In this study, we investigated the formation energies of GICs with the five reported crystal structures using the first-principles calculation under the vdW interactions by varying the elements as intercalants, M. The calculated results are in good agreement with the experimentally reported materials and provide important insights into GIC processing using the Li-based molten alloy and LiCl-KCl molten salts. Furthermore, our results suggest that several GICs with new compositions, which have not been reported to date, are possibly stable.