NiFe Layered Double Hydroxide Nanoparticles on Co,N‐Codoped Carbon Nanoframes as Efficient Bifunctional Catalysts for Rechargeable Zinc–Air Batteries

The future large‐scale deployment of rechargeable zinc–air batteries requires the development of cheap, stable, and efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In this work, a highly efficient bifunctional electrocatalyst is prepared by depositing 3–5 nm NiFe layered double hydroxide (NiFe‐LDH) nanoparticles on Co,N‐codoped carbon nanoframes (Co,N‐CNF). The NiFe‐LDH/Co,N‐CNF electrocatalyst displayed an OER overpotential of 0.312 V at 10 mA cm^?2 and an ORR half‐wave potential of 0.790 V. The outstanding performance of the electrocatalyst is attributable to the high electrical conductivity and excellent ORR activity of Co,N‐CNF, together with the strong anchoring of 3–5 nm NiFe‐LDH nanoparticles, which preserves active sites. Inspired by the excellent OER and ORR performance of NiFe‐LDH/Co,N‐CNF, a prototype rechargeable zinc–air battery is developed. The battery exhibited a low discharge–charge voltage gap (1.0 V at 25 mA cm^?2) and long‐term cycling durability (over 80 h), and superior overall performance to a counterpart battery constructed using a mixture of IrO₂ and Pt/C as the cathode. The strategy developed here can easily be adapted to synthesize other bifunctional CNF‐based hybrid electrodes for ORR and OER, providing a practical route to more efficient rechargeable zinc–air batteries.     

An Effective Lithium Sulfide Encapsulation Strategy for Stable Lithium–Sulfur Batteries

With a high theoretical capacity of 1162 mA h g^?1, Li₂S is a promising cathode that can couple with silicon, tin, or graphite anodes for next‐generation energy storage devices. Unfortunately, Li₂S is highly insulating, exhibits large charge overpotential, and suffers from active‐material loss as soluble polysulfides during battery cycling. To date, low‐cost, scalable synthesis of an electrochemically active Li₂S cathode remains a challenge. This work demonstrates that the low conductivity and material loss issues associated with Li₂S cathodes can be overcome by forming a stable, conductive encapsulation layer at the surface of the Li₂S bulk particles through in situ surface reactions between Li₂S and electrolyte additives containing transition‐metal salts. It is identified that the electronic band structure in the valence band region of the thus‐generated encapsulation layers, consisting largely of transition‐metal sulfides, determines the initial charging resistance of Li₂S. Furthermore, among the transition metals tested, the encapsulation layer formed with an addition of 10 wt% manganese (II) acetylacetonate salt proved to be robust within the cycling window, which is attributed to the chemically generated MnS surface species. This work provides an effective strategy to use micrometer‐sized Li₂S directly as a cathode material and opens up new prospects to tune the surface properties of electrode materials for energy‐storage applications.     

An Operando Mechanistic Evaluation of a Solar‐Rechargeable Sodium‐Ion Intercalation Battery

Solar‐intercalation batteries, which are able to both harvest and store solar energy within the electrodes, are a promising technology for the more efficient utilization of intermittent solar radiation. However, there is a lack of understanding on how the light‐induced intercalation reaction occurs within the electrode host lattice. Here, an in operando synchrotron X‐ray diffraction methodology is introduced, which allows for real‐time visualization of the structural evolution process within a solar‐intercalation battery host electrode lattice. Coupled with ex situ material characterization, direct correlations between the structural evolution of MoO₃ and the photo‐electrochemical responses of the solar‐intercalation batteries are established for the first time. MoO₃ is found to transform, via a two‐phase reaction mechanism, initially into a sodium bronze phase, Na_0.33MoO₃, followed by the formation of solid solutions, Na_xMoO₃ (0.33 < x < 1.1), on further photointercalation. Time‐resolved correlations with the measured voltages indicate that the two‐phase evolution reaction follows zeroth‐order kinetics. The insights achieved from this study can aid the development of more advanced photointercalation electrodes and solar batteries with greater performances.     

Additional Sodium Insertion into Polyanionic Cathodes for Higher‐Energy Na‐Ion Batteries

Na‐ion technology is increasingly studied as a low‐cost solution for grid storage applications. Many positive electrode materials have been reported, mainly among layered oxides and polyanionic compounds. The vanadium oxy/flurophosphate solid solution Na₃V₂(PO₄)₂F_3‐y O_2y (0 ≤ y ≤ 1), in particular, has proven the ability to deliver ≈500 Wh kg^‐1, operating on the V³⁺/V⁴⁺ (y = 0) or V⁴⁺/V⁵⁺ redox couples (y = 1). This paper reports here on a significant increase in specific energy by enabling sodium insertion into Na₃V₂(PO₄)₂FO₂ to reach Na₄V₂(PO₄)₂FO₂ upon discharge. This occurs at ≈1.6 V and increases the theoretical specific energy to 600 Wh kg^?1, rivaling that of several Li‐ion battery cathodes. This improvement is achieved by the judicious modification of the composition either as O for F substitution, or Al for V substitution, both of which disrupt Na‐ion ordering and thereby enable insertion of the 4th Na. This paper furthermore shows from operando X‐Ray Diffraction (XRD) that this energy is obtained in the cycling range Na₄V₂(PO₄)₂FO₂–NaV₂(PO₄)₂FO₂ with a very small overall volume change of 1.7%, which is one of the smallest volume changes for Na‐ion cathodes and which is a crucial requisite for stable long‐term cycling.     

Hierarchical Structures Based on Two‐Dimensional Nanomaterials for Rechargeable Lithium Batteries

Two‐dimensional (2D) nanomaterials (i.e., graphene and its derivatives, transition metal oxides and transition metal dichalcogenides) are receiving a lot attention in energy storage application because of their unprecedented properties and great diversities. However, their re‐stacking or aggregation during the electrode fabrication process has greatly hindered their further developments and applications in rechargeable lithium batteries. Recently, rationally designed hierarchical structures based on 2D nanomaterials have emerged as promising candidates in rechargeable lithium battery applications. Numerous synthetic strategies have been developed to obtain hierarchical structures and high‐performance energy storage devices based on these hierarchical structure have been realized. This review summarizes the synthesis and characteristics of three styles of hierarchical architecture, namely three‐dimensional (3D) porous network nanostructures, hollow nanostructures and self‐supported nanoarrays, presents the representative applications of hierarchical structured nanomaterials as functional materials for lithium ion batteries, lithium‐sulfur batteries and lithium‐oxygen batteries, meanwhile sheds light particularly on the relationship between structure engineering and improved electrochemical performance; and provides the existing challenges and the perspectives for this fast emerging field.     

A High‐Volumetric‐Capacity Cathode Based on Interconnected Close‐Packed N‐Doped Porous Carbon Nanospheres for Long‐Life Lithium–Sulfur Batteries

This study reports a Li–S battery cathode of high volumetric capacity enabled by novel micro‐ and mesostructuring. The cathode is based on monodisperse highly porous carbon nanospheres derived from a facile template‐ and surfactant‐free method. At the mesoscale, the nanospheres structure into interconnected close‐packed clusters of a few microns in extent, thus facilitating the fabrication of dense crack‐free high areal sulfur loading (5 mg cm^?2) cathodes with high electrical conductivity and low cathode impedance. A combination of the nitrogen doping (5 wt%), high porosity (2.3 cm³ g^?1), and surface area (2900 m² g^?1) at the microscale enables high sulfur immobilization and utilization. The cathode delivers among the best reported volumetric capacity to date, above typical Li‐ion areal capacity at 0.2 C over 200 cycles and low capacity fading of 0.1% per cycle at 0.5 C over 500 cycles. The compact cathode structure also ensures a low electrolyte requirement (6 µL mg^?1), which aids a low overall cell weight, and further, among the best gravimetric capacities published to date as well.     

An Iodine Quantum Dots Based Rechargeable Sodium–Iodine Battery

Rechargeable sodium–iodine batteries represent a promising scalable electrochemical energy storage alternative as sodium and iodine are both low cost and widely abundant elements. Here, the authors demonstrate a rechargeable sodium–iodine battery that employs free‐standing iodine quantum dots (IQDs) decorated reduced graphene oxide (IQDs@RGO) as the cathode. Consistent with the density functional theory the authors find the Na⁺ ions to intercalate into the I unit cell forming stable NaI, and the battery exhibits high capacity, outstanding cycle stability (with a reversible specific capacity of 141 mA h g^?1 after 500 cycles at current density of 100 mA g^?1), and high rate performance (170, 146, 127, 112, and 95 mA h g^?1 at current densities of 100, 200, 400, 600, and 1000 mA g^?1, respectively). The reversible reactions, I₂/I₃ ^? and I₃ ^?/I^? redox couples on insertion of Na⁺ ions, are confirmed via in situ Raman spectroscopy. Notably, even after 500 cycles the morphology and structure of the IQDs exhibit no noticeable change implying their use as a stable cathode material for sodium–iodine batteries. Moreover, the IQDs based flexible full‐cells also exhibit high capacity and long cycle life (the capacity with 123 mA h g^?1 at current density of 100 mA g^?1 after 100 cycles).