Improving the performance of all-solid-state supercapacitors by modifying ionic liquid gel electrolytes with graphene nanosheets prepared by arc-discharge

Ionic liquid gel polymers have widely been used as the electrolytes in all-solid-state supercapacitors, but they suffer from low ionic conductivity and poor electrochemical performance. Arc discharge is a fast, low-cost and scalable method to prepare multi-layered graphene nanosheets, and as-made graphene nanosheets （denoted as ad-GNSs） with few defects, high electrical conductivity and high thermal stability should be favorable conductive additive materials. Here, a novel ionic liquid gel polymer electrolyte based on an ionic liquid （EM1MNTF2） and an copolymer （P（VDF-HFP）） was modified by the addition of ad-GNSs as an ionic conducting promoter. This modified gel electrolyte shows excellent thermal stability up to 400 ℃ and a wide electrochemical window of 3 V. An all-solid-state supercapacitor based on commercial activated carbon was fabricated using this modified ionic liquid gel polymer electrolyte, which shows obviously improved electrochemical behaviors compared with those of the corresponding all-solid-state supercapacitor using pure ionic liquid gel polymer electrolyte. Specially, smaller internal resistance, higher specific capacitance, better rate performance and cycling stability are achieved. These results indicate that the ionic liquid gel polymers modified by ad-GNSs would be promising and suitable gel electrolytes for high performance all-solid-state electrochemical devices.     

胶体离子超级电容器

超级电容器具有功率密度大、循环寿命长等优点,但同时面临着能量密度低等缺点. 胶体离子超级电容器是最近开发的一种新型赝电容器,同时具有高功率密度和高能量密度的特点. 胶体离子超级电容器能够充分利用多价态金属阳离子的多电子氧化还原反应,完全释放储存的潜在电能,从而提高超级电容器的能量密度. 由于胶体离子的存在,缩短了电子、离子的扩散长度,加快了氧化还原反应动力学,从而保持高的功率密度. 本文主要介绍胶体离子超级电容器的发展过程、最新研究进展以及需要进一步开展的研究工作,作者希望从一个新的角度去研究发展下一代高性能电化学储能设备,实现新的突破.     

二氧化锰含量对活性炭电极电化学性能的影响

本文采用液相法、热分解MnCO₃法以及电解沉积法制备不同二氧化锰粉末,并将其与活性炭复合,应用于水系超级电容器. 使用X射线衍射（XRD）、扫描电子显微镜（SEM）技术对材料形貌进行表征. 使用循环伏安法以及恒流充放电法对其电化学性能进行测试. 实验数据表明,α-MnO₂（质量分数70%）掺杂活性炭电极的最大比容量为151 F•g^-1,β-MnO₂（质量分数60%）掺杂活性炭电极的最大比容量为172F•g^-1,γ-MnO₂（质量分数50%）掺杂活性炭电极的最大比容量为141F•g^-1,但二氧化锰粉末对电极内阻的影响呈无规律性.     

锂离子电容器(LIC)产业前沿技术研究进展

新能源战略体系的建设和电子技术的飞速发展对储能器件的性能提出了更高的要求,锂离子电容器是将锂离子电池和双电层电容器“内部交叉”的新型混合储能器件,兼具高能量密度和高功率密度,近年来引起了国内外的广泛关注.本文阐述了锂离子电容器的工作原理和国内外产业发展现状,总结了碳负极的预赋锂技术、电极材料与体系匹配性研究等关键技术前沿的研究成果,并提出了后续产业化研究中所需要解决的实际问题.     

A hierarchical porous carbon membrane from polyacrylonitrile/polyvinylpyrrolidone blending membranes:Preparation,characterization and electrochemical capacitive performance

Novel hierarchical porous carbon membranes were fabricated through a simple carbonization procedure of well-defined blending polymer membrane precursors containing the source of carbon polyacrylonitrile （PAN） and an additive of polyvinylpyrrolidone （PVP）, which was prepared using phase inversion method. The as-fabricated materials were further used as the active electrode materials for supercapacitors. The effects of PVP concentration in the casting solution on structure feature and electrochemical capacitive performance of the as-prepared carbon membranes were also studied in detail. As the electrode material for supercapacitor, a high specific capacitance of 278.0 F/g could be attained at a current of 5 mA/cm2 and about 92.90% capacity retention could be maintained after 2000 charge/discharge cycles in 2 mol/L KOH solution with a PVP concentration of 0.3 wt% in the casting solution. The facile hierarchical pore structure preparation method and the good electrochemical capacitive performance make the prepared carbon membrane particularly promising for use in supercapacitor.     

钠离子电池负极材料

钠离子电池具有钠资源丰富和成本低廉等特点,吸引了国内外研究者的广泛关注,被认为是今后在规模储能领域可能替代锂离子电池的最佳候选。近几年钠离子电池的研究相继取得了重要进展,研究体系不断丰富。本文对钠离子电池负极材料的研究现状进行了详细的综述,重点介绍了碳基材料、合金材料、非金属单质、金属氧化物以及有机化合物等嵌钠性能及可能的嵌钠机理。探讨了这些材料目前所面临的主要问题及可能的解决策略,并对钠离子电池今后的研究方向和应用前景进行了展望。     

有序中孔炭的制备及电性能研究

采用微湿含浸法制备了一系列具有不同比表面积和孔径分布的超级电容器有序中孔炭材料,同时采用Al-SBA-15为模板剂制得具有六方排列的空心炭管CMK-5.所制得的有序中孔炭的BET比表面积随糠醇加入量的增加而减小.电化学性能测试结果表明,在1mA·cm-2的充放电电流密度下各中孔炭材料比电容的大小顺序与其BET比表面积的大小顺序相一致.在所有样品中AlSC-0.8由于具有最大的比表面积,因此其比电容最大,达87.8F·g-1.倍率性能测试结果表明,具有CMK-3结构的SC-2.0的倍率性能最好,在50mA·cm-2的放电电流密度下其放电比电容接近AlSC-0.8有序中孔炭的水平.     

喷雾干燥-高温烧结的NaMnPO4制备及其电化学性能

采用喷雾干燥制备前驱体,经高温烧结制得有电化学活性的钠离子电池NaMnPO₄正极材料. X射线衍射分析（XRD）证明,合成的NaMnPO₄材料系正交晶系、Pmnb空间群的磷钠锰矿（Natrophilite）型材料. 扫描电镜（SEM）及透射电镜（TEM）结果显示,喷雾干燥得到的前驱体为空心球粒子,经高温烧结后,该材料由粒径几十纳米的NaMnPO₄纳米晶一次颗粒及无定形碳网络结构相互连接组成的微米级二次颗粒构成. 电化学测试表明,NaMnPO₄/C复合结构显著改善了材料的离子电导与电子电导,首次报道电流密度为7.75 mA·g^-1、电压范围为1.0 ~ 4.5 V (vs. Na⁺/Na)时,钠离子电池NaMnPO₄正极材料的可逆放电比容量达90 mAh·g^-1.     

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.     

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。