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Main Authors: Ahmed, Shamail, Rossi, Federico, Huo, Hanyu, Haust, Johannes, Hueppe, Franziska, Belz, Juergen, Beyer, Andreas, Janek, Juergen, Volz, Kerstin
Format: Preprint
Published: 2025
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Online Access:https://arxiv.org/abs/2507.16561
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author Ahmed, Shamail
Rossi, Federico
Huo, Hanyu
Haust, Johannes
Hueppe, Franziska
Belz, Juergen
Beyer, Andreas
Janek, Juergen
Volz, Kerstin
author_facet Ahmed, Shamail
Rossi, Federico
Huo, Hanyu
Haust, Johannes
Hueppe, Franziska
Belz, Juergen
Beyer, Andreas
Janek, Juergen
Volz, Kerstin
contents Silicon offers great promise as a potential anode active material and the optimum alternative to lithium metal in all-solid-state lithium-ion batteries. However, its practical application is limited by severe volume expansion (~300%) during lithiation, leading to cracking upon delithiation. In this study, we investigated the microstructural evolution of microcrystalline silicon electrodes in a solid-electrolyte-free environment using cryogenic scanning transmission electron microscopy (STEM) during electrochemical cycling. A controlled workflow prevents ambient exposure, and cryo-TEM ensures structural integrity. After the first lithiation, the electrode shows a heterogeneous mix of crystalline Li15Si4, various amorphous LixSi phases, and residual crystalline silicon. After delithiation, the structure becomes predominantly amorphous with thread-like features and minimal remaining crystallinity. By the 10th delithiation, the microstructure is more uniform, with thread-like regions mainly at grain boundaries. Our results reveal that starting from a crystalline phase, a stationary microstructure emerges in bulk silicon only after several cycles. Thus, to have a more controlled behavior of the electrode and minimize cracking, the starting material should be carefully chosen along with an optimized electrode architecture to help stabilize the microstructure throughout cycling.
format Preprint
id arxiv_https___arxiv_org_abs_2507_16561
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Microstructure of Silicon Anodes in Solid-State Batteries -- From Crystalline to Amorphous
Ahmed, Shamail
Rossi, Federico
Huo, Hanyu
Haust, Johannes
Hueppe, Franziska
Belz, Juergen
Beyer, Andreas
Janek, Juergen
Volz, Kerstin
Materials Science
Silicon offers great promise as a potential anode active material and the optimum alternative to lithium metal in all-solid-state lithium-ion batteries. However, its practical application is limited by severe volume expansion (~300%) during lithiation, leading to cracking upon delithiation. In this study, we investigated the microstructural evolution of microcrystalline silicon electrodes in a solid-electrolyte-free environment using cryogenic scanning transmission electron microscopy (STEM) during electrochemical cycling. A controlled workflow prevents ambient exposure, and cryo-TEM ensures structural integrity. After the first lithiation, the electrode shows a heterogeneous mix of crystalline Li15Si4, various amorphous LixSi phases, and residual crystalline silicon. After delithiation, the structure becomes predominantly amorphous with thread-like features and minimal remaining crystallinity. By the 10th delithiation, the microstructure is more uniform, with thread-like regions mainly at grain boundaries. Our results reveal that starting from a crystalline phase, a stationary microstructure emerges in bulk silicon only after several cycles. Thus, to have a more controlled behavior of the electrode and minimize cracking, the starting material should be carefully chosen along with an optimized electrode architecture to help stabilize the microstructure throughout cycling.
title Microstructure of Silicon Anodes in Solid-State Batteries -- From Crystalline to Amorphous
topic Materials Science
url https://arxiv.org/abs/2507.16561