Multivalent metal-ion-based energy storage: A comprehensive review of challenges and technological prospects
Pan X. Zhong Z. Supiyeva Z. Abbas Q.
5 November 2025Elsevier Ltd
Journal of Alloys and Compounds
2025#1044
Multivalent metal ions (MMIs) such as Zn²⁺, Mg²⁺, Al³ ⁺, and Ca²⁺ have attracted significant attention for energy storage systems (ESS) due to their high theoretical capacity (e.g., Zn: 820 mAh/g, Al: 2980 mAh/g), cost-effectiveness, and enhanced safety. This review offers a timely and comprehensive analysis of recent advances in MMI-based ESS, with a focus on material design, electrolyte engineering, and underlying mechanisms. We systematically summarize innovative strategies for enhancing the performance of cathode materials (e.g., layered oxides, polyanionic compounds, and organic electrodes) and anode materials (including metal, alloy, and intercalation-type electrodes), highlighting achieved cycle life improvements. Furthermore, the advantages and limitations of various electrolyte systems—aqueous (conductivity ≈ 0.5–1 S/cm), organic (≈ 1–10 mS/cm), and solid-state (≈ 10⁻⁴–10⁻³ S/cm)—are critically examined in relation to interfacial stability and ion transport kinetics. Mechanistic insights into ion diffusion barriers, solvation effects, and interfacial charge transfer are elucidated. The application potential of MMI-ESS is evaluated in specific use cases, including grid-scale storage, wearable electronics such as flexible health monitors, and micro-devices like embedded sensors, while addressing challenges of electrode degradation, metal dendrite growth, and interfacial instability. Finally, forward-looking strategies involving machine learning-assisted material discovery, interface engineering, and advanced characterization techniques are proposed to accelerate the commercialization of multivalent ion-based energy storage technologies.
Battery , Electrochemical mechanisms , Interface engineering , Metal-ion technology , Multivalent ions , Nanostructured compounds , Supercapacitor
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Zhongshan Advanced New Functional Materials Engineering Technology Research Center, Zhongshan Polytechnic, Zhongshan, 528400, China
Faculty of Chemical Technology, Poznan University of Technology, Berdychowo 4, Poznan, 60965, Poland
Laboratory of Engineering Profile, Satbayev University, Almaty, Kazakhstan
Faculty of Chemistry and Chemical Technology, Al-Farabi Kazakh National University, 71 al-Farabi Ave., Almaty, 050040, Kazakhstan
Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, Graz, 8010, Austria
Zhongshan Advanced New Functional Materials Engineering Technology Research Center
Faculty of Chemical Technology
Laboratory of Engineering Profile
Faculty of Chemistry and Chemical Technology
Institute for Chemistry and Technology of Materials
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