Effect of Zn Addition on the Microstructure and Discharge Performance of Mg-Al-Mn-Ca Alloys for Magnesium-Air Batteries

This study explores the effects of Zn addition through micro-alloying on the microstructure and discharge performance of Mg-Al-Mn-Ca alloy anodes for magnesium-air batteries. The results show that the second-phase particles (d > 1 μm) in a Mg-Al-Mn-Ca alloy promote dynamic recrystallization (DRX) via particle-stimulated nucleation (PSN), resulting in a uniform equiaxed grain structure and fiber texture. In contrast, Zn and Ca co-segregation in a Mg-Al-Mn-Ca-Zn alloy facilitates continuous dynamic recrystallization (CDRX) and, combined with the PSN mechanism, forms a unique structure where three types of grains with different grain boundary densities coexist. The addition of Zn and Ca effectively reduces the c/a axis ratio, promoting texture homogenization. The Mg-Al-Mn-Ca alloy exhibits rough discharge surfaces due to simultaneous discharge at numerous grain boundaries and severe hydrogen evolution corrosion from micro-galvanic effects, inducing the chunk effect (CE). Conversely, the structure where three types of grains with different grain boundary densities coexist in the Mg-Al-Mn-Ca-Zn alloy promotes discharge product detachment through stress cracking, achieving uniform discharge and significantly enhancing discharge performance. The uniform texture reduces hydrogen evolution corrosion, improving anode utilization. This study demonstrates that controlling the microstructure, particularly grain boundary density and grain texture, enables the development of high-performance Mg-Al-Mn-Ca-Zn alloy anodes, especially at higher current densities, offering a new strategy for designing efficient magnesium alloy anode materials.