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.     

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.     

一种新型的碳复合钼掺杂的钒氧化物纳米线钠离子电池正极材料

近年来,由于锂资源逐渐紧缺而导致其成本增加,锂离子电池发展受到了限制. 作为一个有潜力的替代者,有着相似电化学机制且成本较低的钠离子电池则发展迅速. 但由于钠离子与锂离子相较有着更大半径,在钠离子脱嵌过程中,对大多数电极材料的晶体结构破坏严重. 因此,开发新型电极材料对钠离子电池的进一步发展尤为重要. 其中,层状钒氧化物作为正极材料被广泛研究. 在这项工作中,作者基于钒氧化物,引入钼元素并与碳复合,首次设计合成了一种新型的碳复合钼掺杂的钒氧化物纳米线电极材料,并获得了优良的电化学性能（在50 mA•g^-1的电流密度下,最高放电比容量达135.9 mAh•g^-1,并在循环75次后仍有82.6mAh•g^-1的可逆容量,容量保持率高达71.8%;在1000mA•g^-1的高电流密度下循环并回到50mA•g^-1后,可逆放电比容量仍能回复至111.5mAh•g^-1）. 本工作的研究结果证明,这种具有超大层间距的新型碳复合钼掺杂的钒氧化物纳米线是一种非常有潜力的储钠材料,并且我们的工作为钠离子电池的进一步发展提供了一定的理论基础.     

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.     

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.     

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.     

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.      

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.     

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。     

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.     

Synergetic Coupling of Redox-Active Sites on Organic Electrode Material for Robust and High-Performance Sodium-Ion Storage

Organic electrode materials (OEMs), valued for their sustainability and structural tunability, have been attracting increasing attention for wide application in sodium-ion batteries (SIBs) and other rechargeable batteries. However, most OEMs are plagued with insufficient specific capacity or poor cycling stability. Therefore, it′s imperative to enhance their specific capacity and cycling stability through molecular design. Herein, we designed and synthesized a heteroaromatic molecule 2,3,8,9,14,15-hexanol hexaazatrinaphthalene (HATN-6OH) by the synergetic coupling of catechol (the precursor of ortho-quinone)/ortho-quinone functional groups and HATN conjugated core structures. The abundance of catechol/ortho-quinone and imine redox-active moieties delivers a high specific capacity of nine-electron transfer for SIBs. Most notably, the π–π interactions and intermolecular hydrogen bond forces among HATN-6OH molecules secure the stable long-term cycling performance of SIBs. Consequently, the as-prepared HATN-6OH electrode exhibited a high specific capacity (554 mAh g⁻¹ at 0.1 A g⁻¹), excellent rate capability (202 mAh g⁻¹ at 10 A g⁻¹), and stable long-term cycling performance (73 % after 3000 cycles at 10 A g⁻¹) in SIBs. Additionally, the nine-electron transfer mechanism is confirmed by systematic density functional theory (DFT) calculation, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and Raman analysis. The achievement of the synergetic coupling of the redox-active sites on OEMs could be an important key to the enhancement of SIBs and other metal-ion batteries.     

钠离子电池电极材料研究进展

室温钠离子电池由于原料丰富,分布广泛,价格低廉,引起了人们的研究兴趣。然而,由于钠离子相对于锂离子较重且半径较大,这会限制钠离子在电极材料中的可逆脱嵌过程,从而影响电池的电化学性能。因此研发先进的电极材料成为钠离子电池实用化的关键。本文中我们主要介绍了几种典型的钠离子电池电极材料,并对其最新的研究进展进行了简要综述,将为钠离子电池新型电极材料的研究提供基础。     

钠离子电池电极材料研究进展

室温钠离子电池由于原料丰富,分布广泛,价格低廉,引起了人们的研究兴趣。然而,由于钠离子相对于锂离子较重且半径较大,这会限制钠离子在电极材料中的可逆脱嵌过程,从而影响电池的电化学性能。因此研发先进的电极材料成为钠离子电池实用化的关键。本文中我们主要介绍了几种典型的钠离子电池电极材料,并对其最新的研究进展进行了简要综述,将为钠离子电池新型电极材料的研究提供基础。     

基于聚碳酸丙烯酯基聚合物电解质和有机正极的全固态钠电池

Sodium-ion batteries (SIBs) are promising candidates to replace lithium-ion batteries (LIBs) to meet the emergent requirements of various commercial applications. SIBs and LIBs are similar in many aspects, including their reduction potentials, approximate energy densities, and ionic semidiameters. Analogously, safety issues, including liquid leakage, high flammability, and explosiveness limit the usage of SIBs. All-solid-state batteries have the potential to solve the aforementioned problems. However, polycarbonates as promising solid electrolytes have been rarely exploited in all-solid-state SIBs. In addition, organic electrode materials, including non-conjugated redox polymers, carbonyl compounds, organosulfur compounds, and layered compounds, have been intensively investigated as part of various energy storage systems owing to their low cost, environmental friendliness, high energy density, and structural diversity. Nevertheless, the dissolution of small organic compounds in organic-liquid electrolytes has hindered its further applications. Fortunately, the utilization of solid polymer electrolytes combined with organic electrode materials is a promising method to prevent dissolution into the electrolyte and improve the cycling performance of SIBs. Thus, we proposed the utilization of a poly(propylene carbonate) (PPC)-based solid polymer electrolyte and cellulose nonwoven with a 3, 4, 9, 10-perylene-tetracarboxylicacid-dianhydride (PTCDA) cathode in an all-solid-state sodium battery (ASSS). The solid electrolyte significantly enhanced the safety of the SIB and was successfully synthesized via a facile method. The morphology of the as-prepared solid electrolyte was examined by electron scanning microscopy (SEM). Furthermore, the electrochemical performances of the PTCDA/Na battery with organic-liquid and solid electrolytes at room temperature were compared. The SEM results demonstrated that the solid polymer electrolyte and sodium bis(fluorosulfonyl)imide (NaFSI) were evenly distributed inside the pores of the nonwoven cellulose. The ionic conductivity of the composite solid polymer electrolyte (CSPE) at room temperature was 3.01 × 10^-5 S·cm^-1, suggesting that the CSPE was a promising candidate for commercial applications. In addition, the ASSS showed significantly improved cycling performance at a current density of 50 mAh·g^-1 with a high capacity retention of 99.1%, whereas the discharge capacity of the liquid PTCDA/Na battery was only 24.6mAh·g^-1 after 50 cycles. This indicated that the cycling performance of the PTCDA cathode in the SIB was largely improved by preventing the dissolution of the PTCDA cathode material in the electrolyte. Electrochemical impedance spectroscopy results demonstrated that the CSPE was compatible with the organic cathode electrode.     

碳布负载的缺氧型Na2Ti3O7纳米带阵列作为高性能柔性钠离子电池负极材料

作为锂离子电池的理想替代品,钠离子电池因具有能源储备丰富、成本低廉等优点而受到人们的广泛关注。柔性便携式电子产品的发展亟需柔性储能器件的研制。因此,发展一种廉价、高性能的柔性钠离子电池负极材料成了科研工作者的共同目标。在此项工作中,我们通过简单的水热合成和热还原法发展了一种以柔性碳布为基底,与缺氧型的Na₂Ti₃O₇纳米带(NTO)构成三维阵列结构的新型柔性钠离子电池负极材料。复合材料(R-NTO/CC)的导电性和活性位点得到提高,电化学性能也大幅提升,在200 mA·cm^-2的电流密度下,实现100 mAh·cm^-2的面积比容量,且经过200次循环后仍保留最初电容值的80%。此外,这种电极还具有优良的倍率性能,当电流密度提高到400 mA·cm^-2时,仍保持69.7 mAh·cm^-2的面积比容量,是未引入氧空位材料的三倍之多。这种三维缺氧的电极材料可有效提高载流子浓度,缩短离子传输通道,从而大幅提升电极的电化学性能。此工作为设计合成高储钠性能的新型的负极材料提供了一种实用有效的策略。     

Nanowire of WP as a High-Performance Anode Material for Sodium-Ion Batteries

The design and development of electrode materials with high specific capacity and long cycling life for sodium-ion batteries (SIBs) is still a critical challenge. In this communication, we report the development of tungsten phosphide (WP) nanowire on carbon cloth (WP/CC) as an anode for SIBs. The WP/CC exhibits superior sodium storage capability with 502 mA h g⁻¹ at 0.1 A g⁻¹. Moreover, this anode is capable of delivering a long lifespan at 2 A g⁻¹ with an excellent capacity retention of 99 % after 1000 cycles.     

Hard Carbons as Anodes in Sodium-Ion Batteries: Sodium Storage Mechanism and Optimization Strategies

Sodium-ion batteries (SIBs) are regarded as promising alternatives to lithium-ion batteries (LIBs) in the field of energy, especially in large-scale energy storage systems. Tremendous effort has been put into the electrode research of SIBs, and hard carbon (HC) stands out among the anode materials due to its advantages in cost, resource, industrial processes, and safety. However, different from the application of graphite in LIBs, HC, as a disordered carbon material, leaves more to be completely comprehended about its sodium storage mechanism, and there is still plenty of room for improvement in its capacity, rate performance and cycling performance. This paper reviews the research reports on HC materials in recent years, especially the research process of the sodium storage mechanism and the modification and optimization of HC materials. Finally, the review summarizes the sterling achievements and the challenges on the basis of recent progress, as well as the prospects on the development of HC anode materials in SIBs.     

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.     

中空核壳结构Ni1.2Co0.8P@N-C钠离子电池负极材料的制备及拉曼研究

本文设计制备了一种新型的氮掺杂碳包覆镍钴双金属磷化物中空核壳结构纳米立方体(Ni_1.2Co_0.8P@N-C)作为钠离子电池负极材料. 该材料以镍钴类普鲁士蓝(PBA)纳米粒子为模板,先后经水热法、磷化法和高温碳化处理后合成. 将其作为活性材料应用在钠离子电池中,该材料展现出优异的循环稳定性,当以100 mA·g^-1的电流密度循环至200圈时,该材料的库仑效率保持在99.3%. 进一步通过对不同电位下Ni_1.2Co_0.8P@N-C材料中的氮掺杂碳进行原位拉曼光谱测试,结果显示钠离子在氮掺杂的碳壳中的脱嵌行为具有较大程度的可逆性,研究结果对钠离子电池充放电过程的后续电化学研究提供了有价值的信息.