Gallium-based liquid metals (GLMs) are promising anode materials for lithium-ion batteries due to their low-melting point, fluidity, high-electrical and -thermal conductivity, and high-theoretical capacity for Li (769 mAh/g, Li2Ga). Notably, GLMs undergo a reversible liquid-to-solid-to-liquid transition during lithiation and delithiation, enabling a self-healing mechanism that mitigates surface defects. This mechanism extends the cycle life of anodes utilizing GLMs either as active materials( 1–6 ) or in combination with high-volume expansion materials such as silicon (~400%)( 7–9 ).Fundamental studies on the self-healing mechanism of GLMs are limited. Previous investigations have primarily relied on macroscopic characterizations such as X-ray diffraction (XRD) in bulk electrodes( 3,10 ) or in situ transmission electron microscopy (TEM) on individual GLM nanoparticles (NPs) in solid-state cells open to the environment( 6,11 ). In this work, we adopt a multi-scale approach to gain insights into the (de)lithiation mechanism. We conducted: (1) in situ TEM observations of GLM NPs on a TEM grid current collector to simultaneously track lithiation/delithiation dynamics across multiple nanoparticles; (2) cryogenic TEM where GLM NPs on a TEM grid are cycled in a lithium-ion battery electrolyte, and the grid is subsequently transferred to a cryo-TEM for high-resolution interfacial characterization of the GLM NPs; and (3) cryogenic focused-ion beam tomography to analyze structural changes in a composite electrode comprised of GLM NPs, Super P carbon, and PVDF binder on a Cu current collector over continuous cycles within a coin or pouch cell. By investigating GLMs at multiple length scales, this study advances the understanding of how the lithiation/delithiation mechanism of GLM NPs influences capacity fade in lithium-ion batteries. In a broader context, this study establishes a framework for future multi-length scale investigations into battery materials.References Jin, X. et al. Transferring Liquid Metal to form a Hybrid Solid Electrolyte via a Wettability-Tuning Technology for Lithium-Metal Anodes. Adv. Mater. 34, 2200181 (2022).Zhu, M., Li, S., Li, B. & Yang, S. A liquid metal-based self-adaptive sulfur–gallium composite for long-cycling lithium–sulfur batteries. Nanoscale 11, 412–417 (2019).Guo, X. et al. A Self-Healing Room-Temperature Liquid-Metal Anode for Alkali-Ion Batteries. Adv. Funct. Mater. 28, 1804649 (2018).Pu, J. et al. Liquid Metal-Based Stable and Stretchable Zn-Ion Battery for Electronic Textiles. Adv. Mater. 36, 2305812 (2024).Liu, G. et al. Soft, Highly Elastic, and Discharge-Current-Controllable Eutectic Gallium–Indium Liquid Metal–Air Battery Operated at Room Temperature. Adv. Energy Mater. 8, 1703652 (2018).Huang, C. et al. Alkali-ion Batteries by Carbon Encapsulation of Liquid Metal Anode. Adv. Mater. n/a, 2309732.Hapuarachchi, S. N. S. et al. Utilizing Room Temperature Liquid Metals for Mechanically Robust Silicon Anodes in Lithium-Ion Batteries. Batter. Supercaps 1, 122–128 (2018).Ju, Z. et al. Assembled MXene–Liquid Metal Cages on Silicon Microparticles as Self-Healing Battery Anodes. Nano Lett. 24, 6610–6616 (2024).Zhao, Z. et al. Liquid Metal Remedies Silicon Microparticulates Toward Highly Stable and Superior Volumetric Lithium Storage. Adv. Energy Mater. 12, 2103565 (2022).Wang, K. et al. Core-shell GaSn@rGO nanoparticles as high-performance cathodes for room-temperature liquid metal batteries. Scr. Mater. 217, 114792 (2022).Liang, W. et al. Nanovoid Formation and Annihilation in Gallium Nanodroplets under Lithiation–Delithiation Cycling. Nano Lett. 13, 5212–5217 (2013).
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