Maximizing interface stability in all-solid-state lithium batteries through entropy stabilization and fast kinetics.

Kong, Xiangkun; Gu, Run; Jin, Zongzi; Zhang, Lei; Zhang, Chi; Xiang, Wenyi; Li, Cui; Zhu, Kang et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

The positive electrode|electrolyte interface plays an important role in all-solid-state Li batteries (ASSLBs) based on garnet-type solid-state electrolytes (SSEs) like Li<sub>6.4</sub>La<sub>3</sub>Zr<sub>1.4</sub>Ta<sub>0.6</sub>O<sub>12</sub> (LLZTO). However, the trade-off between solid-solid contact and chemical stability leads to a poor positive electrode|electrolyte interface and cycle performance. In this study, we achieve thermodynamic compatibility and adequate physical contact between high-entropy cationic disordered rock salt positive electrodes (HE-DRXs) and LLZTO through ultrafast high-temperature sintering (UHS). This approach constructs a highly stable positive electrode|electrolyte interface, reducing the interface resistance to 31.6 Ω·cm<sup>2</sup> at 25 °C, making a 700 times reduction compared to the LiCoO<sub>2</sub> | LLZTO interface. Moreover, the conformal and tight HE-DRX | LLZTO solid-state interface avoids the transition metal migration issue observed with HE-DRX in liquid electrolytes. At 150 °C, HE-DRXs in ASSLBs (Li|LLZTO | HE-DRXs) exhibit an average specific capacity of 239.7 ± 2 mAh/g at 25 mA/g, with a capacity retention of 95% after 100 cycles relative to the initial cycle-a stark contrast to the 76% retention after 20 cycles at 25 °C in conventional liquid batteries. Our strategy, which considers the principles of thermodynamics and kinetics, may open avenues for tackling the positive electrode|electrolyte interface issue in ASSLBs based on garnet-type SSEs.