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The performance of a lithium metal battery (LMB) with liquid electrolytes depends on the realization of a stable solid electrolyte interphase (SEI) on the Li anode surface. According to a recent experiment, a high-concentrated (HC) dual-salt electrolyte is effective in modulating the SEI formation and improving the battery performance. However, the underlying reaction mechanism between this HC dual-salt electrolyte and the lithium metal anode surface remains unknown. To understand the SEI formation mechanism, we first performed 95 ps ab initio Molecular Dynamics (AIMD) simulation and then extend this AIMD simulation to another 1 ns by using Hybrid ab Initio and Reactive Molecular Dynamics (HAIR) to investigate the deep reactions of such dual-salt electrolytes consists of lithium difluorophosphate and lithium bis(trifluoromethanesulfonyl)imide in dimethoxyethane (DME) solvent at lithium metal anode surface. We observed the detailed reductive decomposition processes of DFP− and TFSI−, which include the formation pathway of CF3 fragments, LiF, and LixPOFy, the three main SEI components observed experimentally. Furthermore, after extending the simulation to 1.1 ns via the HAIR scheme, the decomposition reactions of DME solvent molecules were also observed, producing LiOCH3, C2H4, and precursors of organic oligomers. These microscopic insights provide important guidance in designing the advanced dual-salt electrolytes for developing high-performance LMB. [ABSTRACT FROM AUTHOR]