Wei Wang, Wang Qiao, Zhuo Chen, Jialei Chen, Shan Chen, Zhuang Zhao, Xuelong Liao, Wenge Song, Rong Huang, Tiantian Lu, Youzeng Li, Haonan Liu, Jiacheng Sun, Xing Xu, Zhenhua Yan, Qing Zhao, Zhongfan Liu, Jun Chen, Huan Wang
Low-temperature Li||CFx batteries undergo performance degradation due to the insulating nature of CFx and sluggish Li+ kinetics. Herein, we present a dual-modification strategy integrating porous positive electrode architecture design with customized electrode-electrolyte interphase engineering to overcome these limitations. Our approach features: (i) plasma-enhanced chemical vapor deposition-constructed mesoporous CFx with conformal carbon coating, and (ii) electrolyte-mediated in situ formation of a sulfur-rich inorganic interphase layer on CFx surface. The engineered porous framework establishes efficient Li+ diffusion channels, while the electrolyte-derived interphase significantly enhances Li+ transport and desolvation kinetics. Moreover, the carbon coating substantially improves electronic conductivity and suppresses LiF stacking. The optimized Li||CFx system delivers capacities of 428.4 mAh g-1 at -50 °C and 2 A g-1, and 333.4 mAh g-1 at -70 °C and 0.1 A g-1. Practical 5 Ah pouch cells deliver competitive specific energies of 470 and 332 Wh kg-1 at -50 and -70 °C under 0.01 A g-1, respectively.