2D Tungsten Borides Induced Interfacial Modulation Engineering Toward High-Rate Performance Zinc-Iodine Battery.

Aqueous zinc-iodine batteries are promising candidates for large-scale energy storage due to their high energy density and low cost. However, their development is hindered by several drawbacks, including zinc dendrites, anode corrosion, and the shuttle of polyiodides. Here, the design of 2D-shaped tungsten boride nanosheets with abundant borophene subunits-based active sites is reported to guide the (002) plane-dominated deposition of zinc while suppressing side reactions, which facilitates interfacial nucleation and uniform growth of zinc. Meanwhile, the interfacial d-band orbits of tungsten sites can further enhance the anchoring of polyiodides on the surface, to promote the electrocatalytic redox conversion of iodine. The resulting tungsten boride-based I2 cathodes in zinc-iodine cells exhibit impressive cyclic stability after 5000 cycles at 50 C, which accelerates the practical applications of zinc-iodine batteries.

Insights into Electrode Architectures and Lithium-Ion Transport in Polycrystalline V2 O5 Cathodes of Solid-State Batteries.

Polymer-based solid-state batteries (SSBs) have received increasing attentions due to the absence of interfacial problems in sulfide/oxide-type SSBs, but the lower oxidation potential of polymer-based electrolytes greatly limits the application of conventional high-voltage cathode such as LiNix Coy Mnz O2 (NCM) and lithium-rich NCM. Herein, this study reports on a lithium-free V2 O5 cathode that enables the applications of polymer-based solid-state electrolyte (SSE) with high energy density due to the microstructured transport channels and suitable operational voltage. Using a synergistic combination of structural inspection and non-destructive X-ray computed tomography (X-CT), it interprets the chemo-mechanical behavior that determines the electrochemical performance of the V2 O5 cathode. Through detailed kinetic analyses such as differential capacity and galvanostatic intermittent titration technique (GITT), it is elucidated that the hierarchical V2 O5 constructed through microstructural engineering exhibits smaller electrochemical polarization and faster Li-ion diffusion rates in polymer-based SSBs than those in the liquid lithium batteries (LLBs). By the hierarchical ion transport channels created by the nanoparticles against each other, superior cycling stability (≈91.7% capacity retention after 100 cycles at 1 C) is achieved at 60 °C in polyoxyethylene (PEO)-based SSBs. The results highlight the crucial role of microstructure engineering in designing Li-free cathodes for polymer-based SSBs.

Zinc-Doping Strategy on P2-Type Mn-Based Layered Oxide Cathode for High-Performance Potassium-ion Batteries.

Mn-based layered oxide is extensively investigated as a promising cathode material for potassium-ion batteries due to its high theoretical capacity and natural abundance of manganese. However, the Jahn-Teller distortion caused by high-spin Mn3+ (t2g 3 eg 1 ) destabilizes the host structure and reduces the cycling stability. Here, K0.02 Na0.55 Mn0.70 Ni0.25 Zn0.05 O2 (denoted as KNMNO-Z) is reported to inhibit the Jahn-Teller effect and reduce the irreversible phase transition. Through the implementation of a Zn-doping strategy, higher Mn valence is achieved in the KNMNO-Z electrode, resulting in a reduction of Mn3+ amount and subsequently leading to an improvement in cyclic stability. Specifically, after 1000 cycles, a high retention rate of 97% is observed. Density functional theory calculations reveals that low-valence Zn2+ ions substituting the transition metal position of Mn regulated the electronic structure around the MnO bonding, thereby alleviating the anisotropic coupling between oxidized O2- and Mn4+ and improving the structural stability. K0.02 Na0.55 Mn0.70 Ni0.25 Zn0.05 O2 provided an initial discharge capacity of 57 mAh g-1 at 100 mA g-1 and a decay rate of only 0.003% per cycle, indicating that the Zn-doped strategy is effective for developing high-performance Mn-based layered oxide cathode materials in PIBs.

Interface Coordination Stabilizing Reversible Redox of Zinc for High-Performance Zinc-Iodine Batteries.

Aqueous Zn batteries (AZBs) have attracted extensive attention due to good safety, cost-effectiveness, and environmental benignity. However, the sluggish kinetics of divalent zinc ion and the growth of Zn dendrites severely deteriorate the cycling stability and specific capacity. The authors demonstrate modulation of the interfacial redox process of zinc via the dynamic coordination chemistry of phytic acid with zinc ions. The experimental results and theoretical calculation reveal that the in-situ formation of such inorganic-organic films as a dynamic solid-electrolyte interlayer is efficient to buffer the zinc ion transfer via the energy favorable coordinated hopping mechanism for the reversible zinc redox reactions. Especially, along the interfacial coating layer with porous channel structure is able to regulate the solvation structure of zinc ions along the dynamic coordination of the phytic acid skeleton, efficiently inhibiting the surface corrosion of zinc and dendrite growth. Therefore, the resultant Zn anode achieves low voltage hysteresis and long cycle life at rigorous charge and discharge circulation for fabricating highly robust rechargeable batteries. Such an advanced strategy for modulating ion transport demonstrates a highly promising approach to addressing the basic challenges for zinc-based rechargeable batteries, which can potentially be extended to other aqueous batteries.

Phosphorus Regulated Cobalt Oxide@Nitrogen-Doped Carbon Nanowires for Flexible Quasi-Solid-State Supercapacitors.

Battery-type materials are promising candidates for achieving high specific capacity for supercapacitors. However, their slow reaction kinetics hinders the improvement in electrochemical performance. Herein, a hybrid structure of P-doped Co3 O4 (P-Co3 O4 ) ultrafine nanoparticles in situ encapsulated into P, N co-doped carbon (P, N-C) nanowires by a pyrolysis-oxidation-phosphorization of 1D metal-organic frameworks derived from Co-layered double hydroxide as self-template and reactant is reported. This hybrid structure prevents active material agglomeration and maintains a 1D oriented arrangement, which exhibits a large accessible surface area and hierarchically porous feature, enabling sufficient permeation and transfer of electrolyte ions. Theoretical calculations demonstrate that the P dopants in P-Co3 O4 @P, N-C could reduce the adsorption energy of OH- and regulate the electrical properties. Accordingly, the P-Co3 O4 @P, N-C delivers a high specific capacity of 669 mC cm-2 at 1 mA cm-2 and an ultralong cycle life with only 4.8% loss over 5000 cycles at 30 mA cm-2 . During the fabrication of P-Co3 O4 @P, N-C, Co@P, N-C is simultaneously developed, which can be integrated with P-Co3 O4 @P, N-C for the assembly of asymmetric supercapacitors. These devices achieve a high energy density of 47.6 W h kg-1 at 750 W kg-1 and impressive flexibility, exhibiting a great potential in practical applications.

Phosphorus-Mediated MoS2 Nanowires as a High-Performance Electrode Material for Quasi-Solid-State Sodium-Ion Intercalation Supercapacitors.

Molybdenum disulfide (MoS2 ) is a promising electrode material for electrochemical energy storage owing to its high theoretical specific capacity and fascinating 2D layered structure. However, its sluggish kinetics for ionic diffusion and charge transfer limits its practical applications. Here, a promising strategy is reported for enhancing the Na+ -ion charge storage kinetics of MoS2 for supercapacitors. In this strategy, electrical conductivity is enhanced and the diffusion barrier of Na+ ion is lowered by a facile phosphorus-doping treatment. Density functional theory results reveal that the lowest energy barrier of dilute Na-vacancy diffusion on P-doped MoS2 (0.11 eV) is considerably lower than that on pure MoS2 (0.19 eV), thereby signifying a prominent rate performance at high Na intercalation stages upon P-doping. Moreover, the Na-vacancy diffusion coefficient of the P-doped MoS2 at room temperatures can be enhanced substantially by approximately two orders of magnitude (10-6 -10-4 cm2 s-1 ) compared with pure MoS2 . Finally, the quasi-solid-state asymmetrical supercapacitor assembled with P-doped MoS2 and MnO2 , as the positive and negative electrode materials, respectively, exhibits an ultrahigh energy density of 67.4 W h kg-1 at 850 W kg-1 and excellent cycling stability with 93.4% capacitance retention after 5000 cycles at 8 A g-1 .

Promoting catalytic ozonation of phenol over graphene through nitrogenation and Co3O4 compositing.

Catalytic ozonation is progressively becoming an attractive technique for quick water purification but efficient and stable catalysts remains elusive. Here we solvothermally synthesized highly-dispersed Co3O4 nanocrystals over microscale nitrogen-doping graphene (NG) nanosheets and tested it as a synthetic catalyst in the ozonation of phenol in aqueous solutions. Transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectra and X-ray photoelectron spectroscopy were used to determine its morphology, crystallinity, elemental composition and molecular bonds, respectively. The comparative experiments confirmed the highest catalytic activity and oxidation degree (AOSC) of Co3O4/NG among four nanocomposites (G, NG, Co3O4/G, and Co3O4/NG). Co3O4/NG also has exhibited the highest degradation rate: complete conversion of a near-saturated concentration of phenol (941.1mg/L) was achieved within 30min under ambient conditions with only a small dosage of Co3O4/NG (50mg/L) and ozone (4mg/L, flow rate: 0.5L/min). It also resulted in 34.6% chemical oxygen demand (CODCr) and 24.2% total organic carbon (TOC) reduction. In this work, graphene nanosheets not only functioned as a support for Co3O4 nanocrystals but also functioned as a co-catalyst for the enhancement in phenol removal efficiency. The surface nitridation and Co3O4 modification treatment further improved the removal rate of the phenol pollutants and brought in the higher oxidation degree. Our finding may open new perspectives for pursuing exceptional activity for catalytic ozonation reaction.

Fundamentally Manipulating the Electronic Structure of Polar Bifunctional Catalysts for Lithium-Sulfur Batteries: Heterojunction Design versus Doping Engineering.

Heterogeneous structures and doping strategies have been intensively used to manipulate the catalytic conversion of polysulfides to enhance reaction kinetics and suppress the shuttle effect in lithium-sulfur (Li-S) batteries. However, understanding how to select suitable strategies for engineering the electronic structure of polar catalysts is lacking. Here, a comparative investigation between heterogeneous structures and doping strategies is conducted to assess their impact on the modulation of the electronic structures and their effectiveness in catalyzing the conversion of polysulfides. These findings reveal that Co0.125Zn0.875Se, with metal-cation dopants, exhibits superior performance compared to CoSe2/ZnSe heterogeneous structures. The incorporation of low Co2+ dopants induces the subtle lattice strain in Co0.125Zn0.875Se, resulting in the increased exposure of active sites. As a result, Co0.125Zn0.875Se demonstrates enhanced electron accumulation on surface Se sites, improved charge carrier mobility, and optimized both p-band and d-band centers. The Li-S cells employing Co0.125Zn0.875Se catalyst demonstrate significantly improved capacity (1261.3 mAh g-1 at 0.5 C) and cycle stability (0.048% capacity delay rate within 1000 cycles at 2 C). This study provides valuable guidance for the modulation of the electronic structure of typical polar catalysts, serving as a design directive to tailor the catalytic activity of advanced Li-S catalysts.

Interfacial "Double-Terminal Binding Sites" Catalysts Synergistically Boosting the Electrocatalytic Li2S Redox for Durable Lithium-Sulfur Batteries.

Catalytic conversion of polysulfides emerges as a promising approach to improve the kinetics and mitigate polysulfide shuttling in lithium-sulfur (Li-S) batteries, especially under conditions of high sulfur loading and lean electrolyte. Herein, we present a separator architecture that incorporates double-terminal binding (DTB) sites within a nitrogen-doped carbon framework, consisting of polar Co0.85Se and Co clusters (Co/Co0.85Se@NC), to enhance the durability of Li-S batteries. The uniformly dispersed clusters of polar Co0.85Se and Co offer abundant active sites for lithium polysulfides (LiPSs), enabling efficient LiPS conversion while also serving as anchors through a combination of chemical interactions. Density functional theory calculations, along with in situ Raman and X-ray diffraction characterizations, reveal that the DTB effect strengthens the binding energy to polysulfides and lowers the energy barriers of polysulfide redox reactions. Li-S batteries utilizing the Co/Co0.85Se@NC-modified separator demonstrate exceptional cycling stability (0.042% per cycle over 1000 cycles at 2 C) and rate capability (849 mAh g-1 at 3 C), as well as deliver an impressive areal capacity of 10.0 mAh cm-2 even in challenging conditions with a high sulfur loading (10.7 mg cm-2) and lean electrolyte environments (5.8 µL mg-1). The DTB site strategy offers valuable insights into the development of high-performance Li-S batteries.

Novel Synthesis of 3D Mesoporous FePO4 from Electroflocculation of Iron Filings as a Precursor of High-Performance LiFePO4/C Cathode for Lithium-Ion Batteries.

This study presents an economic and environmentally friendly method for the synthesis of microspherical FePO4·2H2O precursors with secondary nanostructures by the electroflocculation of low-cost iron fillers in a hot solution. The morphology and crystalline shape of the precursors were adjusted by gradient co-precipitation of pH conditions. The effect of precursor structure and morphology on the electrochemical performance of the synthesized LiFePO4/C was investigated. Electrochemical analysis showed that the assembly of FePO4·2H2O submicron spherical particles from primary nanoparticles and nanorods resulted in LiFePO4/C exhibiting excellent multiplicity and cycling performance with first discharge capacities at 0.2C, 1C, 5C, and 10C of 162.8, 134.7, 85.5, and 47.7 mAh·g-1, respectively, and the capacity of LiFePO4/C was maintained at 85.5% after 300 cycles at 1C. The significant improvement in the electrochemical performance of LiFePO4/C was attributed to the enhanced Li+ diffusion rate and the crystallinity of LiFePO4/C. Thus, this work shows a new three-dimensional mesoporous FePO4 synthesized from the iron flake electroflocculation as a precursor for high-performance LiFePO4/C cathodes for lithium-ion batteries.

Sub-Nanometer Pt Clusters on Defective NiFe LDH Nanosheets as Trifunctional Electrocatalysts for Water Splitting and Rechargeable Hybrid Sodium-Air Batteries.

It is challenging to develop highly efficient and stable multifunctional electrocatalysts for improving the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) for sustainable energy conversion and storage systems such as water-alkali electrolyzers (WAEs) and hybrid sodium-air batteries (HSABs). In this work, sub-nm Pt nanoclusters (NCs) on defective NiFe layered double hydroxide nanosheets (NixFe LDHs) are synthesized by a facile electrodeposition method. Due to the synergistic effect between Pt NCs and abundant atomic M(II) defects, along with hierarchical porous nanostructures, the Pt/NixFe LDHs catalysts exhibit superior trifunctional electrocatalytic activity and durability toward the HER/OER/ORR. A WAE fabricated with Pt/NixFe LDHs electrodes needs 1.47 V to reach a current density of 10 mA cm-2, much lower than that of the mixed 20% Pt/C and 20% Ir/C catalysts. An HSAB assembled by Pt/NixFe LDHs as a binder-free air cathode displays a high open-circuit voltage, a narrow overpotential gap, and remarkable rechargeability. This work provides a feasible strategy for constructing freestanding efficient trifunctional electrocatalysts for sustainable energy conversion and storage systems.

Electrocatalytic desalination with CO2 reduction and O2 evolution.

Multifunctional electrocatalytic desalination is a promising method to increase the production of additional valuable chemicals during the desalination process. In this work, a multifunctional desalination device was demonstrated to effectively desalinate brackish water (15 000 ppm) to 9 ppm while generating formate from captured CO2 at the Bi nanoparticle cathode and releasing oxygen at the Ir/C anode. The salt feed channel is sandwiched between two electrode chambers and separated by ion-exchange membranes. The electrocatalytic process accelerates the transportation of sodium ions and chloride ions in the brine to the cathode and anode chamber, respectively. The fastest salt removal rate to date was obtained, reaching up to 228.41 µg cm-2 min-1 with a removal efficiency of 99.94%. The influences of applied potential and the concentrations of salt feed and electrolyte were investigated in detail. The current research provides a new route towards an electrochemical desalination system.

Supercapacitor Performance of Nickel-Cobalt Sulfide Nanotubes Decorated Using Ni Co-Layered Double Hydroxide Nanosheets Grown in Situ on Ni Foam.

In this study, to fabricate a non-binder electrode, we grew nickel-cobalt sulfide (NCS) nanotubes (NTs) on a Ni foam substrate using a hydrothermal method through a two-step approach, namely in situ growth and an anion-exchange reaction. This was followed by the electrodeposition of double-layered nickel-cobalt hydroxide (NCOH) over a nanotube-coated substrate to fabricate NCOH core-shell nanotubes. The final product is called NCS@NCOH herein. Structural and morphological analyses of the synthesized electrode materials were conducted via SEM and XRD. Different electrodeposition times were selected, including 10, 20, 40, and 80 s. The results indicate that the NCSNTs electrodeposited with NCOH nanosheets for 40 s have the highest specific capacitance (SC), cycling stability (2105 Fg-1 at a current density of 2 Ag-1), and capacitance retention (65.1% after 3,000 cycles), in comparison with those electrodeposited for 10, 20, and 80 s. Furthermore, for practical applications, a device with negative and positive electrodes made of active carbon and NCS@NCOH was fabricated, achieving a high-energy density of 23.73 Whkg-1 at a power density of 400 Wkg-1.

2D Black Phosphorus: from Preparation to Applications for Electrochemical Energy Storage.

Black phosphorus (BP) is rediscovered as a 2D layered material. Since its first isolation in 2014, 2D BP has triggered tremendous interest in the fields of condensed matter physics, chemistry, and materials science. Given its unique puckered monolayer geometry, 2D BP displays many unprecedented properties and is being explored for use in numerous applications. The flexibility, large surface area, and good electric conductivity of 2D BP make it a promising electrode material for electrochemical energy storage devices (EESDs). Here, the experimental and theoretical progress of 2D BP is presented on the basis of its preparation methods. The structural and physiochemical properties, air instability, passivation, and EESD applications of 2D BP are discussed systemically. Specifically, the latest research findings on utilizing 2D BP in EESDs, such as lithium-ion batteries, supercapacitors, and emerging technologies (lithium-sulfur batteries, magnesium-ion batteries, and sodium-ion batteries), are summarized. On the basis of the current progress, a few personal perspectives on the existing challenges and future research directions in this developing field are provided.

High-Performance Flexible Quasi-Solid-State Supercapacitors Realized by Molybdenum Dioxide@Nitrogen-Doped Carbon and Copper Cobalt Sulfide Tubular Nanostructures.

Flexible quasi-/all-solid-state supercapacitors have elicited scientific attention to fulfill the explosive demand for portable and wearable electronic devices. However, the use of electrode materials faces several challenges, such as intrinsically slow kinetics and volume change upon cycling, which impede the energy output and electrochemical stability. This study presents well-aligned molybdenum dioxide@nitrogen-doped carbon (MoO2@NC) and copper cobalt sulfide (CuCo2S4) tubular nanostructures grown on flexible carbon fiber for use as electrode materials in supercapacitors. Benefiting from the chemically stable interfaces, affluent active sites, and efficient 1D electron transport, the MoO2@NC and CuCo2S4 nanostructures integrated on conductive substrates deliver excellent electrochemical performance. A flexible quasi-solid-state asymmetric supercapacitor composed of MoO2@NC as the negative electrode and CuCo2S4 as the positive electrode achieves an ultrahigh energy density of 65.1 W h kg-1 at a power density of 800 W kg-1 and retains a favorable energy density of 27.6 W h kg-1 at an ultrahigh power density of 12.8 kW kg-1. Moreover, it demonstrates good cycling performance with 90.6% capacitance retention after 5000 cycles and excellent mechanical flexibility by enabling 92.2% capacitance retention after 2000 bending cycles. This study provides an effective strategy to develop electrode materials with superior electrochemical performance for flexible supercapacitors.

Electrostatic-Induced Assembly of Graphene-Encapsulated Carbon@Nickel-Aluminum Layered Double Hydroxide Core-Shell Spheres Hybrid Structure for High-Energy and High-Power-Density Asymmetric Supercapacitor.

Achieving high energy density while retaining high power density is difficult in electrical double-layer capacitors and in pseudocapacitors considering the origin of different charge storage mechanisms. Rational structural design became an appealing strategy in circumventing these trade-offs between energy and power densities. A hybrid structure consists of chemically converted graphene-encapsulated carbon@nickel-aluminum layered double hydroxide core-shell spheres as spacers among graphene layers (G-CLS) used as an advanced electrode to achieve high energy density while retaining high power density for high-performance supercapacitors. The merits of the proposed architecture are as follows: (1) CLS act as spacers to avoid the close restacking of graphene; (2) highly conductive carbon sphere and graphene preserve the mechanical integrity and improve the electrical conductivity of LDHs hybrid. Thus, the proposed hybrid structure can simultaneously achieve high electrical double-layer capacitance and pseudocapacitance resulting in the overall highly active electrode. The G-CLS electrode exhibited high specific capacitance (1710.5 F g-1 at 1 A g-1) under three-electrode tests. An ASC fabricated using the G-CLS as positive electrode and reduced graphite oxide as negative electrode demonstrated remarkable electrochemical performance. The ASC device operated at 1.4 V and delivered a high energy density of 35.5 Wh kg-1 at a 670.7 W kg-1 power density at 1 A g-1 with an excellent rate capability as well as a robust long-term cycling stability of up to 10 000 cycles.

Structural and optical properties of ZnS thin films deposited by RF magnetron sputtering.

Zinc sulfide [ZnS] thin films were deposited on glass substrates using radio frequency magnetron sputtering. The substrate temperature was varied in the range of 100°C to 400°C. The structural and optical properties of ZnS thin films were characterized with X-ray diffraction [XRD], field emission scanning electron microscopy [FESEM], energy dispersive analysis of X-rays and UV-visible transmission spectra. The XRD analyses indicate that ZnS films have zinc blende structures with (111) preferential orientation, whereas the diffraction patterns sharpen with the increase in substrate temperatures. The FESEM data also reveal that the films have nano-size grains with a grain size of approximately 69 nm. The films grown at 350°C exhibit a relatively high transmittance of 80% in the visible region, with an energy band gap of 3.79 eV. These results show that ZnS films are suitable for use as the buffer layer of the Cu(In, Ga)Se2 solar cells.