纳米碳集流体在电化学储能中的应用进展

电化学储能技术对配置可再生能源和拓展电动器件的广泛使用至关重要。碳纳米集流体具有比表面积高、导电性好、界面可修饰及柔性好等特点,为下一代高比能锂硫电池及目前的锂离子电池和电容器存在的关键科学问题提供了一个良好的研究平台。本文重点对纳米碳基集流体在锂硫电池中的应用及界面作用机理进行了探讨,并介绍了纳米碳基集流体在高比能、高功率锂离子电池和电容器中的作用,最后阐述了纳米碳集流体在这些储能体系中存在的问题及发展空间。     

锂离子电池用纳米碳材料研究进展

锂离子电池作为最有前景的储能器件之一,已经在便携式电子设备上广泛应用。然而使用传统电极材料,电池的能量密度和功率密度不够高、耐久性差、成本高,限制了其在电动汽车等方面的大规模应用。纳米碳材料的发展为设计适合锂离子电池的新型储能材料提供了机会。纳米碳材料作为一种新型碳材料具有许多独特的性能,包括独特的形貌结构、高比表面积、低扩散距离、高电导率和离子导电性能、可控的合成和掺杂等优点。因此,纳米碳材料在高可逆容量、高功率密度、长循环稳定性和高安全性锂离子电池中具有较大的应用前景。然而,纳米碳材料普遍存在首次库仑效率低、电压滞后等缺点,且纳米碳材料的电化学性能取决于碳材料的形貌和微观结构。解决这一问题最常用的方法主要有:(1)通过对纳米碳材料的形貌和微结构调控来改善其电化学性能;(2)通过异质原子掺杂改善纳米碳材料的电化学性能;(3)将纳米碳与其他储锂材料复合形成复合电极材料。本文主要综述了富勒烯、石墨烯、碳纳米管和多孔碳等四种具有代表性的纳米碳材料在锂离子电池中的最新研究进展,系统归纳了纳米结构和形貌对电化学性能的影响,讨论了纳米碳的合成、电化学储锂性能和电极反应机理。本文还对纳米碳材料未来...     

石墨烯导电剂在电池领域中的应用

<正>一、概述当今社会日益增长的能源需求与环境压力对电池提出了新的、更高的要求,对电池技术的发展来说既是机遇也是挑战。石墨烯是目前人类已知导电性能最好的二维尺度纳米碳材料,同时石墨烯还兼有良好的机械性能、最好的传热性能、独特的形貌与结构特征,其在储能电池技术领域中的应用越来越普遍。本文通过简述近年石墨烯分别作为锂离子电池的导电剂材料、新型锂硫电池导电剂材料、铅酸电池导电剂材料的最新应用     

石墨烯在锂系二次电池中的应用:进展与展望

能源危机和环境污染不断加剧,开发绿色、高效的电化学储能器件迫在眉睫。由于锂具有很高的能量密度,锂系二次电池包括锂离子电池、锂硫电池和锂空电池等得到广泛研究和快速发展;而碳基材料是锂系二次电池重要的电极材料和关键组分。石墨烯是"至柔至薄"的碳基材料,良好的力学、热学、电学性能以及高比表面积和柔性片状的结构特征使其在锂系二次电池中展示出很大的应用潜力;作为其它sp2杂化碳基材料的基本结构单元,石墨烯的出现也为构建高性能的新型碳电极材料提供了契机。评述了不同结构形貌的石墨烯基材料在锂系二次电池中的研究进展,并对目前存在的问题和下一步的工作方向进行了分析与展望。     

碳纳米管纸作集流体在柔性锌锰电池中的应用

研究了晶须状碳纳米管导电纸作为集流极对锌锰电池放电性能的影响。使用晶须状碳纳米管(MWCNTs),通过抽滤法制备出碳纳米管纸,利用扫描电子显微镜(SEM)对碳纳米管导电纸进行表征。碳纳米管导电纸作为柔性锌锰电池集流体,正极极片采用二氧化锰为活性材料,负极采用金属锌为电极,使用计算机控制精密电池测试仪测试其电化学性能。实验表明,柔性锌锰电池具有良好的机械柔性,弯曲状依旧保持电压稳定。与采用石墨为集流体的传统锌锰电池相比,在0.3mA恒流放电的情况下,碳纳米管纸作为集流体,锌锰电池的放电时间增加了64.2%,比容量提高186%,比能量提高172%。碳纳米管纸作为集流体的柔性锌锰电池表现出极佳优越性,并且碳纳米管纸的密度对电池放电性能有着较大的影响。     

碳质材料在锂硫电池中的应用研究进展

随着石墨负极的成功商用,锂离子电池在智能手机、笔记本电脑等便携式电子设备中已得到广泛的应用。经过20多年的发展,现有基于嵌锂化合物正极的锂离子电池已接近其理论容量,但仍不能满足高速发展的电子工业和新兴的电动汽车等行业的要求,寻找具有更高能量密度的电池系统迫在眉睫。锂硫电池系统具有极高的理论能量密度,在多种储能系统中是最具潜力的一种二次电池。但是锂硫电池中也存在硫的电导率极低、多硫化物溶解迁移等问题,使其在走向实用化的过程中遇到许多困难。纳米碳质材料在新型锂硫电池的开发过程中处于重要地位,通过纳米炭的引入,可以获得导电复合正极材料,控制多硫化物的穿梭,从而有望实现正极硫材料的高效利用。综述了基于纳米炭-硫复合正极材料,尤其是碳纳米管、石墨烯、多孔炭以及其杂化物等材料复合的电极,分析其结构与锂硫电池性能的关系,并展望锂硫电池的发展方向。     

锂硫电池柔性正极材料研究进展

随着化石能源的日渐枯竭、能源危机和环境问题的日益突出,开发环境友好的二次电池能源体系迫在眉睫。锂硫电池作为一种新型的储能电池,其理论比容量高达1 675 mAh/g,质量密度可达2 600 Wh/kg,且原材料来源广、成本低等优点,使得其有望代替锂离子电池成为下一代理想的能源电池。近年来,可穿戴电子设备、智能纺织品的出现,对储能电池提出了更高的要求—柔性,因此开发柔性锂硫电池已经成为研究热点。作为锂硫电池的重要组成部分,柔性正极材料的研究和制备对柔性锂硫电池系统的开发至关重要。从锂硫电池柔性正极基体材料入手,对碳材料、导电聚合物材料和新兴的MOF材料等3个方面进行了分类总结,详细阐述了各自制备方法及对柔性正极性能影响。碳材料高的导电性和多孔结构设计、导电聚合物和MOF材料对多硫化物优异的化学吸附作用,均有助于抑制多硫化物的"穿梭效应",提升柔性锂硫电池的长循环电化学稳定性能。最后分析了现有锂硫电池柔性正极材料存在的缺陷与问题,对未来发展方向做出了展望。这将为开发新型的锂硫电池用柔性正极材料提供指导,同时为其它二次电池柔性正极材料开发过程中的共性问题提供实验和理论依据。     

多壁碳纳米管纸作正极集流体的锂硫电池性能

为了改善锂硫电池的循环性能,以纸纤维为基体,多壁碳纳米管(MWCNTs)为导电剂,采用真空抽滤法制得MWCNTs导电纸,并将MWCNTs导电纸作为正极集流体代替铝箔应用于锂硫电池。对MWCNTs导电纸进行了形貌结构表征和电化学性能测试,并对循环后的MWCNTs导电纸电极进行EDS检测。结果显示,MWCNTs均匀地附着在纸纤维基体上,多空隙的MWCNTs导电纸三维结构明显。采用MWCNTs导电纸作集流体的锂硫电池在0.05C和1C倍率充放电下循环30次,比容量分别保持615mAh/g、496mAh/g,库伦效率达97.5%以上,且电荷转移电阻在循环后降低。EDS元素分析结果证实MWCNTs导电纸对多硫化锂有吸附作用,从而一定程度抑制了锂硫电池的穿梭效应。因此,以MWCNTs导电纸作为集流体能有效增加活性物质硫的负载量和接触面积,使锂硫电池具有良好的循环稳定性和库伦效率性能。     

碳纳米管用于锂离子电池负极材料的嵌锂机理研究

研究了将纳米碳管用于锂离子电池负极材料的嵌锂机理,包括纳米碳管的充放电容量、充放电前后碳纳米管的IR光谱、循环伏安曲线和充放电过程中的XRD图谱研究。研究结果表明,纳米碳管具有比较高的放电容量,首次放电比容量为649.4mA·h/g,循环20次后充放电效率仍可达94.1%。IR光谱研究表明纳米碳管的充放电过程中在电极界面存在SEI膜;循环伏安法研究表明碳纳米管负极随着循环次数增加,不可逆容量减少,锂离子的嵌入与脱出更加可逆;XRD分析则说明在充放电过程中d002增大,有越层反应发生。     

锂-硫电池用高体积比容量硫/铁酸镍复合正极材料

锂-硫电池因其较高的理论质量能量密度而广为人知.然而,与以重质过渡金属氧化物作为正极材料的传统锂离子电池相比,锂-硫较低的体积能量密度是其实际应用的瓶颈.此外,硫单质通常与轻质导电碳基底材料复合,以实现其电化学循环稳定性.这使得锂-硫电池实际体积能量密度更低.本文通过静电纺丝方法制备了铁酸镍纳米纤维,并将其用作新型载体...     

Carbon nanotube (CNT)-based composites as electrode material for rechargeable Li-ion batteries: A review

The ever-increasing demands for higher energy density and higher power capacity of Li-ion secondary batteries have led to search for electrode materials whose capacities and performance are better than those available today. Carbon nanotubes (CNTs), because of their unique 1D tubular structure, high electrical and thermal conductivities and extremely large surface area, have been considered as ideal additive materials to improve the electrochemical characteristics of both the anode and cathode of Li-ion batteries with much enhanced energy conversion and storage capacities. Recent development of electrode materials for LIBs has been driven mainly by hybrid nanostructures consisting of Li storage compounds and CNTs. In this paper, recent advances are reviewed of the use of CNTs and the methodologies developed to synthesize CNT-based composites for electrode materials. The physical, transport and electrochemical behaviors of the electrodes made from composites containing CNTs are discussed. The electrochemical performance of LIBs affected by the presence of CNTs in terms of energy and power densities, rate capacity, cyclic life and safety are highlighted in comparison with those without or containing other types of carbonaceous materials. The challenges that remain in using CNTs and CNT-based composites, as well as the prospects for exploiting them in the future are discussed.     

The Regulating Role of Carbon Nanotubes and Graphene in Lithium‐Ion and Lithium–Sulfur Batteries

The ever‐increasing demands for batteries with high energy densities to power the portable electronics with increased power consumption and to advance vehicle electrification and grid energy storage have propelled lithium battery technology to a position of tremendous importance. Carbon nanotubes (CNTs) and graphene, known with many appealing properties, are investigated intensely for improving the performance of lithium‐ion (Li‐ion) and lithium–sulfur (Li–S) batteries. However, a general and objective understanding of their actual role in Li‐ion and Li–S batteries is lacking. It is recognized that CNTs and graphene are not appropriate active lithium storage materials, but are more like a regulator: they do not electrochemically react with lithium ions and electrons, but serve to regulate the lithium storage behavior of a specific electroactive material and increase the range of applications of a lithium battery. First, metrics for the evaluation of lithium batteries are discussed, based on which the regulating role of CNTs and graphene in Li‐ion and Li–S batteries is comprehensively considered from fundamental electrochemical reactions to electrode structure and integral cell design. Finally, perspectives on how CNTs and graphene can further contribute to the development of lithium batteries are presented.     

Li-O2 and Li-S batteries with high energy storage

Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.     

锂离子电池硅/碳纳米管/石墨烯自支撑负极材料研究

通过真空驱动自组装法及蒸汽处理得到结构疏松的硅/碳纳米管/石墨烯自支撑负极材料(Si/CNTs/GP)。纳米硅颗粒(50 nm)为活性物质, 均匀分布在石墨烯片层结构中间; 石墨烯作为碳基体, 通过自组装构筑形成二维导电网络; 碳纳米管(CNTs)具有超高导电性和良好的力学强度, 它通过吸附作用均匀分布在石墨烯基体上形成导电的支撑网络结构。经过蒸汽处理后, 石墨烯层间距明显增大, 层与层之间不再是紧密堆叠的结构, 而是形成一种疏松、褶皱、内部空隙丰富的片层结构。Si/CNTs/GP负极材料中丰富的内部空穴和贯穿孔洞, 提供了材料很高的比表面积, 能有效提高电解液对材料的浸润性, 极大缩短了离子传输距离。同时这些内部空穴也有效缓冲硅充放电时的体积膨胀, 提高了材料的结构稳定性和电化学性能。该负极材料在4 A/g的大电流密度下容量维持在600 mAh/g, 表现出良好的大电流循环稳定性能。     

Laser-induced graphene and carbon nanotubes as conductive carbon-based materials in environmental technology

Nanotechnology and nanomaterials have attracted interest due to their potential in mitigating contemporary environmental challenges, such as the stressors imposed by increased industrial and agricultural activities, and the deterioration of air, soil and water quality. In particular, advanced technologies that harness carbon-based nanomaterials are poised to emerge as tools that provide new solutions for the global water crises. These tools include, electrically conductive membrane processes, which uniquely combine a separation process with a functional surface. In this respect, laser-induced graphene (LIG) and carbon nanotubes (CNTs) are electrically conductive carbon nanomaterials that hold great utility in a multitude of environmental applications, including the development of fouling-resistant systems for desalination and water treatment, enhanced separation methods, and innovative pollutant sensing and electrocatalytic platforms. Consequently, this review article describes and compares some important recent advances in LIG- and CNT-based electroactive surfaces. The discussion of LIG as an emerging carbon material set in context with CNTs is intended to shed light on future directions and development possibilities to meet the growing global challenges in terms of water treatment applications of both materials as well as other electrically conductive carbon-based nanomaterials exhibiting exceptional performance and versatility.     

石墨烯及其纳米复合材料作为锂离子电池负极的研究进展

自2004年被发现以来,石墨烯及其纳米复合材料因其特殊的结构和优异的性能而受到广泛关注,并在锂离子电池负极方面展现出巨大的应用价值.首先简单介绍了石墨烯及其常用制备方法,然后详细介绍了石墨烯及其纳米复合材料作为锂离子电池负极材料的研究现状,并阐述了各自的优势与不足,提出了一些改进方案,最后展望了其在锂电负极的应用前景和未来面临的挑战.     

Electrochemical investigation of TiO2/carbon nanotubes nanocomposite as anode materials for lithium-ion batteries

Mechanically blended composite of nanosized TiO₂ and carbon nanotubes (CNTs) was investigated as potential anode materials for Li-ion batteries. It was found that the TiO₂/CNTs nanocomposite exhibits an improved cycling stability and higher reversible capacity than CNTs. The reversible capacity of the TiO₂/CNTs composite reaches 168 mAh g^− 1 at the first cycle and remains almost constant during long-term cycling. The electrochemical results show that the TiO₂ nanoparticles in the composite not only restrain the formation of surface film, but also make a contribution to the overall reversible capacity.     

Graphene enhances Li storage capacity of porous single-crystalline silicon nanowires

We demonstrated that graphene significantly enhances the reversible capacity of porous silicon nanowires used as the anode in Li-ion batteries. We prepared our experimental nanomaterials, viz., graphene and porous single-crystalline silicon nanowires, respectively, using a liquid-phase graphite exfoliation method and an electroless HF/AgNO3 etching process. The Si porous nanowire/graphene electrode realized a charge capacity of 2470 mAh g(-1) that is much higher than the 1256 mAh g(-1) of porous Si nanowire/C-black electrode and 6.6 times the theoretical capacity of commercial graphite. This relatively high capacity could originate from the favorable charge-transportation characteristics of the combination of graphene with the porous Si 1D nanostructure.     

Organic tailored batteries materials using stable open-shell molecules with degenerate frontier orbitals

Secondary batteries using organic electrode-active materials promise to surpass present Li-ion batteries in terms of safety and resource price. The use of organic polymers for cathode-active materials has already achieved a high voltage and cycle performance comparable to those of Li-ion batteries. It is therefore timely to develop approaches for high-capacity organic materials-based battery applications. Here we demonstrate organic tailored batteries with high capacity by using organic molecules with degenerate molecular orbitals (MOs) as electrode-active materials. Trioxotriangulene (TOT), an organic open-shell molecule, with a singly occupied MO (SOMO) and two degenerate lowest-unoccupied MOs (LUMOs) was investigated. A tri-tert-butylated derivative ((t-Bu)(3)TOT)exhibited a high discharge capacity of more than 300 A h kg(-1), exceeding those delivered by Li-ion batteries. A tribrominated derivative (Br(3)TOT) was also shown to increase the output voltage and cycle performance up to 85% after 100 cycles of the charge-discharge processes.     

Binder-free activated carbon/carbon nanotube paper electrodes for use in supercapacitors

Novel inexpensive, light, flexible, and even rollup or wearable devices are required for multi-functional portable electronics and developing new versatile and flexible electrode materials as alternatives to the materials used in contemporary batteries and supercapacitors is a key challenge. Here, binder-free activated carbon (AC)/carbon nanotube (CNT) paper electrodes for use in advanced supercapacitors have been fabricated based on low-cost, industrial-grade aligned CNTs. By a two-step shearing strategy, aligned CNTs were dispersed into individual long CNTs, and then 90 wt%–99 wt% of AC powder was incorporated into the CNT pulp and the AC/CNT paper electrode was fabricated by deposition on a filter. The specific capacity, rate performance, and power density of the AC/CNT paper electrode were better than the corresponding values for an AC/acetylene black electrode. The capacity reached a maximum value of 267.6 F/g with a CNT loading of 5 wt%, and the energy density and power density were 22.5 W·h/kg and 7.3 kW/kg at a high current density of 20 A/g. The AC/CNT paper electrode also showed a good cycle performance, with 97.5% of the original capacity retained after 5000 cycles at a scan rate of 200 mV/s. This method affords not only a promising paper-like nanocomposite for use in low-cost and flexible supercapacitors, but also a general way of fabricating multi-functional paper-like CNT-based nanocomposites for use in devices such as flexible lithium ion batteries and solar cells.