solutions, explorative studies of the electro-redox couples, with the concurrent high retrievable capacity, enlarged nominal voltage gap, and rapid reaction kinetics, hold the key to promote the energy-dense battery construction at the extreme power output. [1] For the lithium ion batteries, the energy densities of traditional formats (LiCoO 2 /LiFePO 4 cathodes and graphite anodes) have approached their theoretical limits. [2] Alternatively, the unit cell prototyping of the high-capacity Li metal anode with the nickel-rich cathode can achieve the enhanced level of energy densities at the device level. [3,4] When soaking this electrode couples in the conventional carbonate-based electrolytes, however, the Fermi-energy incompatibility at the multiscale interface would cause the uncontrollable dendrite growth on the metallic foil and cathode structure collapse upon the high-voltage cycling. [5] Therefore, the reliable operation of the energy-dense battery necessitates the harmony balance of the enlarged voltage gap and the interfacial stability at multiple scales, yet still remains challenging.As the most attractive cathode type of the practical relevance, nickel-rich (Ni content >0.8) layered oxides exhibit the merits of the large specific capacity (>200 mAh g −1 ), environmental benignity and relative lower cost as compared to the LiCoO 2 cathode. Despite of the dominant nickel occupancy in the layered oxides for elevating the Li storage sites, the increased nickel ratio adversely deteriorates the cycle performance. The transition metal (TM) layer of the oxide structure at the highvoltage charged states would oxidize the carbonate solvents in the presence of moisture, leading to serious self-discharge rates upon the high-temperature storage. [6] Additionally, the hydrofluoric acid (HF) formed by the decomposition of the lithium hexafluorophosphate (LiPF 6 ) salt aggravates the TM ions (Co 2+ , Ni 2+ , and Mn 2+ ) dissolution and structural collapse of the layered cathode, meanwhile the TM species would deposit on the anode surface and degrade the solid electrolyte interface (SEI). [7] So far, a plethora of mitigation strategies were implemented to insulate the direct contact of the oxide particles with the electrolyte, for instance the exquisite coatings with The reliable operation of Li metal batteries suffers from cathode collapse due to high-voltage cycling, interfacial reactivity of the Li deposits, self-discharge at the elevated temperatures, as well as the power output deterioration in low-temperature scenarios. In contrast to the individual electrode optimization, herein, a hetero-layered separator with an asymmetric functional coating on polyethylene is proposed in response to the aforementioned issues: On the face-to-cathode side, the hybrid layer of the molecular sieve and sulfonated melamine formaldehyde can scavenge the hydrofluoric acid and moisture residues from the carbonate electrolyte, maintaining the cathode robustness in both the high-voltage cycling or high-temperature storage scenarios; while...