Chronoamperometric investigations on electrochemical synthesis of iron nitrides in molten salt system

A systematic investigation of the electrochemical iron nitride synthesis in a LiCl/KCl salt melt at 723 K shows an optimum of \(\epsilon\) $ϵ$ -Fe \(_3\) ${}_3$ N \(_{1+x}\) ${}_{1+x}$ formation in the range of 2.2 to 2.3 V and for \(\gamma '\) ${\gamma }^{\prime }$ -Fe \(_4\) ${}_4$ N between 2.4 and 2.5 V enabling the control of the desired iron nitride phase by setting the supplied terminal voltage. The product formation of iron nitrides starts when the electrochemical window is reached, which could be verified by linear sweep voltammetry. Hence, a maximum of nitrogen content in the formed iron nitride phases is observed for 2.27 V. During elongated synthesis periods, convection emerges as the predominant transport mechanism hindering an accelerated reaction rate with higher overpotential applied. Real-time analysis of the background current allows conclusions about the remaining nitride concentration. Additionally, there is concurrent iron nitride formation at the electrode surface through nitride adsorption and autonucleation-induced precipitation of iron and nitride ions. The analysis of the amount of sediment in comparison to the layer thickness of the nitrided working electrode suggests that the autonucleation mechanism dominates over the adsorption mechanism with increasing overpotential and can be further enhanced by this feature.