The demand for decarbonizing the ammonia industry by using renewable energy has invoked increasing research interests into catalyst development for effective N2 reduction under mild conditions. Hydride-based materials are among some of the emerging catalysts for ammonia synthesis at ambient pressure and low temperatures (< 673 K). A recent chemical looping process based on Ni/BaH2 showed the most promise as it can realize ammonia production at a temperature as low as 373 K and under ambient pressure. However, the chemical transformation of the hydride catalyst at the molecular level remains unclear in this process. In this work, we report detailed in situ neutron spectroscopy and diffraction investigations along with first-principles simulations on the structural transformation of Ni/BaH2 during the nitridation and hydrogenation steps in the chemical looping process for ammonia synthesis. It was shown that a ball-milling process of the starting Ni/BaH2 could significantly decrease the size of BaH2 and increase the density of defects, thus potentially enhancing the reactivity of the hydride. The evolution from BaH2 to barium imide (BaNH) was evidenced in the inelastic neutron scattering (INS) and neutron diffraction results during the N2 reaction step. During the hydrogenation study, in addition to the recovery of BaH2, a possible intermediate species, N-deficient barium imide, was also detected. In comparing the N2 and H2 reaction steps, the neutron results indicate that the hydrogenation step appears more difficult than the nitridation step, confirming the facile N2 fixation property of Ni/BaH2 catalyst in ammonia synthesis.