Combined operando and ex-situ monitoring of the Zn/electrolyte interface in Zn-ion battery systems.

Operando optical microscopy enables imaging at the interface between the Zn electrode and the electrolyte of 1 M ZnSO4(aq) in the symmetrical Zn/Zn cells assembled as the pouch cells with the mechanical load of 0.8 MPa. The imaging was executed during cycling of Zn plating and stripping at the different current densities of 0.5, 1.0, 2.0, and 4.0 mA cm-2, and the areal capacity of 2 mAh·cm-2. When the current densities are below 4.0 mA cm-2, no intense Zn dendrites are observed. However, at 4.0 mA cm-2, the severe Zn dendrites can penetrate through the separator and cause short-circuiting. From the electrochemical perspective, the voltage profile of such system drops to almost zero volt. Both operando optical and ex-situ synchrotron X-ray imaging further prove the appearance of the Zn dendrites. By Raman spectroscopy and X-ray diffraction, the cycled Zn electrode surface contains passivation species of Zn4(OH)6SO4, ZnO, and Zn(OH)2 that could limit the active surface area for the Zn plating/stripping, accelerating the localized current density and favoring the growth of Zn dendrites. With the SiO2 additive of 0.5% w/v in 1 M ZnSO4(aq), the severe Zn dendrites disappear, as well as the cycled Zn/electrolyte interface becomes close to the pristine state; low degree of the Zn electrode roughness and the Zn surface passivation is noticed. The appearance of the claimed Zn surface morphology was also confirmed by Scanning Electron Microscopy (SEM). In turn, too low or too high SiO2 content in the electrolyte does not generate desirable effects. A high level of Zn dendrites and short circuiting are still recognized. Hence, both the operando and ex-situ characterizations can mutually validate the phenomena at the Zn/electrolyte interface.

Modulating the Combinatorial Target Power of MgSnN2 via RF Magnetron Sputtering for Enhanced Optoelectronic Performance: Mechanistic Insights from DFT Studies.

The unique structural features of many ternary nitride materials with strong chemical bonding and band gaps above 2.0 eV are limited and are experimentally unexplored. It is important to identify candidate materials for optoelectronic devices, particularly for light-emitting diodes (LEDs) and absorbers in tandem photovoltaics. Here, we fabricated MgSnN2 thin films, as promising II-IV-N2 semiconductors, on stainless-steel, glass, and silicon substrates via combinatorial radio-frequency magnetron sputtering. The structural defects of the MgSnN2 films were studied as a function of the Sn power density, while the Mg and Sn atomic ratios remained constant. Polycrystalline orthorhombic MgSnN2 was grown on the (120) orientation within a wide optical band gap range of ∼2.20-2.17 eV. The carrier densities of 2.18× 1020 to 1.02 × 1021 cm-3, mobilities between 3.75 and 2.24 cm2/Vs, and a decrease in resistivity from 7.64 to 2.73 × 10-3 Ω cm were confirmed by Hall-effect measurements. These high carrier concentrations suggested that the optical band gap measurements were affected by a Burstein-Moss shift. Furthermore, the electrochemical capacitance properties of the optimal MgSnN2 film exhibited an areal capacitance of 152.5 mF/cm2 at 10 mV/s with high retention stability. The experimental and theoretical results showed that MgSnN2 films were effective semiconductor nitrides toward the progression of solar absorbers and LEDs.

Rhodamine B dye degradation using used face masks-derived carbon coupled with peroxymonosulfate.

Catalytic carbon materials from used face masks (UFM) activated by peroxymonosulfate (PMS) were developed for the degradation of rhodamine B (RhB) dye in aqueous solution. The UFM-derived carbon (UFMC) catalyst had a relatively large surface area as well as active functional groups and promoted the generation of singlet 1O2 and radicals from PMS, giving a high RhB degradation performance (98.1% after 3 h) in the presence of 3 mM PMS. The UFMC could degrade only 13.7% at a minimal RhB dose of 10-5 M. The principal reactive oxygen species of sulphate (SO4•), hydroxyl radicals (•OH), and singlet 1O2 were discovered using electron paramagnetic resonance and radical scavenger studies. Finally, a toxicological plant and bacterial study was performed to demonstrate the potential non-toxicity of the degraded RhB water sample.

Electrostatic potential-derived charge: a universal OER performance descriptor for MOFs.

Metal-organic frameworks (MOFs) provide opportunities for the design of high-efficiency catalysts attributed to their high compositional and structural tunability. Meanwhile, the huge number of MOFs poses a great challenge to experimental-intensive development of high-performance functional applications. By taking the computationally feasible and structurally representative trigonal prismatic secondary building units (SBUs) of MOFs as the entry point, we introduce a descriptor-based approach for designing high-performance MOFs for the oxygen evolution reaction (OER). The electrostatic potential-derived charge (ESPC) is identified as a robust and universal OER performance descriptor of MOFs, showing a distinct linear relationship with the onset potentials of OER elemental steps. Importantly, we establish an ESPC-based physical pattern of active site-intermediate binding strength, which interprets the rationality of ESPC as an OER performance descriptor. We further reveal that the SBUs with Ni/Cu as active site atoms while Mn/Fe/Co/Ni as spectator atoms have excellent OER activity through the variation pattern of ESPC along with metal composition. The universal correlation between ESPC and OER activity provides a rational rule for designing high-performance MOF-based OER electrocatalysts and can be easily extended to design functional MOFs for a rich variety of catalytic applications.

Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells.

Lithium dendrite (filament) propagation through ceramic electrolytes, leading to short circuits at high rates of charge, is one of the greatest barriers to realizing high-energy-density all-solid-state lithium-anode batteries. Utilizing in situ X-ray computed tomography coupled with spatially mapped X-ray diffraction, the propagation of cracks and the propagation of lithium dendrites through the solid electrolyte have been tracked in a Li/Li6PS5Cl/Li cell as a function of the charge passed. On plating, cracking initiates with spallation, conical 'pothole'-like cracks that form in the ceramic electrolyte near the surface with the plated electrode. The spallations form predominantly at the lithium electrode edges where local fields are high. Transverse cracks then propagate from the spallations across the electrolyte from the plated to the stripped electrode. Lithium ingress drives the propagation of the spallation and transverse cracks by widening the crack from the rear; that is, the crack front propagates ahead of the Li. As a result, cracks traverse the entire electrolyte before the Li arrives at the other electrode, and therefore before a short circuit occurs.

Sodium/Na ß″ Alumina Interface: Effect of Pressure on Voids.

Three-electrode studies coupled with tomographic imaging of the Na/Na-ß″-alumina interface reveal that voids form in the Na metal at the interface on stripping and they accumulate on cycling, leading to increasing interfacial current density, dendrite formation on plating, short circuit, and cell failure. The process occurs above a critical current for stripping (CCS) for a given stack pressure, which sets the upper limit on current density that avoids cell failure, in line with results for the Li/solid-electrolyte interface. The pressure required to avoid cell failure varies linearly with current density, indicating that Na creep rather than diffusion per se dominates Na transport to the interface and that significant pressures are required to prevent cell death, >9 MPa at 2.5 mA·cm-2.

Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells.

A critical current density on stripping is identified that results in dendrite formation on plating and cell failure. When the stripping current density removes Li from the interface faster than it can be replenished, voids form in the Li at the interface and accumulate on cycling, increasing the local current density at the interface and ultimately leading to dendrite formation on plating, short circuit and cell death. This occurs even when the overall current density is considerably below the threshold for dendrite formation on plating. For the Li/Li6PS5Cl/Li cell, this is 0.2 and 1.0 mA cm-2 at 3 and 7 MPa pressure, respectively, compared with a critical current for plating of 2.0 mA cm-2 at both 3 and 7 MPa. The pressure dependence on stripping indicates that creep rather than Li diffusion is the dominant mechanism transporting Li to the interface. The critical stripping current is a major factor limiting the power density of Li anode solid-state cells. Considerable pressure may be required to achieve even modest power densities in solid-state cells.

7Li NMR Chemical Shift Imaging To Detect Microstructural Growth of Lithium in All-Solid-State Batteries.

All-solid-state batteries potentially offer safe, high-energy-density electrochemical energy storage, yet are plagued with issues surrounding Li microstructural growth and subsequent cell death. We use 7Li NMR chemical shift imaging and electron microscopy to track Li microstructural growth in the garnet-type solid electrolyte, Li6.5La3Zr1.5Ta0.5O12. Here, we follow the early stages of Li microstructural growth during galvanostatic cycling, from the formation of Li on the electrode surface to dendritic Li connecting both electrodes in symmetrical cells, and correlate these changes with alterations observed in the voltage profiles during cycling and impedance measurements. During these experiments, we observe transformations at both the stripping and plating interfaces, indicating heterogeneities in both Li removal and deposition. At low current densities, 7Li magnetic resonance imaging detects the formation of Li microstructures in cells before short-circuits are observed and allows changes in the electrochemical profiles to be rationalized.