Doping is regarded as a prominent strategy to optimize the crystal structure and composition of battery materials to withstand the anisotropic expansion induced by the repeated insertion and extraction of guest ions. The well-known knowledge and experience obtained from doping engineering predominate in cathode materials but have not been fully explored for anodes yet. Here, we propose the practical doping of fluorine ions into the host lattice of nickel oxide to unveil the correlation between the crystal structure and electrochemical properties. Multiple ion transmission pathways are created by the orderly two-dimensional nanosheets, and thus the stress/strain can be significantly relieved with trace fluorine doping, ensuring the mechanical integrity of the active particle and superior electrochemical properties. Density functional theory calculations manifest that the F doping in NiO could improve crystal structural stability, modulate the charge distribution, and enhance the conductivity, which promotes the performance of lithium-ion storage.