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Multi-electron reaction can be regarded as an effective way of building high-energy systems (＞ 500 W h kg-1).However,some confusions hinder the development of multi-electron mechanisms,such as clear concept,complex reaction,material design and electrolyte optimization and full-cell fabrication.Therefore,this review discusses the basic theories and application bottlenecks of multi-electron mechanisms from the view of thermodynamic and dynamic principles.In future,high-energy batteries,metal anodes and multi-electron cathodes are promising electrode materials with high theoretical capacity and high output voltage.While the primary issue for the multi-electron transfer process is sluggish kinetics,which may be caused by multiple ionic migration,large ionic radius,high reaction energy barrier,low electron conductivity,poor structural stability,etc.,it is urgent that feasible and versatile modification methods are summarized and new inspiration proposed in order to break through kinetic constraints.Finally,the remaining chagenges and future research directions are revealed in detail,involving the search for high-energy systems,compatibility of full cells,cost control,etc.