In this contribution, we combined electrochemical cycling and X-ray photoelectron spectroscopy (XPS) to understand the nonpassivating behavior of the solid electrolyte interphase (SEI) on Si anodes during the first cycles. Based on galvanostatic measurements, we show that the irreversible capacity loss is reduced after the first cycle, and it stays almost constant from the second cycle onwards. XPS was used to determine the root causes of the Coulombic inefficiency, showing that the rate of decomposition of the organic solvents strongly decreased after the first cycle, whereas the rate of salt decomposition is almost unchanged between cycles. We determine that the inhibition of the decomposition reaction of the organic solvent is responsible for the lower Coulombic loss during the second electrochemical cycle in comparison to the first, whereas the nonpassivating behavior toward the salt decomposition is one of the main causes of capacity loss upon cycling. We further revisit the role of cracking in contributing to capacity loss. Whereas high volumetric expansion remains an issue plaguing the performance of Si anodes, our chronoamperometry studies reveal that the SEI formed on Si anodes does not passivate even when the electrode is fully expanded, and no additional surface is exposed. Overall, our work establishes the need to address the chemical and electrochemical instability of the SEI on the Si anode in addition to the more notorious issue of cracking.

Silicon is a promising alloying anode for lithium-ion batteries because of its high capacity and low cost. However, its use has been hampered by mechanical failure arising from the large volume change upon cycling and by an insufficiently stable solid electrolyte interphase (SEI). SEI formation depends on the Si surface, which is often an oxide (SiOx). In this study we compare three different Si surfaces using Si wafers: 1.3 nm native SiOx, 1.4 nm thermally grown SiO2, and a SiOx-free surface. The oxide-free surface showed the worst electrochemical performance, never exceeding 94% Coulombic efficiency (CE). It also exhibited the thickest SEI and the highest overpotential for lithiation, which correlated with uninhibited electrolyte reduction and the incorporation of P-F species into the SEI. The oxide-coated surfaces performed significantly better, demonstrating a CE above 99% beyond the second cycle, low overpotential for lithiation, and a thinner and more stable SEI. The oxides lower the onset potential for electrolyte reduction and yield an SEI with fewer P-F species. However, it was found that the CE with the native oxide surface decays from the fifth cycle onward and correlates with a resurgence of electrolyte reduction. A 1-2 nm thermal SiO2 coating is optimum for achieving a stable SEI that minimizes side reactions and sustains efficient cycling.

We report on the theoretical prediction and experimental realization of new ternary zinc molybdenum nitride compounds. We used theory to identify previously unknown ternary compounds in the Zn-Mo-N systems, Zn₃MoN₄ and ZnMoN₂, and to analyze their bonding environment. Experiments show that Zn-Mo-N alloys can form in broad composition range from Zn₃MoN₄ to ZnMoN₂ in the wurtzite-derived structure, accommodating very large off-stoichiometry. Interestingly, the measured wurtzite-derived structure of the alloys is metastable for the ZnMoN₂ stoichiometry, in contrast to the Zn₃MoN₄ stoichiometry, where ordered wurtzite is predicted to be the ground state. The formation of Zn₃MoN₄-ZnMoN₂ alloy with wurtzite-derived crystal structure is enabled by the concomitant ability of Mo to change oxidation state from +VI in Zn₃MoN₄ to +IV in ZnMoN₂, and the capability of Zn to contribute to the bonding states of both compounds, an effect that we define as "redox-mediated stabilization". The stabilization of Mo in both the +VI and +IV oxidation states is due to the intermediate electronegativity of Zn, which enables significant polar covalent bonding in both Zn₃MoN₄ and ZnMoN₂ compounds. The smooth change in the Mo oxidation state between Zn₃MoN₄ and ZnMoN₂ stoichiometries leads to a continuous change in optoelectronic properties-from resistive and semitransparent Zn₃MoN₄ to conductive and absorptive ZnMoN₂. The reported redox-mediated stabilization in zinc molybdenum nitrides suggests there might be many undiscovered ternary compounds with one metal having an intermediate electronegativity, enabling significant covalent bonding, and another metal capable of accommodating multiple oxidation states, enabling stoichiometric flexibility.

Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO₂ on Si is often inevitable. However, it is not clear if this layer has a positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties of the SiO₂ lithiation products and by the convolution of chemical and electrochemical effects during the anode lithiation process. In this study, Li _xSiO _y thin films as model materials for lithiated SiO₂ were deposited by magnetron sputtering at ambient temperature, with the goal of (1) decoupling chemical reactivity from electrochemical reactivity and (2) evaluating the physical and electrochemical properties of Li _xSiO _y. X-ray photoemission spectroscopy analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO₂ can be achieved through sputtering. Our density functional theory calculations also confirm that the possible phases formed by lithiating SiO₂ are very close to the measured film compositions. Scanning probe microscopy measurements show that the mechanical properties of the film are strongly dependent on lithium concentration, with a ductile behavior at a higher Li content and a brittle behavior at a lower Li content. The chemical reactivity of the thin films was investigated by measuring the AC impedance evolution, suggesting that Li _xSiO _y continuously reacts with the electrolyte, in part because of the high electronic conductivity of the film determined from solid-state impedance measurements. The electrochemical cycling data of the sputter-deposited Li _xSiO _y/Si films also suggest that Li _xSiO _y is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.

Ternary nitride semiconductors with wurtzite-derived crystal structures are an emerging class of materials for optoelectronic applications compatible with GaN and related III-V compounds. In particular, II-IV-V2 materials such as ZnSnN2 and ZnGeN2 have been very actively studied for applications in photovoltaics and light emitting devices. However, many other possible wurtzite-derived ternary nitrides have not been reported, and hence their optical and electrical properties remain unknown. Here, we report on Zn2SbN3-the first Sb-based nitride and a photoactive semiconductor. Surprisingly, Zn2SbN3 contains Sb in the highest (5+) oxidation state, and in the unusual tetrahedral coordination. This new Zn2SbN3 material has a solar-matched 1.6-1.7 eV band gap and shows near-band-edge room-temperature photoluminescence, demonstrating its promise as an optoelectronic semiconductor. Finally, Zn2SbN3 can be synthesized at low temperature under a wide range of processing conditions, despite being metastable according to theoretical calculations. All these results, as well as the band position measurements, indicate that Zn2SbN3 is a promising emerging semiconductor for applications as an absorber in photovoltaic-and photoelectrochemical solar cells.