Hanjun Li, Yecheng Leng, Wanbao Wu, Tingting Wu, Yuchen Yang, Xuyang Zhang, Chaowei Li, Mingjin Cui, Xinghai Ning, Xi Zhu, Yu Zhao, Haoshen Zhou, Yu Ding
The methodology integrates data-driven high-throughput screening with rational molecular engineering, offering an efficient route toward high-performance, cost-effective, and environmentally benign electrolytes for extreme-condition batteries.
Electrolyte design for advanced lithium-metal batteries faces a persistent challenge: reconciling physicochemical performance, economic viability, and environmental sustainability within a single molecular framework. Here, we introduce an AI-guided protocol that integrates molecular and electronic descriptors to rapidly screen over 1000 solvent candidates. Our design principle centers on introducing asymmetric alkyl or alkoxy substituents along the ether backbone, creating an electronic and steric environment that simultaneously modulates dipole moment distribution, liquid range, and electrochemical potential window. Experimental and computational results demonstrate that extending the ether chain length enhances oxidative stability and volatility resistance through multidentate coordination, eliminating the need for conventional fluorination. Concurrently, molecular asymmetry introduces electronic inequivalence among the coordinating oxygen atoms, generating a solvation environment that preserves the thermodynamic stability of multidentate binding while kinetically facilitating desolvation via a weakened coordination site. The optimized fluorine-free asymmetric ether electrolyte enables Li || LiCoO2 (LCO) coin cells to retain 81.2% of room-temperature capacity at -40 °C and maintain 91.3% capacity after 300 cycles. A 301 Wh kg-1 (1 Ah) pouch cell retains 71.9% capacity at -35 °C, and a 475 Wh kg-1 (5 Ah) pouch cell operates under lean electrolyte conditions (1 g Ah-1). This molecular asymmetry strategy within fluorine-free ether frameworks represents a paradigm shift, uniquely unifying high-voltage stability, volatility resistance, and reliable ultralow-temperature operation. The methodology integrates data-driven high-throughput screening with rational molecular engineering, offering an efficient route toward high-performance, cost-effective, and environmentally benign electrolytes for extreme-condition batteries.