The operational failure of lithium-ion batteries under extreme temperatures (−40~60 °C) stems primarily from electrolyte limitations. While prior efforts improved either low-temperature or high-temperature performance independently, holistic electrolyte design with practical validation remains elusive. Herein, we develop an all-climate electrolyte (ACE) through synergistic coordination of solvent, Li salt, and additive, achieving low viscosity (<10 mPa·s at −40 °C) and high ionic conductivity (7.0 mS cm⁻¹ at −40 °C). Raman and NMR spectra reveal MA and EC co-occupying Li⁺ solvation sheath while EMC acts as a diluent, enabling rapid ion transport. Consequently, LiFePO₄ (LFP)|graphite (Gr) cell delivers unprecedented cyclability: zero capacity decay over 500 cycles at 0 °C, stable operation across −40~60 °C, and 94.1% retention after 100 cycles at 45 °C in Ah-level pouch cells. XPS and SEM analysis demonstrate lithium difluorophosphate (LiDFP) and lithium bis(fluorosulfonyl)imide (LiFSI) collaboratively remodel SEI/CEI interphases, enriching them with LiF, Li₃PO₄, and Li₂SO₄. This inorganic-dominant architecture enhances interfacial Li⁺ kinetics and all-climate stability compared to the baseline electrolyte. Our tripartite electrolyte strategy provides a material-agnostic solution for all-climate energy storage.

The inherent limitations of conventional polyolefin separators, particularly their poor thermal stability and insufficient mechanical strength, pose significant safety risks for lithium-ion batteries (LIBs) by increasing susceptibility to thermal runaway. In this study, we developed a novel multilayer separator through sequential coating of a commercial polyethylene (PE) substrate with aluminum oxide (Al₂O₃), para-aramid (PA), and polyethylene wax microspheres (PEWMs) using a scalable micro-gravure process, denoted as SAPEAS, signifying a PE-based asymmetric structure separator with enhanced thermal shutdown and dimensional stability. The SAPEAS separator exhibits an early thermal shutdown capability at 105 °C, maintains structural integrity with negligible shrinkage at 180 °C, and demonstrates comprehensive performance enhancements, including enhanced mechanical strength (tensile strength: 212.3 MPa; puncture strength: 0.64 kgf), excellent electrolyte wettability (contact angle: 12.8°), a high Li⁺ transference number (0.71), superior ionic conductivity (0.462 mS cm⁻¹), outperforming that of commercial PE separators. In practical LFP|Gr pouch cells with ampere-hour (Ah) level capacity, the SAPEAS separator enables exceptional cycling stability with 97.9% energy retention after 1000 cycles, while significantly improving overcharge tolerance compared to PE. This work provides an effective strategy for simultaneously improving the safety and electrochemical performance of LIBs.