Enabling Ultra‐High‐Rate Performance in Lithium Metal Batteries via a Phenyl‐1 H ‐tetrazole‐Derived Li 3 N‐Rich Solid Electrolyte Interphase

Lithium metal batteries (LMBs) have attracted considerable interest due to their high energy density and excellent cycling stability. However, uncontrolled lithium dendrite growth and low charge transfer rates during fast charging and discharging significantly limit their practical applications. These challenges can be mitigated by constructing a Li 3 N‐rich solid electrolyte interphase (SEI). In this study, a Li 3 N‐rich SEI is in‐situ formed by introducing 0.05 wt.% 5‐phenyl‐1 H ‐tetrazole lithium salt (PTL) as an electrolyte additive. Computational and experimental analyses reveal that this near‐zero‐valent‐nitrogen rich additive not only notably enhances Li + diffusion but also effectively suppresses lithium dendrite growth. Consequently, Li||Li symmetric cells exhibit a low polarization voltage (50.0 mV) and excellent rate capability during cycling. PTL also promotes the formation of more uniform cathode electrolyte interphase (CEI), enabling Li||LiFePO 4 (LFP) cells to retain 77.99% of their capacity after 2,500 cycles at an ultra‐high rate of 10 C. Furthermore, 1.48 Ah commercial Graphite (Gr)||LFP pouch cells with a high active mass achieve 95.95% capacity retention after 120 cycles at 1 C. This work presents a simple and effective strategy for realizing rapid charging and discharging of LMBs.