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Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation^1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 sstate to hybridized Li-s/Ti-dorbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.

 

The use of renewable electricity to prepare materials and fuels from abundant molecules offers a tantalizing opportunity to address concerns over energy and materials sustainability. The oxygen evolution reaction (OER) is integral to nearly all material and fuel electrosyntheses. However, very little is known about the structural evolution of the OER electrocatalyst, especially the amorphous layer that forms from the crystalline structure. Here, we investigate the interfacial transformation of the SrIrO 3 OER electrocatalyst. The SrIrO 3 amorphization is initiated by the lattice oxygen redox, a step that allows Sr 2+ to diffuse and O 2− to reorganize the SrIrO 3 structure. This activation turns SrIrO 3 into a highly disordered Ir octahedral network with Ir square-planar motif. The final Sr y IrO x exhibits a greater degree of disorder than IrO x made from other processing methods. Our results demonstrate that the structural reorganization facilitated by coupled ionic diffusions is essential to the disordered structure of the SrIrO 3 electrocatalyst. 

The fields of brain‐inspired computing, robotics, and, more broadly, artificial intelligence (AI) seek to implement knowledge gleaned from the natural world into human‐designed electronics and machines. In this review, the opportunities presented by complex oxides, a class of electronic ceramic materials whose properties can be elegantly tuned by doping, electron interactions, and a variety of external stimuli near room temperature, are discussed. The review begins with a discussion of natural intelligence at the elementary level in the nervous system, followed by collective intelligence and learning at the animal colony level mediated by social interactions. An important aspect highlighted is the vast spatial and temporal scales involved in learning and memory. The focus then turns to collective phenomena, such as metal‐to‐insulator transitions (MITs), ferroelectricity, and related examples, to highlight recent demonstrations of artificial neurons, synapses, and circuits and their learning. First‐principles theoretical treatments of the electronic structure, and in situ synchrotron spectroscopy of operating devices are then discussed. The implementation of the experimental characteristics into neural networks and algorithm design is then revewed. Finally, outstanding materials challenges that require a microscopic understanding of the physical mechanisms, which will be essential for advancing the frontiers of neuromorphic computing, are highlighted.

 

The emergence of a 2D electron gas (2DEG) on the (001) surface of oxygen‐deficient strontium titanate (SrTiO_3−δ) is investigated. Using in situ soft X‐ray spectroscopy and effective mass modeling, a series of quantitative band diagrams are developed to describe the evolution of near‐surface and bulk carrier concentrations, downward band bending, and Fermi level along a lateral gradient of oxygen vacancies formed on SrTiO_3−δby direct‐current resistive heating under ultrahigh vacuum conditions. Electrons are accumulated over a 3 nm region near the surface, confined within a potential well with saturated 300 meV downward band bending. The relation between Fermi levels and carrier concentrations near the surface suggests the density of states near the surface is much lower than the bulk density of states, which is consistent with the quantum‐confined subbands of a 2DEG. The quantitative relationship between the surface and bulk electronic structures developed in this work provides a guide for precise engineering of the oxygen‐vacancy‐induced 2DEG in SrTiO₃.