Investigation of Graphite Electrode Degradation in Lithium-Ion Cells Using 4D-STEM
Authors: Pidaparthy Saran , Abraham Daniel P. , Rodrigues Marco-Tulio F , Hou Hanyu , Zuo Jian-Min 
Published: July 2022

The development of longer lasting and faster charging lithium-ion batteries (LIBs) remains a critical engineering priority for the U.S. Department of Energy. To enable the next-generation technology, it is essential to understand the nature and extent of materials failure during battery operation. Under fast-charging conditions, it has been shown that graphite particles, which comprise the active material of the LIB anode, suffer irreversible material degradation that limits ultimate battery performance. This damage to the graphite manifests as turbostratic lattice disorder, severe morphological roughening, and anode swelling [1]. While these findings are essential to understand the nature of damage to the anode under fast-charge conditions, it remains to be seen whether such damage occurs at slower rates or is instead accelerated by extreme rate conditions and aging. In this regard, the recent advances in high-resolution electron microscopy (HREM) and four-dimensional scanning transmission electron microscopy (4D-STEM) methods provide the essential tools to enable nanoscopic quantification of battery degradation [2], [3].
In this work, we use advanced analytical electron microscopy and diffraction strategies to analyze nanoscopic degradation of graphite anode material under different cycling rate and aging conditions. The results of this work will demonstrate novel strategies for identifying nanoscale structural disorder that arise in battery materials as well as provide key understanding of graphite material failure to aid in the development of high-performance anode materials. We study (in post-mortem) the graphite particle cross-sections harvested from LIBs at different aging conditions for both C/2 (i.e., 2 hours to full charge) and 6C (i.e., 10 minutes to full charge) rate. At the nano- to atomic-scale, we rely primarily on aberration-corrected STEM for imaging and diffraction acquisition for each sample (see Figure 1 for the results). High resolution imaging reveals the extent of lattice disorder and amorphous character localized at graphite pore edges. The 4D-STEM data helps to further quantify the extent and distribution of nanoscale structural disorder (including permanent strain and turbostratic disorder). The experimental methods employed to acquire the datasets and the strategies employed to interpret the data to understand the nature of the resulting damage, including recent progress into Cepstral STEM, will be discussed. Additional supporting evidences of graphite disorder from Raman spectroscopy studies and rate-dependent anode swelling from scanning electron microscopy will also be presented.

References
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[1] S. Pidaparthy, M.-T. F. Rodrigues, J.-M. Zuo, and D. P. Abraham, “Increased Disorder at Graphite Particle Edges Revealed by Multi-length Scale Characterization of Anodes from Fast-Charged Lithium-Ion Cells,” J. Electrochem. Soc., vol. 168, no. 10, p. 100509, 2021.
[2] J.-M. Zuo et al., “Data-Driven Electron Microscopy: Electron Diffraction Imaging of Materials Structural Properties,” arXiv Prepr. arXiv2110.02070, 2021.
[3] E. Padgett et al., “The exit-wave power-cepstrum transform for scanning nanobeam electron diffraction: robust strain mapping at subnanometer resolution and subpicometer precision,” Ultramicroscopy, vol. 214, p. 112994, 2020.

Acknowledgements: SP acknowledges support from the U. S. Department of Energy Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the U. S. Department of Energy under contract number DE‐SC0014664. This work was carried out in part in the Materials Research Laboratory Central Research Facilities, University of Illinois. DA and MTFR acknowledge support from DOE’s Vehicle Technologies Office. This document has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357.

Figure 1