Given the limitations inherent in current intercalation‐based Li‐ion batteries, much research attention has focused on potential successors to Li‐ion batteries such as lithium–sulfur (Li‐S) batteries and lithium–oxygen (Li‐O2) batteries. In order to realize the potential of these batteries, the use of metallic lithium as the anode is essential. However, there are severe safety hazards associated with the growth of Li dendrites, and the formation of “dead Li” during cycles leads to the inevitable loss of active Li, which in the end is undoubtedly detrimental to the actual energy density of Li‐metal batteries. For Li‐metal batteries under practical conditions, a low negative/positive ratio (N/P ratio), a electrolyte/cathode ratio (E/C ratio) along with a high‐voltage cathode is prerequisite. In this Review, we summarize the development of new electrolyte systems for Li‐metal batteries under practical conditions, revisit the design criteria of advanced electrolytes for practical Li‐metal batteries and provide perspectives on future development of electrolytes for practical Li‐metal batteries.
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