搜索

x
中国物理学会期刊

考虑空间电荷层效应的氧离子导体电解质内载流子传输特性

CSTR: 32037.14.aps.70.20201651

Charge carrier transport in oxygen-ion conducting electrolytes with considering space charge layer effect

CSTR: 32037.14.aps.70.20201651
PDF
HTML
导出引用
  • 晶界或异质界面诱发的空间电荷层(space charge layer, SCL)效应, 被认为是氧离子导体电解质内界面附近区域载流子传输特性显著区别于体相区域的关键原因之一. 现有研究多采用Poisson-Boltzmann (PB)方程预测SCL效应的影响规律, 但其基于载流子电化学平衡假设, 无法用于载流子存在宏观运动的工况, 极大限制了相关传输机理研究. 本文耦合Poisson方程和载流子质量守恒方程, 建立了适用于载流子具有宏观运动时氧离子导体内载流子传输过程的模型, 推导了控制SCL效应的关键无量纲参数. 聚焦固体氧化物燃料电池中常用的AO2-M2O3氧离子导体电解质, 对比研究了传统PB方程和本文建立的Poisson-载流子质量守恒耦合方程的预测结果可靠性. 进一步采用耦合模型深入分析了考虑SCL效应时氧离子导体内部氧空位传输机理, 发现导体界面电流密度增大导致SCL电阻先减小后增大. 增大无量纲Debye长度(表征空间电荷层厚度与导体厚度的比值)可显著增大SCL电阻. 当驱动氧空位移动的过电势与热势数量级相当时, 增大无量纲电势(表征过电势与热势的比值)导致SCL电阻增大; 当过电势远小于热势时, 改变无量纲电势对氧空位传输过程几乎无影响. 本文研究结论可为通过合理设计晶界或异质界面以改善氧离子导体内载流子传输能力及最终提高相关电化学器件性能提供理论依据.

     

    Space charge layer (SCL) effect induced by interfaces, e.g., grain boundaries in the polycrystals or heterointerfaces in the composites, may make the characteristics of the charge carrier transport near the interfaces significantly different from those in the bulk area. In previous studies, the Poisson-Boltzmann (PB) equation was widely used to model the SCL effect, in which all the charge carriers were assumed to be in electrochemical equilibrium. However, the assumption of the electrochemical equilibrium is no longer valid when the charge carriers exhibit macroscopic motion. In this paper, we develop a model to simulate the charge carrier transport within the oxygen-ion conductor, particularly in the SCL, in which the charge carrier mass conservation equation is coupled to the Poisson equation. Our present coupled model, in which the assumption of the electrochemical equilibrium is not employed, is therefore able to simulate charge carrier transport with macroscopic motion. Two key dimensionless parameters governing the SCL effect are deduced, i.e. the dimensionless Debye length characterizing the ratio of Debye length to the thickness of oxygen-ion conductor, and the dimensionless potential representing the relative importance of the overpotential to the thermal potential. Taking AO2-M2O3 oxide for example, the conventional model with using PB equation and our present coupled model are compared for predicting the SCL effect. Furthermore, the mechanism of the oxygen vacancy transport in the oxygen-ion conductor with considering the SCL effect is thoroughly discussed. In a brief summary, with increasing the current density at the interface, the SCL resistance shows a non-monotonical tendency, i.e., it firstly decreases and then increases. Besides, enlarging the dimensionless Debye length significantly increases the SCL resistance. The influence of increasing the dimensionless potential on the oxygen vacancy transport is obvious when the overpotential is comparable to the thermal potential, but it becomes negligible when the overpotential is far less than the thermal potential. These results may offer helpful guidance for enhancing the performance of oxygen-ion conductors by rationally designing the grain boundaries and heterointerfaces.

     

    目录

    /

    返回文章
    返回