Hierarchical Mesoporous SnO Microspheres as High Capacity Anode Materials for Sodium‐Ion Batteries

Mesoporous SnO microspheres were synthesised by a hydrothermal method using NaSO₄ as the morphology directing agent. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high‐resolution transmission electron microscopy (HRTEM) analyses showed that SnO microspheres consist of nanosheets with a thickness of about 20 nm. Each nanosheet contains a mesoporous structure with a pore size of approximately 5 nm. When applied as anode materials in Na‐ion batteries, SnO microspheres exhibited high reversible sodium storage capacity, good cyclability and a satisfactory high rate performance. Through ex situ XRD analysis, it was found that Na⁺ ions first insert themselves into SnO crystals, and then react with SnO to generate crystalline Sn, followed by Na–Sn alloying with the formation of crystalline NaSn₂ phase. During the charge process, there are two slopes corresponding to the de‐alloying of Na–Sn compounds and oxidisation of Sn, respectively. The high sodium storage capacity and good electrochemical performance could be ascribed to the unique hierarchical mesoporous architecture of SnO microspheres.     

High‐Capacity Anode Materials for Sodium‐Ion Batteries

Na‐ion batteries are an attractive alternative to Li‐ion batteries for large‐scale energy storage systems because of their low cost and the abundant Na resources. This Review provides a comprehensive overview of selected anode materials with high reversible capacities that can increase the energy density of Na‐ion batteries. Moreover, we discuss the reaction and failure mechanisms of those anode materials with a view to suggesting promising strategies for improving their electrochemical performance.     

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.     

WS2 Nanowires as a High‐Performance Anode for Sodium‐Ion Batteries

We report the synthesis and anode application for sodium‐ion batteries (SIBs) of WS₂ nanowires (WS₂ NWs). WS₂ NWs with very thin diameter of ≈25 nm and expanded interlayer spacing of 0.83 nm were prepared by using a facile solvothermal method followed by a heat treatment. The as‐prepared WS₂ NWs were evaluated as anode materials of SIBs in two potential windows of 0.01–2.5 V and 0.5–3 V. WS₂ NWs displayed a remarkable capacity (605.3 mA h g^?1 at 100 mA g^?1) but with irreversible conversion reaction in the potential window of 0.01–2.5 V. In comparison, WS₂ NWs showed a reversible intercalation mechanism in the potential window of 0.5–3 V, in which the nanowire‐framework is well maintained. In the latter case, the interlayers of WS₂ are gradually expanded and exfoliated during repeated charge–discharge cycling. This not only provides more active sites and open channels for the intercalation of Na⁺ but also facilitates the electronic and ionic diffusion. Therefore, WS₂ NWs exhibited an ultra‐long cycle life with high capacity and rate capability in the potential window of 0.5–3 V. This study shows that WS₂ NWs are promising as the anode materials of room‐temperature SIBs.     

Antimony/Porous Biomass Carbon Nanocomposites as High‐Capacity Anode Materials for Sodium‐Ion Batteries

Antimony/porous biomass carbon nanocomposites have been prepared by a chemical reduction method and applied as anodes for sodium‐ion batteries. The porous biomass carbon derived from a black fungus had a large Brunauer–Emmett–Teller (BET) surface area of 2233 m² g⁻¹ in which antimony nanoparticles were uniformly distributed in the porous carbon. The as‐prepared antimony/porous biomass carbon nanocomposites exhibited a high reversible sodium storage capacity of 567 mA h g⁻¹ at a current density of 100 mA g⁻¹, extended cycling stability, and good rate capability.     

Recent Developments in Alloying‐type Anode Materials for Potassium‐Ion Batteries

As an energy‐storage system, rechargeable potassium‐ion batteries (PIBs) have aroused widespread attention in recent years due to their earth abundance, low standard redox potential, and high ionic conductivity. The development of high‐performance electrode materials is key to optimize the battery performance and useful to improve the feasibility of PIB technology. In this sense, a minireview on alloying‐type anode materials for advanced PIBs is provided, covering the potassium storage properties, reaction mechanisms, theoretical analysis, electrochemical performance, and suitable binders and electrolytes.     

锂离子电池SnS2基负极材料

随着应用范围的逐渐扩大,锂离子电池对具有高比容量、长循环寿命以及优异倍率性能的新型正负极材料的需求日益迫切。SnS₂材料因具有独特的层状结构和高的理论比容量而被视作潜在的高比容量负极材料,但其也存在首次不可逆容量较大、导电率低、充放电过程中体积变化较大等问题。本文综述了SnS₂负极材料的研究历程以及最新研究进展,介绍了SnS₂负极材料的基本性质,具体论述了SnS₂电化学性能改进的相关措施,主要包括控制纳米SnS₂微观形貌、制备SnS₂/C及SnS₂/氧化物复合材料、掺杂、一体化电极以及优化粘结剂等。文章同时总结了水热（溶剂热）法各工艺参数（原料种类、浓度、比例、溶液pH值、水热温度及时间等）对制备SnS₂纳米材料及SnS₂/C复合材料形貌结构及电化学性能的影响,并对目前SnS₂材料仍然存在的问题进行了分析。研究表明,通过制备片状、花状等高比表面积的SnS₂纳米材料,可明显提升其循环性能;将石墨烯等碳材料与SnS₂复合,有助于提高材料的结构稳定性及导电性,进而改善电极的循环及倍率性能。经工艺优化后的SnS₂/graphene复合材料具有高的比容量（大于1000 mAh/g）、稳定的循环性能和优秀的倍率特性,是一种非常有研究价值的高比容量锂离子电池负极材料。     

锂离子电池硅基复合物负极材料*

作为颇有前途的锂离子电池负极材料,硅基材料的研究日益受到重视。硅基负极材料在充放电循环中体积变化过大导致的循环性能差、首次库仑效率低等始终是阻碍其商业化的主要问题。纳米化、合金化和碳包覆是有效的解决措施。本文详细论述了TiB2、TiN、TiC作为基质的硅-化合物复合物,Fe-Si、Cu-Si、Ni-Si体系的硅-金属复合物和硅-碳复合物的研究进展。在硅-碳复合物的研究上,综述了分别采用热解法、球磨法、球磨-热解法、化学聚合法合成,以聚吡咯、聚氯乙烯、聚丙烯腈、间苯二酚-甲醛、柠檬酸、环氧树脂等为碳源的研究进展,同时也综述了Si/碳纳米管复合电极材料的研究情况。     

Recent Advances in Aerosol‐Assisted Spray Processes for the Design and Fabrication of Nanostructured Metal Chalcogenides for Sodium‐Ion Batteries

Increasing demand for sodium‐ion batteries (SIBs), one of the most feasible alternatives to lithium ion batteries (LIBs), has resulted because of their high energy density, low cost, and excellent cycling stability. Consequently, the design and fabrication of suitable electrode materials that govern the overall performance of SIBs are important. Aerosol‐assisted spray processes have gained recent prominence as feasible, scalable, and cost‐effective methods for preparing electrode materials. Herein, recent advances in aerosol‐assisted spray processes for the fabrication of nanostructured metal chalcogenides (e.g., metal sulfides, selenides, and tellurides) for SIBs, with a focus on improving the electrochemical performance of metal chalcogenides, are summarized. Finally, the improvements, limitations, and direction of future research into aerosol‐assisted spray processes for the fabrication of various electrode materials are presented.     

Bowl‐like SnO2@Carbon Hollow Particles as an Advanced Anode Material for Lithium‐Ion Batteries

Despite the great advantages of hollow structures as electrodes for lithium‐ion batteries, one apparent common drawback which is often criticized is their compromised volumetric energy density due to the introduced hollow interior. Here, we design and synthesize bowl‐like SnO₂@carbon hollow particles to reduce the excessive hollow interior space while retaining the general advantages of hollow structures. As a result, the tap density can be increased about 30 %. The as‐prepared bowl‐like SnO₂@carbon hollow particles with conformal carbon support exhibit excellent lithium storage properties in terms of high capacity, stable cyclability and excellent rate capability.     

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.     

Single Crystalline Na0.7MnO2 Nanoplates as Cathode Materials for Sodium‐Ion Batteries with Enhanced Performance

Single crystalline rhombus‐shaped Na_0.7MnO₂ nanoplates have been synthesized by a hydrothermal method. TEM and HRTEM analyses revealed that the Na_0.7MnO₂ single crystals predominantly exposed their (100) crystal plane, which is active for Na⁺‐ion insertion and extraction. When applied as cathode materials for sodium‐ion batteries, Na_0.7MnO₂ nanoplates exhibited a high reversible capacity of 163 mA h g^?1, a satisfactory cyclability, and a high rate performance. The enhanced electrochemical performance could be ascribed to the predominantly exposed active (100) facet, which could facilitate fast Na⁺‐ion insertion/extraction during the discharge and charge process.     

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.     

Two-Dimensional SnSe2/CNTs Hybrid Nanostructures as Anode Materials for High-Performance Lithium-Ion Batteries

Tin diselenide (SnSe₂), as an anode material, has outstanding potential for use in advanced lithium-ion batteries. However, like other tin-based anodes, SnSe₂ suffers from poor cycle life and low rate capability due to large volume expansion during the repeated Li⁺ insertion/de-insertion process. This work reports an effective and easy strategy to combine SnSe₂ and carbon nanotubes (CNTs) to form a SnSe₂/CNTs hybrid nanostructure. The synthesized SnSe₂ has a regular hexagonal shape with a typical 2D nanostructure and the carbon nanotubes combine well with the SnSe₂ nanosheets. The hybrid nanostructure can significantly reduce the serious damage to electrodes that occurs during electrochemical cycling processes. Remarkably, the SnSe₂/CNTs electrode exhibits a high reversible specific capacity of 457.6 mA h g⁻¹ at 0.1 C and 210.3 mA h g⁻¹ after 100 cycles. At a cycling rate of 0.5 C, the SnSe₂/CNTs electrode can still achieve a high value of 176.5 mA h g⁻¹, whereas a value of 45.8 mA h g⁻¹ is achieved for the pure SnSe₂ electrode. The enhanced electrochemical performance of the SnSe₂/CNTs electrode demonstrates its great potential for use in lithium-ion batteries. Thus, this work reports a facile approach to the synthesis of SnSe₂/CNTs as a promising anode material for lithium-ion batteries.     

锂离子电池纳米级负极材料的研究

综述了锂离子电池纳米级碳材料、锡基材料和合金材料近几年的研究成果及发展方向,探讨了该类材料目前存在的问题及解决的办法,对该类材料的发展趋势进行了展望.     

MoS2 Nanoflowers with Expanded Interlayers as High‐Performance Anodes for Sodium‐Ion Batteries

MoS₂ nanoflowers with expanded interlayer spacing of the (002) plane were synthesized and used as high‐performance anode in Na‐ion batteries. By controlling the cut‐off voltage to the range of 0.4–3 V, an intercalation mechanism rather than a conversion reaction is taking place. The MoS₂ nanoflower electrode shows high discharge capacities of 350 mAh g^?1 at 0.05 A g^?1, 300 mAh g^?1 at 1 A g^?1, and 195 mAh g^?1 at 10 A g^?1. An initial capacity increase with cycling is caused by peeling off MoS₂ layers, which produces more active sites for Na⁺ storage. The stripping of MoS₂ layers occurring in charge/discharge cycling contributes to the enhanced kinetics and low energy barrier for the intercalation of Na⁺ ions. The electrochemical reaction is mainly controlled by the capacitive process, which facilitates the high‐rate capability. Therefore, MoS₂ nanoflowers with expanded interlayers hold promise for rechargeable Na‐ion batteries.     

Electrospun Cu/Sn/C Nanocomposite Fiber Anodes with Superior Usable Lifetime for Lithium‐ and Sodium‐Ion Batteries

Cu/Sn/C composite nanofibers were synthesized by using dual‐nozzle electrospinning and subsequent carbonization. The composite nanofibers are a homogeneous amorphous matrix comprised of Cu, Sn, and C with a trace of crystalline Sn. The Li‐ and Na‐ion storage performance of the Cu/Sn/C fiber electrodes were investigated by using cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. Excellent, stable cycling performance indicates capacities of 490 and 220 mA h g^?1 for Li‐ion (600 cycles) and Na‐ion (200 cycles) batteries, respectively. This is a significant improvement over other reported Sn/C nanocomposite devices. These superior electrochemical properties could be attributed to the advantages of incorporating one‐dimensional nanostructures into the electrodes, such as short electron diffusion lengths, large specific surface areas, ideal homogeneous structures for buffering volume changes, and better electronic conductivity that results from the amorphous copper and carbon matrix.     

Wet‐Chemical Synthesis of Phase‐Pure FeOF Nanorods as High‐Capacity Cathodes for Sodium‐Ion Batteries

It is challenging to prepare phase‐pure FeOF by wet‐chemical methods. Furthermore, nanostructured FeOF has never been reported. In this study, hierarchical FeOF nanorods were synthesized through a facile, one‐step, wet‐chemical method by the use of just FeF₃?3H₂O and an alcohol. It was possible to significantly control the FeOF nanostructure by the selection of alcohols with an appropriate molecular structure. A mechanism for the formation of the nanorods is proposed. An impressive high specific capacity of approximately 250 mAh g^?1 and excellent cycling and rate performances were demonstrated for sodium storage. The hierarchical FeOF nanorods are promising high‐capacity cathodes for SIBs.