Lithium diffusion-controlled Li-Al alloy negative electrode for all-solid-state battery.

Jeon, Yuju; Lee, Dong Ju; Zheng, Hongkui; Behara, Sesha Sai; Lee, Jung-Pil; Wu, Junlin; Li, Feng; Tang, Wei et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Metal alloy negative electrodes are promising candidates for lithium all-solid-state batteries due to their high specific capacity and low cost. However, chemo-mechanical degradation and atomic transport limitations in the solid state remain unresolved challenges. Herein, we demonstrate a lithium-aluminum alloy negative electrode design (Li<sub>x</sub>Al<sub>1</sub>, x = molar ratio of lithium to aluminum) based on a comprehensive understanding of the underlying diffusion mechanisms within the lithium-poor α (0 ≤ x ≤ 0.05) and lithium-rich β phases (0.95 ≤ x ≤ 1). The lithium-aluminum alloy negative electrodes with a higher lithium to aluminum ratio facilitate lithium migration through the β-LiAl phases, which serve as highly lithium-conductive channels with a lithium diffusion coefficient that is ten orders of magnitude higher than that of the α phase. In addition, a bulk dense negative electrode and an intimate negative electrode-electrolyte interface is demonstrated in the cross-sections of the lithium-aluminum alloy negative electrodes. Consequently, a high-rate capability of 7 mA cm<sup>-2</sup> is attained in LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub>-based full-cell operation. The optimal cell configuration of Li<sub>0.5</sub>Al<sub>1</sub> | |LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> shows stable lithium reversibility during 2000 cycles with a capacity retention of 83% at 4 mA cm<sup>-2</sup> with a LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> loading of 5 mAh cm<sup>-2</sup>.