A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries.

He, Yubin; Wang, Chunyang; Zhang, Rui; Zou, Peichao; Chen, Zhouyi; Bak, Seong-Min; Trask, Stephen E; Du, Yonghua et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li<sup>0</sup>) battery applications because, in theory, their high elastic modulus provides better resistance to Li<sup>0</sup> dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm<sup>2</sup>. Key issues that contribute to the breakdown of OCEs include Li<sup>0</sup> penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent -CH<sub>3</sub>⋯CF<sub>3</sub> bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li<sup>0</sup> penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li<sup>0</sup>-Li<sup>0</sup> cells at 1 mA/cm<sup>2</sup>. Furthermore, by introducing a polyacrylate buffer layer between PCE and Li<sup>0</sup>-anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure.