The Holby–Morgan Model of Platinum Catalyst Degradation in PEM Fuel Cells: Range of Feasible Parameters Achieved Using Voltage Cycling

V. A. Kovtunenko
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Abstract

Loss of electrochemical surface area in proton-exchange membrane is of large practical importance, since membrane degradation largely affects the durability and life of fuel cells. In this paper, the electrokinetic model developed by Holby and Morgan is considered. The paper describes degradation mechanisms in membrane catalyst presented by platinum dissolution, platinum diffusion, and platinum oxide formation. A one-dimensional model is governed by nonlinear reaction–diffusion equations given in a cathodic catalyst layer using Butler–Volmer relationships for reaction rates. The governing system is endowed with initial conditions, mixed no-flux boundary condition at the interface with gas diffusion layer, and a perfectly absorbing condition at the membrane boundary. In cyclic voltammetry tests, a non-symmetric square waveform is applied for the electric potential difference between 0.6 and 0.9 V held for 10 and 30 s, respectively, according to the protocol of European Fuel Cell and Hydrogen Joint Undertaking. Aimed at mitigation strategies, the impact of cycling operating conditions and model parameters on the loss rate of active area is investigated. The global behavior with respect to variation of parameters is performed using the method of sensitivity analysis. Finding feasible and unfeasible values helps to determine the range of test parameters employed in the model. Comprehensive results of numerical simulation tests are presented and discussed.
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PEM 燃料电池中铂催化剂降解的 Holby-Morgan 模型:利用电压循环实现的可行参数范围
质子交换膜电化学表面积的损失具有重要的实际意义,因为膜降解在很大程度上会影响燃料电池的耐用性和寿命。本文考虑了 Holby 和 Morgan 建立的电动模型。论文描述了膜催化剂的降解机制,包括铂溶解、铂扩散和铂氧化物形成。一维模型由阴极催化剂层中的非线性反应-扩散方程控制,反应速率采用巴特勒-沃尔默关系。治理系统具有初始条件、与气体扩散层界面的混合无流动边界条件以及膜边界的完全吸收条件。在循环伏安法测试中,根据欧洲燃料电池和氢气联合企业的协议,在 0.6 至 0.9 V 的电势差范围内分别施加非对称方波,保持 10 秒和 30 秒。为了制定缓解策略,研究了循环运行条件和模型参数对有功面积损耗率的影响。使用敏感性分析方法对参数变化的全局行为进行了分析。找到可行值和不可行值有助于确定模型中采用的测试参数范围。对数值模拟测试的综合结果进行了介绍和讨论。
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