Phase segregation and nanoconfined fluid O2 in a lithium-rich oxide cathode.

Lithium-rich oxide cathodes lose energy density during cycling due to atomic disordering and nanoscale structural rearrangements, which are both challenging to characterize. Here we resolve the kinetics and thermodynamics of these processes in an exemplar layered Li-rich (Li1.2-xMn0.8O2) cathode using a combined approach of ab initio molecular dynamics and cluster expansion-based Monte Carlo simulations. We identify a kinetically accessible and thermodynamically favourable mechanism to form O2 molecules in the bulk, involving Mn migration and driven by interlayer oxygen dimerization. At the top of charge, the bulk structure locally phase segregates into MnO2-rich regions and Mn-deficient nanovoids, which contain O2 molecules as a nanoconfined fluid. These nanovoids are connected in a percolating network, potentially allowing long-range oxygen transport and linking bulk O2 formation to surface O2 loss. These insights highlight the importance of developing strategies to kinetically stabilize the bulk structure of Li-rich O-redox cathodes to maintain their high energy densities.

Anion-polarisation-directed short-range-order in antiperovskite Li2FeSO.

Short-range ordering in cation-disordered cathodes can have a significant effect on their electrochemical properties. Here, we characterise the cation short-range order in the antiperovskite cathode material Li2FeSO, using density functional theory, Monte Carlo simulations, and synchrotron X-ray pair-distribution-function data. We predict partial short-range cation-ordering, characterised by favourable OLi4Fe2 oxygen coordination with a preference for polar cis-OLi4Fe2 over non-polar trans-OLi4Fe2 configurations. This preference for polar cation configurations produces long-range disorder, in agreement with experimental data. The predicted short-range-order preference contrasts with that for a simple point-charge model, which instead predicts preferential trans-OLi4Fe2 oxygen coordination and corresponding long-range crystallographic order. The absence of long-range order in Li2FeSO can therefore be attributed to the relative stability of cis-OLi4Fe2 and other non-OLi4Fe2 oxygen-coordination motifs. We show that this effect is associated with the polarisation of oxide and sulfide anions in polar coordination environments, which stabilises these polar short-range cation orderings. We propose that similar anion-polarisation-directed short-range-ordering may be present in other heterocationic materials that contain cations with different formal charges. Our analysis illustrates the limitations of using simple point-charge models to predict the structure of cation-disordered materials, where other factors, such as anion polarisation, may play a critical role in directing both short- and long-range structural correlations.

Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes.

Lithium-rich disordered rocksalt cathodes display high capacities arising from redox chemistry on both transition-metal ions (TM-redox) and oxygen ions (O-redox), making them promising candidates for next-generation lithium-ion batteries. However, the atomic-scale mechanisms governing O-redox behaviour in disordered structures are not fully understood. Here we show that, at high states of charge in the disordered rocksalt Li2MnO2F, transition metal migration is necessary for the formation of molecular O2 trapped in the bulk. Density functional theory calculations reveal that O2 is thermodynamically favoured over other oxidised O species, which is confirmed by resonant inelastic X-ray scattering data showing only O2 forms. When O-redox involves irreversible Mn migration, this mechanism results in a path-dependent voltage hysteresis between charge and discharge, commensurate with the hysteresis observed electrochemically. The implications are that irreversible transition metal migration should be suppressed to reduce the voltage hysteresis that afflicts O-redox disordered rocksalt cathodes.

Shock-formed carbon materials with intergrown sp3- and sp2-bonded nanostructured units.

Studies of dense carbon materials formed by bolide impacts or produced by laboratory compression provide key information on the high-pressure behavior of carbon and for identifying and designing unique structures for technological applications. However, a major obstacle to studying and designing these materials is an incomplete understanding of their fundamental structures. Here, we report the remarkable structural diversity of cubic/hexagonally (c/h) stacked diamond and their association with diamond-graphite nanocomposites containing sp3-/sp2-bonding patterns, i.e., diaphites, from hard carbon materials formed by shock impact of graphite in the Canyon Diablo iron meteorite. We show evidence for a range of intergrowth types and nanostructures containing unusually short (0.31 nm) graphene spacings and demonstrate that previously neglected or misinterpreted Raman bands can be associated with diaphite structures. Our study provides a structural understanding of the material known as lonsdaleite, previously described as hexagonal diamond, and extends this understanding to other natural and synthetic ultrahard carbon phases. The unique three-dimensional carbon architectures encountered in shock-formed samples can place constraints on the pressure-temperature conditions experienced during an impact and provide exceptional opportunities to engineer the properties of carbon nanocomposite materials and phase assemblages.

Probing Mg Intercalation in the Tetragonal Tungsten Bronze Framework V4Nb18O55.

While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg2+ insertion and extraction at high voltages; this is thought to be due to poor Mg2+ diffusion kinetics within the oxide structural framework. Herein, the authors provide conclusive evidence of electrochemical insertion of Mg2+ into the tetragonal tungsten bronze V4Nb18O55, with a maximum reversible electrochemical capacity of 75 mA h g-1, which corresponds to a magnesiated composition of Mg4V4Nb18O55. Experimental electrochemical magnesiation/demagnesiation revealed a large voltage hysteresis with charge/discharge (1.12 V vs Mg/Mg2+); when magnesiation is limited to a composition of Mg2V4Nb18O55, this hysteresis can be reduced to only 0.5 V. Hybrid-exchange density functional theory (DFT) calculations suggest that a limited number of Mg sites are accessible via low-energy diffusion pathways, but that larger kinetic barriers need to be overcome to access the entire structure. The reversible Mg2+ intercalation involved concurrent V and Nb redox activity and changes in crystal structure, as confirmed by an array of complementary methods, including powder X-ray diffraction, X-ray absorption spectroscopy, and energy-dispersive X-ray spectroscopy. Consequently, it can be concluded that the tetragonal tungsten bronzes show promise as intercalation electrode materials for Mg batteries.

Diamond-Graphene Composite Nanostructures.

The search for new nanostructural topologies composed of elemental carbon is driven by technological opportunities as well as the need to understand the structure and evolution of carbon materials formed by planetary shock impact events and in laboratory syntheses. We describe two new families of diamond-graphene (diaphite) phases constructed from layered and bonded sp3 and sp2 nanostructural units and provide a framework for classifying the members of this new class of materials. The nanocomposite structures are identified within both natural impact diamonds and laboratory-shocked samples and possess diffraction features that have previously been assigned to lonsdaleite and postgraphite phases. The diaphite nanocomposites represent a new class of high-performance carbon materials that are predicted to combine the superhard qualities of diamond with high fracture toughness and ductility enabled by the graphitic units and the atomically defined interfaces between the sp3- and sp2-bonded nanodomains.

Quantifying hexagonal stacking in diamond.

Diamond is a material of immense technological importance and an ancient signifier for wealth and societal status. In geology, diamond forms as part of the deep carbon cycle and typically displays a highly ordered cubic crystal structure. Impact diamonds, however, often exhibit structural disorder in the form of complex combinations of cubic and hexagonal stacking motifs. The structural characterization of such diamonds remains a challenge. Here, impact diamonds from the Popigai crater were characterized with a range of techniques. Using the MCDIFFaX approach for analysing X-ray diffraction data, hexagonality indices up to 40% were found. The effects of increasing amounts of hexagonal stacking on the Raman spectra of diamond were investigated computationally and found to be in excellent agreement with trends in the experimental spectra. Electron microscopy revealed nanoscale twinning within the cubic diamond structure. Our analyses lead us to propose a systematic protocol for assigning specific hexagonality attributes to the mineral designated as lonsdaleite among natural and synthetic samples.

Phase stability of intercalated V2O5 battery cathodes elucidated through the Goldschmidt tolerance factor.

Orthorhombic V2O5 is a promising Mg battery cathode material, and reversible intercalation in the layered α-phase has been claimed experimentally. However, these results, based on electrochemistry and XRD, are controversial. Previous computational studies have predicted high activation barriers (∼1 eV) for ionic migration in α-V2O5, although improved Mg2+ mobility is expected in the δ-phase. Here, hybrid-exchange density functional theory is used to discuss structure, stability and intercalation in the α and δ phases, beginning with a model system with MV2O5 stoichiometry, and varying ionic radius of the M cations. The relative stability of the two phases upon intercalation of M is rationalised through a tolerance factor-like behavioural trend, providing a framework for phase selection using intercalants of different ionic size. This tolerance factor behaviour is due to the presence of ferroelectrically distorted (2 × 2 × 2) perovskite blocks within the α-V2O5 structure. The δ-phase is found to undergo a barrierless phase change to α in fully charged (de-intercalated) MgxV2O5 (x = 0), indicating that stabilisation of δ-MgxV2O5 is required at low x if the δ phase is to be retained for higher Mg mobility. By employing dispersion interactions to accurately reproduce the interlayer distance, activation barriers for ion migration are found to be higher than reported in previous studies, clarifying questions regarding the extent of Mg intercalation that can be achieved experimentally. Interlayer ions are found to lower activation barriers for Mg2+ mobility by up to ∼330 meV in the α phase by expanding the interlayer space. The results address open questions about the electrochemical performance of orthorhombic V2O5 as Mg battery cathode material, and indicate atomic level mechanisms that activate ionic mobility in layered V2O5.

Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High-resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.

Thermodynamics and defect chemistry of substitutional and interstitial cation doping in layered α-V2O5.

A systematic study of the location and energetics of cation dopants in α-V2O5 has been conducted using pair-potential methods, supplemented by first-principles calculations. The consequences of doping on intrinsic defect equilibria have been discussed and the effects of selected dopants on Li+ and Mg2+ diffusion energy barriers have been investigated.