High Reversibility of Lattice Oxygen Redox in Na-ion and Li-ion Batteries Quantified by Direct Bulk Probes of both Anionic and Cationic Redox Reactions

The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The bulk-Mn redox emerges from initial discharge and is quantified by inverse-partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen-redox reversibility during initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice-oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice-oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice-oxygen redox from other oxygen activities for clarifying its intrinsic properties.Comment: 33 pages, 8 Figures. Plus 14 pages of Supplementary Materials with 12 Figure

New evidence on palaeoenvironmental conditions in SW Cameroon since the Late Pleistocene derived from alluvial sediments of the Ntem River

An interior delta in the lower course of the Ntem River near the sub-prefecture Ma’an was identified after interpretation of satellite images, topographical maps of SW Cameroon and geological as well as hydrological references and a reconnaissance fieldtrip to the study area. Here neotectonic processes have initiated the establishment of a ‘sediment trap’ (step fault), which in combination with environmental changes strongly generated the fluvial morphology. It transitionally led to temporary lacustrine and palustrine conditions in parts of this river section. Inside the interior delta an anastomosing multi-branched river system has developed, which contains ‘stillwater locations', periodically inundated sections, islands and rapids. Following geomorphological, physiogeographical and sedimentological research approaches, the alluvial plain has been prospected and studied extensively. 91 hand-corings, including three NE–SW transects, were carried out on river benches, levees, cut-off and periodical branches, islands as well as terraces throughout the entire alluvial plain and have unveiled multi-layered, sandy to clayey alluvia reaching up to 440 cm depth. At many locations, fossil organic horizons and palaeosurfaces were discovered, containing valuable palaeoenvironmental proxy data. At these sites, through additional detailed stratigraphical analysis (close-meshed hand-coring and exposure digging) a comprehensive insight into the stratification (lamination) of the alluvia could be gained, clarifying processes and conditions that prevailed in the catchment area during the period of their deposition. 32 Radiocarbon data of macro-rests (leafs, wood), charcoal and organic sediment sampled from these horizons provided ages between 48.230 ± 6.411 and 217 ± 46 years BP (not calibrated). This constitutes the importance of the alluvia as an additional, innovative palaeoarchive for proxy data contributing to the reconstruction of palaeoenvironment and palaeoclimate in western Equatorial Africa. The further examination of the alluvia will not only provide additional information on the dynamics of vegetation, climate and hydrology (esp. fluvial morphology) in SW Cameroon since the ‘First Millennium BC Crisis’ (around 3.000 years BP), the main focus of the DFG-research project, but also on conditions prevailing since the Late Pleistocene, during the Last Glacial Maximum (~18.000 years BP), the Younger Dryas impact (~11.000 years BP) and the ‘Humid African Period’ (~9.000–6.000 years BP). Delta13C-values (–31,4 to –26,4‰) evidence that at the particular drilling sites rain forest has prevailed during the corresponding time period (rain forest refuge theory). The sampled macrorests all indicate rain forest dominated ecosystems, which were able to persist in fluvial habitats, even during arid periods

Western Mediterranean climate and environment since Marine Isotope Stage 3: a 50,000-year record from Lake Banyoles, Spain

We present new stable isotope (δ¹⁸Ocalcite and δ¹³ Ccalcite) and diatom data from a 67-m sediment core (BAN II) from Lake Banyoles, northeastern Spain. We reassessed the chronology of the sequence by correlating stable isotope data with a shorter U-series-dated record from the lake, confirming a sedimentological offset between the two cores and demonstrating that BAN II spans Marine Isotope Stages (MIS) 3–1. Through comparison with previous records, the multi-proxy data are used to improve understanding of palaeolimnological dynamics and, by inference, western Mediterranean climate and environmental change during the past ca. 50,000 years. Three main zones, defined by isotope and diatom data, correspond to the MIS. The basal zone (MIS 3) is characterised by fluctuating δ¹⁸Ocalcite and benthic diatom abundance, indicating a high degree of environmental and climate variability, concomitant with large lake-level changes. During the full glacial (MIS 2), relatively constant δ¹⁸Ocalcite and a poorly preserved planktonic-dominated diatom assemblage suggest stability, and intermittently, unusually high lake level. In MIS 1, δ¹⁸Ocalcite and δ¹³Ccalcite initially transition to lower values, recording a pattern of Late Glacial to Holocene change that is similar to other Mediterranean records. This study suggests that Lake Banyoles responds limnologically to changes in the North Atlantic ocean–atmosphere system and provides an important dataset from the Iberian Peninsula, a region in need of longer-term records that can be used to correlate between marine and terrestrial archives, and between the western and eastern Mediterranean