提高电容性电化学储能装置能量容量的一些尝试

本文从作者所在的课题组在超级电容器和超级电容电池方向的研究内容为基础,在电极材料和装置层面综述了电容性电化学储能装置的发展. 导电聚合物和过渡金属氧化物分别与碳纳米管复合后的复合物能显著提高前两者作为电容性法拉第储能电极的电容性能. 活性炭和碳黑等一类碳材料则可作为非法拉第储能的电极材料. 通过对超级电容器正负极电容做相应的匹配调整可以提高超级电容器的最大充电电压,从而提高超级电容器的能量容量. 此外,为了与实际设备相匹配,超级电容可以以双极板的方式串联堆积,满足高电压的需求. 超级电容电池作为新一代的电容性电化学储能装置,分别由具有电容性和法拉第电荷储存原理的电极组成,具有高比功率和高比能量的特点,也是近年来的研究热点.     

高能量密度的锂离子混合型电容器

锂离子混合型电容器兼有锂离子电池和超级电容器的优点,在电化学储能领域具有广泛的应用前景. 但其产业化仍存在一系列的基础及工艺方面的问题,具体包括器件结构设计、电极材料筛选、预嵌锂工艺和电解液与电极的界面等. 本文结合作者课题组的研究工作介绍了近年来高能量密度的锂离子混合型电容器的研究进展,内容涉及锂离子电容器正/负极材料的筛选、预嵌锂工艺的优化、内并联结构的锂离子电池型超级电容器复合正极组成材料的调控、隔膜的选择、电解液的组成、以及器件的高/低温性能,分析了锂离子电容器的容量衰减机制,探讨了锂离子电池型超级电容器的储能机制,提出了未来对高能量密度的锂离子混合型电容器研究的展望.     

Overview on conducting polymer in energy storage and energy conversion system

Polymer-based electrochemical devices such as supercapacitor, battery, and fuel cell have been developed and advanced for energy related application. In this regard, conducting polymers own several tunable characteristics for energy conversion and energy storage relevance. Consequently, efficient, reliable, low cost, conducting, stable, and environment friendly energy systems have been developed using conducting polymers. To enhance the efficiency and commercialization of energy systems, design, structure, composition, and fabrication technique used for conducting polymers and related composite have been focused. Challenges and future trend associated with current state of the art conducting polymer materials in supercapacitor, battery, and fuel cell are highlighted.     

Self-Standing Hydrogels Composed of Conducting Polymers for All-Hydrogel-State Supercapacitors

Conducting polymer hydrogels that are capable of contacting with electrolytes at the molecular level, represent an important electrode material. However, the fabrication of self-standing hydrogels merely composed of conducting polymers is still challenging owing to the absence of reliable methods. Herein, a novel and facile macromolecular interaction assisted route is reported to fabricate self-standing hydrogels consisting of polyaniline (PANi: providing high electrochemical activity) and poly(3,4-ethylenedioxythiophene) (PEDOT: enabling high electronic conductivity). Owing to the synergistic effect between them, the self-standing hydrogels possess good mechanical properties and electronic/electrochemical performances, making them an excellent potential electrode for solid-state energy storage devices. A proof-of-concept all-hydrogel-state supercapacitor is fabricated, which exhibits a high areal capacitance of 808.2 mF cm⁻², and a high energy density of 0.63 mWh cm⁻³ at high power density of 28.42 mW cm⁻³, superior to many recently reported conducting polymer hydrogels based supercapacitors. This study demonstrates a novel promising strategy to fabricate self-standing conducting polymer hydrogels.     

Design and synthesis of ternary composite of polyaniline-sulfonated graphene oxide-TiO<Subscript>2</Subscript> nanorods: a highly stable electrode material for supercapacitor

Supercapacitor is an important energy storage device. Nature of electrode material plays an important role in the performance of supercapacitor. Carbon, metal oxide, and conducting polymer-based materials are being used as electrode materials. Each type of material has its own advantages and disadvantages. To improve the energy density and cycle life performance of conducting polymer, in this work, metal oxide (TiO₂) and carbon (sulfonated graphene oxide) materials were incorporated on to polyaniline. Presence of polyaniline, titanium dioxide, and sulfonated graphene oxide in the composite material was supported by Fourier transform infrared, XRD, FE-SEM, and EDAX techniques. Composite material of nanorods with sphere morphology in excellent yield and reasonably good conductivity was obtained. Electrochemical performances of the composite material were carried by cyclic voltammetry, charge-discharge, and impedance measurements. Composite material showed much better performances than that of its individual components in terms of specific capacitance, energy density, power density, and cycle life.     

基于碳材料的超级电容器电极材料的研究

超级电容器作为一种新型的能源存储装置,因为其比容量大、充放电速度快、循环寿命长等优点,在储能领域引起了极为广泛的关注。电极材料是决定超级电容器性能的核心因素,其中,常用的超级电容器电极材料主要有如下三类:碳基材料、金属氧化物及氢氧化物材料和导电聚合物材料。本文综述了超级电容器的工作原理并详细介绍了基于碳材料及其二元、三元复合体系的电极材料的研究进展。     

氧化钌/活性炭超电容器复合电极的电化学行为

电化学超电容器作为一种新一代储能系统具有广泛的应用领域. 直流充放电、循环伏安以及交流阻抗等实验显示了本文制备的活性碳材料以及复合电极材料具有良好的电化学性能.活性碳材料的质量比容量为172 F•g－1,采用无定形RuO2与上述活性碳复合制成的新型电极材料具有359 F•g－1以上的比容量和良好的功率特性，并对上述材料的双电层电容和法拉第准电容等电化学特性进行了详细的讨论.     

Recent advances in the synthesis of non-carbon two-dimensional electrode materials for the aqueous electrolyte-based supercapacitors

Supercapacitors (SCs) with high power density and long cycling span life are demanding energy storage devices that will be an attractive power solution to modern electronic and electrical applications. Numerous theoretical and experimental works have been devoted to exploring various possibilities to increase the functionality and the specific capacitance of electrodes for SCs. Non-carbon two-dimensional (2D) materials have been considered as encouraging electrode candidates for their chemical and physical advantages such as tunable surface chemistry, high electronic conductivity, large mechanical strength, more active sites, and dual non-faradaic and faradaic electrochemical performances. Besides, these 2D materials also play particular roles in constructing highway channels for fast ion diffusion. This concise review summarizes cutting-edge progress of some representative 2D non-carbon materials for the aqueous electrolyte-based SCs, including transition metal oxides (TMOs), transition metal hydroxides (TMHs), transition metal chalcogenides (TMCs), MXenes, metal-organic frameworks (MOFs) and some emerging materials. Different synthetic methods, effective structural designs and corresponding electrochemical performances are reviewed in detail. And we finally present a detailed discussion of the current intractable challenges and technical bottlenecks, and highlight future directions and opportunities for the development of next-generation high-performance energy storage devices.     

Research progress on transition metal oxide based electrode materials for asymmetric hybrid capacitors

In the past few years, the increasing energy consumption of traditional fossil fuels has posed a huge threat to human health. It is very imperious to develop the sustainable and renewable energy storage and conversion devices with low cost and environment friendly features. Hybrid supercapacitors are emerging as one of the promising energy devices with high power density, fast charge-discharge process and excellent cycle stability. However, morphology and structure of the electrode materials exert serious effect on their electrochemical performances. In this review, we summarized recent progresses in transition metal oxide based electrode materials for supercapacitors. Different synthesis routes and electrochemical performances of electrode materials and storage mechanisms of supercapacitor devices have been presented in details. The future developing trends of supercapacitor based on metal oxide electrode materials are also proposed.     

Flexible Polyester Cellulose Paper Supercapacitor with a Gel Electrolyte

A low-cost polyester cellulose paper has been used as a substrate for a flexible supercapacitor device that contains aqueous carbon nanotube ink as the electrodes and a polyvinyl alcohol (PVA)-based gel as the electrolyte. Gel electrolytes have attracted much interest due to their solvent-holding capacity and good film-forming capability. The electrodes are characterized for their conductivity and morphology. Because of its high conductivity, the conductive paper is studied in supercapacitor applications as active electrodes and as separators after coating with polyvinylidene fluoride. Carbon nanotubes deposited on porous paper are more accessible to ions in the electrolyte than those on flat substrates, which results in higher power density. A simple fabrication process is achieved and paper supercapacitors are tested for their performance in both aqueous and PVA gel electrolytes by using galvanostatic and cyclic voltammetry methods. A high specific capacitance of 270 F g⁻¹ and an energy density value of 37 W h kg⁻¹ are achieved for devices with PVA gel electrolytes. Furthermore, this device can maintain excellent specific capacitance even under high currents. This is also confirmed by another counter experiment with aqueous sulfuric acid as the electrolyte. The cycle life, one of the most critical parameters in supercapacitor operations, is found to be excellent (6000 cycles) and less than 0.5 % capacitance loss is observed. Moreover, the supercapacitor device is flexible and even after twisting does not show any cracks or evidence of breakage, and shows almost the same specific capacitance of 267 F g⁻¹and energy density of 37 W h kg⁻¹. This work suggests that a paper substrate can be a highly scalable and low-cost solution for high-performance supercapacitors.     

A phosphorus integrated strategy for supercapacitor: 2D black phosphorus–doped and phosphorus-doped materials

In the design and development of energy storage devices, two main factors are considered first high electrochemical performances and second low-cost materials. Phosphorus owns excellent properties such as high carrier mobility, tunable bandgap, anisotropic electronic properties, hydrophilicity, biocompatibility, good electrochemical activity, and high surface area. The interlayer distance of black phosphorus (BP) (0.55 nm) is higher than that of graphene which makes facile ion transportation for supercapacitor application. The phosphorus-based electrode obtained with top-down approaches such as exfoliation and bottom-up approach such as pulsed laser deposition. The BP has been investigated due to its small electronegativity of P which is beneficial to improve the electrical conductivity of the electrode and its abundance nature makes it a desirable candidate for the fabrication of low-cost device. Hence, this review covers the new BP material as the advanced materials for the commercial realization of advanced supercapacitors. This is the first review on phosphorus integrated supercapacitor devices. This review will give a brief idea about BP to researchers in search of outstanding supercapacitor configurations with different electrodes and electrolytes.     

Post-synthetic Modification of Covalent Organic Frameworks through in situ Polymerization of Aniline for Enhanced Capacitive Energy Storage

Covalent organic frameworks (COFs) having layered architecture with open nanochannels and high specific surface area are promising candidates for energy storage. However, the low electrical conductivity of two-dimensional COFs often limits their scope in energy storage applications. The conductivity of COFs can be enhanced through post-synthetic modification with conducting polymers. Herein, we developed polyaniline (PANI) modified triazine-based COFs via in situ polymerization of aniline within the porous frameworks. The composite materials showed high conductivity of 1.4–1.9×10⁻² S cm⁻¹ at room temperature with a 20-fold enhancement of the specific capacitance than the pristine frameworks. The fabricated supercapacitor exhibited a high energy density of 24.4 W h kg⁻¹ and a power density of 200 W kg⁻¹ at 0.5 A g⁻¹ current density. Moreover, the device fabricated using the conducting polymer-triazine COF composite could light up a green light-emitting diode for 1 min after being charged for 10 s.     

炭-/石墨烯量子点在超级电容器中的应用

炭-/石墨烯量子点作为新兴的炭纳米材料,因具有独特的小尺寸效应和丰富的边缘活性位点而在高性能超级电容器电极材料的研发方面展现出巨大潜力。针对目前炭-/石墨烯量子点在超级电容器电极材料方面的应用优势和存在的关键问题,本文以炭-/石墨烯量子点、量子点/导电炭复合材料、量子点/金属氧化物复合材料、量子点/导电聚合物复合材料以及量子点衍生炭这些电极材料为脉络,梳理了近年来该领域的发展状况,尝试阐释炭-/石墨烯量子点在电极材料、复合材料和衍生炭电极材料中所起到的关键作用,最后对炭-/石墨烯量子点电极材料的发展进行了展望。本综述以期为炭-/石墨烯量子点基电极材料的研究提供一定参考和依据。     

An overview on the recent developments in polyaniline‐based supercapacitors

With the ever‐increasing depletion of nonrenewable fossil fuel reserve, greater attention has been directed towards renewable energy storage devices. One of the most important of such devices is the supercapacitor, which exhibits high specific capacitance. Polyaniline (PAni) is a versatile conducting polymer, which has demonstrated excellent electrochemical properties along with good stability and ease of synthesis. Therefore, PAni has been extensively used in the fabrication of supercapacitors. In the last few decades, researchers have studied the effect of morphology, developed during the synthesis of PAni, on its electrochemical properties. It is known that the electrical conductivity and the electrochemical properties of PAni get influenced by the level and type of dopant used, the method of synthesis adopted, and the surface area and porosity possessed. However, it has been realized that supercapacitors based on PAni suffer from short cycle life. This led to development of PAni composites with carbon‐based materials and transition metal oxides. In this review, focus has been laid on the achieved performance levels of the recently developed PAni‐based supercapacitors. In addition, an attempt has been made to study the fundamental aspects of the conductivity and the electrochemical properties of PAni and their effect on the supercapacitor performance. Moreover, several new interesting applications of PAni‐based supercapacitors have also been included in this review.     

基于NiCo2O4纳米片电极的非对称混合电容器

The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo₂O₄) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo₂O₄ nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo₂O₄ products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo₂O₄ electrode materials were studied and the area capacitance was found to be 1.26 C·cm^-2 at a current density of 1 mA·cm^-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm^-2) were achieved. It was found that the Ni foam supporting the NiCo₂O₄ nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo₂O₄ nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm^-3 at 1.56 and 4.5 W·cm^-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo₂O₄ nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems.     

《超级电容器》专辑序言

超级电容器因具有高功率密度、长循环寿命和使用温度范围宽等显著优势,已成为化学电源产业内新的亮点。作为一种大功率储能器件,超级电容器在轨道交通、现代通讯、航空航天、国防等战略新兴领域具有广泛的应用前景,全球需求量迅速增长。目前,限制超级电容器规模应用的关键问题是其能量密度偏低以及成本过高。如何在保证其高功率密度和长循环寿命优势的前提下,提高超级电容器能量密度并降低其成本是当今研究的热点。近年来,全球的超级电容器研究者针对这一关键问题,从电极材料设计、新型电解液开发及器件构筑等方面开展了一系列的工作,从理论研究到工程应用都取得了重要的突破。本刊邀请了超级电容器领域内具有丰富研究经验的8个团队撰写了8篇关于超级电容器的综述或者研究论文,介绍了当前超级电容器领域的研究现状、发展趋势和所面临的挑战,希望籍此能使广大读者更加深入了解超级电容器这一领域,并共同推动我国超级电容器相关研究的进一步发展。在此,对本专辑的所有作者、审稿人及编辑部工作人员的卓有成效的工作和付出表示衷心的感谢！     

Highly flexible pseudocapacitor based on freestanding heterogeneous MnO2/conductive polymer nanowire arrays

Flexible electronics such as wearable electronic clothing, paper-like electronic devices, and flexible biomedical diagnostic devices are expected to be commercialized in the near future. Flexible energy storage will be needed to power these devices. Supercapacitor devices based on freestanding nanowire arrays are promising high power sources for these flexible electronics. Electrodes for these supercapacitor devices consisting of heterogeneous coaxial nanowires of poly (3,4-ethylenedioxythiophene) (PEDOT)-shell and MnO(2)-core materials have been shown in a half cell system to have improved capacitance and rate capabilities when compared to their pure nanomaterials; however, their performance in a full cell system has not been fully investigated. Herein, these coaxial nanowires are tested in both a symmetric and an asymmetric (utilizing a PEDOT nanowire anode) full cell configuration in the aspect of charge storage, charge rate, and flexibility without using any carbon additives and polymer binders. It is found that the asymmetric cell outperforms the symmetric cell in terms of energy density, rate capability, and cycle ability. The asymmetric device's electrode materials display an energy density of 9.8 Wh/kg even at a high power density of 850 W kg(-1). This device is highly flexible and shows fast charging and discharging while still maintaining 86% of its energy density even under a highly flexed state. The total device is shown to have a total capacitance of 0.26 F at a maximum voltage of 1.7 V, which is capable of providing enough energy to power small portable devices.     

High Energy Density Supercapacitors: An Overview of Efficient Electrode Materials,Electrolytes, Design,and Fabrication

Supercapacitors (SCs) are potentially trustworthy energy storage devices, therefore getting huge attention from researchers. However, due to limited capacitance and low energy density, there is still scope for improvement. The race to develop novel methods for enhancing their electrochemical characteristics is still going strong, where the goal of improving their energy density to match that of batteries by increasing their specific capacitance and raising their working voltage while maintaining high power capability and cutting the cost of production. In this light, this paper offers a succinct summary of current developments and fresh insights into the construction of SCs with high energy density which might help new researchers in the field of supercapacitor research. From electrolytes, electrodes, and device modification perspectives, novel applicable methodologies were emphasized and explored. When compared to conventional SCs, the special combination of electrode material/composites and electrolytes along with their fabrication design considerably enhances the electrochemical performance and energy density of the SCs. Emphasis is placed on the dynamic and mechanical variables connected to SCs′ energy storage process. To point the way toward a positive future for the design of high-energy SCs, the potential and difficulties are finally highlighted. Further, we explore a few important topics for enhancing the energy densities of supercapacitors, as well as some links between major impacting factors. The review also covers the obstacles and prospects in this fascinating subject. This gives a fundamental understanding of supercapacitors as well as a crucial design principle for the next generation of improved supercapacitors being developed for commercial and consumer use.     

A high performance solid-state asymmetric supercapacitor based on Anderson-type polyoxometalate-doped graphene aerogel

The manufacture of single-atom transition metal-doping carbon nanocomposites as electrode materials is crucial for electrochemical energy storage with high energy and power density. However, the simple strategy for preparation of such active materials with controlled structure remains a great challenge. Here, cobalt-doped carbon nanocomposites (Co-POM/rGO) were synthesized successfully by deposition of Anderson-type polyoxometalate (POM) on the surface of reduced graphene oxide (rGO) aerogel via one-pot hydrothermal treatment. The resulting Co-POM/rGO possesses three-dimensional graphene-based frameworks with hierarchical porous structure, high surface area and uniform single-atom metal doping. These intriguing features render Co-POM/rGO to be a promising electrode for applications in electrochemical energy storage. As an electrode material of a supercapacitor, Co-POM/rGO shows high-performance electrochemical energy storage (211.3 F g^?1 at 0.5 A g^?1). Furthermore, the solid-state asymmetric supercapacitor (ASC) device, using Co-POM/rGO as a positive electrode, exhibits the outstanding energy density of 37.6 Wh kg^?1 at a power density of 500 W kg^?1, and high capacitance retention of 95.2% after 5000 charge–discharge cycles. These results indicate that the proposed strategy for rational design of single-atom-metal doped carbon nanocomposites for flexible ASC devices with excellent capacitive properties.

     

二氧化锰与二维材料复合应用于超级电容器

现如今世界正面临着与能源相关的一系列问题与挑战,科学家们致力于研究绿色高性能的能量存储器件以适应当前乃至以后长久可持续创新发展的需要。超级电容器作为一种新型的绿色能源储存装置,具有功率密度大、理论比电容高、充放电速度快、循环寿命长、安全性高、环境友好且经济等优点,为人类解决能源危机提出了可能。电极材料是影响超级电容器性能的重要因素。近些年,由于二氧化锰基超级电容器具有理论比电容高、化学稳定性好、环境友好等特点被广泛研究。同时多种二维材料也继石墨烯后被相继用作超级电容器电极材料,具有二维结构特征材料在提高双电层电容器的能量密度、改善赝电容电容器方面发挥着重要作用。实现高比电容和高倍率性能,将二氧化锰与二维材料复合将不失为一个有前景的选择。本文系统介绍了以石墨烯为代表的各类二维材料与二氧化锰复合物在超级电容器中的应用研究,并聚焦于这些二维材料与二氧化锰复合后所展现的优异电化学性能。