The redox processes occurring at the nickel oxyhydroxide electrodes were followed by in
situ neutron diffraction. The aim was to get a deeper insight into the existing phases and
the reactivity mechanisms involved in the reduction process, paying special attention to the
so-called “second plateau” phenomenon, occasionally appearing during electrochemical
reduction at a potential of 0.8 V vs Hg/HgO. Chemically prepared protonated or deuterated
nickel hydroxides, having different phase compositions, oxidation state, and particle size
were studied to serve as reference samples. The electrochemically driven structural evolution
of four samples upon discharge and charge was followed by in situ neutron powder diffraction
using a specially designed cell. For both γ and β-NiOOH phases, the neutron diffraction
results evidenced a direct and continuous structural transformation into the β-Ni(OH)2 phase
upon reduction, on both the first and the second plateau, with no discontinuity when
encountering the second plateau. This confirms that the second plateau phenomenon is not
due to any intrinsic structural properties of the active material but is related to its surface
properties being prone to be strongly dependent upon the electrode preparation.