Nonepitaxial Wafer-Scale Single-Crystal 2D Materials on Insulators.

Next-generation nanodevices require 2D material synthesis on insulating substrates. However, growing high-quality 2D-layered materials, such as hexagonal boron nitride (hBN) and graphene, on insulators is challenging owing to the lack of suitable metal catalysts, imperfect lattice matching with substrates, and other factors. Therefore, developing a generally applicable approach for realizing high-quality 2D layers on insulators remains crucial, despite numerous strategies being explored. Herein, a universal strategy is introduced for the nonepitaxial synthesis of wafer-scale single-crystal 2D materials on arbitrary insulating substrates. The metal foil in a nonadhered metal-insulator substrate system is almost melted by a brief high-temperature treatment, thereby pressing the as-grown 2D layers to well attach onto the insulators. High-quality, large-area, single-crystal, monolayer hBN and graphene films are synthesized on various insulating substrates. This strategy provides new pathways for synthesizing various 2D materials on arbitrary insulators and offers a universal epitaxial platform for future single-crystal film production.

The Role of Metal Substitution in Tuning Anion Redox in Sodium Metal Layered Oxides Revealed by X-Ray Spectroscopy and Theory.

We investigate high-valent oxygen redox in the positive Na-ion electrode P2-Na0.67-x [Fe0.5 Mn0.5 ]O2 (NMF) where Fe is partially substituted with Cu (P2-Na0.67-x [Mn0.66 Fe0.20 Cu0.14 ]O2 , NMFC) or Ni (P2-Na0.67-x [Mn0.65 Fe0.20 Ni0.15 ]O2 , NMFN). From combined analysis of resonant inelastic X-ray scattering and X-ray near-edge structure with electrochemical voltage hysteresis and X-ray pair distribution function profiles, we correlate structural disorder with high-valent oxygen redox and its improvement by Ni or Cu substitution. Density of states calculations elaborate considerable anionic redox in NMF and NMFC without the widely accepted requirement of an A-O-A' local configuration in the pristine materials (where A=Na and A'=Li, Mg, vacancy, etc.). We also show that the Jahn-Teller nature of Fe4+ and the stabilization mechanism of anionic redox could determine the extent of structural disorder in the materials. These findings shed light on the design principles in TM and anion redox for positive electrodes to improve the performance of Na-ion batteries.

Coulombically-stabilized oxygen hole polarons enable fully reversible oxygen redox.

Stabilizing high-valent redox couples and exotic electronic states necessitate an understanding of the stabilization mechanism. In oxides, whether they are being considered for energy storage or computing, highly oxidized oxide-anion species rehybridize to form short covalent bonds and are related to significant local structural distortions. In intercalation oxide electrodes for batteries, while such reorganization partially stabilizes oxygen redox, it also gives rise to substantial hysteresis. In this work, we investigate oxygen redox in layered Na2-XMn3O7, a positive electrode material with ordered Mn vacancies. We prove that coulombic interactions between oxidized oxideanions and the interlayer Na vacancies can disfavor rehybridization and stabilize hole polarons on oxygen (O-) at 4.2 V vs. Na/Na+. These coulombic interactions provide thermodynamic energy saving as large as O-O covalent bonding and enable ~ 40 mV voltage hysteresis over multiple electrochemical cycles with negligible voltage fade. Our results establish a complete picture of redox energetics by highlighting the role of coulombic interactions across several atomic distances and suggest avenues to stabilize highly oxidized oxygen for applications in energy storage and beyond.

Facile diamond synthesis from lower diamondoids.

Carbon-based nanomaterials have exceptional properties that make them attractive for a variety of technological applications. Here, we report on the use of diamondoids (diamond-like, saturated hydrocarbons) as promising precursors for laser-induced high-pressure, high-temperature diamond synthesis. The lowest pressure and temperature (P-T) conditions that yielded diamond were 12 GPa (at ~2000 K) and 900 K (at ~20 GPa), respectively. This represents a substantially reduced transformation barrier compared with diamond synthesis from conventional (hydro)carbon allotropes, owing to the similarities in the structure and full sp3 hybridization of diamondoids and bulk diamond. At 20 GPa, diamondoid-to-diamond conversion occurs rapidly within <19 µs. Molecular dynamics simulations indicate that once dehydrogenated, the remaining diamondoid carbon cages reconstruct themselves into diamond-like structures at high P-T. This study is the first successful mapping of the P-T conditions and onset timing of the diamondoid-to-diamond conversion and elucidates the physical and chemical factors that facilitate diamond synthesis.

Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites.

Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first-principles calculations are performed on (MA/Cs/FA)Pb(I/Br)3 and MASnI3. Across the materials studied, electron small polaron formation is manifested by Jahn-Teller-like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed are established for optimization in specific optoelectronic applications.

Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity.

The cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI's structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting of 1 M lithium perchlorate (LiClO4) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.

Robust NaO2 Electrochemistry in Aprotic Na-O2 Batteries Employing Ethereal Electrolytes with a Protic Additive.

Aprotic metal-oxygen batteries, such as Li-O2 and Na-O2 batteries, are of topical research interest as high specific energy alternatives to state-of-the-art Li-ion batteries. In particular, Na-O2 batteries with NaO2 as the discharge product offer higher practical specific energy with better rechargeability and round-trip energy efficiency when compared to Li-O2 batteries. In this work, we show that the electrochemical deposition and dissolution of NaO2 in Na-O2 batteries is unperturbed by trace water impurities in Na-O2 battery electrolytes, which is desirable for practical battery applications. We find no evidence for the formation of other discharge products such as Na2O2·H2O. Furthermore, the electrochemical efficiency during charge remains near ideal in the presence of trace water in electrolytes. Although sodium anodes react with trace water leading to the formation of a high-impedance solid electrolyte interphase, the increase in discharge overpotential is only ∼100 mV when compared to cells employing nominally anhydrous electrolytes.