非平衡电化学相图：Butler-Volmer动力学之外
Nonequilibrium Electrochemical Phase Maps: Beyond Butler-Volmer Kinetics
摘要：
电极-电解质界面处的电化学动力学对于理解能量存储装置的高倍率行为至关重要。电极的相变通常在平衡热力学条件下处理，而实际操作是在有限速率下。分析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。这以前只在Butler-Volmer动力学中得到证明，在那里它可以通过分析来完成。在这项工作中，我们开发了一个动力学建模包在Julia语言能够有效的数值反演率的一般动力学模型，使用自动微分的关系。我们演示了构建非平衡相图，包括Marcus-Hush-Chidsey等需要计算积分的模型，并讨论了各种假设和模型参数（如温度，重组能，活性和理想溶液相互作用能）的影响，特别是对高速率相行为的影响。即使对于一组固定的参数，临界电流的大小也可以在动力学模型之间变化超过两个因子。
英文摘要：
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.
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