Evidence for electronic and ionic limitations at the origin of the second voltage plateau in nickel electrodes, as deduced from impedance spectroscopy measurements

The second plateau occurring during the reduction of the nickel oxyhydroxide electrode (NOE) was studied by impedance spectroscopy on a cell with a pasted electrode prepared from commercial undoped β-Ni(OH)2. Measurements were performed at diverse states of reduction and a large variation of impedance upon the transition from the first to the second plateau was observed. This variation mainly takes place at low frequencies and is hence related to ionic diffusion. We observed that the impedance becomes more capacitive on the second plateau meaning that the proton diffusion is limited. These results would be consistent with the gradual formation of an insulating layer of nickel hydroxide at the interface between the NOE and the electrolyte upon reduction. Once this layer becomes compact the ionic diffusion would be hindered and forced to occur through this layer, which could explain the voltage drop observed.