Simulations must be able to follow the drastic changes that occur in the material during charge/discharge cycles. The silicon electrode passes through several alloys with different physicochemical properties. After electrode cycling, the Li-Si structures formed are found to be amorphous, making it difficult to collect structural information from experimental X-ray measurements. Two main concerns must be addressed: to count with an atomistic model transferable to the entire loading range (i.e. Li x Si / x ∈ [0, 3.75]) and to achieve a meaningful sampling of that model. During the last decade, progress has been made in both directions. Fan et al. have developed a ReaxFF parameterization using different Li x Si crystal structures. Using this model, we proposed an enhanced sampling method that allowed us to predict several amorphous structures that probably exists in cycled Li x Si electrode. However, improved sampling requires a highly transferable model capable of accurately representing unknown regions of configurational space, allowing true discovery of electrode structures and avoiding false positives.