Multifunctional Effect of Fe Substitution in Na Layered Cathode Materials for Enhanced Storage Stability.

Developing stable cathode materials that are resistant to storage degradation is essential for practical development and industrial processing of Na-ion batteries as many sodium layered oxide materials are susceptible to hygroscopicity and instability upon exposure to ambient air. Among the various layered compounds, Fe-substituted O3-type Na(Ni1/2Mn1/2)1-xFexO2 materials have emerged as a promising option for high-performance and low-cost cathodes. While previous reports have noted the decent air-storage stability of these materials, the role and origin of Fe substitution in improving storage stability remain unclear. In this study, we investigate the air-resistant effect of Fe substitution in O3-Na(Ni1/2Mn1/2)1-xFexO2 cathode materials by performing systematic surface and structural characterizations. We find that the improved storage stability can be attributed to the multifunctional effect of Fe substitution, which forms a surface protective layer containing an Fe-incorporated spinel phase and decreases the thermodynamical driving force for bulk chemical sodium extraction. With these mechanisms, Fe-containing cathodes can suppress the cascades of cathode degradation processes and better retain the electrochemical performance after air storage.

A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a "Fluorine-Free" SEI.

Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid-electrolyte interphase (SEI) are ideal to enable sodium metal and anode-free cells. Herein we present advanced characterization of a novel fluorine-free electrolyte utilizing the [HCB11 H11 ]1- anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm-2 and a high coulombic efficiency of 99.5 % in half-cell configurations. Surface characterization of electrodes post-operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine-free SEI. Furthermore, weak ion-pairing is identified as key towards the successful development of fluorine-free sodium electrolytes.

Tetraruthenium Polyoxometalate as an Atom-Efficient Bifunctional Oxygen Evolution Reaction/Oxygen Reduction Reaction Catalyst and Its Application in Seawater Batteries.

Although development and utilization of efficient catalysts with earth-abundant and cheap elements are desired, precious noble metal-based catalysts are still widely used and studied due to the urgent need to address energy and environmental issues. Polyoxometalates (POMs) can be excellent candidates in this context. In this study, we found that oxo-bridged tetraruthenium polyoxometalate (RuPOM) exhibits excellent electrocatalytic activity for both oxygen evolution and reduction reactions (OER and ORR) with minimal use of noble metal elements and can be used for the development of efficient seawater batteries (SWBs). The deposition of RuPOM on a desired electrode with conducting carbon Ketjen black (KB) by the simple slurry coating method imparted bifunctional OER/ORR activity to the underlying electrode. Although the mass activity was similar, RuPOM/KB mixtures exhibited superior activity even compared to commercially available Pt/C when comparing the activity per noble metal element. Based on these findings, we employed RuPOM to develop efficient SWBs. RuPOM significantly lowered the charging potential and increased the discharging potential of SWBs, which are related to OER and ORR, respectively. This study can provide insights into the development of POM-based electrocatalysts and their application in energy storage and conversion devices.

Nanocrevasse-Rich Carbon Fibers for Stable Lithium and Sodium Metal Anodes.

Metallic lithium (Li) and sodium (Na) anodes have received great attention as ideal anodes to meet the needs for high energy density batteries due to their highest theoretical capacities. Although many approaches have successfully improved the performances of Li or Na metal anodes, many of these methods are difficult to scale up and thus cannot be applied in the production of batteries in practice. In this work, we introduce nanocrevasses in a carbon fiber scaffold which can facilitate the penetration of molten alkali metal into a carbon scaffold by enhancing its wettability for Li/Na metal. The resulting alkali metal/carbon composites exhibit stable long-term cycling over hundreds of cycles. The facile synthetic method is enabled for scalable production using recycled metal waste. Thus, the addition of nanocrevasses to carbon fiber as a scaffold for alkali metals can generate environmentally friendly and cost-effective composites for practical electrode applications.