论文标题
Onsager-Stefan-Maxwell运输中带有带电物种的结构性电负性
Structural electroneutrality in Onsager-Stefan-Maxwell transport with charged species
论文作者
论文摘要
我们提出了一种在Onsager-Stefan-Maxwell电解电脑模型中嵌入局部电负性的方法，从而将其作为具有代数约束的差分系统的配方。通量解释的传输定律是针对一般多组分电解质制定的，其中电导率，成分扩散率和转移数与Stefan-Maxwell系数通过可逆矩阵计算有关。我们称之为“盐收费基础”的结构实现了古根海姆将物种电位电位转化为描述一组中性成分集的组合，从而留下了与电力相关的独特组合。定义保留吉布斯功能和能量耗散结构的共轭成分浓度和通量保留了对称的互惠关系。该框架重现了纽曼的二元电解质法律和熔融盐法律法律；我们还提出了两种溶剂混合物的盐溶液的法律，例如锂离子 - 电池电解质。最后，我们模拟了一个具有浓度依赖性特性的非理想二元电解质的电位壳壳细胞。
We present a method to embed local electroneutrality within Onsager-Stefan-Maxwell electrolytic-transport models, circumventing their formulation as differential systems with an algebraic constraint. Flux-explicit transport laws are formulated for general multicomponent electrolytes, in which the conductivity, component diffusivities, and transference numbers relate to Stefan-Maxwell coefficients through invertible matrix calculations. A construction we call a `salt-charge basis' implements Guggenheim's transformation of species electrochemical potentials into combinations describing a minimal set of neutral components, leaving a unique combination associated with electricity. Defining conjugate component concentrations and fluxes that preserve the structures of the Gibbs function and energy dissipation retains symmetric Onsager reciprocal relations. The framework reproduces Newman's constitutive laws for binary electrolytes and the Pollard-Newman laws for molten salts; we also propose laws for salt solutions in two-solvent blends, such as lithium-ion-battery electrolytes. Finally, we simulate a potentiostatic Hull cell containing a non-ideal binary electrolyte with concentration-dependent properties.
