论文标题
非平衡电化学相图：Butler-Volmer动力学超越
Nonequilibrium Electrochemical Phase Maps: Beyond Butler-Volmer Kinetics
论文作者
论文摘要
电极 - 电解质界面的电化学动力学对于了解储能装置的高速率行为至关重要。通常在平衡热力学条件下处理电极的相变，而现实的操作则以有限的速率处理。分析在非平衡条件下的相变，需要将非线性电化学动力学模型与热力学模型相结合。此前曾在Butler-volmer动力学上进行了证明，可以在其中进行分析。在这项工作中，我们在朱莉娅语言中开发了一个动力学建模套件，能够使用自动分化有效地对一般动力学模型的速率关系进行数值反转。我们展示了建立非平衡相图，包括需要计算积分不可分割的Marcus-Hush-Chidsey等模型，还讨论了各种假设和模型参数（例如温度，重组能，活性和理想的溶液相互作用）的影响，尤其是对高速相位行为的影响。即使对于固定的参数，在动力学模型中，临界电流的幅度也可能多于两倍。
Electrochemical kinetics at electrode-electrolyte interfaces are crucial to understand high-rate behavior of energy storage devices. Phase transformation of electrodes is typically treated under equilibrium thermodynamic conditions, while realistic operation is at finite rates. Analyzing phase transformations under nonequilibrium conditions requires integrating nonlinear electrochemical kinetic models with thermodynamic models. This had only previously been demonstrated for Butler-Volmer kinetics, where it can be done analytically. In this work, we develop a kinetic modeling package in the Julia language capable of efficient numerical inversion of rate relationships for general kinetic models using automatic differentiation. We demonstrate building nonequilibrium phase maps, including for models such as Marcus-Hush-Chidsey that require computation of an integral, and also discuss the impact of a variety of assumptions and model parameters (such as temperature, reorganization energy, activity, and ideal solution interaction energy), particularly on high-rate phase behavior. Even for a fixed set of parameters, the magnitude of the critical current can vary by in excess of a factor of two amongst kinetic models.
