Remote controlled interfacial engineering via high entropy alloy cathodic pre-catalysis unlocks high-performance Li–LiNO₃ batteries

Lithium–lithium nitrate batteries are regarded as a promising high-capacity alternative to lithium–ion batteries due to their superior specific capacity, which is enabled by the unique dual role of LiNO₃ as both lithium salt and active cathode material. However, their practical application is hindered by the unstable lithium anode interface and sluggish cathode kinetics, resulting in limited cycle life and safety concerns. Herein, this work presents a remote interfacial regulation engineering via nanoscale ZnPtFeCuNiCo High-entropy alloy (ZPFCNC–HEA) cathode catalyst. During the initial resting phase, this catalyst effectively decomposes LiNO₃ in the electrolyte to directionally generate active nitrogen intermediates (LiNO₂/LiNO). These intermediates spontaneously migrate to the anode interface, where they induce the in–situ formation of a Li₃N-rich solid electrolyte interphase (SEI) during subsequent electrochemical cycling, achieving remote interfacial regulation. The resulting SEI significantly enhances interfacial stability and charge transfer efficiency. Combined with the exceptional catalytic activity of ZPFCNC–HEA toward the NO₃⁻/NO₂⁻ redox reaction, the assembled Li–LiNO₃ battery employing this cathode catalyst delivers a remarkable specific capacity of 15019 mAh g⁻¹ and maintains stable operation for over 700 cycles. Furthermore, an Ah-level pouch cell (1.522 Ah) is demonstrated, validating a novel remote interfacial regulation of SEI strategy for practical high–energy batteries.