Low‐Temperature Synthesis of Honeycomb CuP2@C in Molten ZnCl2 Salt for High‐Performance Lithium Ion Batteries

Phosphorus‐rich metal phosphides have very high lithium storage capacities, but they are difficult to prepare. A low‐temperature phosphorization method based on Mg reducing PCl₃ in ZnCl₂ molten salt at 300 °C is developed to synthesize phosphorus‐rich CuP₂@C from a Cu‐MOF derived Cu@C composite. Abnormal oxidation of Cu by Zn²⁺ in the molten salt is observed, which leads to the porous honeycomb nanostructure and homogeneously distributed ultrafine CuP₂ nanocrystals. The honeycomb CuP₂@C exhibits excellent lithium storage performance with high reversible capacity (1146 mAh g^?1 at 0.2 A g^?1) and superior cycling stability (720 mAh g^?1 after 600 cycles at 1.0 A g^?1), showing the promising application of P‐rich metal phosphides in lithium ion batteries.     

High‐Performance Sodium‐Ion Batteries and Sodium‐Ion Pseudocapacitors Based on MoS2/Graphene Composites

Sodium‐ion energy storage, including sodium‐ion batteries (NIBs) and electrochemical capacitive storage (NICs), is considered as a promising alternative to lithium‐ion energy storage. It is an intriguing prospect, especially for large‐scale applications, owing to its low cost and abundance. MoS₂ sodiation/desodiation with Na ions is based on the conversion reaction, which is not only able to deliver higher capacity than the intercalation reaction, but can also be applied in capacitive storage owing to its typically sloping charge/discharge curves. Here, NIBs and NICs based on a graphene composite (MoS₂/G) were constructed. The enlarged d‐spacing, a contribution of the graphene matrix, and the unique properties of the MoS₂/G substantially optimize Na storage behavior, by accommodating large volume changes and facilitating fast ion diffusion. MoS₂/G exhibits a stable capacity of approximately 350 mAh g^?1 over 200 cycles at 0.25 C in half cells, and delivers a capacitance of 50 F g^?1 over 2000 cycles at 1.5 C in pseudocapacitors with a wide voltage window of 0.1–2.5 V.     

Double‐Helix Structure in Carrageenan–Metal Hydrogels: A General Approach to Porous Metal Sulfides/Carbon Aerogels with Excellent Sodium‐Ion Storage

The metal sulfide‐carbon nanocomposite is a new class of anode material for sodium ion batteries, but its development is restricted by its relative poor rate ability and cyclic stability. Herein, we report the use of double‐helix structure of carrageenan–metal hydrogels for the synthesis of 3D metal sulfide (M_xS_y) nanostructure/carbon aerogels (CAs) for high‐performance sodium‐ion storage. The method is unique, and can be used to make multiple M_xS_y/CAs (such as FeS/CA, Co₉S₈/CA, Ni₃S₄/CA, CuS/CA, ZnS/CA, and CdS/CA) with ultra‐small nanoparticles and hierarchical porous structure by pyrolyzing the carrageenan–metal hydrogels. The as‐prepared FeS/CA exhibits a high reversible capacity and excellent cycling stability (280 mA h^?1 at 0.5 A g^?1 over 200 cycles) and rate performance (222 mA h^?1 at 5 A g^?1) when used as the anode material for sodium‐ion batteries. The work shows the value of biomass‐derived metal sulfide–carbon heterostuctures in sodium‐ion storage.     

Fiber‐in‐Tube Design of Co9S8‐Carbon/Co9S8: Enabling Efficient Sodium Storage

The sodium‐ion battery is a promising battery technology owing to its low price and high abundance of sodium. However, the sluggish kinetics of sodium ion makes it hard to achieve high‐rate performance, therefore impairing the power density. In this work, a fiber‐in‐tube Co₉S₈‐carbon(C)/Co₉S₈ is designed with fast sodiation kinetics. The experimental and simulation analysis show that the dominating capacitance mechanism for the high Na‐ion storage performance is due to abundant grain boundaries, three exposed layer interfaces, and carbon wiring in the design. As a result, the fiber‐in‐tube hybrid anode shows a high specific capacity of 616 mAh g^?1 after 150 cycles at 0.5 A g^?1. At 1 A g^?1, a capacity of ca. 451 mAh g^?1 can be achieved after 500 cycles. More importantly, a high energy density of 779 Wh kg^?1 and power density of 7793 W kg^?1 can be obtained simultaneously.     

CNT@Fe3O4@C Coaxial Nanocables: One‐Pot,Additive‐Free Synthesis and Remarkable Lithium Storage Behavior

By using carbon nanotubes (CNTs) as a shape template and glucose as a carbon precursor and structure‐directing agent, CNT@Fe₃O₄@C porous core/sheath coaxial nanocables have been synthesized by a simple one‐pot hydrothermal process. Neither a surfactant/ligand nor a CNT pretreatment is needed in the synthetic process. A possible growth mechanism governing the formation of this nanostructure is discussed. When used as an anode material of lithium‐ion batteries, the CNT@Fe₃O₄@C nanocables show significantly enhanced cycling performance, high rate capability, and high Coulombic efficiency compared with pure Fe₂O₃ particles and Fe₃O₄/CNT composites. The CNT@Fe₃O₄@C nanocables deliver a reversible capacity of 1290 mA h g^?1 after 80 cycles at a current density of 200 mA g^?1, and maintain a reversible capacity of 690 mA h g^?1 after 200 cycles at a current density of 2000 mA g^?1. The improved lithium storage behavior can be attributed to the synergistic effect of the high electronic conductivity support and the inner CNT/outer carbon buffering matrix.     

An Ultrastable Anode for Long‐Life Room‐Temperature Sodium‐Ion Batteries

Sodium‐ion batteries are important alternative energy storage devices that have recently come again into focus for the development of large‐scale energy storage devices because sodium is an abundant and low‐cost material. However, the development of electrode materials with long‐term stability has remained a great challenge. A novel negative‐electrode material, a P2‐type layered oxide with the chemical composition Na_2/3Co_1/3Ti_2/3O₂, exhibits outstanding cycle stability (ca. 84.84 % capacity retention for 3000 cycles, very small decrease in the volume (0.046 %) after 500 cycles), good rate capability (ca. 41 % capacity retention at a discharge/charge rate of 10 C), and a usable reversible capacity of about 90 mAh g^?1 with a safe average storage voltage of approximately 0.7 V in the sodium half‐cell. This P2‐type layered oxide is a promising anode material for sodium‐ion batteries with a long cycle life and should greatly promote the development of room‐temperature sodium‐ion batteries.     

Ascorbic Acid‐Assisted Synthesis of Mesoporous Sodium Vanadium Phosphate Nanoparticles with Highly sp2‐Coordinated Carbon Coatings as Efficient Cathode Materials for Rechargeable Sodium‐Ion Batteries

Herein, mesoporous sodium vanadium phosphate nanoparticles with highly sp²‐coordinated carbon coatings (meso‐Na₃V₂(PO₄)₃/C) were successfully synthesized as efficient cathode material for rechargeable sodium‐ion batteries by using ascorbic acid as both the reductant and carbon source, followed by calcination at 750 °C in an argon atmosphere. Their crystalline structure, morphology, surface area, chemical composition, carbon nature and amount were systematically explored. Following electrochemical measurements, the resultant meso‐Na₃V₂(PO₄)₃/C not only delivered good reversible capacity (98 mAh g^?1 at 0.1 A g^?1) and superior rate capability (63 mAh g^?1 at 1 A g^?1) but also exhibited comparable cycling performance (capacity retention: ≈74 % at 450 cycles at 0.4 A g^?1). Moreover, the symmetrical sodium‐ion full cell with excellent reversibility and cycling stability was also achieved (capacity retention: 92.2 % at 0.1 A g^?1 with 99.5 % coulombic efficiency after 100 cycles). These attributes are ascribed to the distinctive mesostructure for facile sodium‐ion insertion/extraction and their continuous sp²‐coordinated carbon coatings, which facilitate electronic conduction.     

Enhanced Lithium‐Ion Storage Capability of a Bismuth Sulfide/Graphene Oxide/Poly(3,4‐ethylenedioxythiophene) Composite

A Bi₂S₃/graphene oxide (GO) composite enwrapped by a poly(3,4‐ethylenedioxythiophene) (PEDOT) coating was prepared for the first time for use as an anode in Li‐ion batteries. Pristine Bi₂S₃ nanoflowers and composites of Bi₂S₃/GO and Bi₂S₃/GO/PEDOT were assembled into half cells with Li metal as the counter electrode, and initial discharge capacities of 833, 1020, and 1300 mAh g^?1, respectively, were obtained. Composites of Bi₂S₃/GO/PEDOT and Bi₂S₃/GO showed superior cycling stability and better rate capability than pristine Bi₂S₃. GO provides highly conducting interconnections, which allow facile propagation of electrons during charge/discharge, and this improves the ion‐uptake capability of the Bi₂S₃ nanoflowers and also increases the rate capability. PEDOT furnishes a protective coating that prevents detachment of the material from the current collector during cycling, and it also imparts better cycling stability to the Bi₂S₃/GO/PEDOT composite.     

A Self‐Standing and Flexible Electrode of Yolk–Shell CoS2 Spheres Encapsulated with Nitrogen‐Doped Graphene for High‐Performance Lithium‐Ion Batteries

Flexible lithium‐ion batteries (LIBs) have recently attracted increasing attention with the fast development of bendable electronic systems. Herein, a facile and template‐free solvothermal method is presented for the fabrication of hybrid yolk–shell CoS₂ and nitrogen‐doped graphene (NG) sheets. The yolk–shell architecture of CoS₂ encapsulated with NG coating is designed for the dual protection of CoS₂ to address the structural and interfacial stability concerns facing the CoS₂ anode. The as‐prepared composite can be assembled into a film, which can be used as a binder‐free and flexible electrode for LIBs that does not require any carbon black conducting additives or current collectors. When evaluating lithium‐storage properties, such a flexible electrode exhibits a high specific capacity of 992 mAh g^?1 in the first reversible discharge capacity at a current rate of 100 mA g^?1 and high reversible capacity of 882 mAh g^?1 after 150 cycles with excellent capacity retention of 89.91 %. Furthermore, a reversible capacity as high as 655 mAh g^?1 is still achieved after 50 cycles even at a high rate of 5 C due to the yolk–shell structure and NG coating, which not only provide short Li‐ion and electron pathways, but also accommodate large volume variation.     

Long‐Life Room‐Temperature Sodium–Sulfur Batteries by Virtue of Transition‐Metal‐Nanocluster–Sulfur Interactions

Room‐temperature sodium–sulfur (RT‐Na/S) batteries hold significant promise for large‐scale application because of low cost of both sodium and sulfur. However, the dissolution of polysulfides into the electrolyte limits practical application. Now, the design and testing of a new class of sulfur hosts as transition‐metal (Fe, Cu, and Ni) nanoclusters (ca. 1.2 nm) wreathed on hollow carbon nanospheres (S@M‐HC) for RT‐Na/S batteries is reported. A chemical couple between the metal nanoclusters and sulfur is hypothesized to assist in immobilization of sulfur and to enhance conductivity and activity. S@Fe‐HC exhibited an unprecedented reversible capacity of 394 mAh g^?1 despite 1000 cycles at 100 mA g^?1, together with a rate capability of 220 mAh g^?1 at a high current density of 5 A g^?1. DFT calculations underscore that these metal nanoclusters serve as electrocatalysts to rapidly reduce Na₂S₄ into short‐chain sulfides and thereby obviate the shuttle effect.     

Cobalt‐Doped FeS2 Nanospheres with Complete Solid Solubility as a High‐Performance Anode Material for Sodium‐Ion Batteries

Considering that the high capacity, long‐term cycle life, and high‐rate capability of anode materials for sodium‐ion batteries (SIBs) is a bottleneck currently, a series of Co‐doped FeS₂ solid solutions with different Co contents were prepared by a facile solvothermal method, and for the first time their Na‐storage properties were investigated. The optimized Co_0.5Fe_0.5S₂ (Fe0.5) has discharge capacities of 0.220 Ah g^?1 after 5000 cycles at 2 A g^?1 and 0.172 Ah g^?1 even at 20 A g^?1 with compatible ether‐based electrolyte in a voltage window of 0.8–2.9 V. The Fe0.5 sample transforms to layered Na_xCo_0.5Fe_0.5S₂ by initial activation, and the layered structure is maintained during following cycles. The redox reactions of Na_xCo_0.5Fe_0.5S₂ are dominated by pseudocapacitive behavior, leading to fast Na⁺ insertion/extraction and durable cycle life. A Na₃V₂(PO₄)₃/Fe0.5 full cell was assembled, delivering an initial capacity of 0.340 Ah g^?1.     

Construction of Hierarchical Nanotubes Assembled from Ultrathin V3S4@C Nanosheets towards Alkali‐Ion Batteries with Ion‐Dependent Electrochemical Mechanisms

Ultrathin core–shell V₃S₄@C nanosheets assembled into hierarchical nanotubes (V₃S₄@C NS‐HNTs) are synthesized by a self‐template strategy and evaluated as general anodes for alkali‐ion batteries. Structural/physicochemical characterizations and DFT calculations bring insights into the intrinsic relationship between crystal structures and electrochemical mechanisms of the V₃S₄@C NS‐HNTs electrode. The V₃S₄@C NS‐HNTs are endowed with strong structural rigidness owing to the layered VS₂ subunits and interlayer occupied V atoms, and efficient alkali‐ion adsorption/diffusion thanks to the electroactive V₃S₄‐C interfaces. The resulting V₃S₄@C NS‐HNTs anode exhibit distinct alkali‐ion‐dependent charge storage mechanisms and exceptional long‐durability cyclic performance in storage of K⁺, benefiting from synergistic contributions of pseudocapacitive and reversible intercalation/de‐intercalation behaviors superior to those of the conversion‐reaction‐based Li⁺‐/Na⁺‐storage counterparts.     

A Facile Synthesis of High‐Surface‐Area Sulfur–Carbon Composites for Li/S Batteries

Small‐grained elemental sulfur is precipitated from sodium thiosulfate (Na₂S₂O₃) in a carbon‐containing oxalic acid (HOOC?COOH) solution through a novel spray precipitation method. Surface area analysis, elemental mapping, and transmission electron micrographs revealed that the spray‐precipitated sulfur particles feature 11 times higher surface area compared to conventional precipitated sulfur, with homogeneous distribution in the carbon. Moreover, the scanning electron micrographs show that these high‐surface‐area sulfur particles are firmly adhered to and covered by carbon. This precipitated S–C composite exhibits high discharge capacity with about 75 % capacity retention. The initial discharge capacity was further improved to 1444 mA h g^?1 by inserting a free‐standing single‐walled carbon nanotube layer in between the cathode and the separator. Moreover, with the help of the fixed capacity charging technique, 91.6 % capacity retention was achieved.     

P2‐NaCo0.5Mn0.5O2 as a Positive Electrode Material for Sodium‐Ion Batteries

As a promising positive electrode material for sodium‐ion batteries (SIBs), layered sodium oxides have attracted considerable attention in recent years. In this work, stoichiometric P2‐phase NaCo_0.5Mn_0.5O₂ was prepared through the conventional solid‐state reaction, and its structural and physical properties were studied in terms of XRD, XPS, and magnetic susceptibility. Furthermore, the P2‐NaCo_0.5Mn_0.5O₂ electrode delivered a discharge capacity of 124.3 mA h g^?1 and almost 100 % initial coulombic efficiency over the potential window of 1.5–4.15 V. It also showed good cycle stability, with a reversible capacity and capacity retention reaching approximately 85 mA h g^?1 and 99 %, respectively, at the 5 C rate after 100 cycles. Additionally, cyclic voltammetry and ex situ XRD were employed to explain the electrochemical behavior at the different electrochemical stages. Owing to the applicable performances, P2‐NaCo_0.5Mn_0.5O₂ can be considered as a potential positive electrode material for SIBs.     

A Porous Network of Bismuth Used as the Anode Material for High‐Energy‐Density Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are plagued by a lack of materials for reversible accommodation of the large‐sized K⁺ ion. Herein we present, the Bi anode in combination with the dimethoxyethane‐(DME) based electrolyte to deliver a remarkable capacity of ca. 400 mAh g^?1 and long cycle stability with three distinct two‐phase reactions of Bi? KBi₂?K₃Bi₂?K₃Bi. These are ascribed to the gradually developed three‐dimensional (3D) porous networks of Bi, which realizes fast kinetics and tolerance of its volume change during potassiation and depotassiation. The porosity is linked to the unprecedented movement of the surface Bi atoms interacting with DME molecules, as suggested by DFT calculations. A full KIB of Bi//DME‐based electrolyte//Prussian blue of K_0.72Fe[Fe(CN)₆] is demonstrated to present large energy density of 108.1 Wh kg^?1 with average discharge voltage of 2.8 V and capacity retention of 86.5 % after 350 cycles.     

Two‐Dimensional Cobalt‐/Nickel‐Based Oxide Nanosheets for High‐Performance Sodium and Lithium Storage

Two‐dimensional (2D) nanomaterials are one of the most promising types of candidates for energy‐storage applications due to confined thicknesses and high surface areas, which would play an essential role in enhanced reaction kinetics. Herein, a universal process that can be extended for scale up is developed to synthesise ultrathin cobalt‐/nickel‐based hydroxides and oxides. The sodium and lithium storage capabilities of Co₃O₄ nanosheets are evaluated in detail. For sodium storage, the Co₃O₄ nanosheets exhibit excellent rate capability (e.g., 179 mA h g^?1 at 7.0 A g^?1 and 150 mA h g^?1 at 10.0 A g^?1) and promising cycling performance (404 mA h g^?1 after 100 cycles at 0.1 A g^?1). Meanwhile, very impressive lithium storage performance is also achieved, which is maintained at 1029 mA h g^?1 after 100 cycles at 0.2 A g^?1. NiO and NiCo₂O₄ nanosheets are also successfully prepared through the same synthetic approach, and both deliver very encouraging lithium storage performances. In addition to rechargeable batteries, 2D cobalt‐/nickel‐based hydroxides and oxides are also anticipated to have great potential applications in supercapacitors, electrocatalysis and other energy‐storage‐/‐conversion‐related fields.     

Mesoporous Carbon Nanofibers Embedded with MoS2 Nanocrystals for Extraordinary Li‐Ion Storage

MoS₂ nanocrystals embedded in mesoporous carbon nanofibers are synthesized through an electrospinning process followed by calcination. The resultant nanofibers are 100–150 nm in diameter and constructed from MoS₂ nanocrystals with a lateral diameter of around 7 nm with specific surface areas of 135.9 m² g^?1. The MoS₂@C nanofibers are treated at 450 °C in H₂ and comparison samples annealed at 800 °C in N₂. The heat treatments are designed to achieve good crystallinity and desired mesoporous microstructure, resulting in enhanced electrochemical performance. The small amount of oxygen in the nanofibers annealed in H₂ contributes to obtaining a lower internal resistance, and thus, improving the conductivity. The results show that the nanofibers obtained at 450 °C in H₂ deliver an extraordinary capacity of 1022 mA h g^?1 and improved cyclic stability, with only 2.3 % capacity loss after 165 cycles at a current density of 100 mA g^?1, as well as an outstanding rate capability. The greatly improved kinetics and cycling stability of the mesoporous MoS₂@C nanofibers can be attributed to the crosslinked conductive carbon nanofibers, the large specific surface area, the good crystallinity of MoS₂, and the robust mesoporous microstructure. The resulting nanofiber electrodes, with short mass‐ and charge‐transport pathways, improved electrical conductivity, and large contact area exposed to electrolyte, permitting fast diffusional flux of Li ions, explains the improved kinetics of the interfacial charge‐transfer reaction and the diffusivity of the MoS₂@C mesoporous nanofibers. It is believed that the integration of MoS₂ nanocrystals and mesoporous carbon nanofibers may have a synergistic effect, giving a promising anode, and widening the applicability range into high performance and mass production in the Li‐ion battery market.     

High‐Loading Nano‐SnO2 Encapsulated in situ in Three‐Dimensional Rigid Porous Carbon for Superior Lithium‐Ion Batteries

Tin oxide nanoparticles (SnO₂ NPs) have been encapsulated in situ in a three‐dimensional ordered space structure. Within this composite, ordered mesoporous carbon (OMC) acts as a carbon framework showing a desirable ordered mesoporous structure with an average pore size (≈6 nm) and a high surface area (470.3 m² g^?1), and the SnO₂ NPs (≈10 nm) are highly loaded (up to 80 wt %) and homogeneously distributed within the OMC matrix. As an anode material for lithium‐ion batteries, a SnO₂@OMC composite material can deliver an initial charge capacity of 943 mAh g^?1 and retain 68.9 % of the initial capacity after 50 cycles at a current density of 50 mA g^?1, even exhibit a capacity of 503 mA h g^?1 after 100 cycles at 160 mA g^?1. In situ encapsulation of the SnO₂ NPs within an OMC framework contributes to a higher capacity and a better cycling stability and rate capability in comparison with bare OMC and OMC ex situ loaded with SnO₂ particles (SnO₂/OMC). The significantly improved electrochemical performance of the SnO₂@OMC composite can be attributed to the multifunctional OMC matrix, which can facilitate electrolyte infiltration, accelerate charge transfer, and lithium‐ion diffusion, and act as a favorable buffer to release reaction strains for lithiation/delithiation of the SnO₂ NPs.     

Realizing Complete Solid‐Solution Reaction in High Sodium Content P2‐Type Cathode for High‐Performance Sodium‐Ion Batteries

P2‐type layered oxides suffer from an ordered Na⁺/vacancy arrangement and P2→O2/OP4 phase transitions, leading them to exhibit multiple voltage plateaus upon Na⁺ extraction/insertion. The deficient sodium in the P2‐type cathode easily induces the bad structural stability at deep desodiation states and limited reversible capacity during Na⁺ de/insertion. These drawbacks cause poor rate capability and fast capacity decay in most P2‐type layered oxides. To address these challenges, a novel high sodium content (0.85) and plateau‐free P2‐type cathode‐Na_0.85Li_0.12Ni_0.22Mn_0.66O₂ (P2‐NLNMO) was developed. The complete solid‐solution reaction over a wide voltage range ensures both fast Na⁺ mobility (10^?11 to 10^?10 cm² s^?1) and small volume variation (1.7 %). The high sodium content P2‐NLNMO exhibits a higher reversible capacity of 123.4 mA h g^?1, superior rate capability of 79.3 mA h g^?1 at 20 C, and 85.4 % capacity retention after 500 cycles at 5 C. The sufficient Na and complete solid‐solution reaction are critical to realizing high‐performance P2‐type cathodes for sodium‐ion batteries.     

Fast,Reversible Lithium Storage with a Sulfur/Long‐Chain‐Polysulfide Redox Couple

The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S₈?Li₂S₄), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li₂S₂ and Li₂S (Li₂S₄?Li₂S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g^?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications.