基于石墨烯及其复合物电极的电容去离子技术研究进展

电容去离子技术是一种高效节能、绿色环保的脱盐方法, 通过施加静电场, 强制离子向两侧电极迁移, 使其被电极表面产生的双电层吸附, 从而达到脱盐的目的。电容去离子技术的关键是高性能电极材料的制备, 要求具有较高的比表面积、合理的孔径分布和良好的导电性。石墨烯具有较高的理论比表面积和优异的导电性, 是一种理想的电极材料。然而由于石墨烯的聚集效应, 实际比表面积远远低于理论值, 将石墨烯制备成三维网络结构或将石墨烯与其他材料进行复合可以克服聚集效应, 提高电极的脱盐性能。本文综述了基于石墨烯及其复合物电极的电容去离子技术研究进展、存在的问题及应用前景。     

石墨烯/CuO锂离子电池负极材料的研究进展

石墨烯作为一种锂离子电池负极材料表现出优异的电化学性能,但石墨烯在充放电过程中容易团聚,导致其容量衰减特别快。而金属氧化物在充放电过程中体积膨胀大,因此其容量衰减也非常快;另外,金属氧化物的电导率低,导致其倍率性能差。将金属氧化物与石墨烯复合,两者性能互补,石墨烯可提高复合材料的电导率,缓解金属氧化物在充放电过程中的体积效应;金属氧化物可提高复合材料的储锂容量,并能阻止石墨烯在充放电过程中团聚。本文介绍了石墨烯/CuO锂离子电池负极材料的制备方法,分析了石墨烯与氧化铜及其复合材料的储锂机制,展望了石墨烯/CuO锂离子电池负极材料的应用前景,并指出了当前研究中存在的问题。     

Carbon-nanofiber composite electrodes for thin and flexible lithium-ion batteries

Addition of vapor-grown carbon nanofiber (VGCF) into a LiCoO₂ composite electrode increases electrode’s conductivity and adhesion strength significantly. These increases are attributed to the uniform distribution of network-like VGCF of high conductivity; VGCF not only connects the surface of the active materials, its network penetrates into and connects each active material particle. VGCF composite electrode also improves the electrochemical performance of thin and flexible lithium-ion batteries such as discharge capacity at high current densities, cycle-life stability, and low-temperature (at −20 °C) discharge capacity. These improved electrochemical properties are attributed to the well-distributed network-like carbon nanofibers, VGCF, within the cathode. The addition of VGCF reduces the electron conducting resistance and decreases the diffusion path for lithium ions, hence increases the utilization of active materials during high-current discharge and low-temperature discharge. In addition, network-like VGCF forms a more uniform cathode structure so as to have a lower deterioration rate and correspondingly better life cycle stability.     

MOFs及衍生复合材料在锂硫电池中的设计应用

在能源危机与环境问题日益凸显的背景下,电化学储能技术得到了迅速发展。在“超越锂”储能领域的竞争者中,锂硫电池(Li-S)因其具有高理论比容量、高质量能量密度并且环境友好、价格低廉等优点,成为最有前途的新储能技术。但是,锂硫电池的发展仍存在一些瓶颈问题需要解决,例如正极材料导电性能差、多硫化物穿梭效应及在充放电过程中电极体积膨胀等。作为锂硫电池的关键组成部分,电极和隔膜材料的设计和制备对解决这些问题及电池整体性能提升起到了重要的作用。金属有机骨架(MOFs)及衍生的复合材料作为锂硫电池电极或隔膜修饰材料,具有质量轻、电子和离子传导性好、孔道丰富和活性位点均匀分布等优势。此外,这类复合材料还具备形貌和组分可控、来源丰富和孔径可调等特性,从而便于机制研究。本文全面介绍了锂硫电池组成、工作原理并综述了近几年MOFs及衍生复合材料在锂硫电池中的研究进展,重点讨论了其在正极材料和隔膜材料中的应用,并对未来该材料在锂硫电池研究方向上的前景和突破进行了展望。      

硅负极添加剂对锂离子电池的影响

选用乙炔黑(AB)、SuperP、VulcanXC-72和BP2000四种导电剂, 研究其物化性能及含量对硅电极电化学性能的影响; 探讨了粘合剂种类和用量对硅电极电化学性能的影响。采用场发射扫描电子显微镜对硅电极的形貌进行表征; 采用恒流充放电测试及循环伏安法对硅电极的电化学性能进行测试。结果表明, 导电剂SuperP具有良好的导电性、适中的比表面积(75.8 m²/g)和颗粒尺寸(39.2 nm), 有利于提高硅负极的循环性能及倍率循环性能。采用15wt%的导电剂 SuperP与15wt%的粘合剂CMC所制备的电极循环50次后可逆比容量保持在1143.8 mAh/g。     

高比能量锂离子电池硅基负极材料研究进展

硅的理论嵌锂比容量是石墨材料比容量的十倍以上, 脱锂电位低, 资源丰富, 倍率特性较好, 故高比能量的硅基材料成为了电动汽车?可再生能源储能系统等领域的研究热点?但由于其在脱嵌锂过程中巨大的体积膨胀效应会导致硅电极材料粉化和结构崩塌, 并且在电解液中硅表面重复形成的固相电解质层(SEI)使极化增大?库伦效率降低, 最终导致电化学性能的恶化?为了解决上述问题, 加快实现硅基电极的商业化应用, 本文系统总结了通过硅基材料的选择和结构设计来解决充放电过程中体积效应的工作, 并深入分析和讨论了具有代表性的硅基复合材料的制备方法?电化学性能和相应机理, 重点介绍了硅碳复合材料和SiO_x(0<x≤2)基复合材料?最后对硅基负极材料存在的问题进行了分析, 并展望了其研究前景?     

Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium‐Ion Storage

Rechargeable lithium‐ion batteries (LIBs), as one of the most important electrochemical energy‐storage devices, currently provide the dominant power source for a range of devices, including portable electronic devices and electric vehicles, due to their high energy and power densities. The interest in exploring new electrode materials for LIBs has been drastically increasing due to the surging demands for clean energy. However, the challenging issues essential to the development of electrode materials are their low lithium capacity, poor rate ability, and low cycling stability, which strongly limit their practical applications. Recent remarkable advances in material science and nanotechnology enable rational design of heterostructured nanomaterials with optimized composition and fine nanostructure, providing new opportunities for enhancing electrochemical performance. Here, the progress as to how to design new types of heterostructured anode materials for enhancing LIBs is reviewed, in the terms of capacity, rate ability, and cycling stability: i) carbon‐nanomaterials‐supported heterostructured anode materials; ii) conducting‐polymer‐coated electrode materials; iii) inorganic transition‐metal compounds with core@shell structures; and iv) combined strategies to novel heterostructures. By applying different strategies, nanoscale heterostructured anode materials with reduced size, large surfaces area, enhanced electronic conductivity, structural stability, and fast electron and ion transport, are explored for boosting LIBs in terms of high capacity, long cycling lifespan, and high rate durability. Finally, the challenges and perspectives of future materials design for high‐performance LIB anodes are considered. The strategies discussed here not only provide promising electrode materials for energy storage, but also offer opportunities in being extended for making a variety of novel heterostructured nanomaterials for practical renewable energy applications.     

Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors

In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film is prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance with maximum specific capacitance of 670 F cm^?3 (134 mF cm^?2), due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as‐prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder‐free electrode effectively reduce electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provide a high specific surface area to improve electron transport, enhancing rapid ion transport, and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/microsize electronic devices.     

Controllable Design of MoS2 Nanosheets Grown on Nitrogen‐Doped Branched TiO2/C Nanofibers: Toward Enhanced Sodium Storage Performance Induced by Pseudocapacitance Behavior

In this work, expanded MoS₂ nanosheets grown on nitrogen‐doped branched TiO₂/C nanofibers (NBT/C@MoS₂ NFs) are prepared through electrospinning and hydrothermal treatment method as anode materials for sodium‐ion batteries (SIBs). The continuous 1D branched TiO₂/C nanofibers provide a large surface area to grow expanded MoS₂ nanosheets and enhance the electronic conductivity and cycling stability of the electrode. The large surface area and doping of nitrogen can facilitate the transfer of both Na⁺ ions and electrons. With the merits of these unique design and extrinsic pseudocapacitance behavior, the NBT/C@MoS₂ NFs can deliver ultralong cycle stability of 448.2 mA h g^?1 at 200 mA g^?1 after 600 cycles. Even at a high rate of 2000 mA g^?1, a reversible capacity of 258.3 mA h g^?1 can still be achieved. The kinetic analysis demonstrates that pseudocapacitive contribution is the major factor to achieve excellent rate performance. The rational design and excellent electrochemical performance endow the NBT/C@MoS₂ NFs with potentials as promising anode materials for SIBs.     

高性能自支撑不锈钢网@MoS2锂离子电池负极材料

为了提高MoS₂作为Li离子电池负极材料整体的导电性和稳定性,将纳米化的MoS₂与其它导电性好的材料进行复合,通过水热法在导电基底不锈钢网(Stainless steel net, SS)上原位合成了一层MoS₂纳米花,制备了无粘结剂的自支撑结构的SS@MoS₂负极材料。纳米花状的MoS₂和导电性优异的SS提高了电子和Li离子的扩散速率,同时改善了电极的反应动力学。当作为Li离子电池负极材料时,SS@MoS₂电极表现出优异的储Li性能,特别是具有显著的大倍率充放电性能,即在1 000 mA/g的大电流密度下循环600次,比容量仍保持在862.1 mA·h/g。      

Recent advances in electrospun carbon nanofibers and their application in electrochemical energy storage

Carbon nanofibers (CNFs) have been widely used in electrochemical energy storage devices because of their excellent conductivities, extremely large surface areas and structural stability. In energy storage devices like rechargeable batteries and supercapacitors, CNFs play multi-functional roles as active electrode materials, conductive additives and substrates for supporting active metal (oxides). Electrospinning offers a low cost and scalable technique to fabricate CNFs and their hybrids with tunable nanostructures. This paper summarizes various design strategies for producing random, aligned and core/shell structured fibers, and elucidates the influences of polymer precursors, processing parameters, conductive additives and catalysts on functional, morphological and structural characteristics of CNFs. The current start-of-the-art developments for applications in Li-ion batteries, supercapacitors, Na-ion batteries, Li–O₂ batteries and Li–S batteries are reviewed. Key issues that affect the electrochemical performance of the electrodes, such as the chemical and atomic structures, electrical conductivities, surface areas and pore size distribution of CNFs, and the particle size, shape and dispersion of metal (oxides) encapsulated in CNFs, are discussed and their solutions suggested. Future prospects on further optimization of the structure and performance, and challenges encountered in large-scale applications of electrospun CNFs are proposed.     

聚丙烯腈基碳纳米纤维在超级电容器电极材料中的应用研究进展

超级电容器是一种介于电池和传统物理电容器之间的新型环保储能器件,近年来得到了研究者的广泛关注。电极材料是超级电容器的核心部分,因此具有更高的研究价值。聚丙烯腈基碳纳米纤维因具有良好的静电纺丝性、较高的碳化产率、优异的纳米结构、超高的比表面积以及优良的导电性和稳定性,已经成为超级电容器电极材料的研究热点。本文主要介绍了聚丙烯腈基交联结构和多孔结构碳纳米纤维电极材料,元素掺杂电极材料以及与碳材料、导电聚合物、金属氧化物复合的电极材料,并对聚丙烯腈基碳纳米纤维电极材料未来的研究方向进行了展望。     

锂硫电池硫正极材料研究现状与展望

综述了锂硫电池硫正极材料的研究现状。针对锂硫电池目前存在的问题,展望了其发展趋势,并指出硫/有序多孔碳纳米复合材料对提升锂硫电池性能有重要研究价值;同时形成三维空间传导网络的导电添加剂和具有良好粘接性、导电性及电化学稳定性的粘结剂对锂硫电池性能提升也具有重要作用。     

煤基球形多孔碳用于锂离子电池负极材料的性能研

因具有较短的锂离子扩散路径、大的比表面积等优势, 球形碳材料在锂离子电池负极材料中展露出良好的应用前景。研究以新疆库车产煤为原料, 采用电弧放电法及化学活化法制备出了具有多孔结构的煤基球形碳。通过X射线衍射(XRD)、扫描电镜(SEM)、拉曼光谱(Raman)、氮气吸脱附法和恒电流充放电等测试手段对材料结构、形貌和电化学性能进行了表征。结果表明, 在100 mA/g的电流密度下, 煤基球形多孔碳的首次放电比容量可达到1188.9 mAh/g, 远高于商业石墨负极372 mAh/g的理论比容量。此外, 该材料还表现出了良好的循环稳定性, 经历200圈循环后的放电比容量为844.9 mAh/g。煤基球形多孔碳优异的电化学性能得益于活化过程所产生的分级孔道结构能为锂离子提供更多储存空间, 从而提高了电极的容量及循环稳定性。     

氧化钒作锂离子电池正极材料的研究进展

V_2O_5具有独特的层状结构,适合于锂离子的存储,与传统的锰酸锂、钴酸锂、磷酸铁锂等正极材料相比,具有高的理论比容量、功率密度以及价格低廉、原材料丰富等优势,在作为锂离子电池正极材料方面备受关注。但V_2O_5低的固有电导率及锂离子扩散系数,导致其容量保持率低和倍率性能差;此外,充放电过程中反复的相变会引起结构的不稳定,而且氧化钒会部分溶于电解液,因此表现出差的循环性能。正是由于这些制约因素的存在,对V_2O_5的固有缺陷进行改性研究以提高氧化钒正极材料的电化学性能成为重要的研究热点。将氧化钒进行纳米化以增大比表面积和缩短离子扩散距离,同时通过复合、掺杂改性等方法提高材料的导电性和循环稳定性,从而使V_2O_5正极材料表现出优异的电化学性能成为可能。文章从氧化钒电极材料纳米化,在纳米化的基础上复合导电材料,调节工作电压窗口,掺杂金属离子这四类方法阐述对氧化钒电化学性能的改善,以及各种方法对电极电化学性能的影响。     

Lithium Silicide Surface Enrichment: A Solution to Lithium Metal Battery

The propensity of lithium dendrite formation during the charging process of lithium metal batteries is linked to inhomogeneity on the lithium surface layer. The high reactivity of lithium and the complex surface structure of the native layer create “hot spots” for fast dendritic growth. Here, it is demonstrated that a fundamental restructuring of the lithium surface in the form of lithium silicide (Li_xSi) can effectively eliminate the surface inhomogeneity on the lithium surface. In situ optical microscopic study is carried out to monitor the electrochemical deposition of lithium on the Li_xSi‐modified lithium electrodes and the bare lithium electrode. It is observed that a much more uniform lithium dissolution/deposition on the Li_xSi‐modified lithium anode can be achieved as compared to the bare lithium electrode. Full cells paring the modified lithium anode with sulfur and LiFePO₄ cathodes show excellent electrochemical performances in terms of rate capability and cycle stability. Compatibility of the anode enrichment method with mass production process also offers a practical way for enabling lithium metal anode for next‐generation lithium batteries.     

An overview of the applications of graphene-based materials in supercapacitors

Due to their unique 2D structure and outstanding intrinsic physical properties, such as extraordinarily high electrical conductivity and large surface area, graphene-based materials exhibit great potential for application in supercapacitors. In this review, the progress made so far for their applications in supercapacitors is reviewed, including electrochemical double-layer capacitors, pseudo-capacitors, and asymmetric supercapacitors. Compared with traditional electrode materials, graphene-based materials show some novel characteristics and mechanisms in the process of energy storage and release. Several key issues for improving the structure of graphene-based materials and for achieving better capacitor performance, along with the current outlook for the field, are also discussed.     

锂离子电池多孔硅/碳复合负极材料的研究

以商业化多晶硅粉为原料, 采用金属银催化剂诱导化学腐蚀的方法制得三维多孔硅材料。通过优化腐蚀条件, 得到孔径约为130 nm, 比表面为4.85 m²/g的多孔硅材料。将多孔硅和PAN溶液混合球磨并经高温烧结后在多孔硅表面包覆上一层致密的无定形碳膜, 从而制得多孔硅/碳复合材料作为锂离子电池的负极材料。3D多孔硅结构可以缓解电化学嵌/脱锂过程中材料的体积效应, 无定形碳膜层可有效改善复合材料的导电性能。电化学性能测试表明, 该多孔硅/碳复合负极材料电池在0.4 A/g的恒电流下, 首次放电容量3345 mAh/g, 首次循环库伦效率85.8%, 循环55次后容量仍保持有1645 mAh/g。并且在4 A/g的倍率下, 容量仍维持有1174 mAh/g。该方法原料成本低廉, 可规模化生产。     

阴离子交换膜燃料电池阳极催化剂的研究进展

阴离子交换膜燃料电池(AEMFC)可使用非贵金属催化剂,且电极反应速率快。阳极催化剂的选择和制备对提高燃料氧化速率和燃料电池的电流密度及降低成本等有很大影响。本文从阴离子交换膜阳极催化剂的种类、制备方法,催化剂的载体等角度对阳极催化剂的研究现状进行分析。分析表明,在阳极催化剂中掺杂金属、金属氧化物或非金属氧化物,能充分发挥各元素的协同作用,从而提高催化剂的电催化性能;改进制备方法可以提高催化剂的比表面积,改变元素的分布。对催化剂载体进行改性以改善载体自身的孔径分布,提高比表面积和稳定性,或寻求导电性好、比表面积大、耐腐蚀的新载体材料(如SiC、Ti等),均可以提高催化剂的载量和催化剂在载体上的分散度等,从而提高阴离子交换膜燃料电池的性能。     

电化学电容器中炭电极的研究及开发Ⅱ.炭电极

总结了各种炭材料作为电化学电容器电极材料的研究和开发现状，分析了炭材料的比表面积、孔分布、孔容、表面官能团、石墨微晶取向等特性，极化电极的制作工艺、电极密度、电极厚度、电极导电性以及附加准电容等电化学特性对电化学电容器性能的影响，着重介绍了近几年来用纳米碳管作电化学电容器极化电极所取得的进展，并展望了纳米碳管在这一领域应用的前景。