Sulfur‐Based Electrodes that Function via Multielectron Reactions for Room‐Temperature Sodium‐Ion Storage

Emerging rechargeable sodium‐ion storage systems—sodium‐ion and room‐temperature sodium–sulfur (RT‐NaS) batteries—are gaining extensive research interest as low‐cost options for large‐scale energy‐storage applications. Owing to their abundance, easy accessibility, and unique physical and chemical properties, sulfur‐based materials, in particular metal sulfides (MS_x) and elemental sulfur (S), are currently regarded as promising electrode candidates for Na‐storage technologies with high capacity and excellent redox reversibility based on multielectron conversion reactions. Here, we present current understanding of Na‐storage mechanisms of the S‐based electrode materials. Recent progress and strategies for improving electronic conductivity and tolerating volume variations of the MS_x anodes in Na‐ion batteries are reviewed. In addition, current advances on S cathodes in RT‐NaS batteries are presented. We outline a novel emerging concept of integrating MS_x electrocatalysts into conventional carbonaceous matrices as effective polarized S hosts in RT‐NaS batteries as well. This comprehensive progress report could provide guidance for research toward the development of S‐based materials for the future Na‐storage techniques.     

Micro‐MoS2 with Excellent Reversible Sodium‐Ion Storage

Low storage capacity and poor cycling stability are the main drawbacks of the electrode materials for sodium‐ion (Na‐ion) batteries, due to the large radius of the Na ion. Here we show that micro‐structured molybdenum disulfide (MoS₂) can exhibit high storage capacity and excellent cycling and rate performances as an anode material for Na‐ion batteries by controlling its intercalation depth and optimizing the binder. The former method is to preserve the layered structure of MoS₂, whereas the latter maintains the integrity of the electrode during cycling. A reversible capacity of 90 mAh g^?1 is obtained on a potential plateau feature when less than 0.5 Na per formula unit is intercalated into micro‐MoS₂. The fully discharged electrode with sodium alginate (NaAlg) binder delivers a high reversible capacity of 420 mAh g^?1. Both cells show excellent cycling performance. These findings indicate that metal chalcogenides, for example, MoS₂, can be promising Na‐storage materials if their operation potential range and the binder can be appropriately optimized.     

Synthesis of Copper‐Substituted CoS2@CuxS Double‐Shelled Nanoboxes by Sequential Ion Exchange for Efficient Sodium Storage

The construction of hybrid architectures for electrode materials has been demonstrated as an efficient strategy to boost sodium‐storage properties because of the synergetic effect of each component. However, the fabrication of hybrid nanostructures with a rational structure and desired composition for effective sodium storage is still challenging. In this study, an integrated nanostructure composed of copper‐substituted CoS₂@Cu_xS double‐shelled nanoboxes (denoted as Cu‐CoS₂@Cu_xS DSNBs) was synthesized through a rational metal–organic framework (MOF)‐based templating strategy. The unique shell configuration and complex composition endow the Cu‐CoS₂@Cu_xS DSNBs with enhanced electrochemical performance in terms of superior rate capability and stable cyclability.     

Sodium‐Ion Storage Properties of FeS–Reduced Graphene Oxide Composite Powder with a Crumpled Structure

The sodium‐ion storage properties of FeS–reduced graphene oxide (rGO) and Fe₃O₄‐rGO composite powders with crumpled structures have been studied. The Fe₃O₄‐rGO composite powder, prepared by one‐pot spray pyrolysis, could be transformed to an FeS‐rGO composite powder through a simple sulfidation treatment. The mean size of the Fe₃O₄ nanocrystals in the Fe₃O₄‐rGO composite powder was 4.4 nm. After sulfidation, FeS nanocrystals of size several hundred nanometers were confined within the crumpled structure of the rGO matrix. The initial discharge capacities of the FeS‐rGO and Fe₃O₄‐rGO composite powders were 740 and 442 mA h g^?1, and their initial charge capacities were 530 and 165 mA h g^?1, respectively. The discharge capacities of the FeS‐rGO and Fe₃O₄‐rGO composite powders at the 50th cycle were 547 and 150 mA h g^?1, respectively. The FeS‐rGO composite powder showed superior sodium‐ion storage performance compared to the Fe₃O₄‐rGO composite powder.     

A Yolk–Shell‐Structured FePO4 Cathode for High‐Rate and Long‐Cycling Sodium‐Ion Batteries

Amorphous iron phosphate (FePO₄) has attracted enormous attention as a promising cathode material for sodium‐ion batteries (SIBs) because of its high theoretical specific capacity and superior electrochemical reversibility. Nevertheless, the low rate performance and rapid capacity decline seriously hamper its implementation in SIBs. Herein, we demonstrate a sagacious multi‐step templating approach to skillfully craft amorphous FePO₄ yolk–shell nanospheres with mesoporous nanoyolks supported inside the robust porous outer nanoshells. Their unique architecture and large surface area enable these amorphous FePO₄ yolk–shell nanospheres to manifest remarkable sodium storage properties with high reversible capacity, outstanding rate performance, and ultralong cycle life.     

Ultrathin 2D Graphitic Carbon Nitride on Metal Films: Underpotential Sodium Deposition in Adlayers for Sodium‐Ion Batteries

Efficient and low‐cost anode materials for the sodium‐ion battery are highly desired to enable more economic energy storage. Effects on an ultrathin carbon nitride film deposited on a copper metal electrode are presented. The combination of effects show an unusually high capacity to store sodium metal. The g‐C₃N₄ film is as thin as 10 nm and can be fabricated by an efficient, facile, and general chemical‐vapor deposition method. A high reversible capacity of formally up to 51 Ah g^?1 indicates that the Na is not only stored in the carbon nitride as such, but that carbon nitride activates also the metal for reversible Na‐deposition, while forming at the same time an solid electrolyte interface layer avoiding direct contact of the metallic phase with the liquid electrolyte.     

A General Approach to the Synthesis of Gold–Metal Sulfide Core–Shell and Heterostructures

Cores and effect : Water‐dispersible core–shell structures and heterostructures incorporating gold nanocrystals of different shapes (polyhedra, cubes, and rods) and a variety of transition metal sulfide semiconductors (ZnS, CdS, NiS, Ag₂S, and CuS) are synthesized using cetyltrimethylammonium bromide‐encapsulated gold nanocrystals and metal thiobenzoates as starting materials.

     

Boosted Charge Transfer in SnS/SnO2 Heterostructures: Toward High Rate Capability for Sodium‐Ion Batteries

Constructing heterostructures can endow materials with fascinating performance in high‐speed electronics, optoelectronics, and other applications owing to the built‐in charge‐transfer driving force, which is of benefit to the specific charge‐transfer kinetics. Rational design and controllable synthesis of nano‐heterostructure anode materials with high‐rate performance, however, still remains a great challenge. Herein, ultrafine SnS/SnO₂ heterostructures were successfully fabricated and showed enhanced charge‐transfer capability. The mobility enhancement is attributed to the interface effect of heterostructures, which induces an electric field within the nanocrystals, giving them much lower ion‐diffusion resistance and facilitating interfacial electron transport.     

Hierarchical Metal Sulfide/Carbon Spheres: A Generalized Synthesis and High Sodium‐Storage Performance

The development of suitable anode materials is far from satisfactory and is a major scientific challenge for a competitive sodium‐ion battery technology. Metal sulfides have demonstrated encouraging results, but still suffer from sluggish kinetics and severe capacity decay associated with the phase change. Herein we show that rational electrode design, that is, building efficient electron/ion mixed‐conducting networks, can overcome the problems resulting from conversion reactions. A general strategy for the preparation of hierarchical carbon‐coated metal sulfide (MS?C) spheres through thermal sulfurization of metal glycerate has been developed. We demonstrate the concept by synthesizing highly uniform hierarchical carbon coated vanadium sulfide (V₂S₃?C) spheres, which exhibit a highly reversibly sodium storage capacity of 777 mAh g^?1 at 100 mA g^?1, excellent rate capability (410 mAh g^?1 at 4000 mA g^?1), and impressive cycling ability.     

Synergistic Ternary Composite (Carbon/Fe3O4@Graphene) with Hollow Microspherical and Robust Structure for Li‐Ion Storage

The electrode materials with hollow structure and/or graphene coating are expected to exhibit outstanding electrochemical performances in energy‐storage systems. 2D graphene‐wrapped hollow C/Fe₃O₄ microspheres are rationally designed and fabricated by a novel facile and scalable strategy. The core@double‐shell structure SPS@FeOOH@GO (SPS: sulfonated polystyrene, GO: graphene oxide) microspheres are first prepared through a simple one‐pot approach and then transformed into C/Fe₃O₄@G (G: graphene) after calcination at 500 °C in Ar. During calcination, the Kirkendall effect resulting from the diffusion/reaction of SPS‐derived carbon and FeOOH leads to the formation of hollow structure carbon with Fe₃O₄ nanoparticles embedded in it. In the rationally constructed architecture of C/Fe₃O₄@G, the strongly coupled C/Fe₃O₄ hollow microspheres are further anchored onto 2D graphene networks, achieving a strong synergetic effect between carbon, Fe₃O₄, and graphene. As an anode material of Li‐ion batteries (LIBs), C/Fe₃O₄@G manifests a high reversible capacity, excellent rate behavior, and outstanding long‐term cycling performance (1208 mAh g^?1 after 200 cycles at 100 mA g^?1).     

Salt‐Based Organic–Inorganic Nanocomposites: Towards A Stable Lithium Metal/Li10GeP2S12 Solid Electrolyte Interface

Solid‐state Li metal battery technology is attractive, owing to the high energy density, long lifespans, and better safety. A key obstacle in this technology is the unstable Li/solid‐state electrolyte (SSE) interface involving electrolyte reduction by Li. Herein we report a novel approach based on the use of a nanocomposite consisting of organic elastomeric salts (LiO‐(CH₂O)_n‐Li) and inorganic nanoparticle salts (LiF, ‐NSO₂‐Li, Li₂O), which serve as an interphase to protect Li₁₀GeP₂S₁₂ (LGPS), a highly conductive but reducible SSE. The nanocomposite is formed in situ on Li via the electrochemical decomposition of a liquid electrolyte, thus having excellent chemical and electrochemical stability, affinity for Li and LGPS, and limited interfacial resistance. XPS depth profiling and SEM show that the nanocomposite effectively restrained the reduction of LGPS. Stable Li electrodeposition over 3000 h and a 200 cycle life for a full cell were achieved.     

2D Titania–Carbon Superlattices Vertically Encapsulated in 3D Hollow Carbon Nanospheres Embedded with 0D TiO2 Quantum Dots for Exceptional Sodium‐Ion Storage

Two‐dimensional (2D) superlattices offer promising technological opportunities in tuning the intercalation chemistry of metal ions. Now, well‐ordered 2D superlattices of monolayer titania and carbon with tunable interlayer‐spacing are synthesized by a molecularly mediated thermally induced approach. The 2D superlattices are vertically encapsulated in hollow carbon nanospheres, which are embedded with TiO₂ quantum dots, forming a 0D‐2D‐3D multi‐dimensional architecture. The multi‐dimensional architecture with the 2D superlattices encapsulated inside exhibits a near zero‐strain characteristic and enriched electrochemical reactivity, achieving a highly efficient Na⁺ storage performance with exceptional rate capability and superior long‐term cyclability.     

Self‐Sustained Cycle of Hydrolysis and Etching at Solution/Solid Interfaces: A General Strategy To Prepare Metal Oxide Micro‐/Nanostructured Arrays for High‐Performance Electrodes

Assembling micro‐/nanostructured arrays on conducting substrates allows the integration of multiple functionalities into modern electronic devices. Herein, a novel self‐sustained cycle of hydrolysis and etching (SCHE) is exploited to selectively synthesize an extensive series of metal oxide micro‐/nanostructured arrays on a wide range of metal substrates, establishing the generality and efficacy of the strategy. To demonstrate the potential application of this method, the as‐prepared NiO porous nanobelt array was directly used as the anode for lithium‐ion batteries, exhibiting excellent capacity and rate capability. Conclusively, the SCHE strategy offers a systematic approach to design metal oxide micro‐/nanostructured arrays on metal substrates, which are valuable not only for lithium‐ion batteries but also for other energy conversion and storage systems and electronic devices at large.     

Towards Highly Stable Storage of Sodium Ions: A Porous Na3V2(PO4)3/C Cathode Material for Sodium‐Ion Batteries

A porous Na₃V₂(PO₄)₃ cathode material coated uniformly with a layer of approximately 6 nm carbon has been synthesized by the sol–gel method combined with a freeze‐drying process. The special porous morphology and structure significantly increases the specific surface area of the material, which greatly enlarges the contact area between the electrode and electrolyte, and consequently supplies more active sites for sodium ions. When employed as a cathode material of sodium‐ion batteries, this porous Na₃V₂(PO₄)₃/C exhibits excellent rate performance and cycling stability; for instance, it shows quite a flat potential plateau at 3.4 V in the potential window of 2.7–4.0 V versus Na⁺/Na and delivers an initial capacity as high as 118.9 and 98.0 mA h g^?1 at current rates of 0.05 and 0.5 C, respectively, and after 50 cycles, a good capacity retention of 92.7 and 93.6 % are maintained. Moreover, even when the discharge current density is increased to 5 C (590 mA g^?1), an initial capacity of 97.6 mA h g^?1 can still be achieved, and an exciting capacity retention of 88.6 % is obtained after 100 cycles. The good cycle performance, excellent rate capability, and moreover, the low cost of Na₃V₂(PO₄)₃/C suggest that this material is a promising cathode for large‐scale sodium‐ion rechargeable batteries.