The carbonate electrolyte chemistry is a primary determinant for the development of high-voltage lithium metal batteries (LMBs). Unfortunately, their implementation is greatly plagued by sluggish electrode interfacial dynamics and insufficient electrolyte thermodynamic stability. Herein, lithium trifluoroacetate-lithium nitrate (LiTFA-LiNO3 ) dual-salt additive-reinforced carbonate electrolyte (LTFAN) is proposed for stabilizing high-voltage LMBs. We reveal that 1) the in situ generated inorganic-rich electrode-electrolyte interphase (EEI) enables rapid interfacial dynamics, 2) TFA- preferentially interacts with moisture over PF6 - to strengthen the moisture tolerance of designed electrolyte, and 3) NO3 - is found to be noticeably enriched at the cathode interface on charging, thus constructing Li+ -enriched, solvent-coordinated, thermodynamically favorable electric double layer (EDL). The superior moisture tolerance of LTFAN and the thermodynamically stable EDL constructed at cathode interface play a decisive role in upgrading the compatibility of carbonate electrolyte with high-voltage cathode. The LMBs with LTFAN realize 4.3 V-NCM523/4.4 V-NCM622 superior cycling reversibility and excellent rate capability, which is the leading level of documented records for carbonate electrode.
Keywords: Dual-salt additive; Electric double layer; Lithium metal battery; Moisture tolerance.
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