Ab Initio Calculations of Open-Cell Voltage in Li-Ion Organic Radical Batteries

In the past decade, radical polymers have been confirmed as promising materials for secondary batteries. Thanks to their processability and structure diversity, their electronic properties can be rationally tuned. To this end, quantum-chemical methods could be used to predict the redox properties of new radical molecules and hence guide experiments. Here we test the agreement between theoretical and experimental reduction potentials for various nitroxide radical polymers. A method based on density functional theory is compared with the higher level many-body perturbation theory and to experimental values. The results indicate that this method allows for fast and accurate estimation of the open-cell voltage of these organic radical Li-ion batteries, suggesting that it would be sufficiently robust to extrapolate to theoretically designed nitroxide radicals.