Nonlinear coupled equations for electrochemical cells as developed by the general equation for nonequilibrium reversible-irreversible coupling.
Nonlinear coupled equations for electrochemical cells as developed by the general equation for nonequilibrium reversible-irreversible coupling.
复制标题
电化学电池的非线性耦合方程由非平衡可逆-不可逆耦合的一般方程开发。
DOI：
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发表时间：
2014
影响因子：
4.4
通讯作者：
H. C. Öttinger
中科院分区：
文献类型：
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作者：
D. Bedeaux;S. Kjelstrup;H. C. Öttinger
我们展示了Butler-Volmer和Nernst方程，以及Peltier效应，如何包含在非平衡可逆和不可逆耦合的一般方程中，GENERIC，具有过电位的独特定义。线性流体-力关系用于描述电化学系统中均匀部分的输运。对于电极界面，我们选择非线性磁链-力关系。我们给出了一个用固体氧化物燃料电池的氧电极和电解质的例子电池的一般热力学基础。在示例细胞中，有两个激活的化学步骤也耦合到表面的热驱动力。平衡交换电流密度得到两个限速步骤的贡献。根据产物和反应物的电化学电位的差异，在恒温和定态下确定测量的过电位。在这些条件之外，新的条款出现了。在一般的热力学基础上，计算了伴随的地表能量通量，以及地表产生的热量。
We show how the Butler-Volmer and Nernst equations, as well as Peltier effects, are contained in the general equation for nonequilibrium reversible and irreversible coupling, GENERIC, with a unique definition of the overpotential. Linear flux-force relations are used to describe the transport in the homogeneous parts of the electrochemical system. For the electrode interface, we choose nonlinear flux-force relationships. We give the general thermodynamic basis for an example cell with oxygen electrodes and electrolyte from the solid oxide fuel cell. In the example cell, there are two activated chemical steps coupled also to thermal driving forces at the surface. The equilibrium exchange current density obtains contributions from both rate-limiting steps. The measured overpotential is identified at constant temperature and stationary states, in terms of the difference in electrochemical potential of products and reactants. Away from these conditions, new terms appear. The accompanying energy flux out of the surface, as well as the heat generation at the surface are formulated, adding to the general thermodynamic basis.