First-Principles Understanding of the Staging Properties of the Graphite Intercalation Compounds towards Dual-Ion Battery Applications

[Image: see text] Graphite-based dual-ion batteries are a promising alternative to the lithium-ion batteries for energy storage because of its potentially lower cost, higher voltage, and better safety. Among the most important materials in the dual-ion battery are the graphite and graphite intercalation compounds (GICs), whose properties determine the performance of electrodes. The GICs are formed at both anode and the cathode sides during the charging process in which the graphene sheets and the intercalants are arranged in an ordered way called the staging of GICs. Staging is one of the important structural features of GICs related to the volume expansion of the electrodes, the charging rate, and the capacity of the battery. However, the details of the staging mechanism, such as the structural properties, the electronic structure, and the voltage dependence on the stages are still poorly understood. In this regard, we perform density functional theory studies to explore these issues in GICs. Using staging models, we examine the stability of GICs at different stages of intercalation with a range of species (i.e., Li, Na, K, PF(6), BF(4), TFSI, AlCl(4), and ClO(4)). We then study the contribution of intercalants to the electronic band structures in GICs. In addition, the voltage profiles of the dual-ion batteries with different intercalation species, intercalation stages, and battery capacities are also analyzed. The present work is important for the better understanding of graphite-based dual-ion batteries and helpful in development of novel energy storage systems.