Spin‐Driven Electrocatalysis for Metal–Sulfur Batteries

ABSTRACT Metal–sulfur batteries (M–S) are recognized as promising candidates for next‐generation energy storage owing to their high theoretical specific energy, potential cost effectiveness, and environmental friendliness of earth‐abundant sulfur. Nevertheless, they still face significant challenges, including the sluggish sulfur conversion dynamics, polysulfide shuttling, and metal dendrite growth. Recent findings reveal that electron spin control overcomes these obstacles via optimizing the efficiency of electrocatalytic M–S chemistry reactions. Therefore, understanding the electron spin's role and regulating it in electrocatalysts is important for enhanced M–S battery performance. In this review, we first discuss the fundamental principles of spin‐driven sulfur conversion and metal deposition. Subsequently, we emphasize advanced strategies for regulating electron spin, involving defect manipulation, heterostructure modulation, single‐atom engineering, and magnetic field regulation. We also summarize the relevant characterization techniques for identifying spin configuration changes. In addition, we review electron spin manipulation optimized M–S batteries, including lithium–sulfur (Li–S), room‐temperature (RT) sodium–sulfur (Na–S), aluminum–sulfur (Al–S), and zinc–sulfur (Zn–S) batteries, offering specific examples and detailed discussion for improving battery application. Finally, this article offers insights into potential research directions in this emerging field, aiming to reveal underlying mechanisms of spin‐state regulation in optimizing catalytic M–S chemistry and stimulate further investigations in spin‐driven high‐energy‐density M–S battery applications.