Direct Probing of Lattice-Strain-Induced Oxygen Release in LiCoO2 and Li2 MnO3 without Electrochemical Cycling.

Since the recognition of a significant oxygen-redox contribution to enhancing the capacity of Li transition-metal oxide cathodes, the oxygen release and subsequent structural variations together with capacity fading are critical issues to achieve better electrochemical performance. As most previous reports dealt with the structural degradation of cathodes after electrochemical cycling, it is fairly difficult to clarify how substantial the effect of lattice strain on the oxygen release will be while exclusively ruling out any electrochemical influences. By utilizing nanoindentation and mechanical surface polishing of single-crystal LiCoO2 and Li2 MnO3 , the local variations of both the atomic structure and oxygen content are scrutinized. Atomic-column-resolved imaging reveals that local LiM (M = Co and Mn) disordering and further amorphization are induced by mechanical strain. Moreover, substantial oxygen deficiency in the regions with these structural changes is directly identified by spectroscopic analyses. Ab initio density functional theory calculations also demonstrate energetically favorable formation of oxygen vacancies under shear strain. Providing direct evidence of oxygen release as a consequence of lattice strain, the findings in this work suggest that efficient strain relaxation will be of great significance for longevity of the anion framework in layered oxide cathodes.

Local-electrostatics-induced oxygen octahedral distortion in perovskite oxides and insight into the structure of Ruddlesden-Popper phases.

As the physical properties of ABX3 perovskite-based oxides strongly depend on the geometry of oxygen octahedra containing transition-metal cations, precise identification of the distortion, tilt, and rotation of the octahedra is an essential step toward understanding the structure-property correlation. Here we discover an important electrostatic origin responsible for remarkable Jahn-Teller-type tetragonal distortion of oxygen octahedra during atomic-level direct observation of two-dimensional [AX] interleaved shear faults in five different perovskite-type materials, SrTiO3, BaCeO3, LaCoO3, LaNiO3, and CsPbBr3. When the [AX] sublayer has a net charge, for example [LaO]+ in LaCoO3 and LaNiO3, substantial tetragonal elongation of oxygen octahedra at the fault plane is observed and this screens the strong repulsion between the consecutive [LaO]+ layers. Moreover, our findings on the distortion induced by local charge are identified to be a general structural feature in lanthanide-based An + 1BnX3n + 1-type Ruddlesden-Popper (RP) oxides with charged [LnO]+ (Ln = La, Pr, Nd, Eu, and Gd) sublayers, among more than 80 RP oxides and halides with high symmetry. The present study thus demonstrates that the local uneven electrostatics is a crucial factor significantly affecting the crystal structure of complex oxides.

Atomic-scale unveiling of multiphase evolution during hydrated Zn-ion insertion in vanadium oxide.

An initial crystalline phase can transform into another phases as cations are electrochemically inserted into its lattice. Precise identification of phase evolution at an atomic level during transformation is thus the very first step to comprehensively understand the cation insertion behavior and subsequently achieve much higher storage capacity in rechargeable cells, although it is sometimes challenging. By intensively using atomic-column-resolved scanning transmission electron microscopy, we directly visualize the simultaneous intercalation of both H2O and Zn during discharge of Zn ions into a V2O5 cathode with an aqueous electrolyte. In particular, when further Zn insertion proceeds, multiple intermediate phases, which are not identified by a macroscopic powder diffraction method, are clearly imaged at an atomic scale, showing structurally topotactic correlation between the phases. The findings in this work suggest that smooth multiphase evolution with a low transition barrier is significantly related to the high capacity of oxide cathodes for aqueous rechargeable cells, where the crystal structure of cathode materials after discharge differs from the initial crystalline state in general.

Atomic-Scale Direct Identification of Surface Variations in Cathode Oxides for Aqueous and Nonaqueous Lithium-Ion Batteries.

The electrochemical (de)intercalation reactions of lithium ions are initiated at the electrode surface in contact with an electrolyte solution. Therefore, substantial structural degradation, which shortens the cycle life of cells, is frequently observed at the surface of cathode particles, including lithium-metal intermixing, phase transitions, and dissolution of lithium and transition metals into the electrolyte. Furthermore, in contrast to the strict restriction of moisture in lithium-ion cells with nonaqueous organic electrolytes, electrode materials in aqueous-electrolyte cells are under much more reactive environments with water and oxygen, thereby leading to serious surface chemical reactions on the cathode particles. The present article presents key results regarding structural and composition variations at the surface of oxide-based cathodes in both high-performance nonaqueous and recently proposed aqueous lithium-ion batteries; in particular, focusing on direct atomic-scale observations preformed by means of scanning transmission electron microscopy. Precise identification of surface degradation at the atomic level is thus emphasized because it can provide significant insights into overcoming the limitations of current lithium-ion batteries.

In situ synthesis of supported metal nanocatalysts through heterogeneous doping.

Supported metal nanoparticles hold great promise for many fields, including catalysis and renewable energy. Here we report a novel methodology for the in situ growth of architecturally tailored, regenerative metal nanocatalysts that is applicable to a wide range of materials. The main idea underlying this strategy is to selectively diffuse catalytically active metals along the grain boundaries of host oxides and then to reduce the diffused metallic species to form nanoclusters. As a case study, we choose ceria and zirconia, the most recognized oxide supports, and spontaneously form various metal particles on their surface with controlled size and distribution. Metal atoms move back and forth between the interior (as cations) and the exterior (as clusters) of the host oxide lattice as the reductive and oxidative atmospheres repeat, even at temperatures below 700 °C. Furthermore, they exhibit excellent sintering/coking resistance and reactivity toward chemical/electrochemical reactions, demonstrating potential to be used in various applications.

Conductive Nature of Grain Boundaries in Nanocrystalline Stabilized Bi2O3 Thin-Film Electrolyte.

Stabilized Bi2O3 has gained a considerable amount of attention as a solid electrolyte material for low-temperature solid oxide fuel cells due to its superior oxygen-ion conductivity at the temperature of relevance (≤500 °C). Despite many research efforts to measure the transport properties of stabilized Bi2O3, the effects of grain boundaries on the electrical conductivity have rarely been reported and their results are even controversial. Here, we attempt quantitatively to assess the grain boundary contribution out of the total ionic conductivity at elevated temperatures (350-500 °C) by fabricating epitaxial and nano-polycrystalline thin films of yttrium-stabilized Bi2O3. Surprisingly, both epitaxial and polycrystalline films show nearly identical levels of ionic conductivity, as measured by alternating current impedance spectroscopy and this is the case despite the fact that the polyfilm possesses nanosized columnar grains and thus an extremely high density of the grain boundaries. The highly conductive nature of grain boundaries in stabilized Bi2O3 is discussed in terms of the clean and chemically uniform grain boundary without segregates, and the implications for device application are suggested.