Transition metal oxides ion diffusion channels have been developed for ammonia-ion batteries (AIBs). However, the influence of microstructural features of diffusion channels on the storage and diffusion behavior of NH4+ is not fully unveiled. In this study, by using MnCo2O4 spinel as a model electrode, the asymmetric ion diffusion channels of MnCo2O4 have been regulated through bond length optimize strategy and investigate the effect of channel size on the diffusion process of NH4+. And the reducing channel size significantly decreases NH4+ adsorption energy, thereby accelerating hydrogen bonds formation/fracture kinetics and NH4+ reversible diffusion within 3D asymmetric channels. The optimized MnCo2O4 with oxygen vacancies/carbon nanotubes (Vo-MCO/CNTs) composite exhibits impressive specific capacity (219.2 mAh g–1 at 0.1 A g–1) and long cycle stability. The full cell with 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) anode demonstrates a remarkable energy density of 52.3 Wh kg–1 and maintains 91.9% capacity after 500 cycles. This finding provides a novel approach for the development of cathode materials in AIBs.