Composition dependent electrochemical properties of earth-abundant ternary nitride anodes

Growing energy storage demands on lithium-ion batteries necessitate exploration of new electrochemical materials as next-generation battery electrode materials. In this work, we investigate the previously unexplored electrochemical properties of earth-abundant and tunable Zn1-xSn1+xN2 (x = -0.4 to x = 0.4) thin films, which show high electrical conductivity and high gravimetric capacity for Li insertion. Enhanced cycling performance is achieved compared to previously published end-members Zn3N2 and Sn3N4, showing decreased irreversible loss and increased total capacity and cycle stability. The average reversible capacity observed is > 1050 mAh/g for all compositions and 1220 mAh/g for Zn-poor (x = 0.2) films. Extremely Zn-rich films (x = -0.4) show improved adhesion; however, Zn-rich films undergo a phase transformation on the first cycle. Zn-poor and stoichiometric films do not exhibit significant phase transformations which often plague nitride materials and show no required overpotential at the 0.5 V plateau. Cation composition x is explored as a mechanism for tuning relevant mechanical and electrochemical properties, such as capacity, overpotential, phase transformation, electrical conductivity, and adhesion. The lithiation/delithiation experiments confirm the reversible electrochemical reactions. Without any binding additives, the as-deposited electrodes delaminate resulting in fast capacity degradation. We demonstrate the mechanical nature of this degradation through decreased electrode thinning, resulting in cells with improved cycling stability due to increased mechanical stability. Combining composition and electrochemical analysis, this work demonstrates for the first time composition dependent electrochemical properties for the ternary Zn1-xSn1+xN2 and proposes earth-abundant ternary nitride anodes for increased reversible capacity and cycling stability

NiGa2_{2}O4_{4} interfacial layers in NiO/Ga2_{2}O3_{3} heterojunction diodes at high temperature

NiO/Ga$_{2}$O$_{3}$ heterojunction diodes have attracted attention for high-power applications, but their high-temperature performance and reliability remain underexplored. Here we report on the time evolution of the static electrical properties in the widely studied p-NiO/n-Ga$_{2}$O$_{3}$heterojunction diodes and the formation of NiGa$_{2}$O$_{4}$ interfacial layers when operated at $550^{\circ}$C. Results of our thermal cycling experiment show an initial leakage current increase which stabilizes after sustained thermal load, due to reactions at the NiO-Ga$_{2}$O$_{3}$ interface. High-resolution TEM microstructure analysis of the devices after thermal cycling indicates that the NiO-Ga$_{2}$O$_{3}$ interface forms ternary compounds at high temperatures, and thermodynamic calculations suggest the formation of the spinel NiGa$_{2}$O$_{4}$ layer between NiO and Ga$_{2}$O$_{3}$. First-principles defect calculations find that NiGa$_{2}$O$_{4}$ shows low p-type intrinsic doping, and hence can also serve to limit electric field crowding at the interface. Vertical NiO/Ga$_{2}$O$_{3}$ diodes with intentionally grown 5 nm thin spinel-type NiGa$_{2}$O$_{4}$ interfacial layers show excellent device ON/OFF ratio of > 10$^{10}$($\pm$3 V), V$_{ON}$ of ~1.9 V, and breakdown voltage of ~ 1.2 kV for an initial unoptimized 300-micron diameter device. These p-n heterojunction diodes are promising for high-voltage, high-temperature applications.Comment: 16 pages, 5 figure

Evidence of a second-order Peierls-driven metal-insulator transition in crystalline NbO2

The metal-insulator transition of NbO2 is thought to be important for the functioning of recent niobium oxide-based memristor devices, and is often described as a Mott transition in these contexts. However, the actual transition mechanism remains unclear, as current devices actually employ electroformed NbOx that may be inherently different to crystalline NbO2. We report on our synchrotron x-ray spectroscopy and density-functional-theory study of crystalline, epitaxial NbO2 thin films grown by pulsed laser deposition and molecular beam epitaxy across the metal-insulator transition at ~810⁰C. The observed spectral changes reveal a second-order Peierls transition driven by a weakening of Nb dimerization without significant electron correlations, further supported by our density-functional-theory modeling. Our findings indicate that employing crystalline NbO2 as an active layer in memristor devices may facilitate analog control of the resistivity, whereby Joule-heating can modulate Nb-Nb dimer distance and consequently control the opening of a pseudogap