Rational Construction of 3D Self-Supported MOF-Derived Cobalt Phosphide-Based Hollow Nanowall Arrays for Efficient Overall Water Splitting At large Current Density.

Developing efficient nonprecious bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) in the same electrolyte with a low overpotential and large current density presents an appealing yet challenging goal for large-scale water electrolysis. Herein, a unique 3D self-branched hierarchical nanostructure composed of ultra-small cobalt phosphide (CoP) nanoparticles embedded into N, P-codoped carbon nanotubes knitted hollow nanowall arrays (CoPʘNPCNTs HNWAs) on carbon textiles (CTs) through a carbonization-phosphatization process is presented. Benefiting from the uniform protrusion distributions of CoP nanoparticles, the optimum CoPʘNPCNTs HNWAs composites with high abundant porosity exhibit superior electrocatalytic activity and excellent stability for OER in alkaline conditions, as well as for HER in both acidic and alkaline electrolytes, even under large current densities. Furthermore, the assembled CoPʘNPCNTs/CTs||CoPʘNPCNTs/CTs electrolyzer demonstrates exceptional performance, requiring an ultralow cell voltage of 1.50 V to deliver the current density of 10 mA cm-2 for overall water splitting (OWS) with favorable stability, even achieving a large current density of 200 mA cm-2 at a low cell voltage of 1.78 V. Density functional theory (DFT) calculation further reveals that all the C atoms between N and P atoms in CoPʘNPCNTs/CTs act as the most efficient active sites, significantly enhancing the electrocatalytic properties. This strategy, utilizing 2D MOF arrays as a structural and compositional material to create multifunctional composites/hybrids, opens new avenues for the exploration of highly efficient and robust non-noble-metal catalysts for energy-conversion reactions.

Polysulfide Regulation by Hypervalent Iodine Compounds for Durable and Sustainable Lithium-Sulfur Battery.

Herein, a type of hypervalent iodine compound-iodosobenzene (PhIO)-is proposed to regulate the LiPSs electrochemistry and enhance the performance of Li-S battery. PhIO owns the practical advantages of low-cost, commercial availability, environmental friendliness and chemical stability. The lone pair electrons of oxygen atoms in PhIO play a critical role in forming a strong Lewis acid-base interaction with terminal Li in LiPSs. Moreover, the commercial PhIO can be easily converted to nanoparticles (≈20 nm) and uniformly loaded on a carbon nanotube (CNT) scaffold, ensuring sufficient chemisorption for LiPSs. The integrated functional PhIO@CNT interlayer affords a LiPSs-concentrated shield that not only strongly obstructs the LiPSs penetration but also significantly enhances the electrolyte wettability and Li+ conduction. The PhIO@CNT interlayer also serves as a "vice current collector" to accommodate various LiPSs and render smooth LiPSs transformation, which suppresses insulating Li2 S2 /Li2 S layer formation and facilitates Li+ diffusion. The Li-S battery based on PhIO@CNT interlayer (6 wt% PhIO) exhibits stable cycling over 1000 cycles (0.033% capacity decay per cycle) and excellent rate performance (686.6 mAh g-1 at 3 C). This work demonstrates the great potential of PhIO in regulating LiPSs and provides a new avenue towards the low-cost and sustainable application of Li-S batteries.

ZnSe Modified Zinc Metal Anodes: Toward Enhanced Zincophilicity and Ionic Diffusion.

Zinc metal is an ideal candidate for aqueous rechargeable batteries due to its high theoretical capacity and natural abundance. However, its commercialization is inevitably challenged by several critical factors such as dendrite growth and parasitic side-reactions, leading to low coulombic efficiency and a limited lifespan. Herein, a modified Zn foil with a zincophilic ZnSe layer deposited by a simple selenization process is proposed. An order of magnitude stronger adsorption capability toward Zn2+ ions and uniform ion diffusion tunnels of ZnSe enables lower nucleation energy barrier and faster ion-diffusion kinetics. Meanwhile, detrimental Zn corrosion in aqueous system is also effectively mitigated. As a result, ZnSe@Zn anode shows reversible Zn plating/stripping (1700 h at 1 mA cm-2 ) with ultra-low voltage hysteresis (41 mV), contributing to exceptional cycling stability over 500 cycles with negligible capacity fading for the ZnSe@Zn/MnO2 full cell.

Tailoring NiO Nanostructured Arrays by Sulfate Anions for Sodium-Ion Batteries.

In this contribution, a novel sulfate-ion-controlled synthesis is developed to fabricate freestanding nickel hydroxide nanoarrays on Ni substrate. As an inorganic morphology-controlled agent, SO42- ions play a critical role in controlling the crystal growth and the nanoarray morphologies, by modulating the growth rate of adsorbed crystal facets or inserting into the metal hydroxide interlayers. By controlling the SO42- concentration, the nanostructured arrays are tailored from one-dimensional (1D) Ni(SO4 )0.3 (OH)1.4 nanobelt arrays to hierarchical ß-Ni(OH)2 nanosheet arrays. With further graphene oxide modification and postheat treatment, the obtained NiO/graphene hybrid nanoarrays show great potential for high-performance sodium-ion batteries, which exhibit a cyclability of 380 mAh g-1 after undergoing 100 cycles at 0.5 C and reach a rate capability of 335 mA h g-1 at 10 C.

Low-Coordinated Zn-N2 Sites as Bidirectional Atomic Catalysis for Room-Temperature Na-S Batteries.

The rational design of advanced catalysts for sodium-sulfur (Na-S) batteries is important but remains challenging due to the limited understanding of sulfur catalytic mechanisms. Here, we propose an efficient sulfur host consisting of atomic low-coordinated Zn-N2 sites dispersed on N-rich microporous graphene (Zn-N2@NG), which realizes state-of-the-art sodium-storage performance with a high sulfur content of 66 wt %, high-rate capability (467 mA h g-1 at 5 A g-1), and long cycling stability for 6500 cycles with an ultralow capacity decay rate of 0.0062% per cycle. Ex situ methods combined with theoretical calculations demonstrate the superior bidirectional catalysis of Zn-N2 sites on sulfur conversion (S8 ↔ Na2S). Furthermore, in situ transmission electron microscopy was applied to visualize the microscopic S redox evolution under the catalysis of Zn-N2 sites without liquid electrolytes. During the sodiation process, both surface S nanoparticles and S molecules in the mircopores of Zn-N2@NG quickly convert into Na2S nanograins. During the following desodiation process, only a small part of the above Na2S can be oxidized into Na2Sx. These results reveal that, without liquid electrolytes, Na2S is difficult to be decomposed even with the assistance of Zn-N2 sites. This conclusion emphasizes the critical role of liquid electrolytes in the catalytic oxidation of Na2S, which was usually ignored by previous works.

Defect-Engineered 3D hierarchical NiMo3S4 nanoflowers as bifunctional electrocatalyst for overall water splitting.

The design and construction of bifunctional electrocatalysts with high activity and durability is essential for overall water splitting. Herein, a unique 3D hierarchical NiMo3S4 nanoflowers with abundant defects and reactive sites were grown directly on carbon textiles (NiMo3S4/CTs) using a facile hydrothermal synthesis method. The defect-rich NiMo3S4 nanoflakes, prepared by doping Ni2+ in the lattice of Mo-S, displays extended d-spacing of (002) crystal plane, resulting in the electrocatalytic activity of hydrogen evolution and oxygen evolution reaction (HER and OER) was improved under alkaline conditions. The self-supported NiMo3S4/CTs electrode delivers a small overpotential of 149.5 mV for HER and 126.2 mV for OER at 10 mA cm-2, respectively. Based on detailed structure analysis and density functional theory (DFT) calculations, the excellent HER and OER activities can be attributed to the unique structure of the nanoflowers, where the metallic characteristics for Ni-doped Mo-S lead to the enhancement of intrinsic conductivity and the rich abundance of Ni3+ active sites. As a result, the NiMo3S4/CTs as efficient bifunctional electrocatalysts for overall water-splitting was performed in alkaline electrolyte, where the system required only 1.55, 1.66 and 1.76 V to deliver current densities of 10, 50 and 100 mA cm-2, respectively. This study provides a new method for improving the electrocatalysis properties of transition metal sulfides by metal-ion doping to generate more active defect sites, thus promoting the development of non-noble-metal electrocatalysts for overall water splitting.

Unlocking Rapid and Robust Sodium Storage Performance of Zinc-Based Sulfide via Indium Incorporation.

Zinc sulfide (ZnS) exhibits promise in sodium-ion batteries (SIBs) because of its low operation voltage and high theoretical specific capacity. However, pristine ZnS is not adequate in realizing rapid and robust sodium storage owing to its low reversibility, poor structure stability, and sluggish kinetics. To date, most efforts focus on utilizing carbonaceous incorporation to improve its electrochemical performances. Nevertheless, it remains an arduous challenge for realizing superior rate capability while obtaining stable cycling. Herein, inspired by the crystal structure of hexagonal ZnIn2S4, which possesses an intrinsic layered feature with larger unit-cell volume versus that of ZnS, indium incorporation is thus deployed as an immediate remedy. In/ex situ investigations combined with density functional theory calculations are conducted to reveal the superior kinetics, high reversibility, and good structure stability of ZnIn2S4. Notably, the formed indium-based derivatives during cycling manifest a Na+ (de)intercalation process, thereby exciting a synergetic mechanism to stabilize electrochemical cycling. As a result, the electrochemical performances of Zn-based sulfide are significantly improved via the indium incorporation. Furthermore, a full cell based on the ZnIn2S4 anode with the superior electrochemical performance is developed. This work provides an effective tactic of heteroatom incorporation for optimizing structure as well as exciting a complementary reaction process toward developing superior anodes for high-performance alkali-ion batteries.

3D Printed Compressible Quasi-Solid-State Nickel-Iron Battery.

The design of a compressible battery with stable electrochemical performance is extremely important in compression-tolerant and flexible electronics. While this remains challenging with the current battery manufacturing method, the field of 3D printing offers the possibility of producing free-standing 3D-printed electrodes with various structural configurations. Through the simple and scalable strategy, various structural configurations can be produced. Herein, we demonstrate a 3D-printed quasi-solid-state Ni-Fe battery (QSS-NFB) that shows excellent compressibility, ultrahigh energy density, and superior long-term cycling durability. Through a rational design and adjustment of chemical components, two electrodes consisting of ultrathin Ni(OH)2 nanosheet array cathode and holey α-Fe2O3 nanorod array anode are achieved with a ultrahigh active material loading over 130 mg cm-3 and excellent compressibility up to 60%. It is noteworthy that the compressible QSS-NFB demonstrated an excellent cycling stability (∼91.3% capacity retentions after 10000 cycles) and ultrahigh energy density (28.1 mWh cm-3 at a power of 10.6 mW cm-3). This work provides a simple method for producing compression-tolerant energy-storage devices, which are expected to have promising applications in next generation stretchable/wearable electronics.

Enhanced sodium storage kinetics by volume regulation and surface engineering via rationally designed hierarchical porous FeP@C/rGO.

Transition metal phosphides, such as iron phosphide (FeP), have been considered as promising anode candidates for high-performance sodium ion batteries (SIBs) owing to their high theoretical capacity. However, the development of FeP is limited by large volume change, low electrical conductivity and sluggish kinetics with sodium ions. Moreover, the sodium storage kinetics and dynamics behavior in FeP are still unclear. Herein, improved sodium storage ability of FeP is achieved by volume regulation and surface engineering via a rationally designed hierarchical porous FeP@C/rGO nanocomposite. This FeP@C/rGO nanocomposite exhibits excellent rate capability and long cycle life as the anode of SIBs. Specifically, the FeP@C/rGO nanocomposite delivers high specific capacities of 635.7 and 343.1 mA h g-1 at 20 and 2000 mA g-1, respectively, and stable cycling with 88.2% capacity retention after 1000 cycles. The kinetics and dynamics studies demonstrate that the superior performance is attributed to the rationally designed hierarchical porous FeP@C/rGO with a high capacitive contribution of 93.9% (at 2 mV s-1) and a small volume expansion of only 54.9% by in situ transmission electron microscopy (TEM) measurement. This work provides valuable insights into understanding the phase evolution of FeP during the sodiation/desodiation process for designing high-performance SIBs.

Mechanism Investigation of High-Performance Li-Polysulfide Batteries Enabled by Tungsten Disulfide Nanopetals.

Understanding the reaction kinetics and mechanism of Li-polysulfide batteries is critical in designing advanced host materials for improved performance. However, up to now, the reaction mechanism within the Li-polysulfide batteries is still unclear. Herein, we study the reaction mechanism of a high-performance Li-polysulfide battery by in situ X-ray diffraction (XRD) and density functional theory (DFT) calculations based on a multifunctional host material composed of WS2 nanopetals embedded in rGO-CNT (WS2-rGO-CNT) aerogel. The WS2 nanopetal serves as a "catalytic center" to chemically bond the polysulfides and accelerate the polysulfide redox reactions, and the 3D porous rGO-CNT scaffold provides fast and efficient e-/Li+ transportation. Thus, the resulting WS2-rGO-CNT aerogel accommodating the polysulfide catholyte enables a stable cycling performance, excellent rate capability (614 mAh g-1 at 2 C), and a high areal capacity (6.6 mAh cm-2 at 0.5 C). In situ XRD results reveal that the Li2S starts to form at an early stage of discharge (at a depth of 25% of the lower voltage plateau) during the discharge process, and ß-S8 nucleation begins before the upper voltage plateau during the recharge process, which are different from the conventional Li-S battery. Moreover, the WS2 itself could be lithiated/delithiated during the cycling, making the lithiated WS2 (Li xWS2, 0 ≤ x ≤ 0.3) a real host material for Li-polysulfide batteries. DFT calculations suggest that Li xWS2 (0 ≤ x ≤ 0.3) exhibits moderate binding/anchoring interactions toward polysulfides with adsorption energies of 0.51-1.4 eV. Our work reveals the reaction mechanism of the Li-polysulfide batteries and indicates that the lithiated host plays an important role in trapping the polysulfides.