A first-principles study on atomic-scale pore design of microporous carbon electrodes for lithium-ion batteries

Porous carbon materials are considered attractive lithium storage media because their large specific surface areas and pore volumes provide high adsorption capacity. This first-principles study elucidates the atomic-scale mechanisms of lithium storage and diffusion in microporous carbon. Microporous carbon structures with initial densities of 1.5, 2.0, and 2.5 g cm^-3 store up to 7.5-8.2 Li ions per C₆ corresponding to the capacities of 2783-3032 mA h g^-1, which are 7-8 times higher than that for graphite. Fully lithiated microporous carbon has about 62% of Li ions inside the pore cavity and on the pore surface, responsible for reversible capacity, and about 38% of Li ions inside the pore wall, responsible for irreversible capacity. As lithiation proceeds, microporous carbon structures with different total pore volumes evolve to have similar total pore volumes but different average pore volumes. The average pore volume has a great influence on Li ion conductivity, as evidenced by the highest conductivity of 103.5 mS cm^-1 for the largest average pore diameter of 9.3 Å. Inside large pore cavities, Li ions diffuse rapidly without encountering carbon atoms that impede Li diffusion, suggesting that a high Li-to-C ratio around Li causes fast Li ion motion. This study offers not only a comprehensive understanding of the lithiation of microporous carbon but also design directions for developing efficient microporous carbon electrodes for lithium-ion batteries.