Investigation of Binary Metal (Ni,Co) Selenite as Li‐Ion Battery Anode Materials and Their Conversion Reaction Mechanism with Li Ions

Highly efficient anode materials with novel compositions for Li‐ion batteries are actively being researched. Multicomponent metal selenite is a promising candidate, capable of improving their electrochemical performance through the formation of metal oxide and selenide heterostructure nanocrystals during the first cycle. Here, the binary nickel–cobalt selenite derived from Ni–Co Prussian blue analogs (PBA) is chosen as the first target material: the Ni–Co PBA are selenized and partially oxidized in sequence, yielding (NiCo)SeO₃ phase with a small amount of metal selenate. The conversion mechanism of (NiCo)SeO₃ for Li‐ion storage is studied by cyclic voltammetry, in situ X‐ray diffraction, ex situ X‐ray photoelectron spectroscopy, in situ electrochemical impedance spectroscopy, and ex situ transmission electron microscopy. The reversible reaction mechanism of (NiCo)SeO₃ with the Li ions is described by the reaction: NiO + CoO + xSeO₂ + (1 ‐ x)Se + (4x + 6)Li⁺ + (4x + 6)e^? ? Ni + Co + (2x + 2)Li₂O + Li₂Se. To enhance electrochemical properties, polydopamine‐derived carbon is uniformly coated on (NiCo)SeO₃, resulting in excellent cycling and rate performances for Li‐ion storage. The discharge capacity of C‐coated (NiCo)SeO₃ is 680 mAh g^?1 for the 1500th cycle when cycled at a current density of 5 A g^?1.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

Ni(OH)2 Nanoflakes Supported on 3D Ni3Se2 Nanowire Array as Highly Efficient Electrodes for Asymmetric Supercapacitor and Ni/MH Battery

Porous Ni(OH)₂ nanoflakes are directly grown on the surface of nickel foam supported Ni₃Se₂ nanowire arrays using an in situ growth procedure to form 3D Ni₃Se₂@Ni(OH)₂ hybrid material. Owing to good conductivity of Ni₃Se₂, high specific capacitance of Ni(OH)₂ and its unique architecture, the obtained Ni₃Se₂@Ni(OH)₂ exhibits a high specific capacitance of 1689 µAh cm^?2 (281.5 mAh g^?1) at a discharge current of 3 mA cm^?2 and a superior rate capability. Both the high energy density of 59.47 Wh kg^?1 at a power density of 100.54 W kg^?1 and remarkable cycling stability with only a 16.4% capacity loss after 10 000 cycles are demonstrated in an asymmetric supercapacitor cell comprising Ni₃Se₂@Ni(OH)₂ as a positive electrode and activated carbon as a negative electrode. Furthermore, the cell achieved a high energy density of 50.9 Wh L^?1 at a power density of 83.62 W L^?1 in combination with an extraordinary coulombic efficiency of 97% and an energy efficiency of 88.36% at 5 mA cm^?2 when activated carbon is replaced by metal hydride from a commercial NiMH battery. Excellent electrochemical performance indicates that Ni₃Se₂@Ni(OH)₂ composite can become a promising electrode material for energy storage applications.     

Pine‐Needle‐Like Cu–Co Skeleton Composited with Li4Ti5O12 Forming Core–Branch Arrays for High‐Rate Lithium Ion Storage

High‐performance of lithium‐ion batteries (LIBs) rely largely on the scrupulous design of nanoarchitectures and smart hybridization of bespoke active materials. In this work, the pine‐needle‐like Cu–Co skeleton is reported to support highly active Li₄Ti₅O₁₂ (LTO) forming Cu–Co/LTO core–branch arrays via a united hydrothermal‐atomic layer deposition (ALD) method. ALD‐formed LTO layer is uniformly anchored on the pine‐needle‐like heterostructured Cu–Co backbone, which consists of branched Co nanowires (diameters in 20 nm) and Cu nanowires (250–300 nm) core. The designed Cu–Co/LTO core–branch arrays show combined advantages of large porosity, high electrical conductivity, and good adhesion. Due to the unique positive features, the Cu–Co/LTO electrodes are demonstrated with enhanced electrochemical performance including excellent high‐rate capacity (155 mAh g^?1 at 20 C) and noticeable long‐term cycles (144 mAh g^?1 at 20 C after 3000 cycles). Additionally, the full cell assembled with activated carbon positive electrode and Cu–Co/LTO negative electrode exhibits high power/energy densities (41.6 Wh kg^?1 at 7.5 kW kg^?1). The design protocol combining binder‐free characteristics and array configuration opens a new door for construction of advanced electrodes for application in high‐rate electrochemical energy storage.     

A High‐Energy‐Density Hybrid Supercapacitor with P‐Ni(OH)2@Co(OH)2 Core–Shell Heterostructure and Fe2O3 Nanoneedle Arrays as Advanced Integrated Electrodes

Transition metal hydro/oxides (TMH/Os) are treated as the most promising alternative supercapacitor electrodes thanks to their high theoretical capacitance due to the various oxidation states and abundant cheap resources of TMH/Os. However, the poor conductivity and logy reaction kinetics of TMH/Os severely restrict their practical application. Herein, hierarchical core–shell P‐Ni(OH)₂@Co(OH)₂ micro/nanostructures are in situ grown on conductive Ni foam (P‐Ni(OH)₂@Co(OH)₂/NF) through a facile stepwise hydrothermal process. The unique heterostructure composed of P‐Ni(OH)₂ rods and Co(OH)₂ nanoflakes boost the charge transportation and provide abundant active sites when used as the intergrated cathode for supercapacitors. It delivers an ultrahigh areal specific capacitance of 4.4 C cm^?2 at 1 mA cm^?2 and the capacitance can maintain 91% after 10 000 cycles, showing an ultralong cycle life. Additionally, a hybrid supercapacitor composed with P‐Ni(OH)₂@Co(OH)₂/NF cathode and Fe₂O₃/CC anode shows a wider voltage window of 1.6 V, a remarkable energy density of 0.21 mWh cm^?2 at the power density of 0.8 mW cm^?2, and outstanding cycling stability with about 81% capacitance retention after 5000 cycles. This innovative study not only supplies a newfashioned electronic apparatus with high‐energy density and cycling stability but offers a fresh reference and enlightenment for synthesizing advanced integrated electrodes for high‐performance hybrid supercapacitors.     

Pseudocapacitive Ni‐Co‐Fe Hydroxides/N‐Doped Carbon Nanoplates‐Based Electrocatalyst for Efficient Oxygen Evolution

The oxygen evolution reaction (OER) catalytic activity of a transition metal oxides/hydroxides based electrocatalyst is related to its pseudocapacitance at potentials lower than the OER standard potential. Thus, a well‐defined pseudocapacitance could be a great supplement to boost OER. Herein, a highly pseudocapacitive Ni‐Fe‐Co hydroxides/N‐doped carbon nanoplates (NiCoFe‐NC)‐based electrocatalyst is synthesized using a facile one‐pot solvothermal approach. The NiCoFe‐NC has a great pseudocapacitive performance with 1849 F g^?1 specific capacitance and 31.5 Wh kg^?1 energy density. This material also exhibits an excellent OER catalytic activity comparable to the benchmark RuO₂ catalysts (an initiating overpotential of 160 mV and delivering 10 mA cm^?2 current density at 250 mV, with a Tafel slope of 31 mV dec^?1). The catalytic performance of the optimized NiCoFe‐NC catalyst could keep 24 h. X‐ray photoelectron spectroscopy, electrochemically active surface area, and other physicochemical and electrochemical analyses reveal that its great OER catalytic activity is ascribed to the Ni‐Co hydroxides with modular 2‐Dimensional layered structure, the synergistic interactions among the Fe(III) species and Ni, Co metal centers, and the improved hydrophily endowed by the incorporation of N‐doped carbon hydrogel. This work might provide a useful and general strategy to design and synthesize high‐performance metal (hydr)oxides OER electrocatalysts.     

“HOT” Alkaline Hydrolysis of Amorphous MOF Microspheres to Produce Ultrastable Bimetal Hydroxide Electrode with Boosted Cycling Stability

Nickel/cobalt hydroxide is a promising battery‐type electrode material for supercapacitors. However, its low cycle stability hinders further applications. Herein, Ni_0.7Co_0.3(OH)₂ core–shell microspheres exhibiting extreme‐prolonged cycling life are successfully synthesized, employing Ni‐Co‐metal–organic framework (MOF) as the precursor/template and a specific hydrolysis strategy. The Ni‐Co‐MOF and KOH aqueous solution are separated and heated to 120 °C before mixing, rather than mixing before heating. Through this hydrolysis strategy, no MOF residual exists in the product, contributing to close stacking of the hydroxide nanoflakes to generate Ni_0.7Co_0.3(OH)₂ microspheres with a robust core–shell structure. The electrode material exhibits high specific capacity (945 C g^?1 at 0.5 A g^?1) and unprecedented cycling performance (100% after 10 000 cycles). The fabricated asymmetric supercapacitor delivers an energy density of 40.14 Wh kg^?1 at a power density of 400.56 W kg^?1 and excellent cycling stability (100% after 20 000 cycles). As far as is known, it is the best cycling performance for pure Ni/Co(OH)₂.     

Ultrafast Sodium Full Batteries Derived from X?Fe (X = Co,Ni, Mn) Prussian Blue Analogs

Exploring high‐rate electrode materials with excellent kinetic properties is imperative for advanced sodium‐storage systems. Herein, novel cubic‐like X? Fe (X = Co, Ni, Mn) Prussian blue analogs (PBAs), as cathodes materials, are obtained through as‐tuned ionic bonding, delivering improved crystallinity and homogeneous particles size. As expected, Ni‐Fe PBAs show a capacity of 81 mAh g^?1 at 1.0 A g^?1, mainly resulting from their physical–chemical stability, fast kinetics, and “zero‐strain” insertion characteristics. Considering that the combination of elements incorporated with carbon may increase the rate of ion transfer and improve the lifetime of cycling stability, they are expected to derive binary metal‐selenide/nitrogen‐doped carbon as anodes. Among them, binary Ni_0.67Fe_0.33Se₂ coming from Ni‐Fe PBAs shows obvious core–shell structure in a dual‐carbon matrix, leading to enhanced electron interactions, electrochemical activity, and “metal‐like” conductivity, which could retain an ultralong‐term stability of 375 mAh g^?1 after 10 000 loops even at 10.0 A g^?1. The corresponding full‐cell Ni‐Fe PBAs versus Ni_0.67Fe_0.33Se₂ deliver a remarkable Na‐storage capacity of 302.2 mAh g^?1 at 1.0 A g^?1. The rational strategy is anticipated to offer more possibilities for designing advanced electrode materials used in high‐performance sodium‐ion batteries.     

Exploration of Advanced Electrode Materials for Approaching High‐Performance Nickel‐Based Superbatteries

The surging interest in high performance, low‐cost, and safe energy storage devices has spurred tremendous research efforts in the development of advanced electrode active materials. Herein, the in situ growth of zinc–iron layered double hydroxide (Zn–Fe LDH) on graphene aerogel (GA) substrates through a facile, one‐pot hydrothermal method is reported. The strong interaction and efficient electronic coupling between LDH and graphene substantially improve interfacial charge transport properties of the resulting nanocomposite and provide more available redox active sites for faradaic reactions. An LDH–GA||Ni(OH)₂ device is also fabricated that results in greatly enhanced specific capacity (187 mAh g^?1 at 0.1 A g^?1), outstanding specific energy (147 Wh kg^?1), excellent specific power (16.7 kW kg^?1), along with 88% capacity retention after >10 000 cycles. This approach is further extended to Ni–MH and Ni–Cd batteries to demonstrate the feasibility of compositing with graphene for boosting the energy storage performance of other well‐known Ni‐based batteries. In contrast to conventional Ni‐based batteries, the nearly flat voltage plateau followed by a sloping potential profile of the integrated supercapacitor–battery enables it to be discharged down to 0 V without being damaged. These findings provide new prospects for the design of high‐performance and affordable superbatteries based on earth‐abundant elements.     

Biomass‐Derived Nitrogen‐Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel‐Cobalt Layered Double Hydroxide Nanosheets as High‐Performance Asymmetric Supercapacitor Electrode

The development of biomass‐based energy storage devices is an emerging trend to reduce the ever‐increasing consumption of non‐renewable resources. Here, nitrogen‐doped carbonized bacterial cellulose (CBC‐N) nanofibers are obtained by one‐step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio‐template for further deposition of ultrathin nickel‐cobalt layered double hydroxide (Ni‐Co LDH) nanosheets. The as‐obtained CBC‐N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g^?1 at a discharge current density of 1 A g^?1, based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g^?1 and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC‐N@LDH composites as positive electrode materials and CBC‐N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC‐N@LDH composites and 3D nitrogen‐doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg^?1 at the power density of 800.2 W kg^?1. Therefore, this work presents a novel protocol for the large‐scale production of biomass‐derived high‐performance electrode materials in practical supercapacitor applications.     

Rapid and Controllable Synthesis of Nanocrystallized Nickel‐Cobalt Boride Electrode Materials via a Mircoimpinging Stream Reaction for High Performance Supercapacitors

Nickel‐cobalt borides (denoted as NCBs) have been considered as a promising candidate for aqueous supercapacitors due to their high capacitive performances. However, most reported NCBs are amorphous that results in slow electron transfer and even structure collapse during cycling. In this work, a nanocrystallized NCBs‐based supercapacitor is successfully designed via a facile and practical microimpinging stream reactor (MISR) technique, composed of a nanocrystallized NCB core to facilitate the charge transfer, and a tightly contacted Ni‐Co borates/metaborates (NCB_i) shell which is helpful for OH^? adsorption. These merits endow NCB@NCB_i a large specific capacity of 966 C g^?1 (capacitance of 2415 F g^?1) at 1 A g^?1 and good rate capability (633.2 C g^?1 at 30 A g^?1), as well as a very high energy density of 74.3 Wh kg^?1 in an asymmetric supercapacitor device. More interestingly, it is found that a gradual in situ conversion of core NCBs to nanocrystallized Ni‐Co (oxy)‐hydroxides inwardly takes place during the cycles, which continuously offers large specific capacity due to more electron transfer in the redox reaction processes. Meanwhile, the electron deficient state of boron in metal‐borates shells can make it easier to accept electrons and thus promote ionic conduction.     

Robust Electrodes Based on Coaxial TiC/C–MnO2 Core/Shell Nanofiber Arrays with Excellent Cycling Stability for High‐Performance Supercapacitors

A coaxial electrode structure composed of manganese oxide‐decorated TiC/C core/shell nanofiber arrays is produced hydrothermally in a KMnO₄ solution. The pristine TiC/C core/shell structure prepared on the Ti alloy substrate provides the self‐sacrificing carbon shell and highly conductive TiC core, thus greatly simplifying the fabrication process without requiring an additional reduction source and conductive additive. The as‐prepared electrode exhibits a high specific capacitance of 645 F g^?1 at a discharging current density of 1 A g^?1 attributable to the highly conductive TiC/C and amorphous MnO₂ shell with fast ion diffusion. In the charging/discharging cycling test, the as‐prepared electrode shows high stability and 99% capacity retention after 5000 cycles. Although the thermal treatment conducted on the as‐prepared electrode decreases the initial capacitance, the electrode undergoes capacitance recovery through structural transformation from the crystalline cluster to layered birnessite type MnO₂ nanosheets as a result of dissolution and further electrodeposition in the cycling. 96.5% of the initial capacitance is retained after 1000 cycles at high charging/discharging current density of 25 A g^?1. This study demonstrates a novel scaffold to construct MnO₂ based SCs with high specific capacitance as well as excellent mechanical and cycling stability boding well for future design of high‐performance MnO₂‐based SCs.     

Suppression of Persistent Photoconductivity of Rubrene Crystals using Gate‐Tunable Rubrene/Bi2Se3 Diodes with Photoinduced Negative Differential Resistance

Organic single‐crystalline semiconductors show great potential in high‐performance photodetectors. However, they suffer from persistent photoconductivity (PPC) due to the charge trapping, which has severely hindered high‐speed imaging applications. Here, a universal strategy of solving the PPC by integrating with topological insulator Bi₂Se₃ is provided. The rubrene/Bi₂Se₃ heterojunctions are selected as an example for general demonstration due to the reproducibly high mobility and broad optoelectronic applications of rubrene crystals. By virtue of high carrier concentration on Bi₂Se₃ surface and the strong built‐in electrical field, the photoresponse of the heterotransistor is significantly reduced for more than two orders (from over 10 s to 54 ms), meanwhile the photoresponsivity can reach 124 A W^?1. To the best of knowledge, this operating speed is among the fastest responses in organic–inorganic heterojunctions. The heterotransistor also shows unique negative differential resistance under positive gate bias, which can be explained by photoinduced de‐trapping of electron trap states in the bulk rubrene crystals. Besides, the rubrene/Bi₂Se₃ heterojunction behaves as a gate‐tunable backward‐like diode due to the inhomogenous carrier distribution in the thick rubrene crystal and inversion of relative Fermi level positions. The findings demonstrate versatile functionalities of the rubrene/Bi₂Se₃ heterojunctions for various emerging optoelectronic applications.     

Composition and Architecture Design of Double‐Shelled Co0.85Se1−xSx@Carbon/Graphene Hollow Polyhedron with Superior Alkali (Li,Na, K)‐Ion Storage

The exploration of materials with reversible and stable electrochemical performance is crucial in energy storage, which can (de) intercalate all the alkali‐metal ions (Li⁺, Na⁺, and K⁺). Although transition‐metal chalcogenides are investigated continually, the design and controllable preparation of hierarchical nanostructure and subtle composite withstable properties are still great challenges. Herein, component‐optimal Co_0.85Se_1?xS_x nanoparticles are fabricated by in situ sulfidization of metal organic framework, which are wrapped by the S‐doped graphene, constructing a hollow polyhedron framework with double carbon shells (CoSSe@C/G). Benefiting from the synergistic effect of composition regulation and architecture design by S‐substitution, the electrochemical kinetic is enhanced by the boosted electrochemistry‐active sites, and the volume variation is mitigated by the designed structure, resulting in the advanced alkali‐ion storage performance. Thus, it delivers an outstanding reversible capacity of 636.2 mAh g^?1 at 2 A g^?1 after 1400 cycles for Li‐ion batteries. Remarkably, satisfactory initial charge capacities of 548.1 and 532.9 mAh g^?1 at 0.1 A g^?1 can be obtained for Na‐ion and K‐ion batteries, respectively. The prominent performance combined with the theory calculation confirms that the synergistic strategy can improve the alkali‐ion transportation and structure stability, providing an instructive guide for designing high‐performance anode materials for universal alkali‐ion storage.     

Influence of the Al(Co,Ni) layer on the corrosion resistance of a cobalt based alloy (Mar‐M‐509®)

In the present work, the results of studies on the structure and corrosion resistance of Al(Co, Ni) layer are shown. The diffusion Al(Co, Ni) layer was created on the cobalt alloy Mar‐M‐509 substrate by chemical vapor deposition (CVD) method with aluminum trichloride (AlCl₃) under the hydrogen atmosphere. The scanning electron microscope (SEM) observations and microtomography measurements of layers were performed. Also an analysis of the chemical (energy‐dispersive X‐ray spectroscopy (EDS)) and phase (X‐ray diffraction (XRD)) composition was carried out. By the X‐ray diffraction method (sin² φ) also the residual stresses were calculated in the matrix of the material. The corrosion resistance was tested with impedance and potentiodynamic methods in 0.1 M Na₂SO₄, 0.1 M H₂SO₄ solutions and acidulous 0.1 M NaCl solution (pH = 4.2) at room temperature. The results indicate that the analyzed layer with a thickness of about 14 μm have a similar corrosion resistance compared to the base material – Mar‐M‐509^® cobalt alloy. Only in the strongly acidic environments, the corrosion resistance of the layer is remarkably decreased.     

Bimetal‐Organic‐Framework Derivation of Ball‐Cactus‐Like Ni‐Sn‐P@C‐CNT as Long‐Cycle Anode for Lithium Ion Battery

Metal phosphides are a new class of potential high‐capacity anodes for lithium ion batteries, but their short cycle life is the critical problem to hinder its practical application. A unique ball‐cactus‐like microsphere of carbon coated NiP₂/Ni₃Sn₄ with deep‐rooted carbon nanotubes (Ni‐Sn‐P@C‐CNT) is demonstrated in this work to solve this problem. Bimetal‐organic‐frameworks (BMOFs, Ni‐Sn‐BTC, BTC refers to 1,3,5‐benzenetricarboxylic acid) are formed by a two‐step uniform microwave‐assisted irradiation approach and used as the precursor to grow Ni‐Sn@C‐CNT, Ni‐Sn‐P@C‐CNT, yolk–shell Ni‐Sn@C, and Ni‐Sn‐P@C. The uniform carbon overlayer is formed by the decomposition of organic ligands from MOFs and small CNTs are deeply rooted in Ni‐Sn‐P@C microsphere due to the in situ catalysis effect of Ni‐Sn. Among these potential anode materials, the Ni‐Sn‐P@C‐CNT is found to be a promising anode with best electrochemical properties. It exhibits a large reversible capacity of 704 mA h g^?1 after 200 cycles at 100 mA g^?1 and excellent high‐rate cycling performance (a stable capacity of 504 mA h g^?1 retained after 800 cycles at 1 A g^?1). These good electrochemical properties are mainly ascribed to the unique 3D mesoporous structure design along with dual active components showing synergistic electrochemical activity within different voltage windows.     

Large‐Area,Uniform, Aligned Arrays of Na3(VO)2(PO4)2F on Carbon Nanofiber for Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors

Sodium–vanadium fluorophosphate (Na₃V₂O_2x(PO₄)₂F_3?2x, NVPF, 0 ≤ x ≤ 1) is considered to be a promising Na‐storage cathode material due to its high operation potentials (3.6–4 V) and minor volume variation (1.8%) during Na⁺‐intercalation. Research about NVPF is mainly focused on powder‐type samples, while its ordered array architecture is rarely reported. In this work, large‐area and uniform Na₃(VO)₂(PO₄)₂F cuboid arrays are vertically grown on carbon nanofiber (CNF) substrates for the first time. Owing to faster electron/ion transport and larger electrolyte–electrode contact area, the as‐prepared NVPF array electrode exhibits much improved Na‐storage properties compared to its powder counterpart. Importantly, a quasi‐solid‐state sodium‐ion hybrid capacitor (SIHC) is constructed based on the NVPF array as an intercalative battery cathode and porous CNF as a capacitive supercapacitor anode together with the P(VDF‐HFP)‐based polymer electrolyte. This novel hybrid system delivers an attractive energy density of ≈227 W h kg^?1 (based on total mass of two electrodes), and still remains as high as 107 Wh kg^?1 at a high specific power of 4936 W kg^?1, which pushes the energy output of sodium hybrid capacitors toward a new limit. In addition, the growth mechanism of NVPF arrays is investigated in detail.     

Fe2+‐Doped Layered Double (Ni,Fe) Hydroxides as Efficient Electrocatalysts for Water Splitting and Self‐Powered Electrochemical Systems

Developing nonprecious electrocatalysts with superior activity and durability for electrochemical water splitting is of great interest but challenging due to the large overpotential required above the thermodynamic standard potential of water splitting (1.23 V). Here, in situ growth of Fe²⁺‐doped layered double (Ni, Fe) hydroxide (NiFe(II,III)‐LDH) on nickel foam with well‐defined hexagonal morphology and high crystallinity by a redox reaction between Fe³⁺ and nickel foam under hydrothermal conditions is reported. Benefiting from tuning the local atomic structure by self‐doping Fe²⁺, the NiFe(II,III)‐LDH catalyst with higher amounts of Fe²⁺ exhibits high activity toward oxygen evolution reaction (OER) as well as hydrogen evolution reaction (HER) activity. Moreover, the optimized NiFe(II,III)‐LDH catalyst for OER (O‐NiFe(II,III)‐LDH) and catalyst for HER (H‐NiFe(II,III)‐LDH) show overpotentials of 140 and 113 mV, respectively, at a current density of 10 mA cm^?2 in 1 m KOH aqueous electrolyte. Using the catalysts for overall water splitting in two‐electrode configuration, a low overpotential of just 1.54 V is required at a benchmark current density of 10 mA cm^?2. Furthermore, it is demonstrated that electrolysis of the water device can be drived by a self‐powered system through integrating a triboelectric nanogenerator and battery, showing a promising way to realize self‐powered electrochemical systems.     

Co(OH)2 Nanoparticle‐Encapsulating Conductive Nanowires Array: Room‐Temperature Electrochemical Preparation for High‐Performance Water Oxidation Electrocatalysis

It is highly desired but still remains challenging to design and develop a Co‐based nanoparticle‐encapsulated conductive nanoarray at room temperature for high‐performance water oxidation electrocatalysis. Here, it is reported that room‐temperature anodization of a Co(TCNQ)₂ (TCNQ = tetracyanoquinodimethane) nanowire array on copper foam at alkaline pH leads to in situ electrochemcial oxidation of TCNQ^? into water‐insoluable TCNQ nanoarray embedding Co(OH)₂ nanoparticles. Such Co(OH)₂‐TCNQ/CF shows superior catalytic activity for water oxidation and demands only a low overpotential of 276 mV to drive a geometrical current density of 25 mA cm^?2 in 1.0 m KOH. Notably, it also demonstrates strong long‐term electrochemical durability with its activity being retrained for at least 25 h, a high turnover frequency of 0.97 s^?1 at an overpotential of 450 mV and 100% Faradic efficiency. This study provides an exciting new method for the rational design and development of a conductive TCNQ‐based nanoarray as an interesting 3D material for advanced electrochemical applications.     

Superior Photocatalytic H2 Production with Cocatalytic Co/Ni Species Anchored on Sulfide Semiconductor

Downsizing transition metal‐based cocatalysts on semiconductors to promote photocatalytic efficiency is important for research and industrial applications. This study presents a novel and facile strategy for anchoring well‐dispersed metal species on CdS surface through controlled decarboxylation of the ethylenediaminetetraacetate (EDTA) ligand in the metal–EDTA (M–EDTA) complex and CdS mixture precursor to function as a cocatalyst in the photocatalytic H₂ evolution. Microstructure characterization and performance evaluation reveal that under visible light the resulting pentacoordinated Co(II) and hexacoordinated Ni(II) on CdS exhibits a high activity of 3.1 mmol h^?1 (with turnover frequency (TOF) of 626 h^?1 and apparent quantum efficiency (AQE) of 56.2% at 420 nm) and 4.3 mmol h^?1 (with TOF of 864 h^?1 and AQE of 67.5% at 420 nm), respectively, toward cocatalytic hydrogen evolution, and the cocatalytic activity of such a hexacoordinated Ni(II) even exceeds that of platinum. Further mechanistic study and theoretical modeling indicate that the fully utilized Co(II)/Ni(II) active sites, efficient charge transfer, and favorable kinetics guarantee the efficient activities. This work introduces a promising precursor, i.e., M–EDTA for planting well‐dispersed transition metal species on the sulfide supports by a facile wet‐chemistry approach, providing new opportunities for photocatalytic H₂ production at the atomic/molecular scale.