Qingping Meng

A Size-Dependent Sodium Storage Mechanism in Li4Ti5O12 Investigated by a Novel Characterization Technique Combining in Situ X-ray Diffraction and Chemical Sodiation

A novel characterization technique using the combination of chemical sodiation and synchrotron based in situ X-ray diffraction (XRD) has been detailed illustrated. The power of this novel technique was demonstrated in elucidating the structure evolution of Li4Ti5O12 upon sodium insertion. The sodium insertion behavior into Li4Ti5O12 is strongly size dependent. A solid solution reaction behavior in a wide range has been revealed during sodium insertion into the nanosized Li4Ti5O12 (~44 nm), which is quite different from the well-known two-phase reaction of Li4Ti5O12/Li7Ti5O12 system during lithium insertion, and also has not been fully addressed in the literature so far. On the basis of this in situ experiment, the apparent Na(+) ion diffusion coefficient (DNa+) of Li4Ti5O12 was estimated in the magnitude of 10(-16) cm(2) s(-1), close to the values estimated by electrochemical method, but 5 order of magnitudes smaller than the Li(+) ion diffusion coefficient (D(Li+) ~10(-11) cm(2) s(-1)), indicating a sluggish Na(+) ion diffusion kinetics in Li4Ti5O12 comparing with that of Li(+) ion. Nanosizing the Li4Ti5O12 will be critical to make it a suitable anode material for sodium-ion batteries. The application of this novel in situ chemical sodiation method reported in this work provides a facile way and a new opportunity for in situ structure investigations of various sodium-ion battery materials and other systems.

Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy

Spinel transition metal oxides are important electrode materials for lithium-ion batteries, whose lithiation undergoes a two-step reaction, whereby intercalation and conversion occur in a sequential manner. These two reactions are known to have distinct reaction dynamics, but it is unclear how their kinetics affects the overall electrochemical response. Here we explore the lithiation of nanosized magnetite by employing a strain-sensitive, bright-field scanning transmission electron microscopy approach. This method allows direct, real-time, high-resolution visualization of how lithiation proceeds along specific reaction pathways. We find that the initial intercalation process follows a two-phase reaction sequence, whereas further lithiation leads to the coexistence of three distinct phases within single nanoparticles, which has not been previously reported to the best of our knowledge. We use phase-field theory to model and describe these non-equilibrium reaction pathways, and to directly correlate the observed phase evolution with the batterys discharge performance.

Kinetic Phase Evolution of Spinel Cobalt Oxide during Lithiation

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. This work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.

Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale.

An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. This work characterizes the pathways that can control the morphology in binary oxide materials.

Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods

Multiple lithium-ion transport pathways and local phase changes upon lithiation in silver hollandite are revealed via in situ microscopy including electron diffraction, imaging and spectroscopy, coupled with density functional theory and phase field calculations. We report unexpected inter-nanorod lithium-ion transport, where the reaction fronts and kinetics are maintained within the neighbouring nanorod. Notably, this is the first time-resolved visualization of lithium-ion transport within and between individual nanorods, where the impact of oxygen deficiencies is delineated. Initially, fast lithium-ion transport is observed along the long axis with small net volume change, resulting in two lithiated silver hollandite phases distinguishable by orthorhombic distortion. Subsequently, a slower reaction front is observed, with formation of polyphase lithiated silver hollandite and face-centred-cubic silver metal with substantial volume expansion. These results indicate lithium-ion transport is not confined within a single nanorod and may provide a paradigm shift for one-dimensional tunnelled materials, particularly towards achieving high-rate capability.

Revealing and Rationalizing the Rich Polytypism of Todorokite MnO2

Polytypism, or stacking disorder, in crystals is an important structural aspect that can impact materials properties and hinder our understanding of the materials. One example of a polytypic system is todorokite-MnO2, which has a unique structure among the transition-metal oxides, with large ionic conductive channels formed by the metal oxide framework that can be utilized for potential functionalization, from molecular/ion sieving to charge storage. In contrast to the perceived 3 × 3 tunneled structure, we reveal a coexistence of a diverse array of tunnel sizes in well-crystallized, chemically homogeneous one-dimensional todorokite-MnO2. We explain the formation and persistence of this distribution of tunnel sizes thermochemically, demonstrating the stabilization of a range of coherent large-tunnel environments by the intercalation of partially solvated Mg2+ cations. Based on structural behavior of the system, compared to the common well-ordered alkali-stabilized polymorphs of MnO2, we suggest generalizable principles determining the selectivity of structure selection by dopant incorporation.

Retrieving the energy-loss function from valence electron energy-loss spectrum: Separation of bulk-, surface-losses and Cherenkov radiation

With recent rapid advancement in electron microscopy instrumentation, in particular, bright electron sources and monochromators, valence electron energy-loss spectroscopy (VEELS) has become attractive for retrieving band structures, optical properties, dielectric functions and phonon information of materials. However, Cherenkov radiation and surface-loss contribution significantly alter fine structures of VEELS, even in simple semiconductors and insulators. This leads to the problem that dielectric function or bandgap structure of these materials cannot be determined correctly if these effects are not removed. In this work we present a solution to this dilemma. We demonstrate that energy-loss function and real part of inverse complex dielectric function can be retrieved from raw data of VEELS. Based on the calculated example of Si, the limitation of our approach is discussed. We believe that our approach represents an improvement over previous procedures and has a broad prospect for applications.

Non-uniform Stress-free Strains in a Spherically Symmetrical Nano-sized Particle and Its Applications to Lithium-ion Batteries

The stress-free strain originated from local chemical composition and phase transformation can significantly alter the microstructures of materials; and then affect their properties. In this paper, we developed an analytical method to calculate stress-strain field due to the non-uniform stress-free strain in a spherically symmetrical particle. Applying the method to a lithium ion (Li-ion) battery electrode, the evolution of Li-ion concentration and strain field during the lithiation process is studied. Our studies reveal that the maximum strain in the electrode generally occurs on surface of sample, and is mainly dependent on the difference of Li-ion concentration of surface and of center in sample. Decreasing the difference of Li-ion concentration can efficiently decrease the maximum strain so that cracks of electrodes can been prevented. Our analytical results provide a useful guidance for practical applications of energy storage materials.

Bimetallic Nanoparticle Oxidation in Three Dimensions by Chemically Sensitive Electron Tomography and in Situ Transmission Electron Microscopy

The formation of hollow-structured oxide nanoparticles is primarily governed by the Kirkendall effect. However, the degree of complexity of the oxidation process multiplies in the bimetallic system because of the incorporation of more than one element. Spatially dependent oxidation kinetics controls the final morphology of the hollow nanoparticles, and the process is highly dependent on the elemental composition. Currently, a theoretical framework that can predict how different metal elements result in different oxide morphologies remains elusive. In this work, utilizing a combination of state-of-the-art in situ environmental transmission electron microscopy and three-dimensional (3D) chemically sensitive electron tomography, we provide an in situ and 3D investigation of the oxidation mechanism of the Ni-Fe nanoparticles. The direct measurements allow us to correlate the 3D elemental segregation in the particles with the oxidation morphologies, that is, single-cavity or dual-cavity hollow structure, and multicavity porous structures. Our findings in conjunction with theoretical calculations show that metal concentration, diffusivity, and particle size are important parameters that dictate the mechanical and phase stabilities of the hollow oxide shell, which in turn determine its barrier properties and the final hollow oxide morphology. It sheds light on how to use multielemental oxidation to control morphology in nanomaterials and demonstrates the power of 3D chemical imaging.

Strain Coupling During Lithiation of a Fe3O4/SrTiO3 Epitaxial Thin Film

Strain-related issues are of the extraordinary importance for the performance of lithium ion batteries. For the conversionand alloy-types electrode compounds, the cracks originated from the electrochemicallyinduced-strains are considered as the primary reason for their capacity fading and short cycle life[1]. Further, the transport of lithium ions themselves is affected by the strain during insertion/extraction into/from active materials. Besides electrochemically-induced-strain instigated inside single particles, the external strain also exist due to solid-to-solid interfaces in the electrode. For example, during operation, each particle undergoes volumetric changes, which generates external strain to neighboring particles. In all-solid-state-batteries, external strain is a more important issue due to the solid nature of electrolyte. Even though the electrode in lithium ion batteries can be influenced by various external and internal sources of strains, it is still not clear that how they affect the kinetics of lithiation. Especially, the coupling effect of electrochemically induced strain and external strain on electrode materials have not been investigated yet.