A. Pre-reactive simulations We first consider the radial distribution function (RDF) of the Li + cations with the PF6 -anions and the EC molecule. The reference point for the EC/Li + RDF is defined as the double bonded oxygen, and for the PF6 -/Li + RDF the reference point is defined as the phosphorus atom. In the two cases we recognize in Figure (a) a well-defined first peak going from about 0.2 nm to 0.35 nm before the saturation. The area under the first peak of the EC(O)/Li + RDF results in a coordination number equal to 4.1 in agreement with the literature. This large value reflects the solvation of Li + by 4