl-KCl Salt With Liquid Bismuth System

  • Woods, Michael E.;Phongikaroon, Supathorn
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.18 no.4
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    • pp.421-437
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    • 2020
  • This study provides an assessment on a proposed method for separation of cesium, strontium, and barium using electrochemical reduction at a liquid bismuth cathode in LiCl-KCl eutectic salt, investigated via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS). CV studies were performed at temperatures of 723-823 K and concentrations of the target species up to 4.0wt%. Redox reactions occurring during potential sweeps were observed. Concentration of BaCl2 in the salt did not seem to influence the diffusivity in the studied concentration range up to 4.0wt%. The presence of strontium in the system affected the redox reaction of lithium; however, there were no distinguishable redox peaks that could be measured. Impedance spectra obtained from EIS methods were used to calculate the exchange current densities of the electroactive active redox couple at the bismuth cathode. Results show the rate-controlling step in deposition to be the mass transport of Cs+ ions from the bulk salt to the cathode surface layer. Results from SEM-EDS suggest that Cs-Bi and Sr-Bi intermetallics from LiCl-KCl salt are not thermodynamically favorable.