Abstract
Polyanion compounds offer a playground for designing prospective electrode active materials for sodium-ion storage due to their structural diversity and chemical variety. Here, by combining ...a NaVPO
4
F composition and KTiOPO
4
-type framework via a low-temperature (e.g., 190 °C) ion-exchange synthesis approach, we develop a high-capacity and high-voltage positive electrode active material. When tested in a coin cell configuration in combination with a Na metal negative electrode and a NaPF
6
-based non-aqueous electrolyte solution, this cathode active material enables a discharge capacity of 136 mAh g
−1
at 14.3 mA g
−1
with an average cell discharge voltage of about 4.0 V. Furthermore, a specific discharge capacity of 123 mAh g
−1
at 5.7 A g
−1
is also reported for the same cell configuration. Through ex situ and
operando
structural characterizations, we also demonstrate that the reversible Na-ion storage at the positive electrode occurs mostly via a solid-solution de/insertion mechanism.
The Last Glacial Maximum (LGM, ∼ 21 000 years ago) has been a major focus for evaluating how well state-of-the-art climate models simulate climate changes as large as those expected in the future ...using paleoclimate reconstructions. A new generation of climate models has been used to generate LGM simulations as part of the Paleoclimate Modelling Intercomparison Project (PMIP) contribution to the Coupled Model Intercomparison Project (CMIP). Here, we provide a preliminary analysis and evaluation of the results of these LGM experiments (PMIP4, most of which are PMIP4-CMIP6) and compare them with the previous generation of simulations (PMIP3, most of which are PMIP3-CMIP5). We show that the global averages of the PMIP4 simulations span a larger range in terms of mean annual surface air temperature and mean annual precipitation compared to the PMIP3-CMIP5 simulations, with some PMIP4 simulations reaching a globally colder and drier state. However, the multi-model global cooling average is similar for the PMIP4 and PMIP3 ensembles, while the multi-model PMIP4 mean annual precipitation average is drier than the PMIP3 one. There are important differences in both atmospheric and oceanic circulations between the two sets of experiments, with the northern and southern jet streams being more poleward and the changes in the Atlantic Meridional Overturning Circulation being less pronounced in the PMIP4-CMIP6 simulations than in the PMIP3-CMIP5 simulations. Changes in simulated precipitation patterns are influenced by both temperature and circulation changes. Differences in simulated climate between individual models remain large. Therefore, although there are differences in the average behaviour across the two ensembles, the new simulation results are not fundamentally different from the PMIP3-CMIP5 results. Evaluation of large-scale climate features, such as land–sea contrast and polar amplification, confirms that the models capture these well and within the uncertainty of the paleoclimate reconstructions. Nevertheless, regional climate changes are less well simulated: the models underestimate extratropical cooling, particularly in winter, and precipitation changes. These results point to the utility of using paleoclimate simulations to understand the mechanisms of climate change and evaluate model performance.
Using the strong reduction potential of the liquid NaK-78 alloy, we present a new versatile template-free approach to the synthesis of porous metal- and metalloid-based nanomaterials. With this novel ...approach, NaK can be simultaneously used as an agent for reduction, structure directing, and pore formation without the use of additional reagents.
Using the liquid NaK alloy, we present a new versatile approach to the synthesis of porous metal- and metalloid-based nanomaterials. NaK alloy can be simultaneously used as an agent for reduction, structure directing, and pore formation.
The mid-Holocene (6000 years ago) is a standard time period for the evaluation of the simulated response of global climate models using palaeoclimate reconstructions. The latest mid-Holocene ...simulations are a palaeoclimate entry card for the Palaeoclimate Model Intercomparison Project (PMIP4) component of the current phase of the Coupled Model Intercomparison Project (CMIP6) – hereafter referred to as PMIP4-CMIP6. Here we provide an initial analysis and evaluation of the results of the experiment for the mid-Holocene. We show that state-of-the-art models produce climate changes that are broadly consistent with theory and observations, including increased summer warming of the Northern Hemisphere and associated shifts in tropical rainfall. Many features of the PMIP4-CMIP6 simulations were present in the previous generation (PMIP3-CMIP5) of simulations. The PMIP4-CMIP6 ensemble for the mid-Holocene has a global mean temperature change of −0.3 K, which is −0.2 K cooler than the PMIP3-CMIP5 simulations predominantly as a result of the prescription of realistic greenhouse gas concentrations in PMIP4-CMIP6. Biases in the magnitude and the sign of regional responses identified in PMIP3-CMIP5, such as the amplification of the northern African monsoon, precipitation changes over Europe, and simulated aridity in mid-Eurasia, are still present in the PMIP4-CMIP6 simulations. Despite these issues, PMIP4-CMIP6 and the mid-Holocene provide an opportunity both for quantitative evaluation and derivation of emergent constraints on the hydrological cycle, feedback strength, and potentially climate sensitivity.
The modeling of paleoclimate, using physically based tools, is increasingly seen as a strong out-of-sample test of the models that are used for the projection of future climate changes. New to the ...Coupled Model Intercomparison Project (CMIP6) is the Tier 1 Last Interglacial experiment for 127 000 years ago (lig127k), designed to address the climate responses to stronger orbital forcing than the midHolocene experiment, using the same state-of-the-art models as for the future and following a common experimental protocol. Here we present a first analysis of a multi-model ensemble of 17 climate models, all of which have completed the CMIP6 DECK (Diagnostic, Evaluation and Characterization of Klima) experiments. The equilibrium climate sensitivity (ECS) of these models varies from 1.8 to 5.6°C. The seasonal character of the insolation anomalies results in strong summer warming over the Northern Hemisphere continents in the lig127k ensemble as compared to the CMIP6 piControl and much-reduced minimum sea ice in the Arctic. The multi-model results indicate enhanced summer monsoonal precipitation in the Northern Hemisphere and reductions in the Southern Hemisphere. These responses are greater in the lig127k than the CMIP6 midHolocene simulations as expected from the larger insolation anomalies at 127 than 6 ka.
New synthesis for surface temperature and precipitation, targeted for 127 ka, have been developed for comparison to the multi-model ensemble. The lig127k model ensemble and data reconstructions are in good agreement for summer temperature anomalies over Canada, Scandinavia, and the North Atlantic and for precipitation over the Northern Hemisphere continents. The model–data comparisons and mismatches point to further study of the sensitivity of the simulations to uncertainties in the boundary conditions and of the uncertainties and sparse coverage in current proxy reconstructions.
The CMIP6–Paleoclimate Modeling Intercomparison Project (PMIP4) lig127k simulations, in combination with the proxy record, improve our confidence in future projections of monsoons, surface temperature, and Arctic sea ice, thus providing a key target for model evaluation and optimization.
El Niño–Southern Oscillation (ENSO) is the strongest mode of interannual climate variability in the current climate, influencing ecosystems, agriculture, and weather systems across the globe, but ...future projections of ENSO frequency and amplitude remain highly uncertain. A comparison of changes in ENSO in a range of past and future climate simulations can provide insights into the sensitivity of ENSO to changes in the mean state, including changes in the seasonality of incoming solar radiation, global average temperatures, and spatial patterns of sea surface temperatures. As a comprehensive set of coupled model simulations is now available for both palaeoclimate time slices (the Last Glacial Maximum, mid-Holocene, and last interglacial) and idealised future warming scenarios (1 % per year CO2 increase, abrupt four-time CO2 increase), this allows a detailed evaluation of ENSO changes in this wide range of climates. Such a comparison can assist in constraining uncertainty in future projections, providing insights into model agreement and the sensitivity of ENSO to a range of factors. The majority of models simulate a consistent weakening of ENSO activity in the last interglacial and mid-Holocene experiments, and there is an ensemble mean reduction of variability in the western equatorial Pacific in the Last Glacial Maximum experiments. Changes in global temperature produce a weaker precipitation response to ENSO in the cold Last Glacial Maximum experiments and an enhanced precipitation response to ENSO in the warm increased CO2 experiments. No consistent relationship between changes in ENSO amplitude and annual cycle was identified across experiments.
Alzheimer's disease (AD) is the leading cause of dementia among the elderly. Neuropathologically, AD is characterized by the deposition of a 39- to 42-amino acid long β-amyloid (Aβ) peptide in the ...form of senile plaques. Several post-translational modifications (PTMs) in the N-terminal domain have been shown to increase the aggregation and cytotoxicity of Aβ, and specific Aβ proteoforms (e.g., Aβ with isomerized D7 (isoD7-Aβ)) are abundant in the senile plaques of AD patients. Animal models are indispensable tools for the study of disease pathogenesis, as well as preclinical testing. In the presented work, the accumulation dynamics of Aβ proteoforms in the brain of one of the most widely used amyloid-based mouse models (the 5xFAD line) was monitored. Mass spectrometry (MS) approaches, based on ion mobility separation and the characteristic fragment ion formation, were applied. The results indicated a gradual increase in the Aβ fraction of isoD7-Aβ, starting from approximately 8% at 7 months to approximately 30% by 23 months of age. Other specific PTMs, in particular, pyroglutamylation, deamidation, and oxidation, as well as phosphorylation, were also monitored. The results for mice of different ages demonstrated that the accumulation of Aβ proteoforms correlate with the formation of Aβ deposits. Although the mouse model cannot be a complete analogue of the processes occurring in the human brain in AD, and several of the observed parameters differ significantly from human values supposedly due to the limited lifespan of the model animals, this dynamic study provides evidence on at least one of the possible mechanisms that can trigger amyloidosis in AD, i.e., the hypothesis on the relationship between the accumulation of isoD7-Aβ and the progression of AD-like pathology.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Potassium-ion batteries are an emerging post-lithium technology that are considered ecologically and economically benign in terms of raw materials’ abundance and cost. Conventional cell ...configurations employ flammable liquid electrolytes that impose safety concerns, as well as considerable degrees of irreversible side reactions at the reactive electrode interfaces (especially against potassium metal), resulting in a rapid capacity fade. While being inherently safer, solid polymer electrolytes may present a solution to capacity losses owing to their broad electrochemical stability window. Herein, we present for the first time a stable solid-state potassium battery composed of a potassium metal negative electrode, a Prussian blue analogue K2FeFe(CN)6 positive electrode, and a poly(ethylene oxide)-potassium bis(trifluoromethanesulfonyl)imide polymer electrolyte. At an elevated operating temperature of 55 °C, the solid-state battery achieved a superior capacity retention of 90% over 50 cycles in direct comparison to a conventional carbonate-based liquid electrolyte operated at ambient temperature with a capacity retention of only 66% over the same cycle number interval.
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IJS, KILJ, NUK, PNG, UL, UM
The early Eocene (∼56–48 Myr ago) is characterized by high CO2 estimates (1,200–2,500 ppmv) and elevated global temperatures (∼10°C–16°C higher than modern). However, the response of the hydrological ...cycle during the early Eocene is poorly constrained, especially in regions with sparse data coverage (e.g., Africa). Here, we present a study of African hydroclimate during the early Eocene, as simulated by an ensemble of state‐of‐the‐art climate models in the Deep‐time Model Intercomparison Project (DeepMIP). A comparison between the DeepMIP pre‐industrial simulations and modern observations suggests that model biases are model‐ and geographically dependent, however, these biases are reduced in the model ensemble mean. A comparison between the Eocene simulations and the pre‐industrial suggests that there is no obvious wetting or drying trend as the CO2 increases. The results suggest that changes to the land sea mask (relative to modern) in the models may be responsible for the simulated increases in precipitation to the north of Eocene Africa. There is an increase in precipitation over equatorial and West Africa and associated drying over northern Africa as CO2 rises. There are also important dynamical changes, with evidence that anticyclonic low‐level circulation is replaced by increased south‐westerly flow at high CO2 levels. Lastly, a model‐data comparison using newly compiled quantitative climate estimates from paleobotanical proxy data suggests a marginally better fit with the reconstructions at lower levels of CO2.
Plain Language Summary
Approximately 50 Myr ago, a period known as the early Eocene, atmospheric carbon dioxide levels were significantly higher than today, and were more similar to what they could be in the future, if efforts to reduce human greenhouse gas emissions are unsuccessful. However, rainfall changes during this period are less well understood, especially over data‐sparse regions such as Africa. Here, a collection of state‐of‐the‐art climate models are used to study African rainfall during this period, comparing the simulations first to present‐day African rainfall (to validate the models), second to varying levels of atmospheric carbon dioxide, and lastly to newly compiled reconstructions of early Eocene rainfall (from plant fossils). The main findings are that although the models can reproduce present‐day rainfall over Africa, and compare reasonably well with the reconstructions, there is no clear rainfall signal when atmospheric carbon dioxide is increased. Nevertheless, the combination of a different continental configuration, vegetation, topography, and atmospheric carbon dioxide leads to changing rainfall patterns, connected to temperature and low‐level wind changes.
Key Points
State‐of‐the‐art climate models are used to study African hydroclimate during the early Eocene (approximately 50 Myr ago)
With increasing levels of CO2, there are changes to African precipitation, due to dynamical changes such as low‐level circulation
A comparison between the models and newly compiled climate estimates shows a marginally better match at lower levels of CO2
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The Prussian Blue analogue K2−δMnFe(CN)61−ɣ∙nH2O is regarded as a key candidate for potassium-ion battery positive electrode materials due to its high specific capacity and redox potential, easy ...scalability, and low cost. However, various intrinsic defects, such as water in the crystal lattice, can drastically affect electrochemical performance. In this work, we varied the water content in K2−δMnFe(CN)61−ɣ∙nH2O by using a vacuum/air drying procedure and investigated its effect on the crystal structure, chemical composition and electrochemical properties. The crystal structure of K2−δMnFe(CN)61−ɣ∙nH2O was, for the first time, Rietveld-refined, based on neutron powder diffraction data at 10 and 300 K, suggesting a new structural model with the Pc space group in accordance with Mössbauer spectroscopy. The chemical composition was characterized by thermogravimetric analysis combined with mass spectroscopy, scanning transmission electron microscopy microanalysis and infrared spectroscopy. Nanosized cathode materials delivered electrochemical specific capacities of 130–134 mAh g−1 at 30 mA g−1 (C/5) in the 2.5–4.5 V (vs. K+/K) potential range. Diffusion coefficients determined by potentiostatic intermittent titration in a three-electrode cell reached 10−13 cm2 s−1 after full potassium extraction. It was shown that drying triggers no significant changes in crystal structure, iron oxidation state or electrochemical performance, though the water level clearly decreased from the pristine to air- and vacuum-dried samples.
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