Anhydrous Grotthuss mechanism for fast proton transport in a dense oxide-ion array of α-MoO3

Developing high-power battery chemistry is an urgent task to buffer fluctuating renewable energies and achieve a sustainable and flexible power supply. Owing to the small size of proton and its ultrahigh mobility in water via the Grotthuss mechanism, aqueous proton batteries are an attractive candidate for high-power energy storage devices. Although Grotthuss proton transfer usually occurs in hydrogen-bonded networks of water molecules, in this work, we discover anhydrous Grotthuss-type proton transport in a dense oxide-ion array of solid α-MoO3 even without structural water. The fast proton transfer and accumulation that occurs during (de)intercalation in α-MoO3 is unveiled using both experiments and first-principles calculations. Coupled with a zinc anode and a superconcentrated dual-ion Zn2+/H+ electrolyte, the solid-state anhydrous Grotthuss proton transport mechanism realizes an aqueous MoO3-Zn battery with both high energy and power densities.

Generalized Poisson-Nernst-Planck-Based Physical Model of the O2|LSM|YSZ Electrode

The paper presents a generalized Poisson-Nernst-Planck model of an yttria-stabilized zirconia electrolyte developed from first principles of nonequilibrium thermodynamics which allows for spatial resolution of the space charge layer. It takes into account limitations in oxide ion concentrations due to the limited availability of oxygen vacancies. The electrolyte model is coupled with a reaction kinetic model describing the triple phase boundary with electron conducting lanthanum strontium manganite and gaseous phase oxygen. By comparing the outcome of numerical simulations based on different formulations of the kinetic equations with the results of EIS and CV measurements we attempt to discern the existence of separate surface lattice sites for oxygen adatoms and surface oxides from the assumption of shared ones. Moreover, we show that the mass-action kinetics model is sensitive to oxygen partial pressure unlike exponential kinetics models. The resulting model is fitted to a dataset of EIS and CVs spanning multiple temperatures and pressures, using various relative weights of EIS and CV data in the fitness function. The model successfully describes the physics of the interface around the OCV.

Sillén-Aurivillius phase bismuth niobium oxychloride, Bi4NbO8Cl, as a New Oxide Ion Conductor

Sillén-Aurivillius phase Bi4NbO8Cl consists of Bi2O22+/NbO43-/Bi2O22+/Cl- layers and the partial substitution of Bi was successfully performed by Ca2+, Sr2+, Ba2+, La3+, Ga3+ and Sn4+. It was found that substitution with...