The aluminum chemistry involved redox mechanisms in transition metal dichalcogenides

Transition metal dichalcogenides (TMDs) featured an open framework structure and versatile electronic properties are attractive for their higher capacitance when used as cathodes for aluminum-ion batteries (AIBs). However, the inexhaustive understanding of cell chemistry involving complicated charge transfer stalls the deployment of this type AIBs electrode materials. Here the sulfide materials of MS2 (M = Fe, Ni, Co) served as emblematic conversion-type electrodes are taken as models to shed light on the regularity among the Al storage mechanisms in TMDs cathodes. To explain such chemistry, we therefore interrogate the redox mechanisms between MS2 (M = Fe, Ni, Co) from a broad range of experimental and mechanistic characterization perspectives. Remarkably, as indicated by characterization results, the detailed Al insertion and removal processes occurring in MS2 (M = Fe, Ni, Co) cathodes are revealed, accompanied by the anionic-redox reaction of sulfide anion (S2−), whereas the valence state transitions of the metal element in CoS2 (Co2+∼Co3+) also occur simultaneously during the insertion/extraction of Al3+. Using theoretical calculations, we further clarify the essential reasons for the mechanistic discrepancy, and discuss the energy storage regularity in TMDs. These foundations not only contribute to a profound understanding for the charge storage mechanisms in TMDs but also expand the palette of property boosting electrode materials for practical AIBs.