Utilization of Pt Nanoparticle Catalysts during Capillary Condensation Phenomenon in PEMFC: A Lattice DFT Simulation Based on 3D Reconstruction of TEM Images
Authors: Otic Clint John Cortes , Arao Masazumi , Matsumoto Masashi , Imai Hideto , Kinefuchi Ikuya 
Published: February 2024

The use of porous carbon support particles in Cathode Catalyst Layer (CCL) of Polymer Electrolyte Membrane Fuel Cell (PEMFC) has gained significant interest due to their ability to enable proper dispersion of Platinum (Pt) nanoparticles [1]. This offers a key advantage of avoiding the Pt nanoparticles from potential poisoning by sulfonate anion functional groups in the ionomer that is deposited on the surface of the support particles [2]. Furthermore, the presence of condensed liquid water is essential for effective utilization of the Pt nanoparticles that are dispersed both inside and outside of the porous carbon support particles. This is because water plays a crucial role as a proton pathway for hydrogen ions during the electrochemical reaction, thus a requisite amount of condensed liquid water is also needed to promote efficient catalytic activity and maximize the performance of Pt nanoparticle catalysts. It has been demonstrated that the microstructure characteristics of the porous carbon support particles have a significant impact on the performance of Pt utilization, which is attributed to the varying behavior of water condensation [2]. Microstructure properties such as pore size, surface area, and wettability properties, can influence the distribution of condensed liquid water, thereby affecting the electrochemical performance of Pt nanoparticles in the catalyst layer of PEMFC. Understanding the effect of capillary water condensation in the porous carbon support particles is therefore crucial for maximizing the utilization and catalytic activity of Pt nanoparticles in fuel cell systems.
To investigate the behavior of water condensation in the CCL particles of PEMFC, we conducted simulations based on reconstructed structural data obtained from Transmission Electron Microscopy (TEM) images, as shown in Figure 1. The CCL particle used in this study is taken from the Toyota MIRAI Gen 2 model, an emerging commercial PEMFC-based vehicle in Japan. Here, we used the lattice Density Functional Theory (DFT) to simulate the process of capillary water condensation within the pore network of the particle. The lattice DFT method, which is based on the mean-field lattice gas model, can be interpreted as a coarse-grained equivalent of the conventional DFT [3]. The significant advantage of using lattice DFT is to provide a simple model and computationally efficient approach for studying the behavior of capillary water condensation. To validate the parameters used in our lattice DFT simulations, we compared the isotherm curve obtained from our simulation results with experimental data. Through this comparison, we were able to fine-tune the parameters of the lattice DFT simulation to fit the simulated isotherm curve with that of the experiment. When the parameters are optimized, the resulting water distribution obtained from the lattice DFT simulation, as illustrated in Figure 1, serves as a crucial input to investigate the utilization/activation of Pt nanoparticles within and outside the carbon support particle under varying relative humidity (RH) conditions. Since the resulting water distribution depends on RH, we expect that the utilization/activation of Pt nanoparticles also depend on RH. In this study, we defined utilization/activation of Pt nanoparticle when there is a continuous path of condensed water connecting the Pt nanoparticle to the surface of the carbon support particle. This criterion is similar to the case when we assume that the ionomer is distributed uniformly on the surface of the carbon support particle. Our investigation shows that the utilization/activation behavior of Pt nanoparticles follows closely the isotherm curve of the capillary water condensation.
The complex internal structure of CCL particles in PEMFC makes it challenging to visualize and understand their workings through experiments alone. Therefore, our approach of using lattice DFT simulations offers valuable insights to the role of capillary water condensation behavior in the utilization/activation of Pt nanoparticles. This approach may also pave the way for future research in optimization strategies for PEMFC, ultimately contributing to the advancement of clean energy technologies.
This work was supported by the New Energy and Industrial Technology Development Organization (NEDO) of Japan (Grant number JPNP20003).
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Figure 1. Reconstructed structural data obtained from TEM images of a PEMFC CCL particle used in Toyota MIRAI Gen 2 model, with visualization of condensed water obtained from a sample lattice DFT simulation.

Figure 1