Ultrahigh reversible hydrogen storage in K and Ca decorated 4-6-8 biphenylene sheet

Abstract

By applying density functional theory (DFT) and ab-initio molecular dynamics (AIMD) simulations, we predict the ultrahigh hydrogen storage capacity of K and Ca decorated single-layer biphenylene sheet (BPS). We have kept various alkali and alkali-earth metals, including Na, Be, Mg, K, Ca, at different sites of BPS and found that K and Ca atoms prefer to bind individually on the BPS instead of forming clusters. It was found that 2⨯2⨯1 supercell of biphenylene sheet can adsorb eight K, or eight Ca atoms, and each K or Ca atom can adsorb 5H2, leading to 11.90% or 11.63% of hydrogen uptake, respectively, which is significantly higher than the DOE-US demands of 6.5%. The average adsorption energy of H2 for K and Ca decorated BPS is −0.24 eV and −0.33 eV, respectively, in the suitable range for reversible H2 storage. Hydrogen molecules get polarized in the vicinity of ionized metal atoms hence get attached to the metal atoms through electrostatic and van der Waals interactions. We have estimated the desorption temperatures of H2 and found that the adsorbed H2 can be utilized for reversible use. We have found that a sufficient energy barrier of 2.52 eV exists for the movement of Ca atoms, calculated using the climbing-image nudged elastic band (CI-NEB) method. This energy barrier can prevent the clustering issue of Ca atoms. The solidity of K and Ca decorated BPS structures were investigated using AIMD simulations.