Antimony‐ and Bismuth‐Based Chalcogenides for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have received much attention, owing to their great potential for large‐scale application. A lack of efficient anode materials with high reversible capacity is one main challenge facing the development of SIBs. Antimony‐ and bismuth‐based chalcogenides materials can store large amounts of Na⁺ ions, owing to the alloying/dealloying reaction mechanism within a low potential range, and thus, are regarded as promising anodes for SIBs. However, these materials face great challenges of poor ion diffusion rate, multiple phase transformations, and severe morphology pulverization. Herein, recent developments in antimony‐ and bismuth‐based chalcogenides materials, mainly rational structural design strategies used and the electrochemical reaction mechanisms involved, are summarized. Perspectives for further improving antimony‐ and bismuth‐based chalcogenides anodes are also provided.     

In‐Situ Fabrication of Bone‐Like CoSe2 Nano‐Thorn Loaded on Porous Carbon Cloth as a Flexible Electrode for Na‐Ion Storage

Sodium‐ion batteries (SIBs) based on flexible electrode materials are being investigated recently for improving sluggish kinetics and developing energy density. Transition metal selenides present excellent conductivity and high capacity; nevertheless, their low conductivity and serious volume expansion raise challenging issues of inferior lifespan and capacity fading. Herein, an in‐situ construction method through carbonization and selenide synergistic effect is skillfully designed to synthesize a flexible electrode of bone‐like CoSe₂ nano‐thorn coated on porous carbon cloth. The designed flexible CoSe₂ electrode with stable structural feature displays enhanced Na‐ion storage capabilities with good rate performance and outstanding cycling stability. As expected, the designed SIBs with flexible BL?CoSe₂/PCC electrode display excellent reversible capacity with 360.7 mAh g^?1 after 180 cycles at a current density of 0.1 A g^?1.     

Bismuth Nanoparticles Embedded in Carbon Spheres as Anode Materials for Sodium/Lithium‐Ion Batteries

Sodium‐ion batteries (SIBs) are regarded as an attractive alternative to lithium‐ion batteries (LIBs) for large‐scale commercial applications, because of the abundant terrestrial reserves of sodium. Exporting suitable anode materials is the key to the development of SIBs and LIBs. In this contribution, we report on the fabrication of Bi@C microspheres using aerosol spray pyrolysis technique. When used as SIBs anode materials, the Bi@C microsphere delivered a high capacity of 123.5 mAh g^?1 after 100 cycles at 100 mA g^?1. The rate performance is also impressive (specific capacities of 299, 252, 192, 141, and 90 mAh g^?1 are obtained under current densities of 0.1, 0.2, 0.5, 1, and 2 A g^?1, respectively). Furthermore, the Bi@C microsphere also proved to be suitable LIB anode materials. The excellent electrochemical performance for both SIBs and LIBs can attributed to the Bi@C microsphere structure with Bi nanoparticles uniformly dispersed in carbon spheres.     

A Biodegradable Polydopamine‐Derived Electrode Material for High‐Capacity and Long‐Life Lithium‐Ion and Sodium‐Ion Batteries

Polydopamine (PDA), which is biodegradable and is derived from naturally occurring products, can be employed as an electrode material, wherein controllable partial oxidization plays a key role in balancing the proportion of redox‐active carbonyl groups and the structural stability and conductivity. Unexpectedly, the optimized PDA derivative endows lithium‐ion batteries (LIBs) or sodium‐ion batteries (SIBs) with superior electrochemical performances, including high capacities (1818 mAh g^?1 for LIBs and 500 mAh g^?1 for SIBs) and good stable cyclabilities (93 % capacity retention after 580 cycles for LIBs; 100 % capacity retention after 1024 cycles for SIBs), which are much better than those of their counterparts with conventional binders.     

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.     

Switching between Local and Global Aromaticity in a Conjugated Macrocycle for High‐Performance Organic Sodium‐Ion Battery Anodes

Aromatic organic compounds can be used as electrode materials in rechargeable batteries and are expected to advance the development of both anode and cathode materials for sodium‐ion batteries (SIBs). However, most aromatic organic compounds assessed as anode materials in SIBs to date exhibit significant degradation issues under fast‐charge/discharge conditions and unsatisfying long‐term cycling performance. Now, a molecular design concept is presented for improving the stability of organic compounds for battery electrodes. The molecular design of the investigated compound, [2.2.2.2]paracyclophane‐1,9,17,25‐tetraene (PCT), can stabilize the neutral state by local aromaticity and the doubly reduced state by global aromaticity, resulting in an anode material with extraordinarily stable cycling performance and outstanding performance under fast‐charge/discharge conditions, demonstrating an exciting new path for the development of electrode materials for SIBs and other types of batteries.     

Carbon and Carbon Hybrid Materials as Anodes for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have attracted much attention for application in large‐scale grid energy storage owing to the abundance and low cost of sodium sources. However, low energy density and poor cycling life hinder practical application of SIBs. Recently, substantial efforts have been made to develop electrode materials to push forward large‐scale practical applications. Carbon materials can be directly used as anode materials, and they show excellent sodium storage performance. Additionally, designing and constructing carbon hybrid materials is an effective strategy to obtain high‐performance anodes for SIBs. In this review, we summarize recent research progress on carbon and carbon hybrid materials as anodes for SIBs. Nanostructural design to enhance the sodium storage performance of anode materials is discussed, and we offer some insight into the potential directions of and future high‐performance anode materials for SIBs.     

Multiple Active Sites of Carbon for High‐Rate Surface‐Capacitive Sodium‐Ion Storage

Although sodium ion batteries (SIBs) possess many beneficial features, their rate performance, cycling stability, and safety need improvement for commercial applications. Based on the mechanisms of the sodium ions storage in carbon materials, herein we present a multiple active sites decorated amorphous carbon (MAC) with rich structural defects and heteroatom doping as an anode material for SIBs. The full utilization of fast bonding–debonding processes between the active sites and sodium ions could bring a capacitive strategy to achieve superior sodium storage properties. Consequently, after materials characterization and electrochemical evaluation, the as‐prepared electrode could deliver high rate and long‐life performance. This active‐site‐related design could be extended to other types of electrode materials, thereby contributing to future practical SIB applications.     

钠离子电池用高性能锑基负极材料的调控策略研究进展

Na-ion batteries (SIBs) are promising alternatives for Li-ion batteries owing to the natural abundance of sodium resources and similar energy storage mechanisms. Although significant progress has been achieved in research on SIBs, there remain several challenges to be addressed. One of the major challenges in the construction of high-performance SIBs is the development of suitable anode materials with a large reversible capacity, high cycling stability, and good rate performance. Alloying anode materials mainly composed of elements from Groups IVA and VA, as well as their alloys, have attracted widespread attention because of their low working voltage, high cost-effectiveness, and large theoretical capacity. Alloying-type anode materials can be alloyed with metallic Na to achieve large reversible capacities, ensuring a high energy density. Antimony is a promising anode material for SIBs owing to its high theoretical specific capacity (660 mAh·g⁻¹, corresponding to the full sodiation Na₃Sb alloy), small degree of electrode polarization (~0.25 V), appropriate Na⁺ deintercalation potential (0.5–0.75 V), low price, and environmental friendliness. However, an important challenge for using Sb-based anode materials is that the high specific capacity is accompanied by large volume changes during cycling. Such changes lead to the pulverization of the active materials and their falling off from the collector, which significantly limit their large-scale application in the field of sodium-ion batteries. Therefore, mitigating the volume expansion issue of Sb-based anode materials in the charge-discharge process is very important for the design of high-performance SIBs. In recent years, researchers have attempted to address this issue by designing special structures to prepare various composites, and substantial progress has been achieved in improving the electrochemical performance of SIBs. In this review, the relationship between the structure and properties of Sb-based materials and their applications in SIBs are presented and discussed in detail. The latest research progress on using Sb-based anode materials for SIBs in redox reaction mechanisms along with their morphology design, structure-performance relationship, etc. have been reviewed. The main objective of this review is to explore the determining factors of the performance of Sb-based anode materials to propose suitable modification strategies for improving their reversible capacity and cycle stability. Finally, future developments, challenges, and prospects of Sb-based anode materials for SIBs are discussed. Despite several challenges, Sb-based materials are very promising anode materials for SIBs with alloying reaction mechanisms. To further improve the large-scale application of Sb-based anode materials, it is necessary to optimize the binder, electrode structure, and electrolyte composition. The combination of in-depth studies on the electrochemical reaction mechanisms and advanced characterization technologies is important for the development and construction of advanced Sb-based anode materials for SIBs. Finally, to achieve extensive large-scale applications, it is necessary to further explore environmentally friendly, low-cost, and controllable synthetic technologies to prepare high-performance Sb-based anode materials. This review provides specific perspectives for the construction and optimization of Sb-based anode materials and suggests scope for future work on Sb-based anode materials, thereby promoting the rapid development and practical application of SIBs.      

Formation of Polypyrrole‐Coated Sb2Se3 Microclips with Enhanced Sodium‐Storage Properties

Antimony‐based electrode materials with high specific capacity have aroused considerable interest as anode materials for sodium‐ion batteries (SIBs). Herein, we develop a template‐engaged ion‐exchange method to synthesize Sb₂Se₃ microclips, and the as‐obtained Sb₂Se₃ microclips are further in situ coated with polypyrrole (PPy). Benefiting from the structural and compositional merits, these PPy‐coated Sb₂Se₃ microclips exhibit enhanced sodium‐storage properties in terms of high reversible capacity, superior rate capability, and stable cycling performance.     

Copper fluoride as a low-cost sodium-ion battery cathode with high capacity

Sodium-ion batteries（SIBs） are promising alternatives to lithium-ion batteries（LIBs） for large-scale energy storage considering the abundance and low cost of Na-containing resources. However, the energy density of SIBs has been limited by the typically low specific capacities of traditional intercalation-based cathodes. Metal fluorides, in contrast, can deliver much higher capacities based on multi-electron conversion reactions. Among metal fluorides, CuF₂ presents a theoretical speci...     

钠离子电池用高性能锑基负极材料的调控策略研究进展

锑(Sb)具有高的理论比容量、较小的电极极化、合适的Na⁺脱嵌电位、价格低廉以及环境友好的优势,而成为一种具有较大应用前景的钠离子电池负极材料。但是,Sb基负极材料的一个重要挑战是在循环过程中高比容量伴随着大的体积变化,进而导致活性材料粉化,并从集流体上脱落,这大大限制了其在钠离子电池领域的大规模应用。因此,如何解决Sb基负极材料充放电过程中体积膨胀问题对于高性能的钠离子电池设计是至关重要的。本文详细综述和讨论了Sb基材料的结构-性能关系及其在钠离子电池中的应用,详细介绍了钠离子电池Sb基负极材料在氧化还原反应机理、形貌设计、结构-性能关系等方面的最新研究进展。本综述的主要目的是探讨影响Sb基负极材料性能的决定因素,从而提出有前途的改性策略,以提高其可逆容量和循环稳定性。最后,对Sb基钠离子电池负极材料的未来发展、面临的挑战和前景进行了展望。本文可为Sb负极材料的构建和优化提供具体的观点,阐明了Sb基负极材料未来的发展方向,从而促进钠离子电池的快速发展和实际应用。     

Suppressing the P2–O2 Phase Transition of Na0.67Mn0.67Ni0.33O2 by Magnesium Substitution for Improved Sodium‐Ion Batteries

Room‐temperature sodium‐ion batteries (SIBs) have shown great promise in grid‐scale energy storage, portable electronics, and electric vehicles because of the abundance of low‐cost sodium. Sodium‐based layered oxides with a P2‐type layered framework have been considered as one of the most promising cathode materials for SIBs. However, they suffer from the undesired P2–O2 phase transition, which leads to rapid capacity decay and limited reversible capacities. Herein, we show that this problem can be significantly mitigated by substituting some of the nickel ions with magnesium to obtain Na_0.67Mn_0.67Ni_0.33?xMg_xO₂ (0≤x≤0.33). Both the reversible capacity and the capacity retention of the P2‐type cathode material were remarkably improved as the P2–O2 phase transition was thus suppressed during cycling. This strategy might also be applicable to the modulation of the physical and chemical properties of layered oxides and provides new insight into the rational design of high‐capacity and highly stable cathode materials for SIBs.     

Active material and interphase structures governing performance in sodium and potassium ion batteries

Development of energy storage systems is a topic of broad societal and economic relevance, and lithium ion batteries (LIBs) are currently the most advanced electrochemical energy storage systems. However, concerns on the scarcity of lithium sources and consequently the expected price increase have driven the development of alternative energy storage systems beyond LIBs. In the search for sustainable and cost-effective technologies, sodium ion batteries (SIBs) and potassium ion batteries (PIBs) have attracted considerable attention. Here, a comprehensive review of ongoing studies on electrode materials for SIBs and PIBs is provided in comparison to those for LIBs, which include layered oxides, polyanion compounds and Prussian blue analogues for positive electrode materials, and carbon-based and alloy materials for negative electrode materials. The importance of the crystal structure for electrode materials is discussed with an emphasis placed on intrinsic and dynamic structural properties and electrochemistry associated with alkali metal ions. The key challenges for electrode materials as well as the interface/interphase between the electrolyte and electrode materials, and the corresponding strategies are also examined. The discussion and insights presented in this review can serve as a guide regarding where future investigations of SIBs and PIBs will be directed.

The importance of the active material structure and the interface/interphase between the electrode and electrolyte in enhancing the electrochemical performance of sodium and potassium ion batteries.     

The recent progress of pitch-based carbon anodes in sodium-ion batteries

Sodium-ion batteries(SIBs)have attracted significant attentions as promising alternatives to lithium-ion batteries for large-scale energy storage applications.Here carbon materials are considered as the most competitive anodes for SIBs based on their low-cost,abundant availability and excellent structural stability.Pitch,with high carbon content and low cost,is an ideal raw precursor to prepare carbon materials for large-scale applications.Nevertheless,the microstructures of pitch-based carbon are highly ordered with smaller interlayer distances,which are unfavorable for Na ion storage.Many efforts have been made to improve the sodium storage performance of pitch-based carbon materials.This review summarizes the recent progress about the application of pitch-based carbons for SIBs anodes in the context of carbon’s morphology and structure regulation strategies,including morphology adjustment,heteroatoms doping,fabricating heterostructures,and the increase of the degree of disorder.Besides,the advantages,present challenges,and possible solutions to current issues in pitch-based carbon anode are discussed,with the highlight of future research directions.This review will provide a deep insight into the development of low-cost and high-performance pitch-based carbon anode for SIBs.     

Ni3S2@碳纳米管复合材料的制备及其储钠性能

采用一步固相煅烧工艺制备了碳纳米管原位封装Ni₃S₂纳米颗粒（Ni₃S₂@CNT）,并研究了其作为钠离子电池（SIBs）负极材料的电化学性能. 通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、循环伏安测试、恒流充放电以及交流阻抗等研究了Ni₃S₂@CNT的物相结构、形貌特征以及电化学性能. 电化学测试表明,材料在100 mA·g ^-1电流密度下,放电容量可以达到541.6 mAh·g ^-1,甚至在2000 mA·g ^-1的大电流密度下其放电比容量也可以维持在274.5 mAh·g ^-1. 另外,材料在100 mA·g ^-1电流密度下,经过120周充放电循环后其放电和充电比容量仍然可以保持在374.5 mAh·g ^-1和359.3 mAh·g ^-1,说明其具有良好倍率性能和循环稳定性能. 良好的电化学性能归因于这种独特的碳纳米管原位封装Ni₃S₂纳米颗粒结构. 碳纳米管不但可以提高复合材料的导电性,也可以缓冲Ni₃S₂纳米颗粒在反复充放电过程中产生的体积膨胀效应,明显改善了Ni₃S₂@CNT负极复合材料的电化学性能.     

Rational Design of Anode Materials Based on Group IVA Elements (Si,Ge, and Sn) for Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) represent the state‐of‐the‐art technology in rechargeable energy‐storage devices and they currently occupy the prime position in the marketplace for powering an increasingly diverse range of applications. However, the fast development of these applications has led to increasing demands being placed on advanced LIBs in terms of higher energy/power densities and longer life cycles. For LIBs to meet these requirements, researchers have focused on active electrode materials, owing to their crucial roles in the electrochemical performance of batteries. For anode materials, compounds based on Group IVA (Si, Ge, and Sn) elements represent one of the directions in the development of high‐capacity anodes. Although these compounds have many significant advantages when used as anode materials for LIBs, there are still some critical problems to be solved before they can meet the high requirements for practical applications. In this Focus Review, we summarize a series of rational designs for Group IVA‐based anode materials, in terms of their chemical compositions and structures, that could address these problems, that is, huge volume variations during cycling, unstable surfaces/interfaces, and invalidation of transport pathways for electrons upon cycling. These designs should at least include one of the following structural benefits: 1) Contain a sufficient number of voids to accommodate the volume variations during cycling; 2) adopt a “plum‐pudding”‐like structure to limit the volume variations during cycling; 3) facilitate an efficient and permanent transport pathway for electrons and lithium ions; or 4) show stable surfaces/interfaces to stabilize the in situ formed SEI layers.     

Single‐Step Synthesis of Mesoporous Carbon Nitride/Molybdenum Sulfide Nanohybrids for High‐Performance Sodium‐Ion Batteries

Molybdenum disulfide (MoS₂) is a promising candidate as a high‐performing anode material for sodium‐ion batteries (SIBs) due to its large interlayer spacing. However, it suffers from continued capacity fading. This problem could be overcome by hybridizing MoS₂ with nanostructured carbon‐based materials, but it is quite challenging. Herein, we demonstrate a single‐step strategy for the preparation of MoS₂ coupled with ordered mesoporous carbon nitride using a nanotemplating approach which involves the pyrolysis of phosphomolybdic acid hydrate (PMA), dithiooxamide (DTO) and 5‐amino‐1H‐tetrazole (5‐ATTZ) together in the porous channels of 3D mesoporous silica template. The sulfidation to MoS₂, polymerization to carbon nitride (CN) and their hybridization occur simultaneously within a mesoporous silica template during a calcination process. The CN/MoS₂ hybrid prepared by this unique approach is highly pure and exhibits good crystallinity as well as delivers excellent performance for SIBs with specific capacities of 605 and 431 mAhg^?1 at current densities of 100 and 1000 mAg^?1, respectively, for SIBs.     

钠离子电池关键材料研究及应用进展

钠离子资源丰富,分布广泛,价格低廉,因而钠离子电池被认为是下一代大规模储能技术的理想选择之一. 然而,钠离子较大的半径和质量不利于它与电极材料的可逆反应. 开发能够快速、稳定储钠的基质材料是提升钠离子电池性能的关键之一. 此外,如何合理地优化电解质,匹配正负极材料,以实现高性能、高安全、低成本钠离子全电池的构建,切实将其推向市场,也是亟待解决的问题. 本文综述了国内外钠离子电池关键材料（包括正极材料、负极材料和电解质）的研究进展,介绍了一些具有代表性的钠离子全电池实例. 对钠离子电池的基础研究和实际应用具有一定参考价值和借鉴意义.     

钠离子电池用铁基正极材料的研究进展

气候变化和化石燃料枯竭等问题将促进新型绿色能源的开发和利用。因此,高效率、低成本、安全的储能系统,得到了越来越多的关注和研究。在各类储能系统中,二次电池是存储电能、为电子设备供电的最理想选择。目前,锂离子电池(LIBs)的应用最广泛。然而,地球上锂资源的短缺和分布不均造成的成本较高,急需研究和开发其他高性能的新型二次电池。钠元素具有地壳中储量丰富、均匀且与锂具有相似化学性质等优势,使得钠离子电池(SIBs)成为了取代LIBs最有前景的备选二次电池之一。然而,钠离子的体积较大、离子传导动力学更缓慢、导电性更差等问题,限制了SIBs高性能的实现,这是目前研究的难点和重点。此外,铁具有储量丰富、环境友好的特点,其在SIBs中的应用引起了电池领域科研工作者的广泛关注。因此,寻找良好的铁基正极材料成为SIBs高性能电极材料开发的一个重要研究方向。本综述对近年来SIBs铁基正极材料方面的研究进展进行了总结,并按照聚阴离子型化合物、过渡金属氧化物、普鲁士蓝及类似物和氟化物分类,进行了系统的阐述和分析。