Li-Functionalized Carbon Nanotubes for Hydrogen Storage: Importance of Size Effects

We investigated Li-doped carbon nanotubes (CNTs) as a promising hydrogen storage media. In this computational model, we considered isolated lithium atom adsorbed on a CNT wall as an adsorption site for hydrogen. We focused on the influence of size effects on the structural and energetic characteristics of CNT(n,n)@Li+kH2 complexes where n = 5, 7, 9; k = 1, ..., 6; Nc = 4, 5, 6 (Nc is translation length of CNT, expressed in terms of a number of CNT unit cells). We proved that modeled CNT length substantially influences internal sorption of Li and hydrogen on the narrow tube (5,5), which subsequently alters the adsorption energies of H2 molecules and causes the deformation of the carbon framework. Moreover, the size effects are not pronounced in the case of external sorption for all considered CNT translation lengths and diameters. We have not observed any noticeable qualitative difference between internal and external hydrogen sorption in the nanotube wider than CNT(5,5). In the case of external adsorption on all considered nanotubes, doping with Li increases hydrogen adsorption energies of up to four H2 molecules by 100 meV in comparison with pure CNTs. And the local density approximation estimations (∼250 meV/H2) of adsorption energy on Li-decorated CNTs exceed the lowest requirement proposed by the U.S. Department of Energy (200 meV/H2). In the case of internal sorption on Li-functionalized tubes, the generalized gradient approximation also gives hydrogen adsorption energies in the desired range of 200–600 meV/H2. However, steric hindrances could prevent sufficient hydrogen uptakes (less than 2 wt % inside CNT(5,5)). We believe that our findings on the size effects are important for estimation of CNT’s hydrogen storage properties.