The adsorption equilibrium constants of monovalent and divalent cations to material surfaces in aqueous media are central to many technological, natural, and geochemical processes. Cation adsorption-desorption is often proposed to occur in concert with proton transfer on hydroxyl-covered mineral surfaces, but to date this cooperative effect has been inferred indirectly. This work applies density functional theory-based molecular dynamics simulations of explicit liquid water/mineral interfaces to calculate metal ion desorption free energies. Monodentate adsorption of Na+, Mg2+, and Cu2+ on partially deprotonated silica surfaces are considered. Na+ is predicted to be unbound, while Cu2+ exhibits binding free energies to surface SiO- groups that are larger than those of Mg2+. The predicted trends agree with competitive adsorption measurements on fumed silica surfaces. As desorption proceeds, Cu2+ dissociates one of the H2O molecules in its first solvation shell, turning into Cu2+(OH-)(H2O)3, while Mg remains Mg2+(H2O)6. The protonation state of the SiO- group at the initial binding site does not vary monotonically with cation desorption.
Detailed understanding of solid–solid interface structure–function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and LixCoO2 cathode, have been reported to generate solid–electrolyte interphase (SEI)-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P−N−P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy LixCoO2(104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures.
Effective passivation of lithium metal surfaces, and prevention of battery-shorting lithium dendrite growth, are critical for implementing lithium metal anodes for batteries with increased power densities. Nanoscale surface heterogeneities can be "hot spots" where anode passivation breaks down. Motivated by the observation of lithium dendrites in pores and grain boundaries in all-solid batteries, we examine lithium metal surfaces covered with Li2O and/or LiF thin films with grain boundaries in them. Electronic structure calculations show that at >0.25 V computed equilibrium overpotential Li2O grain boundaries with sufficiently large pores can accommodate Li0 atoms which aid e- leakage and passivation breakdown. Strain often accompanies Li insertion; applying an ∼1.7% strain already lowers the computed overpotential to 0.1 V. Lithium metal nanostructures as thin as 12 Å are thermodynamically favored inside cracks in Li2O films, becoming "incipient lithium filaments". LiF films are more resistant to lithium metal growth. The models used herein should in turn inform passivating strategies in all-solid-state batteries.
The complexation of toxic and/or radioactive ions on to mineral surfaces is an important topic in geochemistry. We apply periodic-boundary-conditions density functional theory (DFT) molecular dynamics simulations to examine the coordination of Pb(II), SeO2-3, and their contact ion pairs to goethite (1 0 1) and (2 1 0) surfaces. The multitude of Pb(II) adsorption sites and possibility of Pb(II)-induced FeOH deprotonation make this a complex problem. At surface sites where Pb(II) is coordinated to three FeO and/or FeOH groups, and with judicious choices of FeOH surface group protonation states, the predicted Fe-Pb distances are in good agreement with EXAFS measurements. Trajectories where Pb(II) is in part coordinated to only two surface Fe-O groups exhibit larger fluctuations in Pb-O distances. Pb(II)/ SeO2-3 contact ion pairs are at least metastable on goethite (2 1 0) surfaces if the SeO2-3has a monodentate Se-O-Fe bond. Our DFT-based molecular dynamics calculations are a prerequisite for calculations of finite temperature equilibrium binding constants of Pb(II) and Pb(II)/ ion pairs to goethite adsorption sites.