No abstract

Sophisticated electrode design for high power and energy density batteries will require a more thorough understanding of how electrode porosity affects cell failure mechanisms such as solid electrolyte interphase (SEI) formation. This study uses high resolution three dimensional (3D) mapping to examine the anode SEI deposits in off the shelf Li-ion cells that have been deeply cycled to complete failure. Scanning electron microscopy (SEM) was used to show the buildup of SEI on the surface of the graphite anode, while nano-scale resolution X-ray computed tomography (nano-CT) was used to show the SEI accumulation within the anode's pore structure. Through a combination of phase contrast and absorption contrast imaging, it was shown that the average pore diameter and total internal pore volume fraction decreased significantly after cycling, while there was a corresponding increase of absorption contrast from heavier elements throughout the anode. We propose this is due to buildup of electrolyte decomposition products within the pores.

While some commercially available primary batteries have lithium metal anodes, there has yet to be a commercially viable secondary battery with this type of electrode. Research prototypes of these cells typically exhibit a limited cycle life before dendrites form and cause internal cell shorting, an occurrence that is more pronounced during high-rate cycling. To better understand the effects of high-rate cycling that can lead to cell failure, we use ex situ nanoscale-resolution X-ray computed tomography (nano-CT) with the aid of Zernike phase contrast to image the internal morphologies of lithium metal electrodes on copper wire current collectors that have been cycled at low and high current densities. The Li that is deposited on a Cu wire and then stripped and deposited at low current density appears uniform in morphology. Those cycled at high current density undergo short voltage transients to >3 V during Li-stripping from the electrode, during which electrolyte oxidation and Cu dissolution from the current collector may occur. The effect of temperature is also explored with separate cycling experiments performed at 5 and 33 °C. The resulting morphologies are nonuniform films filled with voids that are semispherical in shape with diameters ranging from hundreds of nanometers to tens of micrometers, where the void size distributions are temperature-dependent. Low-temperature cycling elicits a high proportion of submicrometer voids, while the higher-temperature sample morphology is dominated by voids larger than 2 μm. In evaluating these morphologies, we consider the importance of nonidealities during extreme charging, such as electrolyte decomposition. We conclude that nano-CT is an effective tool for resolving features and aggressive cycling-induced anomalies in Li films in the range of 100 nm to 100 μm.

Zernike phase contrast is a useful technique for nanoscale X-ray computed tomography (CT) imaging of materials with a low X-ray absorption coefficient. It enhances the image contrast by phase shifting X-ray waves to create changes in amplitude. However, it creates artifacts that hinder the use of traditional image segmentation techniques. We propose an image restoration method that models the X-ray phase contrast optics and the three-dimensional image reconstruction method. We generate artifact-free images through an optimization problem that inverts this model. Though similar approaches have been used for Zernike phase contrast in visible light microscopy, this optimization employs an effective edge detection method tailored to handle Zernike phase contrast artifacts. We characterize this optics-based restoration method by removing the artifacts in and thresholding multiple Zernike phase contrast X-ray CT images to produce segmented results that are consistent with the physical specimens. We quantitatively evaluate and compare our method to other segmentation techniques to demonstrate its high accuracy.

A grating interferometer (GI) system has been installed in an X-ray microscope equipped with a Zernike phase contrast (ZPC) system and a Cu rotating anode X-ray source. The GI and ZPC systems are switchable, and their performances of phase information extraction have been compared. The GI system is based on a Lau interferometer consisting of an absorption grating and a π/2 phase grating, which extracts a magnified phase shift map of a sample via a phase-stepping measurement. The ZPC system generates a phase contrast image by using a phase plate and a corresponding condenser device. The ZPC system and the GI system are compared in terms of detectability of phase objects. By the Fourier analysis of images of a logarithmic ruler pattern, the spatial resolution was found to be identical between the two systems. Although the sensitivity depends on the sample size, the signal-to-noise ratio of polystyrene spheres with a few microns in diameter was used for sensitivity comparison, showing the superior sensitivity of the GI system to that of the ZPC system. The quantitativeness of the GI system with the phase-stepping measurement was also demonstrated over the ZPC system, which generates halo and shade-off artifacts. The GI system exhibits twin image artifacts that need to be resolved for practical applications of the technique.