Solvent-dependent iodide interactions in LiO2 electrolytes - a molecular dynamics study.

Iodide-based redox mediation in Li-O2 batteries is regarded as a promising system due to its relatively high round-trip efficiency, compared to alternative systems. Here we explore the role of electrolyte composition in the solvation of I-, which has been shown to be critical for the efficient operation of this redox mediator, using a molecular dynamics approach. A combinatorial exploration of I- and H2O concentrations was performed, for a fixed concentration of Li+, across a series of glymes, with increasing chain length (mono- to tetraglyme). The resulting radial distribution functions show that shorter glymes allow for a closer packing of the I- redox mediator. Furthermore, increasing the I- concentration also reduces the solvation of Li+ in the glymes, especially in G2. The presence of water further pulls the I- and Li+ together. With increasing water content, its presence in the iodide's coordination shell increases markedly - an effect most pronounced for monoglyme. Competition between Li+ and I- for the coordination of water is modulated by the different solvents as they perturb the local coordination shell of these important complexes, with longer chain lengths being less affected by increases in water concentrations.

Clarifying the Dopant Local Structure and Effect on Ionic Conductivity in Garnet Solid-State Electrolytes for Lithium-Ion Batteries.

The high Li-ion conductivity and wide electrochemical stability of Li-rich garnets (Li7La3Zr2O12) make them one of the leading solid electrolyte candidates for solid-state batteries. Dopants such as Al and Ga are typically used to enable stabilization of the high Li+ ion-conductive cubic phase at room temperature. Although numerous studies exist that have characterized the electrochemical properties, structure, and lithium diffusion in Al- and Ga-LLZO, the local structure and site occupancy of dopants in these compounds are not well understood. Two broad 27Al or 69,71Ga resonances are often observed with chemical shifts consistent with tetrahedrally coordinated Al/Ga in the magic angle spinning nuclear magnetic resonance (MAS NMR) spectra of both Al- and Ga-LLZO, which have been assigned to either Al and/or Ga occupying 24d and 96h/48g sites in the LLZO lattice or the different Al/Ga configurations that arise from different arrangements of Li around these dopants. In this work, we unambiguously show that the side products γ-LiAlO2 and LiGaO2 lead to the high frequency resonances observed by NMR spectroscopy and that both Al and Ga only occupy the 24d site in the LLZO lattice. Furthermore, it was observed that the excess Li often used during synthesis leads to the formation of these side products by consuming the Al/Ga dopants. In addition, the consumption of Al/Ga dopants leads to the tetragonal phase formation commonly observed in the literature, even after careful mixing of precursors. The side-products can exist even after sintering, thereby controlling the Al/Ga content in the LLZO lattice and substantially influencing the lithium-ion conductivity in LLZO, as measured here by electrochemical impedance spectroscopy.

Revealing carbon capture chemistry with 17-oxygen NMR spectroscopy.

Carbon dioxide capture is essential to achieve net-zero emissions. A hurdle to the design of improved capture materials is the lack of adequate tools to characterise how CO2 adsorbs. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a promising probe of CO2 capture, but it remains challenging to distinguish different adsorption products. Here we perform a comprehensive computational investigation of 22 amine-functionalised metal-organic frameworks and discover that 17O NMR is a powerful probe of CO2 capture chemistry that provides excellent differentiation of ammonium carbamate and carbamic acid species. The computational findings are supported by 17O NMR experiments on a series of CO2-loaded frameworks that clearly identify ammonium carbamate chain formation and provide evidence for a mixed carbamic acid - ammonium carbamate adsorption mode. We further find that carbamic acid formation is more prevalent in this materials class than previously believed. Finally, we show that our methods are readily applicable to other adsorbents, and find support for ammonium carbamate formation in amine-grafted silicas. Our work paves the way for investigations of carbon capture chemistry that can enable materials design.

Quantifying the roles of seed dispersal, filtering, and climate on regional patterns of grassland biodiversity.

Seed dispersal and local filtering interactively govern community membership and scale up to shape regional vegetation patterns, but data revealing how and why particular species are excluded from specific communities in nature are scarce. This lack of data is a missing link between our theoretical understanding of how diversity patterns can form and how they actually form in nature, and it hampers our ability to predict community responses to climate change. Here, we compare seed, seedling, and adult plant communities at 12 grassland sites with different climates in southern Norway to examine how community membership is interactively shaped by seed dispersal and local filtering, and how this process varies with climate across sites. To do this, we divide species at each site into two groups: locally transient species, which occur as seeds but are rare or absent as adults (i.e., they arrive but are filtered out), and locally persistent species, which occur consistently as adults in annual vegetation surveys. We then ask how and why locally transient species are disfavored during community assembly. Our results led to four main conclusions: (1) the total numbers of seeds and species that arrived, but failed to establish locally persistent populations, rose with temperature, indicating an increase in the realized effects of local filtering on community assembly, as well as an increase in the number of species poised to rapidly colonize those warmer sites if local conditions change in their favor, (2) locally transient species were selectively filtered out during seedling emergence, but not during seedling establishment, (3) selective filtering was partly driven by species climate preferences, exemplified by the poor performance of seeds dispersing outside of their realized climate niches into colder and drier foreign climates, and (4) locally transient species had traits that likely made them better dispersers (i.e., smaller seeds) but poorer competitors for light (i.e., shorter statures and less persistent clonal connections) than locally persistent species, potentially explaining why these species arrived to new sites but did not establish locally persistent adult populations. Our study is the first to combine seed, seedling, and adult survey data across sites to rigorously characterize how seed dispersal and local filtering govern community membership and shape climate-associated vegetation patterns.