Transition‐Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium‐and Sodium‐Ion Batteries with Exce...

We report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe Mössbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe–NCN into Li/Na–NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides Mx(NCN)y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Their electrochemical activity and performances open the way to the design of a novel family of anode materials.