415 research outputs found
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Morphology Control to Enable High Capacity Li-Rich Disordered Rock Salt Cathodes
Li-rich disordered rock salt (DRS) oxides are a promising class of cathode materials with the wide chemical space to be explored. The high capacity (>300mAh/g) of this class of material can be explained by the reversible redox chemistry of the oxide anions, which sets it apart from the conventional layered cathode materials that rely only on the transition metal redox. However, these materials suffer from poor ionic and electronic transport properties: Most previous studies report electrochemical performance at low current rate and elevated temperature. Even then, the particle size needs to be reduced to sub-micrometer size, often by high-energy ball milling, to get reasonable capacities.
To mitigate this issue, we performed a detailed study of the synthesis of three different Nb-based Li-rich DRS materials - Li3NbO4, Li1.3Fe0.4Nb0.3O2, and Li1.3Mn0.4Nb0.3O2. Systematic evaluation shows that both the synthesis conditions and the reagents used have a large effect on the phase and morphology of the material synthetized, and therefore on its electrochemical performance. Without varying the synthesis method, the extent of cation ordering, the particle morphology, and the degree of elemental segregation can be controlled by a careful choice of the metal oxide precursors. This study helps the community to distinguish important synthesis criteria in order to design Li-rich DRS cathode materials with improved electrochemical performance
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Nanostructure Transformation as a Signature of Oxygen Redox in Li-Rich 3d and 4d Cathodes.
Lithium-rich nickel manganese cobalt oxide (LRNMC) is being explored as an alternative to stoichiometric nickel manganese cobalt oxide (NMC) cathode materials due to its higher, initially accessible, energy-storage capacity. This higher capacity has been associated with reversible O oxidation; however, the mechanism through which the change in O chemistry is accommodated by the surrounding cathode structure remains incomplete, making it challenging to design strategies to mitigate poor electrode performance resulting from extended cycling. Focusing on LRNMC cathodes, we identify nanoscale domains of lower electron density within the cathode as a structural consequence of O oxidation using small-angle X-ray scattering (SAXS) and operando X-ray diffraction (XRD). A feature observed in the small angle scattering region suggests the formation of nanopores, which first appears during O oxidation, and is partially reversible. This feature is not present in traditional cathode materials, including stoichiometric NMC and lithium nickel cobalt aluminum oxide (NCA) but appears to be common to other Li-rich systems tested here, Li2RuO3 and Li1.3Nb0.3Mn0.4O2
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Nanostructure Transformation as a Signature of Oxygen Redox in Li-Rich 3d and 4d Cathodes.
Lithium-rich nickel manganese cobalt oxide (LRNMC) is being explored as an alternative to stoichiometric nickel manganese cobalt oxide (NMC) cathode materials due to its higher, initially accessible, energy-storage capacity. This higher capacity has been associated with reversible O oxidation; however, the mechanism through which the change in O chemistry is accommodated by the surrounding cathode structure remains incomplete, making it challenging to design strategies to mitigate poor electrode performance resulting from extended cycling. Focusing on LRNMC cathodes, we identify nanoscale domains of lower electron density within the cathode as a structural consequence of O oxidation using small-angle X-ray scattering (SAXS) and operando X-ray diffraction (XRD). A feature observed in the small angle scattering region suggests the formation of nanopores, which first appears during O oxidation, and is partially reversible. This feature is not present in traditional cathode materials, including stoichiometric NMC and lithium nickel cobalt aluminum oxide (NCA) but appears to be common to other Li-rich systems tested here, Li2RuO3 and Li1.3Nb0.3Mn0.4O2
Synthesis and optimized formulation for high-capacity manganese fluoride (MnF2) electrodes for lithium-ion batteries
International audienceElectrochemical activity of poorly conductive metal fluorides in Li-ion batteries is contingent on their nanostructuration to reduce diffusion lengths and increase reaction kinetics. In that regard, we optimize the synthesis and electrode formulation of MnF2 to enable sufficient electrochemical activity required to study its electrochemical conversion reaction mechanism. Solvothermal synthesis in a water–ethanol mixture (1:1 Vol.), using Mn acetate and a slight excess of hydrofluoric acid (HF), results in pure phase, nanosized (˜30 nm diameter) rutile-type MnF2 (P42/mnm). High energy ball-milling of MnF2‒carbon mixtures leads to an amorphization of MnF2 and its partial phase transformation to the α-PbO2-type structure, without significant improvement of the electrochemical performance. Changing the electrode binder, however, from typical polyvinylidene fluoride (PVDF) to water-soluble Na-alginate, leads to a significant improvement of the reversibility of the electrochemical reaction. We attribute this drastic improvement to the improved adherence and homogeneity of the electrode film prepared with Na-alginate
A multimodal analytical toolkit to resolve correlated reaction pathways: the case of nanoparticle formation in zeolites
Unraveling the complex, competing pathways that can govern reactions in multicomponent systems is an experimental and technical challenge. We outline and apply a novel analytical toolkit that fully leverages the synchronicity of multimodal experiments to deconvolute causal from correlative relationships and resolve structural and chemical changes in complex materials. Here, simultaneous multimodal measurements combined diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and angular dispersive X-ray scattering suitable for pair distribution function (PDF), X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) analyses. The multimodal experimental data was interpreted via multi-level analysis; conventional analyses of each data series were integrated through meta-analysis involving non-negative matrix factorization (NMF) as a dimensional reduction algorithm and correlation analysis. We apply this toolkit to build a cohesive mechanistic picture of the pathways governing silver nanoparticle formation in zeolite A (LTA), which is key to designing catalytic and separations-based applications. For this Ag-LTA system, the mechanisms of zeolite dehydration, framework flexing, ion reduction, and cluster and nanoparticle formation and transport through the zeolite are elucidated. We note that the advanced analytical approach outline here can be applied generally to multimodal experiments, to take full advantage of the efficiencies and self-consistencies in understanding complex materials and go beyond what can be achieved by conventional approaches to data analysis.ISSN:2041-6520ISSN:2041-653
Reaction heterogeneity in LiNi0.8Co0.15Al0.05O2 induced by surface layer
Through operando synchrotron powder X-ray diffraction (XRD) analysis of layered transition metal oxide electrodes of composition LiNi0.8Co0.15Al0.05O2 (NCA), we decouple the intrinsic bulk reaction mechanism from surface-induced effects. For identically prepared and cycled electrodes stored in different environments, we demonstrate that the intrinsic bulk reaction for pristine NCA follows solid-solution mechanism, not a two-phase as suggested previously. By combining high resolution powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and surface sensitive X-ray photoelectron spectroscopy (XPS), we demonstrate that adventitious Li2CO3 forms on the electrode particle surface during exposure to air through reaction with atmospheric CO2. This surface impedes ionic and electronic transport to the underlying electrode, with progressive erosion of this layer during cycling giving rise to different reaction states in particles with an intact versus an eroded Li2CO3 surface-coating. This reaction heterogeneity, with a bimodal distribution of reaction states, has previously been interpreted as a “two-phase” reaction mechanism for NCA, as an activation step that only occurs during the first cycle. Similar surface layers may impact the reaction mechanism observed in other electrode materials using bulk probes such as operando powder XRD
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