Quite recently, Chen and coworkers synthesized K-doped Li The available reported values of the calculated overpotentials present considerable dispersion and they sometimes match with the ones experimentally observed and sometimes not. As said before, the absolute value of this quantity depends on many factors. Some of them have to do with variables that not always are considered in the theoretical calculations such as the characteristic of the electrolyte, the presence of complex extended defects, the presence of undesired secondary products or particular of the experimental setup. Other factors of technical origin are directly related to the particular model considered to describe the discharge product. For instance, the theoretical overpotential value strongly depends on the exchange and correlation functional, on the supercell size, on the calculation of the oxygen molecule chemical potential and the criteria to correct the well known overbinding error of GGA functionals. Despite this, if all these technicalities are properly taken into account, we believe that DFT can still provide deep understanding of the underlying mechanism of the Li 2 O 2 formation and decomposition in the LOB and it is a powerful tool to propose new routes to face the limitations of this promising technology.