Customizing Helmholtz Plane with N, F, P Tri‐Doped rGO/CNT Aerogel Protective Layer for Long‐Life Zinc‐Ion Batteries

Abstract The practical application of aqueous zinc‐ion batteries (AZIBs) is impeded by dendrite formation and water‐induced parasitic reactions at the anodes. In this article, a relatively hydrophobic inner Helmholtz plane (IHP) and an outer Helmholtz plane (OHP) with abundant nucleation sites are engineered through coating a N, F, and P heteroatom doped reduced graphene oxide/carbon nanotube (NFP‐rGO‐CNT) multifunctional aerogel protective layer. The rGO with certain hydrophobicity construct a lean‐water environment at IHP, effectively blocking adverse parasitic reactions between water and metallic Zn, while zincophilic and uniformly distributed N, F, and P heteroatoms facilitate Zn 2+ migration and homogenize Zn 2+ flux at the OHP, thereby promoting the directional deposition of Zn 2+ along the (002) crystal plane. Consequently, the fabricated NFP‐rGO‐CNT/Zn//Cu asymmetric cell exhibits a high Coulombic efficiency close to 100% for 3200 cycles. In addition, the symmetric cell assembled with NFP‐rGO‐CNT/Zn electrodes presents an impressive lifespan of 1990 h at 5 mA cm −2 and 2 mAh cm −2 , significantly outperforming the control group (about 27 h). More remarkably, a NFP‐rGO‐CNT/Zn//V 2 O 3 pseudo‐pouch cell is capable of powering a small fan to rotate steadily. This aerogel protective layer strategy offers a novel perspective for HP regulation, enabling textured and reversible Zn anodes.