We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x ∼ 0.18). At 400 °C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi(3.82+)O2.82H0.18, leading to the N(3-)/H(-)-exchanged product EuTi(4+)O2.82N0.12□0.06. When the ammonolysis temperature was increased up to 800 °C, we observed a further nitridation involving N(3-)/O(2-) exchange, yielding a fully oxidized Eu(3+)Ti(4+)O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N(3-) with O(2-) only above 600 °C and resulted in incomplete nitridation to EuTiO2.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N(3-)/O(2-)) exchange at high temperatures. Hence, by using (hydride-induced) anion-deficient precursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.

Crystalline aromatic dicarboxylate, also known as intercalated metal–organic frameworks, electrodes can be used in sustainable lithium-ion batteries owing to their low resource risks and eco-friendly syntheses via CO2 sequestration. However, little consideration has been given to understanding the phase transition mechanism during electrochemical charge–discharge processes. Here, we report a comparative study on the phase transition mechanism and associated Li+ diffusivity (D Li) in crystalline aromatic dicarboxylate lithium salts with naphthalene and biphenyl frameworks by electrochemical techniques and energy-state analyses using synchrotron radiation. The naphthalene framework, with a strong Li+ interaction and two stable Li+-intercalated structures, forms an energetically stable Li+-storage state through a metastable state, predominantly providing a two-phase reaction, and, at the end of charge and discharge, a solid-solution reaction with low D Li of 10–14–10–12 cm2 s–1. In contrast, the biphenyl framework, weakly interacting with Li+, forms an energetically unstable Li+-storage state, providing a solid-solution reaction with high D Li of 10–12–10–8 cm2 s–1 over the entire region. These findings contribute toward superior stability and high-rate capability in organic electrodes.

Intercalated metal-organic frameworks (iMOFs) based on aromatic dicarboxylate are appealing negative electrode active materials for Li-based electrochemical energy storage devices. They store Li ions at approximately 0.8 V vs. Li/Li+ and, thus, avoid Li metal plating during cell operation. However, their fast-charging capability is limited. Here, to circumvent this issue, we propose iMOFs with multi-aromatic units selected using machine learning and synthesized via solution spray drying. A naphthalene-based multivariate material with nanometric thickness allows the reversible storage of Li-ions in non-aqueous Li metal cell configuration reaching 85% capacity retention at 400 mA g−1 (i.e., 30 min for full charge) and 20 °C compared to cycling at 20 mA g−1 (i.e., 10 h for full charge). The same material, tested in combination with an activated carbon-based positive electrode, enables a discharge capacity retention of about 91% after 1000 cycles at 0.15 mA cm−2 (i.e., 2 h for full charge) and 20 °C. We elucidate the charge storage mechanism and demonstrate that during Li intercalation, the distorted crystal structure promotes electron delocalization by controlling the frame vibration. As a result, a phase transition suppresses phase separation, thus, benefitting the electrode’s fast charging behavior.

A unique demonstration with ball-rolling mechanisms has been developed to illustrate the basic principles of mass analyzers as components of mass spectrometers. Three ball-rolling mechanisms mimicking the currently used mass analyzers (i.e., a quadrupole mass filter, a magnetic sector, and a time-offlight) have been constructed. Each mechanism was designed to separate balls with three different weights (representing three ionized analytes with different weights) in an attempt to imitate the separation process employed by real mass analyzers. This demonstration helped students understand the basic principles of mass analyzers.