钠离子电池硬碳负极储钠机理及优化策略

钠离子电池因具有成本低、安全性高等优势, 被认为是一种非常适合应用于大规模储能领域的电化学储能技术. 合适的负极材料是促进钠离子电池实现商业化的关键之一. 硬碳材料由于具有丰富的碳源、低成本、无毒环保, 且储钠电位低而被认为是最可能被实用化的钠离子电池负极材料. 然而硬碳负极的实际应用中也面临着首周库伦效率低、长循环稳定性不足以及倍率性能较差等问题, 近年来众多研究者致力于硬碳负极的性能优化研究, 本Review从结构调控、形貌设计、界面构造、电解液优化四方面总结了近年来钠离子电池硬碳负极的性能优化策略研究进展, 分析了每种优化策略的优点和不足, 并进一步讨论了钠离子电池硬碳负极实用化进程中面临的瓶颈问题和挑战.     

钠离子电池碳负极材料的研究进展

钠离子电池具有资源丰富和成本低等优势,在大规模储能领域受到广泛的关注.开发具有高比容量和长循环稳定性的电极材料是钠离子电池走向应用的关键.碳材料作为钠离子电池的负极材料,具有可调控性高与稳定性好等优势,具有应用潜力.目前,研究较为广泛的碳材料主要包括石墨、无定形碳、杂原子掺杂碳、生物质合成碳,但这些碳负极材料存在着钠-石墨化合物热力学不稳定、较大的体积变化以及初始库伦效率低等问题,制约了钠离子电池的发展与广泛应用.通过对碳材料的结构进行修饰改性及将其与电解液进行匹配,可以有效提升其储钠性能.本文对这几类碳材料的结构特点、电化学性能、储钠机理、面临的问题、改进方法以及商业化前景进行总结,为钠离子电池碳负极材料的发展提供新见解.     

电化学储钠材料的研究进展

大规模储能的二次电池不仅需要具有适宜的电化学性能,更需考虑资源、成本和环境效益等应用要求. 锂离子电池储能的大规模应用也将受到制约. 从资源与环境方面考虑,钠离子电池作为储能电池更具应用优势. 然而,从目前的技术现状来看,几类不同的嵌钠正极材料虽显现出可观的嵌钠容量与较好的循环性,但能量密度与功率密度尚待提高. 硬碳材料和合金负极最有希望用于钠离子电池,这类材料的初始充放电效率和循环稳定性仍有待改善. 本文简要分析了锂离子电池与钠离子电池在材料要求方面的差异,回顾了近年来钠离子电池材料探索中的突破性进展,并主要结合本课题组的研究工作讨论了钠离子电池及其关键材料的发展方向.     

钠离子电池用碳负极材料研究进展

相较于目前主流的锂离子电池,钠离子电池成本相对较低,因而有望在未来大规模储能系统中获得重要应用,然而其实用化进程仍受制于缺少合适的正负极材料,特别是性能优异且实用化的负极材料.钠离子电池与锂离子电池具有相似的工作原理,但钠离子和锂离子在碳负极材料中的储存行为却有着很大的不同.总体而言,碳材料仍是目前最有望促进钠离子电池实用化的关键负极材料.本文系统总结并分析了目前已有碳材料中钠离子的储存机制,对负极材料的设计思路和研究进展进行了概述,着重阐述了商用化碳分子筛在钠离子电池中的实用化前景.最后,本文对钠离子电池中碳负极材料的未来发展方向进行了展望.     

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。     

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.     

钠离子电池合金化负极材料研究及应用进展

钠离子电池凭借钠资源丰富、分布广泛、价格低廉的优势在大规模储能领域具有重要的应用前景,可与锂离子电池形成优势互补.负极材料是电池化学的关键组成,其能量密度、使用寿命等直接影响着电池性能.合金化材料具有理论比容量高、工作电压适宜等优势,被认为是一类有应用潜力的储钠负极.然而,这类材料发生合金化反应时体积膨胀严重,电极材料易粉化脱落,造成电化学稳定性欠佳.目前,主要通过材料微纳结构设计、界面化学调控、碳材料复合、表面包覆、电解液优化等方法来改善其电化学性能.本文综述了合金化负极材料的最新研究进展,探讨了其发展面临的瓶颈以及解决方案,介绍了基于合金化负极的钠离子全电池构筑策略和应用实例,为高性能钠离子电池的发展提供一定参考依据.     

钠离子电池炭基负极材料研究进展

钠离子电池是目前新兴的低成本储能技术,因在大规模电化学储能中具有较好的应用前景而受到了国内外学者广泛的关注与研究。作为钠离子电池的关键电极材料之一,非石墨的炭质材料因具有储钠活性高、成本低廉、无毒无害等诸多优点,而被认为是钠离子电池实际应用时负极的最佳选择。本文详细综述了目前钠离子电池炭基负极材料的研究进展,重点介绍了炭质材料的储钠机理与特性,分析了炭材料结构与电化学性能之间的关系,探讨了其存在的问题,为钠离子电池炭基负极材料的发展提供有益的认识。     

钠离子电池用生物质基硬碳的研究进展

生物质基硬碳具有原材料资源丰富、可持续、成本低和储钠容量高等特点,是钠离子电池的理想负极材料。生物质基硬碳材料的微结构是决定钠离子存储性能的关键。本综述回顾了硬碳负极对钠离子存储机理的研究现状。从生物质原料的角度,分类总结了高性能生物质基硬碳材料的制备方法。探讨了生物质基硬碳结构的调控与钠离子存储性能提升的关系,对钠离子电池用生物质基硬碳负极材料的研究方向进行了展望。     

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.      

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.     

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.     

一步法高效制备纳米Si/C复合材料及其在高性能锂离子电池中的应用

开发了一种一步高效合成纳米硅/碳复合材料的新方法, 该方法通过球磨SiCl₄、 Mg₂Si和商业碳片, 使SiCl₄自下而上还原, 原位形成的纳米硅均匀生长在碳片上, 高效制备了纳米硅与碳片均匀复合物(Nano-Si/C). 该Nano-Si/C用作锂离子电池负极材料展现出高的可逆储锂容量(2450 mA·h/g)、 良好的倍率性能及优异的长循环稳定性, 在2 A/g电流密度下, 经过600次循环后, 容量仍然稳定在1400 mA·h/g. 其突出的电化学性能主要归因于小尺寸纳米硅与碳片均匀复合的纳米结构, 在循环嵌锂/脱锂过程中仍能保持结构和电化学性质的稳定性.     

Multilayer Porous Vanadium Nitride Microsheets Anodes for Highly Stable Na-ion Batteries

Sodiumion batteries(SIBs)have attracted intensive attention as promising alternative to lithium-ionbatteries(LIBs)for large scale energy storage systems because of low cost of sodium,similar energy storage mechanism and the reasonable performance.However,it is still a great challenge to search and design a robust structure of anode materials with excellent cycling stability and high rate capability for SIBs.Herein,multilayer porous vanadium nitride(VN)microsheets are synthesized through a facile and scalable hydrothermal synthesis-nitrogenization strategy as an effective anode material for SIBs.The multilayer porous VN microsheets not only offer more active sites for fast Na+insertion/extraction process and short diffusion pathway,but also effectively buffer the volume change of anode due to more space in the multilayer porous structure.The large proportions of capacitive behavior imply that the Na+charge storage depends on the intercalation pseudocapacitive mechanism.The multilayer porous VN microsheets electrodes manifest excellent cycling stability and rate capability,delivering a discharge capacity of 156.1 mA·h/g at 200 mA/g after 100 cycles,and a discharge capacity of 111.9 mA·h/g at 1.0 A/g even after 2300 cycles with the Coulombic efficiency of nearly 100%.     

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.