Search

In this work we report the solid reaction products from the chemical reaction of aprotic battery electrolyte and three purported components of the Si-based anode SEI : SiO2 nanoparticles (NPs), lithium silicate (LixSiOy) powders, and Si NPs. We use FTIR and classical molecular dynamics/density functional perturbation theory to assess the solid products remaining with these model materials after exposure to electrolyte. The absence of electrochemical bias provides a view of the chemical speciation resulting from early-stage chemical reactivity during battery assembly as well as under open circuit storage conditions. We believe these species represent the initial stages of SEI growth and predict they likely drive subsequent chemical and electrochemical reactions by controlling molecular interactons at the Si active material interface. We find that nominally equivalent materials react differently even before any electrochemistry is performed (e.g., acidic SiO2 dissolves whereas alkaline SiO2 is relatively robust), and derive new understanding of the chemical species that could and could not form stable SEI components in Si-based anodes. These results can be used to inform how to passivate Si anode surfaces and potentially generate an artificially engineered SEI that would be stable and enable next-generation battery anodes.

Cathode surface coatings are widely used industrially as a means to suppress degradation and improve electrochemical performance of lithium-ion batteries. However, developing an optimal coating is challenging, as different coating materials may enhance one aspect of performance while hindering another. To elucidate the fundamental thermodynamic and transport properties of amorphous cathode coating materials, here, we present a framework for calculating and analyzing the Li+ and O2- transport and the stability against delithiation in such materials. Our framework includes systematic workflows of ab-initio molecular dynamics calculations to obtain amorphous structures and diffusion trajectories coupled with an analysis of critical changes of the active-ion local environment during diffusion. Based on these data, we provide an estimate of room-temperature diffusivities, including statistical error bars, and the evaluation of the coating suitability in terms of its ability to facilitate Li+ transport while blocking O2- transport. Finally, we add the thermodynamic stability analysis of the coating chemistry within the operating voltage of common Li-ion cathodes. We apply this framework to two commonly used amorphous coating materials, Al2O3 and ZnO. We find that (1) in general, a higher Li+ content increases both Li+ and O2- diffusivities in both Al2O3 and ZnO. Also, Li+ and O2- diffuse much faster in ZnO than in Al2O3. (2) However, neither Al2O3 nor ZnO is expected to retain a significant concentration of Li+ at high charge. (3) ZnO performs much more poorly in terms of O2- blocking, and hence, Al2O3 is preferred for high-voltage cathode applications. These results will help to quantitatively evaluate amorphous materials, such as metal oxides and fluorides, for different performance metrics and facilitate the development of optimal cathode coatings.

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.

A simple hydrothermal route to the eulytite phase of bismuth germanium oxide (E-BGO: Bi4(GeO4)3) that required no post-processing has been developed. The E-BGO material was isolated from a mixture of bismuth nitrate pentahydrate and a slight excess of germanium oxide in water under hydrothermal conditions (185 °C for 24 h). The resultant materials were characterized by powder x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and luminescence measurements to verify the particle’s phase (eulytite), morphology, size, and response to a variety of excitation energy sources, respectively. Photoluminescence spectroscopic response from E-BGO pellets indicated that the samples exhibited a strong emission peak consistent with an x-ray induced luminescence of a E-BGO single crystal (500 nm excited at 285 nm). Cathodoluminescent properties of the E-BGO displayed a broadband spectrum with a maximum at 487 nm. The growth process was consistent with a standard Oswald ripening and LaMer growth processes.