Metal carbodiimides and cyanamides, a new family of electrode materials for Li-ion batteries

Li-ion batteries are currently the most common choice for all portable electronic devices but also for hybrid electric vehicles and renewable energy sectors. At present, graphite is routinely employed as the anode material for Li-ion-batteries due to its excellent attributes such as long cycle life, abundance, and relatively cost effective. However, the disadvantages of graphitic anode include low energy density and safety concerns. As a consequence, alternative cost effective anode materials with high energy density and long cycle life have been widely explored. Among this transition metal based compounds are an exciting and reasonable alternative for graphite owing to their high specific capacity. Compounds with the formula MX where M is a divalent metal and X = O, S, PO4, and CO3 have been reported to be electrochemically active at average voltages around 1 volts. In spite of their high theoretical specific capacities, high irreversible capacity in the first lithiation and the weak cycling life prevent the practical use of these materials. Since 2015, the possibility of using transition metal carbodiimides (MNCN, with M = Fe, Mn, Co, Cu, Zn, Ni) have been reported, and some of them have shown promising electrochemical performance as anode materials for both Li and Na ion batteries. Like all divalent metal based electrode materials, carbodiimides have been found to suffer from high initial irreversible capacity and high operating voltage, however they show a better cycle life. The application of transition metal carbodiimides in the field of energy storage (and conversion) is still in its early stages and despite progress in electrochemical evaluation much remains to be done in order to establish the reaction mechanisms that govern the reported promising performances. Besides the transition metal carbodiimides there are still many other inorganic cyanamides and carbodiimides materials to explore. Therefore the main targets of this PhD work are (i) to assess the properties of new carbodiimides/cyanamides as electrode materials for LiBs and (ii) to establish their electrochemical reaction mechanisms via advanced operando techniques and DFT calculations. Concerning the electrochemical performance, Cr2(NCN)3 turned out to be by the far the best carbodiimide anode material with stable specific capacity of more than 600 mAh.g-1 for more than 900 cycles at 2C rate. CoNCN and FeNCN have also shown excellent electrochemical properties since they can sustain a specific capacity higher than 500 mAh.g-1 for more than 100 cycles at 2C rate. Poor performance was observed for PbNCN, Ag2NCN and ZnNCN since the practical capacities are well below the theoretical ones. These phase show also fast capacity fading during the first 20 cycles. These three performance categories correlate well with the three different reaction mechanisms established for the investigated phases. Up to now, three types of reaction mechanism have been identified including (i) Combined intercalation and conversion processes in the case of Cr2(NCN)3 as evidenced by both theoretical and experimental methods, (ii) pure conversion reaction in the case of CoNCN and finally (iii) a combined conversion and alloying mechanism in the case of Pb, Zn and Ag compounds. It is worth noting that whatever the reaction pathway, all the carbodiimide/cyanamide anode materials face the limitation of a significantly low coulombic efficiency during the first cycles. To overcome this obstacle, much effort is needed to clarify the nature and the role of SEI in the overall performance of this family of materials. The promising results reported in this work do not probably yet meet the standards needed to take carbodiimides/cyanamides into the practical applications, but they clearly evidence the rich possibilities offered by this young family of molecular inorganic materials.