A 3D Lithiophilic Mo2N‐Modified Carbon Nanofiber Architecture for Dendrite‐Free Lithium‐Metal Anodes in a Full Cell

The pursuit for high‐energy‐density batteries has inspired the resurgence of metallic lithium (Li) as a promising anode, yet its practical viability is restricted by the uncontrollable Li dendrite growth and huge volume changes during repeated cycling. Herein, a new 3D framework configured with Mo2N‐mofidied carbon nanofiber (CNF) architecture is established as a Li host via a facile fabrication method. The lithiophilic Mo2N acts as a homogeneously pre‐planted seed with ultralow Li nucleation overpotential, thus spatially guiding a uniform Li nucleation and deposition in the matrix. The conductive CNF skeleton effectively homogenizes the current distribution and Li‐ion flux, further suppressing Li‐dendrite formation. As a result, the 3D hybrid Mo2N@CNF structure facilitates a dendrite‐free morphology with greatly alleviated volume expansion, delivering a significantly improved Coulombic efficiency of ≈99.2% over 150 cycles at 4 mA cm−2. Symmetric cells with Mo2N@CNF substrates stably operate over 1500 h at 6 mA cm−2 for 6 mA h cm−2. Furthermore, full cells paired with LiNi0.8Co0.1Mn0.1O2 (NMC811) cathodes in conventional carbonate electrolytes achieve a remarkable capacity retention of 90% over 150 cycles. This work sheds new light on the facile design of 3D lithiophilic hosts for dendrite‐free lithium‐metal anodes. A 3D lithiophilic Mo2N@CNF structure is established as a Li host to mitigate Li‐dendrite growth and volume changes during repeated Li plating/stripping. With the Mo2N@CNF substrate, symmetric cells stably operate over 1500 h at 6 mA cm−2, and full cells paired with NMC811 cathodes in carbonate electrolytes achieve a high capacity retention of 90% after 150 cycles.