Advances in Mechanisms and Computational Insights into Calcium-Based Batteries

The escalating demand for advanced energy storage is fueling research into multivalent battery systems. Calcium-based batteries have emerged as a pivotal candidate due to their compelling advantages, including high natural abundance, low redox potential, and competitive theoretical energy density. However, their practical development is hindered by considerable challenges arising from the complex electrochemistry of the multivalent Ca²⁺ ion. This review provides a methodical examination of the fundamental charge storage mechanisms in these systems, encompassing intercalation, conversion, organic redox, and alloying reactions. Through multi-scale computational modeling, primarily utilizing DFT and MD simulations, these mechanisms are examined in depth at the microscopic scale. We highlight how theoretical simulation offers critical guidance for experimental work, facilitating accelerated performance optimization. Finally, we outline prospective research directions and stress the vital synergy between theory and experiment as essential for advancing practical calcium-based batteries.