30 research outputs found
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The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides.
In the synthesis of inorganic materials, reactions often yield non-equilibrium kinetic byproducts instead of the thermodynamic equilibrium phase. Understanding the competition between thermodynamics and kinetics is a fundamental step towards the rational synthesis of target materials. Here, we use in situ synchrotron X-ray diffraction to investigate the multistage crystallization pathways of the important two-layer (P2) sodium oxides Na0.67MO2 (Mâ=âCo, Mn). We observe a series of fast non-equilibrium phase transformations through metastable three-layer O3, O3' and P3 phases before formation of the equilibrium two-layer P2 polymorph. We present a theoretical framework to rationalize the observed phase progression, demonstrating that even though P2 is the equilibrium phase, compositionally unconstrained reactions between powder precursors favour the formation of non-equilibrium three-layered intermediates. These insights can guide the choice of precursors and parameters employed in the solid-state synthesis of ceramic materials, and constitutes a step forward in unravelling the complex interplay between thermodynamics and kinetics during materials synthesis
Identifying the Structure of the Intermediate, Li2/3CoPO4, Formed during Electrochemical Cycling of LiCoPO4.
In situ synchrotron diffraction measurements and subsequent Rietveld refinements are used to show that the high energy density cathode material LiCoPO4 (space group Pnma) undergoes two distinct two-phase reactions upon charge and discharge, both occurring via an intermediate Li2/3(Co2+)2/3(Co3+)1/3PO4 phase. Two resonances are observed for Li2/3CoPO4 with intensity ratios of 2:1 and 1:1 in the 31P and 7Li NMR spectra, respectively. An ordering of Co2+/Co3+ oxidation states is proposed within a (a Ă 3b Ă c) supercell, and Li+/vacancy ordering is investigated using experimental NMR data in combination with first-principles solid-state DFT calculations. In the lowest energy configuration, both the Co3+ ions and Li vacancies are found to order along the b-axis. Two other low energy Li+/vacancy ordering schemes are found only 5 meV per formula unit higher in energy. All three configurations lie below the LiCoPO4-CoPO4 convex hull and they may be readily interconverted by Li+ hops along the b-direction.This is the final version. It was first published by ACS Publications at http://pubs.acs.org/doi/abs/10.1021/cm502680
Giant Modulation of Refractive Index from Correlated Disorder
Correlated disorder has been shown to enhance and modulate magnetic,
electrical, dipolar, electrochemical and mechanical properties of materials.
However, the possibility of obtaining novel optical and opto-electronic
properties from such correlated disorder remains an open question. Here, we
show unambiguous evidence of correlated disorder in the form of anisotropic,
sub-angstrom-scale atomic displacements modulating the refractive index tensor
and resulting in the giant optical anisotropy observed in BaTiS3, a
quasi-one-dimensional hexagonal chalcogenide. Single crystal X-ray diffraction
studies reveal the presence of antipolar displacements of Ti atoms within
adjacent TiS6 chains along the c-axis, and three-fold degenerate Ti
displacements in the a-b plane. 47/49Ti solid-state NMR provides additional
evidence for those Ti displacements in the form of a three-horned NMR lineshape
resulting from low symmetry local environment around Ti atoms. We used scanning
transmission electron microscopy to directly observe the globally disordered Ti
a-b plane displacements and find them to be ordered locally over a few unit
cells. First-principles calculations show that the Ti a-b plane displacements
selectively reduce the refractive index along the ab-plane, while having
minimal impact on the refractive index along the chain direction, thus
resulting in a giant enhancement in the optical anisotropy. By showing a strong
connection between correlated disorder and the optical response in BaTiS3, this
study opens a pathway for designing optical materials with high refractive
index and functionalities such as a large optical anisotropy and nonlinearity.Comment: 24 pages, 3 figure
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UltrahighâCapacity Rocksalt Cathodes Enabled by CyclingâActivated Structural Changes
Mn-redox-based oxides and oxyfluorides are considered the most promising earth-abundant high-energy cathode materials for next-generation lithium-ion batteries. While high capacities are obtained in high-Mn content cathodes such as Li- and Mn-rich layered and spinel-type materials, local structure changes and structural distortions (often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn-rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation-disordered rocksalt (DRX) cathode (Li1.1Mn0.8Ti0.1O1.9F0.1, an ultrahigh capacity of â320 mAh gâ1 (energy density of â900 Wh kgâ1) can be obtained through dynamic structural rearrangements upon cycling, along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn4+ and Li+ vacancies promotes local cation ordering, leading to the formation of domains of a âÎŽ phaseâ within the disordered framework. On deep discharge, Mn4+ reduction, along with Li+ insertion transform the structure to a partially ordered DRX phase with a ÎČâČ-LiFeO2-type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high-Mn DRXbut also provide guidance for the future development of Mn-based, high-energy density oxide, and oxyfluoride cathode materials
Importance of superstructure in stabilizing oxygen redox in P3- Na0.67Li0.2Mn0.8O2
This work was supported by the Faraday Institution (grant number FIRG018) and the Australian Research Council (discovery and future fellowship programs DP170100269/DP200100959 and FT200100707). E.B. acknowledges funding from the Engineering Physical Sciences Research Council (EPSRC) via the National Productivity Interest Fund (NPIF) 2018 and is also grateful for use of the ARCHER UK National Supercomputing Service via our membership in the UK's HEC Materials Chemistry Consortium, funded by the EPSRC (EP/L000202).Activation of oxygen redox represents a promising strategy to enhance the energy density of positive electrode materials in both lithium and sodium-ion batteries. However, the large voltage hysteresis associated with oxidation of oxygen anions during the first charge represents a significant challenge. Here, P3-type Na0.67Li0.2Mn0.8O2 is reinvestigated and a ribbon superlattice is identified for the first time in P3-type materials. The ribbon superstructure is maintained over cycling with very minor unit cell volume changes in the bulk while Li ions migrate reversibly between the transition metal and Na layers at the atomic scale. In addition, a range of spectroscopic techniques reveal that a strongly hybridized Mn 3dâO 2p favors ligand-to-metal charge transfer, also described as a reductive coupling mechanism, to stabilize reversible oxygen redox. By preparing materials under three different synthetic conditions, the degree of ordering between Li and Mn is varied. The sample with the maximum cation ordering delivers the largest capacity regardless of the voltage windows applied. These findings highlight the importance of cationic ordering in the transition metal layers, which can be tuned by synthetic control to enhance anionic redox and hence energy density in rechargeable batteries.Publisher PDFPeer reviewe
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Exploring Oxygen Activity in the High Energy P2-Type Na0.78Ni0.23Mn0.69O2 Cathode Material for Na-Ion Batteries.
Large-scale electric energy storage is fundamental to the use of renewable energy. Recently, research and development efforts on room-temperature sodium-ion batteries (NIBs) have been revitalized, as NIBs are considered promising, low-cost alternatives to the current Li-ion battery technology for large-scale applications. Herein, we introduce a novel layered oxide cathode material, Na0.78Ni0.23Mn0.69O2. This new compound provides a high reversible capacity of 138 mAh g-1 and an average potential of 3.25 V vs Na+/Na with a single smooth voltage profile. Its remarkable rate and cycling performances are attributed to the elimination of the P2-O2 phase transition upon cycling to 4.5 V. The first charge process yields an abnormally excess capacity, which has yet to be observed in other P2 layered oxides. Metal K-edge XANES results show that the major charge compensation at the metal site during Na-ion deintercalation is achieved via the oxidation of nickel (Ni2+) ions, whereas, to a large extent, manganese (Mn) ions remain in their Mn4+ state. Interestingly, electron energy loss spectroscopy (EELS) and soft X-ray absorption spectroscopy (sXAS) results reveal differences in electronic structures in the bulk and at the surface of electrochemically cycled particles. At the surface, transition metal ions (TM ions) are in a lower valence state than in the bulk, and the O K-edge prepeak disappears. On the basis of previous reports on related Li-excess LIB cathodes, it is proposed that part of the charge compensation mechanism during the first cycle takes place at the lattice oxygen site, resulting in a surface to bulk transition metal gradient. We believe that by optimizing and controlling oxygen activity, Na layered oxide materials with higher capacities can be designed
ÎČ-NaMnO2: a high-performance cathode for sodium-ion batteries.
There is much interest in Na-ion batteries for grid storage because of the lower projected cost compared with Li-ion. Identifying Earth-abundant, low-cost, and safe materials that can function as intercalation cathodes in Na-ion batteries is an important challenge facing the field. Here we investigate such a material, ÎČ-NaMnO2, with a different structure from that of NaMnO2 polymorphs and other compounds studied extensively in the past. It exhibits a high capacity (of ca. 190 mA h g(-1) at a rate of C/20), along with a good rate capability (142 mA h g(-1) at a rate of 2C) and a good capacity retention (100 mA h g(-1)after 100 Na extraction/insertion cycles at a rate of 2C). Powder XRD, HRTEM, and (23)Na NMR studies revealed that this compound exhibits a complex structure consisting of intergrown regions of α-NaMnO2 and ÎČ-NaMnO2 domains. The collapse of the long-range structure at low Na content is expected to compromise the reversibility of the Na extraction and insertion processes occurring upon charge and discharge of the cathode material, respectively. Yet stable, reproducible, and reversible Na intercalation is observed.RJC acknowledges support from the European Research Council (ERC). PGB acknowledges support from EPSRC including the SUPERGEN programme. JCV is grateful to MAT2010-19837-C06-C04 for funding.This is the accepted manuscript. The final published version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/ja509704t
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Probing reaction processes and reversibility in Earth-abundant Na3FeF6 for Na-ion batteries.
Sodium (Na)-ion batteries are the most explored 'beyond-Li' battery systems, yet their energy densities are still largely limited by the positive electrode material. Na3FeF6 is a promising Earth-abundant containing electrode and operates through a conversion-type charge-discharge reaction associated with a high theoretical capacity (336 mA h g-1). In practice, however, only a third of this capacity is achieved during electrochemical cycling. In this study, we demonstrate a new rapid and environmentally-friendly assisted-microwave method for the preparation of Na3FeF6. A comprehensive understanding of charge-discharge processes and of the reactivity of the cycled electrode samples is achieved using a combination of electrochemical tests, synchrotron X-ray diffraction, 57Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, magnetometry, and 23Na/19F solid-state nuclear magnetic resonance (NMR) complemented with first principles calculations of NMR properties. We find that the primary performance limitation of the Na3FeF6 electrode is the sluggish kinetics of the conversion reaction, while the methods employed for materials synthesis and electrode preparation do not have a significant impact on the conversion efficiency and reversibility. Our work confirms that Na3FeF6 undergoes conversion into NaF and Fe(s) nanoparticles. The latter are found to be prone to oxidation prior to ex situ measurements, thus necessitating a robust analysis of the stable phases (here, NaF) formed upon conversion
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Rapid and EnergyâEfficient Synthesis of Disordered Rocksalt Cathodes
Abstract:
Lithiumârich transition metal oxides with a cationâdisordered rocksalt structure (disordered rocksalt oxides or DRX) are promising candidates for sustainable, nextâgeneration Liâion cathodes due to their high energy densities and compositional flexibility, enabling Coâ and Niâfree battery chemistries. However, current methods to synthesize DRX compounds require either high temperature (â1000 °C) sintering for several hours, or high energy ball milling for several days in an inert atmosphere. Both methods are timeâ and energyâintensive, limiting the scale up of DRX production. The present study reports the rapid synthesis of various DRX compositions in ambient air via a microwaveâassisted solidâstate technique resulting in reaction times as short as 5 min, which are more than two orders of magnitude faster than current synthesis methods. The DRX compounds synthesized via microwave are phaseâpure and have a similar shortâ and longârange structure as compared to DRX materials synthesized via a standard solidâstate route, resulting in nearly identical electrochemical performance. In some cases, microwave heating allows for better particle size and morphology control. Overall, the rapid and energyâefficient microwave technique provides a more sustainable route to produce DRX materials, further incentivizes the development of nextâgeneration DRX cathodes, and is key to accelerating their optimization via highâthroughput studies