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首页> 外文期刊>Electrochimica Acta >An investigation of the electrochemical intercalation of lithium into a Li{sub}1-δCoO{sub}2 electrode based upon numerical analysis of potentiostatic current transients
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An investigation of the electrochemical intercalation of lithium into a Li{sub}1-δCoO{sub}2 electrode based upon numerical analysis of potentiostatic current transients

机译：基于恒电流瞬态的数值分析研究锂在Li {sub}1-δCoO{sub} 2电极中的电化学嵌入

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摘要

Lithium insertion into a porous Li{sub}(1-δCoO{sub}2 electrode was investigated by numerical analysis of potentiostatic cathodic current transients. As lithium was intercalated, the current transients at first exhibited two-stage behavior in thepresence of a single phase. This was later replaced by a three-stage character when a Li-diluted ~ phase coexisted with a Li-concentrated ~ phase. From the comparison of derivatives of the experimental logarithmic current transients with those numerically simulated, it is suggested that the chemical diffusivity of lithium ion predominantly determines the shapes of the first stage of the current transients when the two phases coexist and of the later stage of the current transients when only a single phaseexists. The derivatives of the second stages of the linear and logarithmic current transients during the coexistence of two phases were observed to be characterized by an upward concave shape, indicating that lithium insertion proceeds via phase boundarymovement (PBM). Transition times t{sub}tr(1) and t{sub}tr(2) were determined as the times of the local maxima on the derivatives of the experimental linear and logarithmic transients, respectively. These time values correspond to the onset and end ofthe PBM. The current transient and its derivative were simulated as functions of equilibrium stoichiometry through the numerical analysis for lithium transport under the condition for potentiostatic lithium injection into the electrode subjected to thelimitation placed by the 'pinning of the phase boundary and the impermeable constraint to lithium. The numerically simulated current transient and the derivative of the second stage of the transient qualitatively matched those experimentally determined as functions of applied potential in their three-stage character and upward concave shape, respectively.
机译：通过对恒电位阴极电流瞬态的数值分析，研究了锂在多孔Li {sub}（1-δCoO{sub} 2）电极中的插入过程;当嵌入锂时，在单相存在时，电流瞬变首先表现出两阶段行为。然后，当Li稀释的〜相与Li浓缩的〜相共存时，由三阶段特征代替。从实验对数电流瞬态的导数与数值模拟的比较中可以看出，化学扩散性当两相共存时，锂离子的主要决定电流瞬变的第一阶段的形状，而当仅存在单相时，决定第二阶段的电流瞬变的形状。观察到两相共存的特征是向上凹的形状，表明锂插入通过相进行边界运动（PBM）。过渡时间t {sub} tr（1）和t {sub} tr（2）被确定为分别是实验线性和对数瞬态导数的局部最大值的时间。这些时间值对应于PBM的开始和结束。电流瞬态及其导数是通过平衡条件下化学计量的函数进行模拟的，方法是在将恒电位锂注入电极的过程中，通过受相边界钉扎和对锂的不可渗透约束的限制，对锂的传输进行数值分析。数值模拟的电流瞬态和瞬态第二阶段的导数在性质上与实验确定的那些分别以三阶段特征和向上凹入形状作为施加电势的函数相匹配。

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