Improved ion adsorption capacities and diffusion dynamics in surface anchored MoS2⊥Mo4/3B2 and MoS2⊥Mo4/3B2O2 heterostructures as anodes for alkaline metal-ion batteries

First-principles calculations were performed to analyze the atomic structures and electrochemical energy storage properties of novel MoS2⊥boridene heterostructures by anchoring MoS2 nanoflakes on Mo4/3B2 and Mo4/3B2O2 monolayers. Both thermodynamic and thermal stabilities of each heterostructure were thoroughly evaluated from the obtained binding energies and through first-principles molecular dynamics simulations at room temperature, confirming the high formability of the heterostructures. The electrochemical properties of MoS2⊥Mo4/3B2 and MoS2⊥Mo4/3B2O2 heterostructures were investigated for their potential use as anodes for alkaline metal ion batteries (Li+, Na+ and K+). It was revealed that Li+ and Na+ can form multiple stable full adsorption layers on both heterostructures, while K+ forms only a single full adsorption layer. The presence of a negative electron cloud (NEC) contributes to the stabilization of a multi-layer adsorption mechanism. For all investigated alkaline metal ions, the predicted ion diffusion dynamics are relatively sluggish for the adsorbates in the first full adsorption layer on MoS2⊥boridene heterostructures due the relatively large migration energies (>0.50 eV), compared to those of second or third full adsorption layers (<0.30 eV). MoS2⊥Mo4/3B2O2 exhibited higher onset and mean open circuit voltages as anodes for alkaline metal-ion batteries than MoS2⊥Mo4/3B2 hybrids because of enhanced interactions between the adsorbate and the Mo4/3B2O2 monolayer with the presence of O-terminations. Tailoring the size and horizontal spacing between two neighboring MoS2 nano-flakes in heterostructures led to high theoretical capacities for LIBs (531 mA h g−1), SIBs (300 mA h g−1) and PIBs (131 mA h g−1) in the current study.