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This paper presents an overview of the various types of lithium salts used to conduct Li⁺ ions in electrolyte solutions for lithium rechargeable batteries. More emphasis is paid towards lithium salts and their ionic conductivity in conventional solutions, solid–electrolyte interface (SEI) formation towards carbonaceous anodes and the effect of anions on the aluminium current collector. The physicochemical and functional parameters relevant to electrochemical properties, that is, electrochemical stabilities, are also presented. The new types of lithium salts, such as the bis(oxalato)borate (LiBOB), oxalyldifluoroborate (LiODFB) and fluoroalkylphosphate (LiFAP), are described in detail with their appropriate synthesis procedures, possible decomposition mechanism for SEI formation and prospect of using them in future generation lithium‐ion batteries. Finally, the state‐of‐the‐art of the system is given and some interesting …