ABSTRACT The growing demand for high‐performance lithium‐ion batteries necessitates the development of cathode materials that combine high capacity, structural stability, and rapid charge–discharge capability. First‐principles calculations predict that layered CrSe2 possesses a robust framework capable of accommodating one Li+ per formula unit while intrinsically supporting fast Li‐ion diffusion. Muon spin rotation (µ+SR) measurements validate this prediction, revealing fast Li+ diffusion in pre‐lithiated CrSe2. Consistent with these findings, electrochemical testing demonstrates a reversible capacity of 125.3 mAh g−1 at 0.1 C, approaching the theoretical value of 127.7 mAh g−1, with stable cycling and good rate capability. In operando X‐ray diffraction and electrochemical impedance spectroscopy further reveal a reversible topotactic transition and a lithiation‐driven core‐shell evolution during cycling. These results show that lithiation‐induced conductivity changes govern the electrochemical behavior of CrSe2, highlighting its potential as a high‐performance cathode for LIBs. This study provides new insight into intercalation processes in layered transition‐metal chalcogenides and informs the design of fast‐charging electrodes.

Abstract The synthesis of Er- and Nd-doped MoS2 powders by the co-pyrolysis of molecular precursors is demonstrated by heating tetrakis-(diethyldithiocarbamato) molybdenum(IV) (Mo(DTC)4) and mono-1,10-phenanthroline tris-(diethyl dithiocarbamato) erbium(III) or mono-1,10-phenanthroline tris-(diethyl dithiocarbamato) neodymium(III) (Ln(DTC)3phen, where Ln = Er, Nd) to 500 °C for 1 h. Powder x-ray diffraction and Raman spectroscopy indicated that the resulting powders produced from this reaction are comprised of 0D nanoscale crystallites of the 2 H phase of MoS2. Spatial mapping of elements in these samples was performed in the scanning electron microscope at the microscale using energy dispersive X-ray spectroscopic mapping, which showed that the dopants are homogeneously distributed throughout the samples. Synchrotron radiation x-ray absorption measurements tentatively indicate that the dopants are incorporated within the MoS2 layers rather than being intercalated between them. Electron paramagnetic resonance spectroscopy and SQUID magnetometry demonstrated that rare earth doping of MoS2 significantly enhances the magnetic response of the material. Remarkably, the samples are found to remain paramagnetic down to temperature at least as low as 2 K.

Refractory BCC high entropy alloy TiVZrNbHf is a promising material for solid-state hydrogen storage with high hydrogen sorption capacity but unfavourable thermodynamics of hydride phase, i.e. too stable hydride that need high temperature to reversibly recover the absorbed hydrogen. As an attempt to destabilize the hydride phase, this study reports on the effect of Al addition (limited concentrations: 5 and 10 at.%) into this alloy on the physicochemical and hydrogen sorption properties. Despite traces of a V-Al secondary phase, the BCC (TiVZrNbHf)1-xAlx alloys are random solid solutions which form high-capacity FCC hydride phases under hydrogen atmosphere at room temperature, as proven by synchrotron and neutron diffraction. Although Al decreases the hydrogen sorption capacity, the presence of a p element destabilizes the FCC hydride phase. A comparison with previous literature data helps understanding the role of Al which strongly depends on the chemical composition of the initial alloys. XANES studies allowed access to details of the electronic structure of the unoccupied levels complemented by density functional theory calculations. Moreover, the addition of Al favours the formation of larger open volume defects during hydride formation than the initial Al-free alloy which might explain the faster absorption kinetics in Al-containing alloys.

In the pursuit of more affordable battery technologies, potassium-ion batteries (KIBs) have emerged as a promising alternative to lithium-ion systems, owing to the abundance and wide distribution of potassium resources. While chalcogenides are uncommon as intercalation cathodes in KIBs, this study's electrochemical tests on CrSe2 revealed a reversible K+ intercalation/deintercalation process. The CrSe2 cathode achieved a KIB battery capacity of 125 mA h g-1 at a 0.1C rate within a practical 1-3.5 V vs. K+/K operation range, nearly matching the theoretical capacity of 127.7 mA h g-1. Notably, the battery retained 85% of its initial capacity at a high 1C rate, suggesting that CrSe2 is competitive for high-power applications with many current state-of-the-art cathodes. In-operando PXRD studies uncovered the nature of the intercalation behavior, revealing an initial biphasic region followed by a solid-solution formation during the potassium intercalation process. DFT calculations helped with the possible assignment of intermediate phase structures across the entire CrSe2-K1.0CrSe2 composition range, providing insights into the experimentally observed phase transformations. The results of this work underscore CrSe2's potential as a high-performance cathode material for KIBs, offering valuable insights into the intercalation mechanisms of layered transition metal chalcogenides and paving the way for future advancements in optimizing KIB cathodes.

The present work investigates the influence of ultrasonic irradiation on the properties of ZnO nanostructures. Slurries of ZnO prior formed by co-precipitation were irradiated by low-power ultrasound for different times. The properties of the samples were characterized by X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), Fourier transformed infrared (FTIR) absorption, scanning electron microscopy (SEM) and photoluminescence (PL). Ultrasonic waves induced significant variation in morphology of the particles. Needles, rods, rice-like and fragmented particles were detected in different treated samples. The irradiation also led to the formation of different types of point defects in the ZnO structure, varying in nature and density, which in turn affected the structural local ordering and luminescent efficiency. A possible growth mechanism of the particles is presented, and the type and origin of the formed point defects are discussed.

Magnesium batteries attract interest as alternative energy-storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg 2+ and the host structure. V 2 PS 10 is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g −1 is achieved with fast Mg 2+ diffusion of 7.2 10 −11 –4 10 −14  cm 2  s −1 . The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S 2 ) 2− site; enabled by reversible cleavage of S−S bonds, identified by X-ray photoelectron and X-ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred.

V2Se9 displays facile electrochemical insertion of up to 1.6 Mg2+ per unit formula with fast diffusion (coefficients of 10-10-10-12 cm2 s-1) surpassing best-in-class materials like Mo6S8. Detailed structural characterization of synchrotron X-ray diffraction data with ab initio Maximum Entropy Method analysis reveals Mg2+ insertion into octahedral sites within the large vdW space between [V4Se18]infinity chains. Fast rate performance is attributed to low structural perturbation and low diffusion barriers, calculated by bond valence pathway analysis, resulting from the low charge-per-size of anionic selenium. X-ray photoelectron spectroscopy and X-ray absorption spectroscopy reveal that reversible insertion of Mg2+ is facilitated by V5+/V3+ redox. V2Se9 demonstrates that selenides, despite their larger molecular weight, offer potential as fast-rate positive electrode materials for magnesium batteries over well-explored oxides and sulfides.

This article provides insights into building research capacity in computational modelling of materials at the University of Limpopo (UL), formerly University of the North, in South Africa, through a collaboration with a consortium of universities in the United Kingdom (UK) through the support of the National Research Foundation (NRF), formerly the Foundation for Research and Development, and the Royal Society (RS). A background that led to the choice of building research capacity at historically disadvantaged universities in South Africa, including the UL, is given. The modus operandi of the collaboration between the UL and several UK universities on computational modelling of materials is outlined, together with the scientific highlights that were achieved in themes of minerals, energy storage and alloy development. The capacity built in terms of human capital and institutions set up is shared, which is followed by a discussion of the continuing research activities after the formal NRF-RS collaboration ceased with more alignment to industrial applications with national and international support. We conclude by highlighting the success of the project in capacity-building and consolidating the Materials Modelling Centre with developments of high-performance computing in South Africa and the African continent. We comment on the lessons learned regarding successful capacity-building programmes.

The development of multielectron redox-active cathode materials is a top priority for achieving high energy density with long cycle life in the next-generation secondary battery applications. Triggering anion redox activity is regarded as a promising strategy to enhance the energy density of polyanionic cathodes for Li/Na-ion batteries. Herein, K2Fe(C2O4)2 is shown to be a promising new cathode material that combines metal redox activity with oxalate anion (C2O42-) redox. This compound reveals specific discharge capacities of 116 and 60 mAh g-1 for sodium-ion batterie (NIB) and lithium-ion batterie (LIB) cathode applications, respectively, at a rate of 10 mA g-1, with excellent cycling stability. The experimental results are complemented by density functional theory (DFT) calculations of the average atomic charges.

Aurivillius oxides have been a research focus due to their ferroelectric properties, but by replacing oxide ions by fluoride, divalent magnetic cations can be introduced, giving Bi2MO2F4 (M = Fe, Co, and Ni). Our combined experimental and computational study on Bi2CoO2F4 indicates a low-temperature polar structure of P21ab symmetry (analogous to ferroelectric Bi2WO6) and a ferrimagnetic ground state. These results highlight the potential of Aurivillius oxide-fluorides for multiferroic properties. Our research has also revealed some challenges associated with the reduced tendency for polar displacements in the more ionic fluoride-based systems.

Abstract Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‐ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‐doping on the electrochemical properties of P3‐type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‐Na0.67Mn0.9Zn0.1O2 and Oxy‐Na0.67Mn0.9Zn0.1O2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96 % of their initial capacity after 30 cycles, where Mn3+/Mn4+ redox dominates. Increasing the voltage range to 1.8–4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‐capacity and structurally stable oxygen redox‐based materials for SIBs.

Increased demand for lithium products for use in lithium-ion batteries has led to a search for new lithium resources in recent years to meet projected future consumption. One potential lithium resource is low lithium bearing brines that are discharged from hydraulically fractured oil and gas wells as flowback and produced water (FPW). In this way, hydraulic fracturing presents an opportunity to turn what is normally considered wastewater into a lithium resource. In this research, two manganese-based lithium-selective adsorbents were prepared using a co-precipitation method and were employed for lithium recovery from FPW. At optimized conditions, lithium uptake reached 18 mg g(-1) , with a > 80% lithium recovery within 30 min. The recovered lithium was isolated and concentrated to 15 mM in an acidic final product. The degree of sorbent loss during acid desorption of lithium was significantly higher for sorbents used in the FPW as compared to recovery from a synthetic lithium bearing brine (4.5% versus 0.8%). Thus, we propose that organic molecules present in the FPW reduce manganese in the sorbent structure during lithium sorption, leading to increased sorbent loss through reductive dissolution. Systematic characterization including wet chemical manganese valence measurements, along with EXAFS, XPS, and TEM-EELS show that exposure to FPW causes tetravalent manganese in the bulk sorbent structure to be reduced during lithium sorption, which subsequently dissolves during acid desorption. Partial removal of these organic molecules by nanofiltration leads to decreased sorbent dissolution in acid. In this way, we show that dissolved organic molecules represent a critical control on the reductive dissolution of manganese based lithium ion exchange sorbents. This research provides promising results on the use of manganese-based lithium sorbents in FPW.

We present a personal account of both the developments in technique and instrumentation led by Neville Greaves and the scientific applications which they enabled. We focus on the pioneering period at the Synchrotron Radiation Source, Daresbury in the 1980s and 90s. We discuss and illustrate the lasting impact of these key developments on chemistry, materials and catalytic science

Bulk isocubanite (CuFe2S3) was synthesized via a multistep high-temperature synthesis and was investigated as an anode material for sodium-ion batteries. CuFe2S3 exhibits an excellent electrochemical performance with a capacity retention of 422 mA h g-1 for more than 1000 cycles at a current rate of 0.5 A g-1 (0.85 C). The complex reaction mechanism of the first cycle was investigated via PXRD and X-ray absorption spectroscopy. At the early stages of Na uptake, CuFe2S3 is converted to form crystalline CuFeS2 and nanocrystalline NaFe1.5S2 simultaneously. By increasing the Na content, Cu+ is reduced to nanocrystalline Cu, followed by the reduction of Fe2+ to amorphous Fe0 while reflections of nanocrystalline Na2S appear. During charging up to -5 Na/f.u., the intermediate NaFe1.5S2 appears again, which transforms in the last step of charging to a new unknown phase. This unknown phase together with NaFe1.5S2 plays a key role in the mechanism for the following cycles, evidenced by the PXRD investigation of the second cycle. Even after 400 cycles, the occurrence of nanocrystalline phases made it possible to gain insights into the alteration of the mechanism, which shows that CuxS phases play an important role in the region of constant specific capacity.

Platinum functions exceptionally well as a nanoparticulate catalyst in many important fields, such as in the removal of atmospheric pollutants, but it is scarce, expensive and not always sufficiently durable. Here, we report a perovskite system in which 0.5 wt% Pt is integrated into the support and its subsequent conversion through exsolution to achieve a resilient catalyst. Owing to the instability of most Pt oxides at high temperatures, a thermally stable platinum oxide precursor, barium platinate, was used to preserve the platinum as an oxide during the solid-state synthesis in an approach akin to the Trojan horse legend. By tailoring the procedure, it is possible to produce a uniform equilibrated structure with active emergent Pt nanoparticles strongly embedded in the perovskite surface that display better CO oxidation activity and stability than those of conventionally prepared Pt catalysts. This catalyst was further evaluated for a variety of reactions under realistic test environments—CO and NO oxidation, diesel oxidation catalysis and ammonia slip reactions were investigated.

The effects of mechanochemical synthesis and postsynthetic grinding on the spin crossover material [Fe(atrz)3](BF4)2 was examined in detail using a combination of X-ray diffraction, magnetometry, EXAFS and TEM. Mechanochemical synthesis yielded a different polymorph (β-phase) to the solution synthesised sample (α-phase), with a lower temperature spin crossover. Milling duration did not significantly affect this temperature but did result in the production of smaller nanoparticles with a narrower size distribution. It is also possible to convert from α- to the β-phase via postsynthetic grinding.

A synthesis method for the preparation of mixed manganese-ruthenium oxides is presented along with a detailed characterisation of the solids produced. The use of 1 M aqueous sulfuric acid mediates the redox reaction between KRuO4, KMnO4 and Mn2+ to form ternary oxides. At reaction temperature of 100 °C the products are mixtures of α-MnO2 (hollandite-type) and β-MnO2 (rutile-type), with some evidence of Ru incorporation in each from their expanded unit cell volumes. At reaction temperature of 200 °C solid-solutions β-Mn1-xRuxO2 are formed and materials with x ≤ 0.6 have been studied. The amount of Ru included in the oxide is greater than expected from the ratio of metals used in the synthesis, as determined by elemental analysis, implying that some Mn remains unreacted in solution. Powder X-ray diffraction (XRD) shows that while the unit cell volume expands in a linear manner, following Vegard's law, the tetragonal lattice parameters, and the a/c ratio, do not follow the extrapolated trends: this anisotropic behaviour is consistent with the different local coordination of the metals in the end members. Powder XRD patterns show increased peak broadening with increasing ruthenium content, which is corroborated by electron microscopy that shows nanocrystalline material. X-ray absorption near-edge spectra show that the average oxidation state of Mn in the solid solutions is reduced below +4 while that of Ru is increased above +4, suggesting some redistribution of charge. Analysis of the extended X-ray absorption fine structure provides complementary local structural information, confirming the formation of a solid solution, while X-ray photoelectron spectroscopy shows that the surface oxidation states of both Ru and Mn are on average lower than +4, suggesting a disordered surface layer may be present in the materials.

Determining the nature, evolution, and impact of acid-generating sulfur deposits in the Mary Rose wooden hull is crucial for protecting Henry VIII's famous warship for generations to come. Here, a comprehensive X-ray absorption near-edge spectroscopy (XANES) and X-ray fluorescence (XRF) study sheds vital light on the evolution of complex sulfur-based compounds lodged in Mary Rose timbers as a function of drying time. Combining insights from infrared spectroscopy correlates the presence of oxidized sulfur species with increased wood degradation via the loss of major wood components (holocellulose). Intriguingly, zinc is found to co-exist with iron and sulfur in the most degraded wood regions, indicating its potential contributing role to wood degradation. This study provides crucial information on the degradation processes and resulting products within the wood, which can be used to develop remediation strategies to save the Mary Rose.

Lithium-rich layered oxides and sodium layered oxides represent attractive positive electrode materials exhibiting excess capacity delivered by additional oxygen redox activity. However, structural degradation in the bulk and detrimental reactions with the electrolyte on the surface often occur, leading to limited reversibility of oxygen redox processes. Here, we present the properties of P3-type Na0.67Mg0.2Mn0.8O2 synthesized under both air and oxygen. Both materials exhibit stable cycling performance in the voltage range of 1.8-3.8 V, where the Mn3+/Mn4+ redox couple entirely dominates the electrochemical reaction. Oxygen redox activity is triggered for both compounds in the wider voltage window 1.8-4.3 V with typical large voltage hysteresis from nonbonding O 2p states generated by substituted Mg. Interestingly, for the compound prepared under oxygen, an additional novel reversible oxygen redox activity is shown with an exceptionally small voltage hysteresis (20 mV). The presence of vacancies in the transition-metal layers is shown to play a critical role not only in forming unpaired O 2p states independent of substituted elements but also in stabilizing the P3 structure during charge with reduced structural transformation to the O'3 phase at the end of discharge. This study reveals the important role of vacancies in P3-type sodium layered oxides to increase energy density using both cationic and anionic redox processes.

Increasing dependence on rechargeable batteries for energy storage calls for the improvement of energy density of batteries. Toward this goal, introduction of positive electrode materials with high...