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首页> 外文期刊>Electrochimica Acta >Investigation of the electrochemical intercalation of lithium into a Li sub(1- delta )CoO sub(2) electrode based upon numerical analysis of potentiostatic current transients
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Investigation of the electrochemical intercalation of lithium into a Li sub(1- delta )CoO sub(2) electrode based upon numerical analysis of potentiostatic current transients

机译：基于恒电位电流瞬态的数值分析研究锂在Li sub（1- delta）CoO sub（2）电极中的电化学嵌入

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Lithium insertion into a porous Li sub(1- delta )CoO 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 the presence of a single phase. This was later replaced by a three-stage character when a Li-diluted alpha phase coexisted with a Li-concentrated beta 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 phase exists. 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 boundary movement (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 of the 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 the limitation 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变的数值分析，研究了锂插入多孔Li sub（1- delta）CoO sub（2）电极中的过程。当插入锂时，电流瞬变首先在单相存在下表现出两阶段行为。后来，当Li稀释的α相与Li浓缩的β相共存时，将其替换为三阶段字符。从实验对数电流瞬态的导数与数值模拟的导数的比较可以看出，锂离子的化学扩散率主要决定了两相共存时电流瞬态第一阶段的形状和第二阶段的形状。仅存在单相时的电流瞬变。观察到两相共存期间线性和对数电流瞬态的第二阶段的导数具有向上凹入的形状，表明锂的插入通过相界移动（PBM）进行。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。电流瞬变及其导数通过平衡状态化学计量的函数，通过在将恒电位锂注入电极中受相边界“钉扎”和对锂的不可渗透约束施加限制的条件下，通过锂传输的数值分析而模拟为平衡化学计量的函数。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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