Jens Eller

Progress in In Situ X-Ray Tomographic Microscopy of Liquid Water in Gas Diffusion Layers of PEFC

Water management is an important factor for optimizing polymer electrolyte fuel cells (PEFC) under high current density conditions as required for the automotive application. The characteristics of the local liquid saturation of the gas diffusion layer (GDL) is of particular interest. Here we report on the development of in-situ X-ray tomographic microscopy (XTM) with a pixel sizes in the order of 2 μm and sensitivity for carbon and liquid water for the quantitative analysis of liquid water in GDLs. In-situ XTM of PEFC is a major experimental challenge. A complete cell needs to be operated under realistic conditions in the constraint space of the small field of view on the beamline sample stage. Further phase segmentation of the images is required to successfully analyze the quantitative properties of the different phases. For this a workflow, applying differential images between dry and wet structures has been developed. Cells with Toray TGP-H-060 GDLs were analyzed in-situ. Droplets that appear on the GDL surface are connected to a significant water structure inside the GDL. Further the water cluster size distribution in the GDL shows that while small droplets (<100 pl) are numerous, most of the water is contained in few larger clusters.

Quantifying microstructural dynamics and electrochemical activity of graphite and silicon-graphite lithium ion battery anodes

Despite numerous studies presenting advances in tomographic imaging and analysis of lithium ion batteries, graphite-based anodes have received little attention. Weak X-ray attenuation of graphite and, as a result, poor contrast between graphite and the other carbon-based components in an electrode pore space renders data analysis challenging. Here we demonstrate operando tomography of weakly attenuating electrodes during electrochemical (de)lithiation. We use propagation-based phase contrast tomography to facilitate the differentiation between weakly attenuating materials and apply digital volume correlation to capture the dynamics of the electrodes during operation. After validating that we can quantify the local electrochemical activity and microstructural changes throughout graphite electrodes, we apply our technique to graphite-silicon composite electrodes. We show that microstructural changes that occur during (de)lithiation of a pure graphite electrode are of the same order of magnitude as spatial inhomogeneities within it, while strain in composite electrodes is locally pronounced and introduces significant microstructural changes.

Combining operando synchrotron X-ray tomographic microscopy and scanning X-ray diffraction to study lithium ion batteries.

We present an operando study of a lithium ion battery combining scanning X-ray diffraction (SXRD) and synchrotron radiation X-ray tomographic microscopy (SRXTM) simultaneously for the first time. This combination of techniques facilitates the investigation of dynamic processes in lithium ion batteries containing amorphous and/or weakly attenuating active materials. While amorphous materials pose a challenge for diffraction techniques, weakly attenuating material systems pose a challenge for attenuation-contrast tomography. Furthermore, combining SXRD and SRXTM can be used to correlate processes occurring at the atomic level in the crystal lattices of the active materials with those at the scale of electrode microstructure. To demonstrate the benefits of this approach, we investigate a silicon powder electrode in lithium metal half-cell configuration. Combining SXRD and SRXTM, we are able to (i) quantify the dissolution of the metallic lithium electrode and the expansion of the silicon electrode, (ii) better understand the formation of the Li15Si4 phase, and (iii) non-invasively probe kinetic limitations within the silicon electrode. A simple model based on the 1D diffusion equation allows us to qualitatively understand the observed kinetics and demonstrates why high-capacity electrodes are more prone to inhomogeneous lithiation reactions.

Polymer electrolyte fuel cell performance degradation at different synchrotron beam intensities.

The degradation of cell performance of polymer electrolyte fuel cells under monochromatic X-ray irradiation at 13.5 keV was studied in galvanostatic and potentiostatic operation modes in a through-plane imaging direction over a range of two orders of magnitude beam intensity at the TOMCAT beamline of the Swiss Light Source. The performance degradation was found to be a function of X-ray dose and independent of beam intensity, whereas the degradation rate correlates with beam intensity. The cell performance was more sensitive to X-ray irradiation at higher temperature and gas feed humidity. High-frequency resistance measurements and the analysis of product water allow conclusions to be drawn on the dominating degradation processes, namely change of hydrophobicity of the electrode and sulfate contamination of the electrocatalyst.

Determination of Local GDL Saturation on the Pore Level by In Situ Synchrotron Based X-ray Tomographic Microscopy

In-situ synchrotron-based tomographic microscopy (SRXTM) with a spatial resolution in the order of 1μm and sensitivity for carbon and liquid water, has the potential to provide fundamental information for the understanding of the wetting properties of gas diffusion layer (GDL) materials on the pore level. This is important for the understanding of the solid-water interactions in the porous structures since water transport in GDLs is considered a key transport mechanism polymer electrolyte fuel cells (PEFC). However SRXTM of PEFC is a major experimental challenge. To obtain quantitative results, a complete cell needs to be operated under realistic conditions in the constrained space of the small field of view on the beamline sample stage without disturbing the sample rotation.