Utilization of Li-Rich Phases in Aluminum Anodes for Improved Cycling Performance through Strategic Thermal Control

Lithium-ion batteries with aluminum anodes had appeared to resolve critical dendrite issues of lithium metal cells in the 1970s. However, the poor cycling performance attributed to aluminum anodes would lead to their obsolescence. In this work, we demonstrate how strategic thermal control in cycling aluminum anodes circumvents the problematic α/β phase transformations that yield poor cycling life. Instead, electrochemical formation of the Li₃Al₂ and Li_2-xAl phases necessitates temperatures slightly above ambient, as the Li₃Al₂ and Li_2-xAl phases are key enablers for high capacity and stable cycling. While delivering a competitive capacity level (ca. 1 Ah kg^-1-Al), cycling among those higher-order phases is found to be significantly improved, from several cycles to 100 cycles with ca. 67% capacity retention. Importantly, because modern battery charging is likely to occur above room temperature due to ohmic heating, the thermal conditions explored here are expected to be realized in a variety of applications. Furthermore, we show that elevated temperature is not necessary for aluminum anode delithiation, thus creating additional synergies with many practical scenarios.