Magnesium-Based Anode Materials for Metal-Air/Seawater Batteries：Advances and Challenges AITranslate

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY25040003

Chinese Library Classification Number:TQ152

Citation Information:

In the context of the global energy transition，the development of advanced energy storage systems is crucial for achieving sustainable development. Among these，magnesium-air batteries have attracted considerable attention due to their significant advantages，including high theoretical energy density，low cost，and environmental friendliness. Magnesium，serving as the sole active material in this battery system，directly determines the discharge capacity and energy density. However，the practical application of magnesium-air batteries is substantially constrained by severe anodic self-corrosion and passivation caused by discharge products. In addition，researchers highlight the "negative difference effect"，wherein the corrosion rate of magnesium can paradoxically increase under higher anodic polarization，leading to unexpected material loss and reduced anodic utilization. This review systematically addressed the primary technological bottlenecks and current research progress associated with magnesium-air batteries，emphasizing strategies aimed at optimizing anode performance. The analysis specifically examined alloying methods to introduce beneficial elements that enhance the anode's microstructure，as well as thermal treatment and plastic deformation techniques to refine grain size and optimize crystallographic texture. A core finding was that refining grain structures and achieving homogeneous distribution of secondary phases significantly enhanced anodic discharge efficiency and corrosion resistance. Specifically，grain refinement increased the density of active reaction sites at grain boundaries，promoting electrochemical reaction kinetics and producing thinner，more brittle discharge products that crack and detach more readily. This process maintained active contact between the anode and electrolyte，thus improving discharge stability and capacity. The uniform distribution of secondary phases further aided in creating evenly distributed corrosion sites，minimizing localized corrosion，and stabilizing the discharge voltage. Texture optimization was recognized as another critical factor for improving electrochemical behavior. Certain crystallographic orientations，when preferentially aligned，could promote more uniform dissolution during discharge，yielding improved electrode utilization. Indeed，studies reported that fine-tuning crystallographic texture led to thinner，more uniform oxide and hydroxide layers on the anode surface，reducing the blockage that typically hinders ionic transport and electron flow. As such，texture engineering stood out as a promising approach in tandem with alloy design. Detailed discussions illustrated that alloying magnesium with elements such as Al，Zn，Li，Ca，Bi，Sr，and various rare earth elements （RE） could significantly mitigate anodic corrosion，reduce parasitic hydrogen evolution，and improve discharge properties. Rare earth elements，including Gd，Y，and Ce，had shown promise in promoting grain refinement，modifying second-phase morphologies，and stabilizing discharge processes. Thermal treatments also played a vital role. Homogenization annealing could reduce compositional segregation and the coarseness of secondary phases，thereby improved corrosion resistance and facilitating more uniform dissolution. Solid-solution treatments could reduce the volume fraction of coarse intermetallics，allowing for a more continuous and uniform passivation layer. Meanwhile，aging treatments could precipitate finely dispersed intermetallic particles，boosting mechanical strength while adjusting local galvanic interactions. Plastic deformation methods-such as extrusion，rolling，equal channel angular pressing （ECAP），friction stir processing （FSP），and multidirectional forging （MDF）-further refined grain size and redistribute second-phase particles. Extrusion dispersed detrimental phases more homogeneously throughout the matrix. Rolling processes could tune crystallographic texture，resulting in improved corrosion resistance and higher anodic utilization. ECAP and MDF subjected the alloy to severe plastic deformation，promoting ultrafine grain structures and breaking apart large，continuous second-phase particles. FSP facilitated localized modifications，enabling microstructure homogenization and elimination of casting defects. These techniques not only enhanced corrosion performance but also stabilized discharge voltages and increase current efficiencies. Notably，magnesium-air batteries exhibited distinct operational differences compared to other metal-air counterparts-such as zinc-air or aluminum-air-given magnesium's relatively low electrode potential and high chemical reactivity. The formation of a porous discharge layer，predominantly composed of Mg（OH）₂，could significantly affect anodic dissolution kinetics. Hence，controlling discharge-product morphology and shedding behavior was central to stable long-term performance. Finally，this review provided an outlook on the prospective development of magnesium anode materials. Future research should concentrate on elucidating multi-scale relationships among grain structure，second-phase distribution，crystallographic texture，and electrochemical performance. Novel alloy systems-particularly those incorporating multiple beneficial elements without exacerbating self-corrosion-were paramount. Likewise，advanced manufacturing techniques，in-situ characterization，and computational modeling would refine the understanding of corrosion and discharge processes. Together，these approaches aimed to establish a robust framework for the large-scale application of magnesium-air batteries，supporting their potential to serve as lighter，environmentally friendly，and economically viable power solutions in consumer electronics，marine systems，and grid-level energy storage.