The conventional LiPF6/carbonate-based electrolytes have been widely used in graphite (Gr)-based lithium (Li) ion batteries (LIBs) for more than 30 years because a stable solid electrolyte interphase (SEI) layer forms on the graphite surface and enables its long-term cycling stability. However, few of these electrolytes are stable under the more stringent conditions needed with a Li metal anode (LMA) and other anodes, such as silicon (Si), which exhibit large volume changes during charge/discharge processes. Many different approaches have been developed lately to stabilize Li metal batteries (LMBs) and Si-based LIBs. From this aspect, localized high-concentration electrolytes (LHCEs) have unique advantages: not only are they stable in a wide electrochemical window, they can also form stable SEI layers on LMA and Si anode surfaces to enable their long-term cycling stability. The ultrathin SEI layer formed on a Gr anode can also improve the safety and high-rate operation of conventional LIBs. In this paper, we give a brief summary of our recent work on LHCEs, including their design principle and applications in both LMBs and LIBs. A perspective on the future development of LHCEs is also discussed.

Lithium metal batteries (LMBs) are one of the most promising candidates for next‐generation high‐energy‐density rechargeable batteries. Solid electrolyte interphase (SEI) on Li metal anodes plays a significant role in influencing the Li deposition morphology and the cycle life of LMBs. However, a thorough understanding on the mechanisms of SEI formation and evolution is still inadequate. In this review, the progress in understanding structures, properties, and influencing factors of SEI, as well as efficient strategies of tailoring SEI are focused upon. First, the compositions, models, and recent progress in characterizing atomic structures of SEI are summarized. Second, the properties of SEI, including electronic conduction, ionic conduction, stability, and mechanical properties are elucidated. Structures and properties of SEI are greatly affected by multiple factors, thus interactions between these factors and SEI are systematically discussed. Correlations of SEI with Li deposition morphology, rate capability, and cycle life are further summarized. Moreover, efficient strategies of tailoring SEI with desired properties, including in situ SEI and ex situ SEI, are also reviewed. Finally, future directions, including in‐operando techniques, multi‐modality approaches for characterization of SEI, and artificial intelligence assisted understanding of correlations between electrolyte components and SEI properties are proposed.

Functional electrolyte is the key to stabilize the highly reductive lithium (Li) metal anode and the high-voltage cathode for long-life, high-energy-density rechargeable Li metal batteries (LMBs). However, fundamental mechanisms on the interactions between reactive electrodes and electrolytes are still not well understood. Recently localized high-concentration electrolytes (LHCEs) are emerging as a promising electrolyte design strategy for LMBs. Here, we use LHCEs as an ideal platform to investigate the fundamental correlation between the reactive characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. The effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate, and ether) on the stability of high-voltage LMBs are systematically studied. The stabilities of electrodes in different LHCEs indicate the intrinsic synergistic effects between the salt and the solvent when they coexist on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte interphases and thus the battery performances.

Perspective on recent improvements in experiment and theory towards realizing lithium metal electrodes with liquid electrolytes.

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