Nano-channel-based physical and chemical synergic regulation for dendrite-free lithium plating

Uncontrollable dendrite growth resulting from the non-uniform lithium ion (Li⁺) flux and volume expansion in lithium metal (Li) negative electrode leads to rapid performance degradation and serious safety problems of lithium metal batteries. Although N-containing functional groups in carbon materials are reported to be effective to homogenize the Li⁺ flux, the effective interaction distance between lithium ions and N-containing groups should be relatively small (down to nanometer scale) according to the Debye length law. Thus, it is necessary to carefully design the microstructure of N-containing carbon materials to make the most of their roles in regulating the Li⁺ flux. In this work, porous carbon nitride microspheres (PCNMs) with abundant nanopores have been synthesized and utilized to fabricate a uniform lithiophilic coating layer having hybrid pores of both the nano- and micrometer scales on the Cu/Li foil. Physically, the three-dimensional (3D) porous framework is favorable for absorbing volume changes and guiding Li growth. Chemically, this coating layer can render a suitable interaction distance to effectively homogenize the Li⁺ flux and contribute to establishing a robust and stable solid electrolyte interphase (SEI) layer with Li-F, Li-N, and Li-O-rich contents based on the Debye length law. Such a physical-chemical synergic regulation strategy using PCNMs can lead to dendrite-free Li plating, resulting in a low nucleation overpotential and stable Li plating/stripping cycling performance in both the Li‖Cu and the Li‖Li symmetric cells. Meanwhile, a full cell using the PCNM coated Li foil negative electrode and a LiFePO₄ positive electrode has delivered a high capacity retention of ~ 80% after more than 200 cycles at 1 C and achieved a remarkable rate capability. The pouch cell fabricated by pairing the PCNM coated Li foil negative electrode with a NCM 811 positive electrode has retained ~ 73% of the initial capacity after 150 cycles at 0.2 C.