Deformed Butler–Volmer Models for Convex Semilogarithmic Current-Overpotential Profiles of Li-ion Batteries
Deformed Butler–Volmer Models for Convex Semilogarithmic Current-Overpotential Profiles of Li-ion Batteries
复制标题
DOI：
10.1021/acs.jpcc.1c09620
复制
发表时间：
2022-01
期刊：
影响因子：
--
通讯作者：
A. Allagui;Hachemi B. Benaoum;Chunlei Wang
中科院分区：
文献类型：
--
作者：
A. Allagui;Hachemi B. Benaoum;Chunlei Wang
在Arrhenius动力学和玻尔兹曼因子的假设下，Butler-Volmer(BV)方程将穿过电化学界面的电流通量与穿过该界面的电势降联系起来。应用半对数塔菲尔分析，其中绘制了电流的对数与过电势的对数，其中预期的直线可以计算出动力学过程的基本反应速率。然而，一些锂离子电池的数据，这是这里的重点，显示出非线性凸型曲线，不能完全符合标准的BV模型。相反，我们提出了两个变形的BV模型来分析这种类型的行为，1由仅表现出局部平衡的细胞的叠加构造而成，从而产生了幂定律q指数和κ指数函数。非玻尔兹曼分布已经成功地用于非平衡情况下的广泛的物理系统的建模，但还没有用于电池的建模。我们用LiFePO4和Li-O2电池的实验数据验证了变形BV模型的有效性。
The Butler-Volmer (BV) equation links the current flux crossing an electrochemical interface to the electric potential drop across it with the assumption of Arrhenius kinetics and the Boltzmann factor. Applying the semilogarithmic Tafel analysis in which the logarithm of current is plotted vs. the overpotential one expects straight lines from which the fundamental reaction rate of the kinetic process can be computed. However, some Li-ion battery data, which is the focus here, show nonlinear convex profiles that cannot be adequately fitted with the standard BV model. We propose instead two deformed BV models for the analysis of such types of behaviors constructed 1 from the superposition of cells exhibiting only local equilibrium and thus giving rise to the power-law q-exponential and κ-exponential functions. Non-Boltzmann distributions have been successfully employed for the modeling of a wide spectrum of physical systems in nonequilibrium situations, but not yet for batteries. We verify the validity of the deformed BV models on experimental data obtained from LiFePO4 and Li-O2 batteries.