Damage-Free Femtosecond X-Ray Laser Snapshot Imaging of Catalyst Layer Nano-Structures of Polymer Electrolyte Fuel Cells
Authors: Suzuki Akihiro , Niida Yoshiya , Joti Yasumasa , Bessho Yoshitaka , Nishino Yoshinori 
Published: November 2022

The realization of the hydrogen society, where hydrogen is used as clean and renewable energy, is desired to reduce carbon dioxide emissions and achieve sustainable development. The polymer electrolyte fuel cell (PEFC) is a key technology for automobiles in the hydrogen society as an alternative to conventional internal combustion engines. However, further improvements in PEFC performances are required for the full-scale spread of fuel cell vehicles. This study aims to image the nanostructures of the catalyst layer, which is particularly important in determining the performance of PEFCs, and correlate the observed structures with mass transfer in the catalyst layer. The catalyst layer contains catalyst-loaded carbon supports thinly covered with an ionomer responsible for proton conduction. We are especially interested in observing the support structure and ionomer coverage.
We performed coherent X-ray imaging studies on the catalyst particles of PEFCs using an X-ray free-electron laser (XFEL) facility: SACLA (SPring-8 Angstrom Compact free electron LAser). Femtosecond XFEL allows us to capture radiation-damage-free snapshot images by outrunning major radiation damage processes. Damage-free imaging is of great value because radiation damage often causes a problem in high-resolution electron microscopy observation of ionomers. We used the coherent diffractive imaging (CDI) technique to observe catalyst particles of PEFCs. In CDI, sample images are reconstructed from measured coherent diffraction patterns using phase-retrieval calculation instead of objective lenses. CDI enables quantitative phase imaging and allows high-contrast imaging of the catalyst particles, which are almost transparent to X-rays.
The measurement was carried out for catalyst particles in the dried condition and in solution. Our study showed that the image contrast can be adjusted by changing the electron density of the volume surrounding the sample1). The dried sample was prepared by dropping catalyst ink onto a silicon nitride membrane and air-dried. The solution sample was enclosed in micro-liquid enclosure arrays2,3) developed at Hokkaido University. The coherent diffraction patterns were measured by irradiating the sample catalyst particles with the 100-nm-focused XFEL beam with a photon energy of 4 keV using MAXIC-S (Multiple Application X-ray Imaging Chamber-S)4). The phase-retrieval calculation reconstructed the sample images. Fig. 1 shows a reconstructed image of a catalyst particle in water. The reconstructed image shows many white spots, which can be interpreted as platinum-cobalt catalysts. The pixel size of the reconstructed image is 1.3 nm, demonstrating among the highest spatial resolution in X-ray imaging. We will continue our study to observe the support structures and their ionomer coverage to understand the mass transfer in the catalyst layer.
This work was supported by the FC-Platform of NEDO (New Energy and Industrial Technology Development Organization). The XFEL experiments were performed at SACLA with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Nos. 2020A8106, 2021A8010, and 2021B8019).
References:
1) A. Suzuki1, H. Tanaka, H. Yamashige, Y. Orikasa, Y. Niida, T. Kimura, K. Tono, M. Yabashi, T. Ishikawa, Y. Bessho, Y. Joti, and Y. Nishino, Femtosecond X-ray laser reveals intact sea-island structures of metastable solid-state electrolytes for batteries, submitted (2022).
2) T. Kimura, Y. Joti, A. Shibuya, C. Song, S. Kim, K. Tono, M. Yabashi, M. Tamakoshi, T. Moriya, T. Oshima, T. Ishikawa, Y. Bessho and Y. Nishino, Imaging live cell in micro-liquid enclosure by X-ray laser diffraction, Nat. Commun. 5, 3052 (2014).
3) T. Kimura, A. Suzuki, Y. Yang, Y. Niida, A. Nishioka, M. Takei, J. Wei, H. Mitomo, Y. Matsuo, K. Niikura, K. Ijiro, K. Tono, M. Yabashi, T. Ishikawa, T. Oshima, Y. Bessho, Y. Joti, and Y. Nishino, Micro-liquid enclosure array and its semi-automated assembling system for x-ray free-electron laser diffractive imaging of samples in solution, Rev. Sci. Instrum. 91, 083706 (2020).
4) H. Yumoto, T. Koyama, A. Suzuki, Y. Joti, Y. Niida, K. Tono, Y. Bessho, M. Yabashi, Y. Nishino, and H. Ohashi, High-fluence high-gain multilayer focusing optics to enhance spatial resolution in femtosecond X-ray laser imaging, submitted (2022).

Figure 1