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Comparative computational study of lithium and sodium insertion in van der Waals and covalent tetracyanoethylene (TCNE) -based crystals as promising materials for organic lithium and sodium ion batteries

We present a comparative ab initio study of Li and Na insertion in molecular (van der Waals) crystals of TCNE (tetracyanoethylene) as well as in covalent Li/Na-TCNE crystals. We confirm the structure of previously synthesized (covalent) Li-TCNE crystal as well as predict the existence of its Na-TCNE analogue. In the molecular/covalent TCNE crystals, insertion sites are identified with the binding energy of Li and Na up to 2.7/1.8 and 2.6/1.8 eV stronger than Li and Na cohesive energy, respectively, in dilute concentrations. Up to 5.5/2.5 and 3/2 Li and Na atoms per TCNE unit can be inserted in the molecular/covalent crystals, respectively, while preserving the structure, with maximum voltages, respectively, 3.5/2.2 and 3.3/2.7 V. Significantly, up to capacity of 418 mAh g-1 for both Li and Na in the molecular crystal and 198 mAh g-1 for Li and 177 mAh g-1 for Na in the covalent crystal, the insertion of Li and Na would not lead to reactions with common electrolytes. Tetracyanoethylene-based molecular and covalent crystals could therefore become efficient organic cathode and anode materials for Li and Na ion batteries.