Sulfur-Bridged Bonds Heightened Na-Storage Properties in MnS Nanocubes Encapsulated by S-Doped Carbon Matrix Synthesized via Solvent-Free Tactics for High-Performance Hybrid Sodium Ion Capacitors

The exploitation of electrode materials with ability to balance capacity and kinetics between cathode and anode is a challenge for sodium-ion hybrid capacitors (SIHCs). Mn-based anode materials are limited by poor electrical conductivity, sluggish reaction kinetics, large volume variation, weak cycling stability, and inferior reversible capacity. Herein, MnS nanocubes encapsulated in S-doped porous carbon matrix (MSC) with strong sulfur-bridged bond interactions (C S Mn) are successfully synthesized by solvent-free tactics. The C S Mn bonds generated between MnS and carbon significantly inhibit the aggregation of nanostructural MnS cubes, restrict the volume expansion, and stabilize the nanostructure, which improves the Na⁺ storage reversibility and stability. Moreover, S-doped porous carbon enhances the electrical conductivity and electrons/ions diffusion rate, which boosts a fast kinetic reaction. As expected, MSC anode presents an outstanding reversible capacity of 600 mAh g^-1 at 0.2 A g^-1 and a long-term stable capacity of 357 mAh g^-1 for 1000 cycles at a high current density of 10 A g^-1 in sodium-ion batteries (SIBs). The as-assembled SIHCs deliver a high energy density of 109 W h kg^-1 and a high power output of 98 W kg^-1, with 88% capacity retention at 2 A g^-1 after 2000 cycles and practical applications (55 LEDs can be lighted for 10 min).     

Nanostructured MoS2 with Interlayer Controllably Regulated by Ionic Liquids/Cellulose for High-Capacity and Durable Sodium Storage Properties

Low intrinsic conductivity and structural instability of MoS₂ as an anode of sodium-ion batteries limit the liberation of its theoretical capacity. Herein, density functional theory simulations for the first time optimize MoS₂ interlayer distance between 0.80 and 1.01 nm for sodium storage. 1-Butyl-3-methyl-imidazolium acetate ([BMIm]Ac) induces cellulose oligomers to intercalate MoS₂ interlayers for achieving controllable distance by changing the mass ratio of cellulose to [BMIm]Ac. Based on these findings, porous carbon loading the interlayer-expanded MoS₂ allowing Na⁺ to insert with fast kinetics is synthesized. A carbon layer derived from [BMIm]Ac and cellulose coating the composite prevents the MoS₂ from contacting electrolytes, leading to less sulfur loss for a more reversible specific capacity. Meanwhile, MoS₂ and carbon have a strong interfacial connection through Mo N binding, contributing to enhanced structural stability. As expected, while cycling 250 times at 0.1 A g^-1, the MoS₂-porous carbon composite displays an optimal reversible capacity at 517.79 mAh g^-1 as a sodium-ion batteries anode. The cyclic test of 1.0 A g^-1 also shows considerable stability (310.74 mAh g^-1 after 1000 cycles with 86.26% retentive capacity). This study will open up new possibilities of modifying MoS₂ that serves as an applicable material as sodium-ion battery anode.     

Hard Carbon Nanosheets with Uniform Ultramicropores and Accessible Functional Groups Showing High Realistic Capacity and Superior Rate Performance for Sodium-Ion Storage

Hard carbon attracts considerable attention as an anode material for sodium-ion batteries; however, their poor rate capability and low realistic capacity have motivated intense research effort toward exploiting nanostructured carbons in order to boost their comprehensive performance. Ultramicropores are considered essential for attaining high-rate capacity as well as initial Coulombic efficiency by allowing the rapid diffusion of Na⁺ and inhibiting the contact of the electrolyte with the inner carbon surfaces. Herein, hard carbon nanosheets with centralized ultramicropores (≈0.5 nm) and easily accessible carbonyl groups (CO)/hydroxy groups (O H) are synthesized via interfacial assembly and carbonization strategies, delivering a large capacity (318 mA h g⁻¹ at 0.02 A g⁻¹), superior rate capability (145 mA h g⁻¹ at 5.00 A g⁻¹), and approximately 95% of reversible capacity below 1.00 V. Notably, a new charge model favoring fast capacitive sodium storage with dual potential plateaus is proposed. That is, the deintercalation of Na⁺ from graphitic layers is manifested as the low-potential plateau region (0.01−0.10 V), contributing to stable insertion capacity; meanwhile, the surface desodiation process of the CO and O H groups corresponds to the high-potential plateau region (0.40−0.70 V), contributing to a fast capacitive storage.     

Boosting the Reversible,High-Rate Na+ Storage Capability of the Hard Carbon Anode Via the Synergistic Structural Tailoring and Controlled Presodiation

Hard carbons (HCs) are extensively investigated as the potential anodes for commercialization of sodium-ion batteries (SIBs). However, the practical deployment of HC anode suffers from the retarded Na⁺ diffusion at the high-rate or low-temperature operation scenarios. Herein, a multiscale modification strategy by tuning HC microstructure on the particle level as well as replenishing extra Na⁺ reservoir for the electrode through a homogeneous presodiation therapy is presented. Consequently, the coulombic efficiency of HC anode can be precisely controlled till the close-to-unit value. Detailed kinetics analysis observes that the Na⁺ diffusivity can be drastically enhanced by two orders of magnitude at the low potential region (< 0.1 V vs. Na⁺/Na), which accelerates the rate-limiting step. As pairing the presodiated HC anode (≈5.0 ± 0.2 mg cm⁻²) with the NaVPO₄F cathode (≈10.3 mg cm⁻²) in the 200 mAh pouch cell, the optimal balance of the cyclability (83% over 1000 cycles), low-temperature behavior till −40 °C as well as the maximized power output of 1500 W kg⁻¹ can be simultaneously achieved. This synergistic modification strategy opens a new avenue to exploit the reversible, ultrafast Na⁺ storage kinetics of HC anodes, which thus constitutes a quantum leap forward toward high-rate SIB prototyping.     

Anion-Vacancy Modified WSSe Nanosheets on 3D Cross-Networked Porous Carbon Skeleton for Non-Aqueous Sodium-Based Dual-Ion Storage

Sodium-based dual-ion batteries (SDIBs) have become a new type of energy storage device with great application value because of their high operating voltage, high energy density, and low cost. However, transition-metal dichalcogenide (TMD) anodes show unsatisfactory Na⁺ electrochemical performance owing to the low intrinsic conductivity and inferior ion transport kinetics. Here, an elaborate design is developed to prepare a composite of WSSe nanosheets supported on a 3D cross-networked porous carbon skeleton (WSSe@CPCS), which possesses en-rich anion vacancies and WSSe with expanded inter-layer spacing, as well as an interconnected porous structure. As a result, the WSSe@CPCS anode for sodium-ion batteries (SIBs) exhibits preeminent reversible capacities, excellent cycle stability, and superior rate capability. The systematic electrochemical kinetic analysis and density functional theory results further show that the effect of anion vacancies and CPCS synergistically enhances the conductivity and reduces charge transfer resistance, thus making a great contribution to fast reaction kinetics. Finally, the implementations of the WSSe@CPCS anode in progressive SIB and DIB full-cell configurations exhibit satisfactory performance, which reveals their widely practical application. This research will provide an exciting approach to designing advanced defect-structured tungsten-based TMD materials for SIBs, DIBs, and even a broad range of energy storage.     

Amine–Aldehyde Condensation-Derived N-Doped Hard Carbon Microspheres for High-Capacity and Robust Sodium Storage

Hard carbon is generally accepted as the choice of anode material for sodium-ion batteries. However, integrating high capacity, high initial Coulombic efficiency (ICE), and good durability in hard carbon materials remains challenging. Herein, N-doped hard carbon microspheres (NHCMs) with abundant Na⁺ adsorption sites and tunable interlayer distance are constructed based on the amine–aldehyde condensation reaction using m-phenylenediamine and formaldehyde as the precursors. The optimized NHCM-1400 with a considerable N content (4.64%) demonstrates a high ICE (87%), high reversible capacity with ideal durability (399 mAh g⁻¹ at 30 mA g⁻¹ and 98.5% retention over 120 cycles), and decent rate capability (297 mAh g⁻¹ at 2000 mA g⁻¹). In situ characterizations elucidate the adsorption–intercalation-filling sodium storage mechanism of NHCMs. Theoretical calculation reveals that the N-doping decreases the Na⁺ adsorption energy on hard carbon.     

Novel Structural Design and Adsorption/Insertion Coordinating Quasi-Metallic Na Storage Mechanism toward High-performance Hard Carbon Anode Derived from Carboxymethyl Cellulose

Hard Carbon have become the most promising anode candidates for sodium-ion batteries, but the poor rate performance and cycle life remain key issues. In this work, N-doped hard carbon with abundant defects and expanded interlayer spacing is constructed by using carboxymethyl cellulose sodium as precursor with the assistance of graphitic carbon nitride. The formation of N-doped nanosheet structure is realized by the C N• or C C• radicals generated through the conversion of nitrile intermediates in the pyrolysis process. This greatly enhances the rate capability (192.8 mAh g⁻¹ at 5.0 A g⁻¹) and ultra-long cycle stability (233.3 mAh g⁻¹ after 2000 cycles at 0.5 A g⁻¹). In situ Raman spectroscopy, ex situ X-ray diffraction and X-ray photoelectron spectroscopy analysis in combination with comprehensive electrochemical characterizations, reveal that the interlayer insertion coordinated quasi-metallic sodium storage in the low potential plateau region and adsorption storage in the high potential sloping region. The first-principles density functional theory calculations further demonstrate strong coordination effect on nitrogen defect sites to capture sodium, especially with pyrrolic N, uncovering the formation mechanism of quasi-metallic bond in the sodium storage. This work provides new insights into the sodium storage mechanism of high-performance carbonaceous materials, and offers new opportunities for better design of hard carbon anode.     

Construction of Bimetallic Selenides Encapsulated in Nitrogen/Sulfur Co‐Doped Hollow Carbon Nanospheres for High‐Performance Sodium/Potassium‐Ion Half/Full Batteries

Metallic selenides have been widely investigated as promising electrode materials for metal‐ion batteries based on their relatively high theoretical capacity. However, rapid capacity decay and structural collapse resulting from the larger‐sized Na⁺/K⁺ greatly hamper their application. Herein, a bimetallic selenide (MoSe₂/CoSe₂) encapsulated in nitrogen, sulfur‐codoped hollow carbon nanospheres interconnected reduced graphene oxide nanosheets (rGO@MCSe) are successfully designed as advanced anode materials for Na/K‐ion batteries. As expected, the significant pseudocapacitive charge storage behavior substantially contributes to superior rate capability. Specifically, it achieves a high reversible specific capacity of 311 mAh g^?1 at 10 A g^?1 in NIBs and 310 mAh g^?1 at 5 A g^?1 in KIBs. A combination of ex situ X‐ray diffraction, Raman spectroscopy, and transmission electron microscopy tests reveals the phase transition of rGO@MCSe in NIBs/KIBs. Unexpectedly, they show quite different Na⁺/K⁺ insertion/extraction reaction mechanisms for both cells, maybe due to more sluggish K⁺ diffusion kinetics than that of Na⁺. More significantly, it shows excellent energy storage properties in Na/K‐ion full cells when coupled with Na₃V₂(PO₄)₂O₂F and PTCDA@450 °C cathodes. This work offers an advanced electrode construction guidance for the development of high‐performance energy storage devices.     

Amorphous Vanadium Oxide Nanosheets with Alterable Polyhedron Configuration for Fast-Charging Lithium-Ion Batteries

Transition metal oxides with high theoretical capacities are promising anode materials for lithium-ion batteries (LIBs). However, the sluggish reaction kinetics remain a bottleneck for fast-charging applications due to its slow Li⁺ migration rate. Herein, a strategy is reported of significantly reducing the Li⁺ diffusion barrier of amorphous vanadium oxide by constructing a specific ratio of the V O local polyhedron configuration in amorphous nanosheets. The optimized amorphous vanadium oxide nanosheets with a ratio ≈1:4 for octahedron sites (O_h) to pyramidal sites (C_4v) revealed by Raman spectroscopy and X-ray absorption spectroscopy (XAS) demonstrate the highest rate capability (356.7 mA h g⁻¹ at 10.0 A g⁻¹) and long-term cycling life (455.6 mA h g⁻¹ at 2.0 A g⁻¹ over 1200 cycles). Density functional theory (DFT)calculations further verify that the local structure (O_h:C_4v = 1:4) intrinsically changes the degree of orbital hybridization between V and O atoms and contributes to a higher intensity of electron occupied states near the Fermi level, thus resulting in a low Li⁺ diffusion barrier for favorable Li⁺ transport kinetics. Moreover, the amorphous vanadium oxide nanosheets possess a reversible V O vibration mode and volume expansion rate close to 0.3%, as determined through in situ Raman and in situ transmission electron microscopy.     

1D Nanomaterials: Design,Synthesis, and Applications in Sodium–Ion Batteries

Sodium–ion batteries (SIBs) have received extensive attention as ideal candidates for large‐scale energy storage systems (ESSs) owing to the rich resources and low cost of sodium (Na). However, the larger size of Na⁺ and the less negative redox potential of Na⁺/Na result in low energy densities, short cycling life, and the sluggish kinetics of SIBs. Therefore, it is necessary to develop appropriate Na storage electrode materials with the capability to host larger Na⁺ and fast ion diffusion kinetics. 1D materials such as nanofibers, nanotubes, nanorods, and nanowires, are generally considered to be high‐capacity and stable electrode materials, due to their uniform structure, orientated electronic and ionic transport, and strong tolerance to stress change. Here, the synthesis of 1D nanomaterials and their applications in SIBs are reviewed. In addition, the prospects of 1D nanomaterials on energy conversion and storage as well as the development and application orientation of SIBs are presented.     

3D Graphene Networks Encapsulated with Ultrathin SnS Nanosheets@Hollow Mesoporous Carbon Spheres Nanocomposite with Pseudocapacitance‐Enhanced Lithium and Sodium Storage Kinetics

The lithium and sodium storage performances of SnS anode often undergo rapid capacity decay and poor rate capability owing to its huge volume fluctuation and structural instability upon the repeated charge/discharge processes. Herein, a novel and versatile method is described for in situ synthesis of ultrathin SnS nanosheets inside and outside hollow mesoporous carbon spheres crosslinked reduced graphene oxide networks. Thus, 3D honeycomb‐like network architecture is formed. Systematic electrochemical studies manifest that this nanocomposite as anode material for lithium‐ion batteries delivers a high charge capacity of 1027 mAh g^?1 at 0.2 A g^?1 after 100 cycles. Meanwhile, the as‐developed nanocomposite still retains a charge capacity of 524 mAh g^?1 at 0.1 A g^?1 after 100 cycles for sodium‐ion batteries. In addition, the electrochemical kinetics analysis verifies the basic principles of enhanced rate capacity. The appealing electrochemical performance for both lithium‐ion batteries and sodium‐ion batteries can be mainly related to the porous 3D interconnected architecture, in which the nanoscale SnS nanosheets not only offer decreased ion diffusion pathways and fast Li⁺/Na⁺ transport kinetics, but also the 3D interconnected conductive networks constructed from the hollow mesoporous carbon spheres and reduced graphene oxide enhance the conductivity and ensure the structural integrity.     

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.     

Fluorinated Interface Engineering toward Controllable Zinc Deposition and Rapid Cation Migration of Aqueous Zn-Ion Batteries

Metallic zinc (Zn) is a highly promising anode material for aqueous energy storage systems due to its low redox potential, high theoretical capacity, and low cost. However, rampant dendrites/by-products and torpid Zn²⁺ transfer kinetics at electrode/electrolyte interface severely threaten the cycling stability, which deteriorate the electrochemical performance of Zn-ion batteries. Herein, an interfacial engineering strategy to construct alkaline earth fluoride modified metal Zn electrodes with long lifespan and high capacity retention is reported. The compact fluoride layer is revealed to guide uniform Zn stripping/plating and accelerate the transfer/diffusion of Zn²⁺ via Maxwell-Wagner polarization. A series of in situ and ex situ spectroscopic studies verified that the fluoride layer can guide uniform Zn stripping/plating. Electrochemical kinetics analyses reveal that positive effect on the removal of Zn²⁺ solvation sheath provided by fluoride layer. Meanwhile, this fluoride coating layer can act as a barrier between the Zn electrode and electrolyte, providing a high electrode overpotential toward hydrogen evolution reaction to hold back H₂ evolution. Consequently, the fluoride-modified Zn anode exhibited a capacity retention of 88.2% after 4000 cycles under10 A g⁻¹. This work opens up a new path to interface engineering for propelling the exploration of advanced rechargeable aqueous Zn-ion batteries.     

High-Entropy Doping Boosts Ion/Electronic Transport of Na4Fe3(PO4)2(P2O7)/C Cathode for Superior Performance Sodium-Ion Batteries

Fe-based mixed phosphate cathodes for Na-ion batteries usually possess weak rate capacity and cycle stability challenges resulting from sluggish diffusion kinetics and poor conductivity under the relatively low preparation temperature. Here, the excellent sodium storage capability of this system is obtained by introducing the high-entropy doping to enhance the electronic and ionic conductivity. As designed high-entropy doping Na₄Fe_2.85(Ni,Co,Mn,Cu,Mg)_0.03(PO₄)₂P₂O₇ (NFPP-HE) cathode can release 122 mAh g⁻¹ at 0.1 C, even 85 mAh g⁻¹ at ultrahigh rate of 50 C, and keep a high retention of 82.3% after 1500 cycles at 10 C. Besides, the cathode also exhibits outstanding fast charge capacity in terms of the cyclability and capacity with 105 mAh g⁻¹ at 5 C/1 C, corresponding 94.3% retention after 500 cycles. The combination of in situ X-ray diffraction, density functional theory, conductive-atomic force microscopy, and galvanostatic intermittent titration technique tests reveal that the reversible structure evolution with optimized Na⁺ migration path and energy barrier boost the Na⁺ kinetics and improve the interfacial electronic transfer, thus improving performance.     

Engineering C?S?Fe Bond Confinement Effect to Stabilize Metallic-Phase Sulfide for High Power Density Sodium-Ion Batteries (Small 37/2023)

Metallic-phase iron sulfide (e.g., Fe₇S₈) is a promising candidate for high power density sodium storage anode due to the inherent metal electronic conductivity and unhindered sodium-ion diffusion kinetics. Nevertheless, long-cycle stability can not be achieved simultaneously while designing a fast-charging Fe₇S₈-based anode. Herein, Fe₇S₈ encapsulated in carbon-sulfur bonds doped hollow carbon fibers (NHCFs-S-Fe₇S₈) is designed and synthesized for sodium-ion storage. The NHCFs-S-Fe₇S₈ including metallic-phase Fe₇S₈ embrace higher electron specific conductivity, electrochemical reversibility, and fast sodium-ion diffusion. Moreover, the carbonaceous fibers with polar C S Fe bonds of NHCFs-S-Fe₇S₈ exhibit a fixed confinement effect for electrochemical conversion intermediates contributing to long cycle life. In conclusion, combined with theoretical study and experimental analysis, the multinomial optimized NHCFs-S-Fe₇S₈ is demonstrated to integrate a suitable structure for higher capacity, fast charging, and longer cycle life. The full cell shows a power density of 1639.6 W kg⁻¹ and an energy density of 204.5 Wh kg⁻¹, respectively, over 120 long cycles of stability at 1.1 A g⁻¹. The underlying mechanism of metal sulfide structure engineering is revealed by in-depth analysis, which provides constructive guidance for designing the next generation of durable high-power density sodium storage anodes.     

Engineering Crystal Growth and Surface Modification of Na3V2(PO4)2F3 Cathode for High-Energy-Density Sodium-Ion Batteries

Na₃V₂(PO₄)₂F₃ (NVPF) is a suitable cathode for sodium-ion batteries owing to its stable structure. However, the large radius of Na⁺ restricts diffusion kinetics during charging and discharging. Thus, in this study, a phosphomolybdic acid (PMA)-assisted hydrothermal method is proposed. In the hydrothermal process, the NVPF morphologies vary from bulk to cuboid with varying PMA contents. The optimal channel for accelerated Na⁺ transmission is obtained by cuboid NVPF. With nitrogen-doping of carbon, the conductivity of NVPF is further enhanced. Combined with crystal growth engineering and surface modification, the optimal nitrogen-doped carbon-covered NVPF cuboid (c-NVPF@NC) exhibits a high initial discharge capacity of 121 mAh g⁻¹ at 0.2 C. Coupled with a commercial hard carbon (CHC) anode, the c-NVPF@NC||CHC full battery delivers 118 mAh g⁻¹ at 0.2 C, thereby achieving a high energy density of 450 Wh kg⁻¹. Therefore, this work provides a novel strategy for boosting electrochemical performance by crystal growth engineering and surface modification.     

Bundled Defect‐Rich MoS2 for a High‐Rate and Long‐Life Sodium‐Ion Battery: Achieving 3D Diffusion of Sodium Ion by Vacancies to Improve Kinetics

Molybdenum disulfide (MoS₂), a 2D‐layered compound, is regarded as a promising anode for sodium‐ion batteries (SIBs) due to its attractive theoretical capacity and low cost. The main challenges associated with MoS₂ are the low rate capability suffering from the sluggish kinetics of Na⁺ intercalation and the poor cycling stability owning to the stack of MoS₂ sheets. In this work, a unique architecture of bundled defect‐rich MoS₂ (BD‐MoS₂) that consists of MoS₂ with large vacancies bundled by ultrathin MoO₃ is achieved via a facile quenching process. When employed as anode for a SIB, the BD‐MoS₂ electrode exhibits an ultrafast charge/discharge due to the pseudocapacitive‐controlled Na⁺ storage mechanism in it. Further experimental and theoretical calculations show that Na⁺ is able to cross the MoS₂ layer by vacancies, not only limited to diffusion along the layer, thus realizing a 3D Na⁺ diffusion with faster kinetics. Meanwhile, the bundling architecture reduces the stack of sheets with a superior cycle life illustrating the highly reversible capacities of 350 and 272 mAh g^?1 at 2 and 5 A g^?1 after 1000 cycles.     

Heterostructures of 2D Molybdenum Dichalcogenide on 2D Nitrogen-Doped Carbon: Superior Potassium-Ion Storage and Insight into Potassium Storage Mechanism

Constructing 2D heterostructure materials by stacking different 2D materials can combine the merits of the individual building blocks while eliminating their shortcomings. Dichalcogenides are attractive anodes for potassium-ion batteries (KIBs) due to their high theoretical capacity. However, the practical application of dichalcogenide is greatly hampered by the poor electrochemical performance due to sluggish kinetics of K⁺ insertion and the electrode structure collapse resulting from the large K⁺ insertion. Herein, heterostructures of 2D molybdenum dichalcogenide on 2D nitrogen-doped carbon (MoS₂, MoSe₂-on-NC) are prepared to boost their potassium storage performance. The unique 2D heterostructures possess built-in heterointerfaces, facilitating K⁺ diffusion. The robust chemical bonds (C S, C Se, C Mo bonds) enhance the mechanical strength of electrodes, thus suppressing the volume expansion. The 2D N-doped carbon nanosheets interconnected as a 3D structure offer a fast diffusion path for electrons. Benefitting from these merits, both the MoS₂-on-NC and the MoSe₂-on-NC exhibit unprecedented cycle life. Moreover, the electrochemical reaction mechanism of MoSe₂ is revealed during the process of potassiation and depotassiation.     

Covalently Interlayer-Confined Organic–Inorganic Heterostructures for Aqueous Potassium Ion Supercapacitors (Small 4/2023)

Artificial assembly of organic–inorganic heterostructures for electrochemical energy storage at the molecular level is promising, but remains a great challenge. Here, a covalently interlayer-confined organic (polyaniline [PANI])–inorganic (MoS₂) hybrid with a dual charge-storage mechanism is developed for boosting the reaction kinetics of supercapacitors. Systematic characterizations reveal that PANI induces a partial phase transition from the 2H to 1T phases of MoS₂, expands the interlayer spacing of MoS₂, and increases the hydrophilicity. More in-depth insights from the synchrotron radiation-based X-ray technique illustrate that the covalent grafting of PANI to MoS₂ induces the formation of Mo N bonds and unsaturated Mo sites, leading to increased active sites. Theoretical analysis reveals that the covalent assembly facilitates cross-layer electron transfer and decreases the diffusion barrier of K⁺ ions, which favors reaction kinetics. The resultant hybrid material exhibits high specific capacitance and good rate capability. This design provides an effective strategy to develop organic–inorganic heterostructures for superior K-ion storage. The K-ion storage mechanism concerning the reversible insertion/extraction upon charge/discharge is revealed through ex situ X-ray photoelectron spectroscopy.     

In Situ Carbon‐Doped Mo(Se0.85S0.15)2 Hierarchical Nanotubes as Stable Anodes for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are promising energy storage devices, but suffer from poor cycling stability and low rate capability. In this work, carbon doped Mo(Se_0.85S_0.15)₂ (i.e., Mo(Se_0.85S_0.15)₂:C) hierarchical nanotubes have been synthesized for the first time and serve as a robust and high‐performance anode material. The hierarchical nanotubes with diameters of 300 nm and wall thicknesses of 50 nm consist of numerous 2D layered nanosheets, and can act as a robust host for sodiation/desodiation cycling. The Mo(Se_0.85S_0.15)₂:C hierarchical nanotubes deliver a discharge capacity of 360 mAh g⁻¹ at a high current density of 2000 mA g⁻¹ and keep a 81.8% capacity retention compared to that at a current density of 50 mA g⁻¹, showing superior rate capability. Comparing with the second cycle discharge capacities, the nanotube anode can maintain capacities of 102.2%, 101.9%, and 97.8% after 100 cycles at current densities of 200, 500, and 1000 mA g⁻¹, respectively. This work demonstrates the best cycling performance and high‐rate sodium storage capabilities of MoSe₂ for SIBs to date. The hollow interior, hierarchical organization, layered structure, and carbon doping are beneficial for fast Na⁺‐ion and electron kinetics and are responsible for the stable cycling performance and high rate capabilities.