Electronic State‐Modulated Ni₄N/Zn₃N₂ Heterogeneous Nanosheet Arrays Toward Dendrite‐Free and Kinetic‐Enhanced Li‐S Full Batteries

Abstract The applications of lithium (Li)–sulfur (S) batteries are simultaneously hampered by the unlimited dendritic Li growth and the sluggish redox kinetics of polysulfides (LiPSs). In this work, an electronic state‐modulated Ni₄N/Zn₃N₂ heterogeneous nanosheet arrays is painstakingly fabricated on the surface of carbon cloth (CC@Ni₄N/Zn₃N₂) as an efficient bi‐service host to promote uniform Li deposition and boost efficient LiPSs catalysis. It is found that the electronic structure of Ni₄N/Zn₃N₂ heterostructure is modulated to realize a rational transition metal d‐band center, and its built‐in electric field (BIEF) within the heterointerfaces facilitates the interfacial charge transfer, resulting in low Li deposition/migration energy barrier and efficient LiPSs adsorption/catalytic conversion kinetics. As a result, the as‐prepared CC@Ni₄N/Zn₃N₂‐Li anode can enable the Li||Li symmetrical cells to possess a long‐term lifespan over 500 h even at 10 mA cm⁻²/20 mAh cm⁻², and the as‐assembled LiNi_0.8Co_0.1Mn_0.1O₂||CC@Ni₄N/Zn₃N₂‐Li full cell also shows an excellent cycling performance (95.8% capacity retention after 100 cycles). When used for both S and Li loading, the as‐assembled CC@Ni₄N/Zn₃N₂‐S||CC@Ni₄N/Zn₃N₂‐Li full cell exhibits an outstanding cycling stability (744 mAh g⁻¹ after 1000 cycles at 2C). This work highlights the great potential of heterostructures for fabricating ideal bi‐serve hosts for both Li and S electrodes.