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Laser powder bed fusion additive manufacturing is an emerging 3D printing technique for the fabrication of advanced metal components. Widespread adoption of it and similar additive technologies is hampered by poor understanding of laser-metal interactions under such extreme thermal regimes. Here, we elucidate the mechanism of pore formation and liquid-solid interface dynamics during typical laser powder bed fusion conditions using in situ X-ray imaging and multi-physics simulations. Pores are revealed to form during changes in laser scan velocity due to the rapid formation then collapse of deep keyhole depressions in the surface which traps inert shielding gas in the solidifying metal. We develop a universal mitigation strategy which eliminates this pore formation process and improves the geometric quality of melt tracks. Our results provide insight into the physics of laser-metal interaction and demonstrate the potential for science-based approaches to improve confidence in components produced by laser powder bed fusion.

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li + in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li 2-x Ir 1-y Sn y O 3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal that this structure-redox coupling arises from the local stabilization of short approximately 1.8 Å metal-oxygen π bonds and approximately 1.4 Å O-O dimers during oxygen redox, which occurs in Li 2-x Ir 1-y Sn y O 3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI 3 ) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl 2  + 3MAI) (MA = CH 3 NH 3 ). The as-spun film consists of crystalline MA 2 PbI 3 Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. This enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.

Hydrothermal synthesis is challenging in metal oxide systems with diverse polymorphism, as reaction products are often sensitive to subtle variations in synthesis parameters. This sensitivity is rooted in the non-equilibrium nature of low-temperature crystallization, where competition between different metastable phases can lead to complex multistage crystallization pathways. Here, we propose an ab initio framework to predict how particle size and solution composition influence polymorph stability during nucleation and growth. We validate this framework using in situ X-ray scattering, by monitoring how the hydrothermal synthesis of MnO 2 proceeds through different crystallization pathways under varying solution potassium ion concentrations ([K + ] = 0, 0.2, and 0.33 M). We find that our computed size-dependent phase diagrams qualitatively capture which metastable polymorphs appear, the order of their appearance, and their relative lifetimes. Our combined computational and experimental approach offers a rational and systematic paradigm for the aqueous synthesis of target metal oxides.

Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.