Hierarchical Electrode Architecture Enabling Ultrahigh-Capacity LiFePO4 Cathodes with Low Tortuosity

Thickening electrodes are expected to increase the energy density of batteries. Unfortunately, the manufacturing issues, sluggish electrolyte infiltration, and restrictions on electron/ion transport seriously hamper the development of thick electrodes. In this work, an ultrathick LiFePO₄ (LFP) electrode with hierarchically vertical microchannels and porous structures (I-LFP) is rationally designed by combining the template method and the mechanical channel-making method. By using ultrasonic transmission mapping technology, it is proven that the open and vertical microchannels and interconnected pores can successfully overcome the electrolyte infiltration difficulty of conventional thick electrodes. Meanwhile, both the electrochemical and simulation characterizations reveal the fast ion transport kinetics and low tortuosity (1.44) in the I-LFP electrode. As a result, the I-LFP electrode delivers marked improvements in rate performance and cycling stability even under a high areal loading of 180 mg cm^-2. Moreover, according to the results of operando optical fiber sensors, the stress accumulation in the I-LFP electrode is effectively alleviated, which further confirms the improvement of mechanical stability.