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High-nickel content cathode materials offer high energy density. However, the structural and surface instability may cause poor capacity retention and thermal stability of them. To circumvent this problem, nickel concentration-gradient materials have been developed to enhance high-nickel content cathode materials' thermal and cycling stability. Even though promising, the fundamental mechanism of the nickel concentration gradient's stabilization effect remains elusive because it is inseparable from nickel's valence gradient effect. To isolate nickel's valence gradient effect and understand its fundamental stabilization mechanism, we design and synthesize a LiNi0.8Mn0.1Co0.1O2 material that is compositionally uniform and has a hierarchical valence gradient. The nickel valence gradient material shows superior cycling and thermal stability than the conventional one. The result suggests creating an oxidation state gradient that hides the more capacitive but less stable Ni3+ away from the secondary particle surfaces is a viable principle towards the optimization of high-nickel content cathode materials.

LiCoO2 is a dominant cathode material for lithium-ion (Li-ion) batteries due to its high volumetric energy density, which could potentially be further improved by charging to high voltages. However, practical adoption of high-voltage charging is hindered by LiCoO2’s structural instability at the deeply delithiated state and the associated safety concerns. Here, we achieve stable cycling of LiCoO2 at 4.6 V (versus Li/Li+) through trace Ti–Mg–Al co-doping. Using state-of-the-art synchrotron X-ray imaging and spectroscopic techniques, we report the incorporation of Mg and Al into the LiCoO2 lattice, which inhibits the undesired phase transition at voltages above 4.5 V. We also show that, even in trace amounts, Ti segregates significantly at grain boundaries and on the surface, modifying the microstructure of the particles while stabilizing the surface oxygen at high voltages. These dopants contribute through different mechanisms and synergistically promote the cycle stability of LiCoO2 at 4.6 V.

Recent efforts to reduce battery costs and enhance sustainability have focused on eliminating Cobalt (Co) from cathode materials. While Co-free designs have shown notable success in polycrystalline cathodes, their impact on single crystalline (SC) cathodes remains less understood due to the significantly extended lithium diffusion pathways and the higher-temperature synthesis involved. Here, we reveal that removing Co from SC cathodes is structurally and electrochemically unfavorable, exhibiting unusual voltage fade behavior. Using multiscale diffraction and imaging techniques, we identify lithium-rich nanodomains (LRNDs) as a heterogeneous phase within the layered structure of Co-free SC cathodes. These LRNDs act as critical tipping points, inducing significant chemo-mechanical lattice strain and irreversible structural degradation, which exacerbates the voltage and capacity loss in electrochemical performance. Our findings highlight the considerable challenges of developing Co-free SC cathodes compared to polycrystalline ones and emphasize the need for new strategies to balance the interplay between cost, sustainability, and performance. In Li-ion batteries, single crystalline cobalt-free lithium transition metal oxides are less understood than their polycrystalline counterparts. Here, authors show that the absence of cobalt in single crystalline oxides results in structural degradation that ultimately degrades battery performance. [ABSTRACT FROM AUTHOR]

Understanding the growth pathway of faceted alloy nanoparticles at the atomic level is crucial to morphology control and property tuning. Yet, it remains a challenge due to complexity of the growth process and technical limits of modern characterization tools. We report a combinational use of multiple cutting-edge in situ techniques to study the growth process of octahedral Pt3Ni nanoparticles, which reveal the particle growth and facet formation mechanisms. Our studies confirm the formation of octahedral Pt3Ni initiates from Pt nuclei generation, which is followed by continuous Pt reduction that simultaneously catalyzes Ni reduction, resulting in mixed alloy formation with moderate elemental segregation. Carbon monoxide molecules serve as a facet formation modulator and induce Ni segregation to the surface, which inhibits the (111) facet growth and causes the particle shape to evolve from a spherical cluster to an octahedron as the (001) facet continues to grow.

In situ microscopy of colloidal nanocrystal growth offers a unique opportunity to acquire direct and straightforward data for assessing classical growth models. Here, we observe the growth trajectories of individual Ag nanoparticles in solution using in situ scanning transmission electron microscopy. For the first time, we provide experimental evidence of growth rates of Ag nanoparticles in the presence of Pt in solution that are significantly faster than predicted by Lifshitz-Slyozov-Wagner theory. We attribute these observed anomalous growth rates to the synergistic effects of the catalytic properties of Pt and the electron beam itself. Transiently reduced Pt atoms serve as active sites for Ag ions to grow, thereby playing a key role in controlling the growth kinetics. Electron beam illumination greatly increases the local concentration of free radicals, thereby strongly influencing particle growth rate and the resulting particle morphology. Through a systematic investigation, we demonstrate the feasibility of utilizing these synergistic effects for controlling the growth rates and particle morphologies at the nanoscale. Our findings not only expand the current scope of crystal growth theory, but may also lead to a broader scientific application of nanocrystal synthesis.

As x-ray and electron tomography is pushed further into the nanoscale, the limitations of rotation stages become more apparent, leading to challenges in the alignment of the acquired projection images. Here we present an approach for rapid post-acquisition alignment of these projections to obtain high quality three-dimensional images. Our approach is based on a joint estimation of alignment errors, and the object, using an iterative refinement procedure. With simulated data where we know the alignment error of each projection image, our approach shows a residual alignment error that is a factor of a thousand smaller, and it reaches the same error level in the reconstructed image in less than half the number of iterations. We then show its application to experimental data in x-ray and electron nanotomography.

Surface properties of electrode materials play a critical role in the function of batteries. Therefore, surface modifications, such as coatings, have been widely used to improve battery performance. Understanding how these coatings function to improve battery performance is crucial for both scientific research and applications. In this study the electrochemical performance of coated and uncoated LiNi0.5Mn1.5O4 (LNMO) electrodes is correlated with ensemble-averaged soft X-ray absorption spectroscopy (XAS) and spatially resolved scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) to illustrate the mechanism of how ultrathin layer Al2O3 coatings improve the cycle life of LiNi0.5Mn1.5O4. Mn2+ evolution on the surface is clearly observed in the uncoated sample, which results from the reaction between the electrolytic solution and the surfaces of LiNi0.5Mn1.5O4 particles, and also possibly atomic structure reconstructions and oxygen loss from the surface region in LiNi0.5Mn1.5O4. The coating effectively suppresses Mn2+ evolution and improves the battery performance by decelerating the impedance buildup from the surface passivation. This study demonstrates the importance of combining ensemble-averaged techniques (e.g., XAS) with localized techniques (e.g., STEM-EELS), as the latter may yield unrepresentative information due to the limited number of studied particles, and sheds light on the design of future coating processes and materials.

Here, we report photocatalytic CO2 reduction with water to produce methanol using TiO2-passivated InP nanopillar photocathodes under 532 nm wavelength illumination. In addition to providing a stable photocatalytic surface, the TiO2-passivation layer provides substantial enhancement in the photoconversion efficiency through the introduction of O vacancies associated with the nonstoichiometric growth of TiO2 by atomic layer deposition. Plane wave-density functional theory (PW-DFT) calculations confirm the role of oxygen vacancies in the TiO2 surface, which serve as catalytically active sites in the CO2 reduction process. PW-DFT shows that CO2 binds stably to these oxygen vacancies and CO2 gains an electron (-0.897e) spontaneously from the TiO2 support. This calculation indicates that the O vacancies provide active sites for CO2 absorption, and no overpotential is required to form the CO2(-) intermediate. The TiO2 film increases the Faraday efficiency of methanol production by 5.7× to 4.79% under an applied potential of -0.6 V vs NHE, which is 1.3 V below the E(o)(CO2/CO2(-)) = -1.9 eV standard redox potential. Copper nanoparticles deposited on the TiO2 act as a cocatalyst and further improve the selectivity and yield of methanol production by up to 8-fold with a Faraday efficiency of 8.7%.