Carbon/carbon supercapacitors

Supercapacitors, or electrochemical capacitors, are a power storage system applied for harvesting energy and delivering pulses during short periods of time. The commercially available technology is based on charging an electrical double-layer (EDL), and using high surface area carbon electrodes in an organic electrolyte. This review first presents the state-of-the-art on EDL capacitors, with the objective to better understand their operating principles and to improve their performance. In particular, it is shown that capacitance might be enhanced for carbons having subnanometric pores where ions of the electrolyte are distorted and partly desolvated. Then, strategies for using environment friendly aqueous electrolytes are presented. In this case, the capacitance can be enhanced through pseudo-faradaic contributions involving i) surface functional groups on carbons, ii) hydrogen electrosorption, and iii) redox reactions at the electrode/electrolyte interface. The most promising system is based on the use of aqueous alkali sulfate as electrolyte allowing voltages as high as 2 V to be reached, due to the high overpotential for di-hydrogen evolution at the negative electrode.     

多孔碳材料的化学气相后处理及其超级电容性能

以廉价的椰壳为原料制备了高比表面积的多孔碳材料,然后在密闭的反应釜中以硝酸蒸汽对多孔碳材料进行了后处理,制备了亲水性更好的多孔碳材料。采用扫描透射电子显微镜(TEM)、物理吸附、X射线粉末衍射(XRD)、拉曼光谱(Raman)和接触角测试对材料的微观形貌、孔道结构、组成和亲水性进行了表征,探究了不同温度下硝酸蒸汽对多孔碳材料的形貌、结构的影响,并采用循环伏安法、恒电流充放电法和交流阻抗法考察了多孔碳材料的超级电容性能。结果表明,经过硝酸蒸汽处理后的多孔碳材料的比表面积和孔体积均有所降低,且随着处理温度的升高,降低得更加明显,而亲水性却越来越好。电化学测试结果表明,经过100℃硝酸蒸汽处理的多孔碳材料(CSC-100)具有最佳的超级电容性能。在以6 mol·L^-1 KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时CSC-100的比电容可达452.9 F·g^-1,而未经硝酸蒸汽处理的多孔碳材料(CSC)的比电容仅为350.4 F·g^-1。电容贡献分析表明CSC-100良好的亲水性和表面官能团不仅提高了双电层电容,也提高了赝电容。     

胶体离子超级电容器的比容量评价

胶体离子超级电容器作为一种新型的超级电容器,其同时具有能量密度和功率密度高的独特优势。 目前已经发展了包括多种过渡金属阳离子和稀土阳离子,例如Mn²⁺、Fe²⁺、Co²⁺、Ni²⁺、Cu²⁺、Sn²⁺、Sn⁴⁺、La³⁺、Ce³⁺、Er³⁺和Yb³⁺的胶体离子超级电容器体系。 在电化学反应中,识别出电活性物质的存在形式对研究电极反应机理和提高比容量具有重要价值。 本文主要通过对电活性物质比容量的探讨,理解这种新型胶体离子超级电容器的电化学储能机理。 评述了胶体离子超级电容器的比容量核算方式,提出了以阳离子为标准核算比容量的原因,并与传统超级电容器的核算方式进行了比较,表明胶体离子超级电容器在提高能量密度方面具有潜在优势,有望突破现有电化学储能设备的技术瓶颈,实现下一代高能量储能器件的开发。     

介孔氧化镍的合成、表征和在电化学电容器中的应用

以十二烷基硫酸钠为模板剂, 采用尿素为沉淀剂, 用均匀沉淀法, 适当控制尿素的水解速度, 制备具有介孔结构的氢氧化镍胶体, 在不同温度下焙烧处理得到孔分布集中的氧化镍介孔分子筛. 结果表明, 在523 K下焙烧得到的氧化镍BET比表面达到477.7 m²•g^－1. 结构表征还显示, 介孔氧化镍的孔壁为多晶结构, 其孔结构形成机理应为准反胶束模板机理. 循环伏安法表明用NiO介孔分子筛制备的电极有很好的电容性能. 与浸渍法和阴极沉淀法制得的NiO相比, 这种介孔结构的NiO能够大量用来制作电化学电容器电极, 并且保持较高的比电容量和良好的电容性能.     

MoS2 Nanoflowers with Expanded Interlayers as High‐Performance Anodes for Sodium‐Ion Batteries

MoS₂ nanoflowers with expanded interlayer spacing of the (002) plane were synthesized and used as high‐performance anode in Na‐ion batteries. By controlling the cut‐off voltage to the range of 0.4–3 V, an intercalation mechanism rather than a conversion reaction is taking place. The MoS₂ nanoflower electrode shows high discharge capacities of 350 mAh g^?1 at 0.05 A g^?1, 300 mAh g^?1 at 1 A g^?1, and 195 mAh g^?1 at 10 A g^?1. An initial capacity increase with cycling is caused by peeling off MoS₂ layers, which produces more active sites for Na⁺ storage. The stripping of MoS₂ layers occurring in charge/discharge cycling contributes to the enhanced kinetics and low energy barrier for the intercalation of Na⁺ ions. The electrochemical reaction is mainly controlled by the capacitive process, which facilitates the high‐rate capability. Therefore, MoS₂ nanoflowers with expanded interlayers hold promise for rechargeable Na‐ion batteries.     

Liquid Crystalline Dispersions of Graphene‐Oxide‐Based Hybrids: A Practical Approach towards the Next Generation of 3D Isotropic Architectures for Energy Storage Applications

We report the use of the spray pyrolysis method to design self‐assembled isotropic ternary architectures made up of reduced graphene oxide (GO), functionalized multiwalled carbon nanotubes, and nickel oxide nanoparticles for cost‐effective high‐performance supercapacitor devices. Electrodes fabricated from this novel ternary system exhibit exceptionally high capacitance (2074 Fg^?1) due to the highly conductive network, synergistic link between GO and carbon nanotubes and achieving high surface area monodispersed NiO decorated rGO/CNTs composite employing the liquid crystallinity of GO dispersions. To further assess the practicality of this material for supercapacitor manufacture, we assembled an asymmetric supercapacitor device incorporating activated carbon as the anode. The asymmetric supercapacitor device showed remarkable capacity retention (>96%), high energy density (23 Wh kg^?1), and a coulombic efficiency of 99.5%.     

介孔碳/石墨烯复合材料的制备及其醌类改性电容性能

首先利用硬模板法制备出介孔碳/石墨烯复合材料,然后向复合材料中引入具有赝电容活性的醌类分子进一步增大材料的电容性能。研究结果表明,负载30%(w/w)叔丁基氢醌的介孔碳/石墨烯复合材料具有最佳的电容性能,在电流密度为0.5 A·g~(-1)时,比电容值为355 F·g~(-1);当电流密度高达30 A·g~(-1)时,其比电容值高达226 F·g~(-1),比电容保持率为64%,表现出良好的速率特性。     

Enhancement of Electrochemical Capacitance of Carbon Nanotubes by Polythionine Modification

Thionine molecules have been electropolymerized onto different types of carbon nanotubes (CNT) using a cyclic voltammetry scanning technology, including multi‐walled carbon nanotubes, single‐walled carbon nanotubes and aligned carbon nanotubes. Results indicate that such prepared nanocomposites have combined the intrinsic faradic capacitance of polythionine with the double layer capacitance of polythionine‐CNT, and thus the polythionine modification obviously enhanced the CNT capacitance. Especially the carboxyl group modified multi‐walled carbon nanotubes, which have made their nanotube tips opened, allowed much more electropolymerization cycles and then obtained a most significant increment in capacitance than the other three ones.     

Flower-like Spherical α-Ni(OH)2 Derived NiP2 as Superior Anode Material of Sodium-Ion Batteries

Transition metal phosphides (TMPs) are promising anode candidates for sodium-ion batteries, due to their high theoretical specific capacity and working potential. However, the low conductivity and excessive volume variation of TMPs during insertion/extraction of sodium ions result in a poor rate performance and long-term cycling stability, largely limiting their practical application. In this paper, NiP₂ nanoparticles encapsulated in three-dimensional graphene (NiP₂@rGO) were obtained from the flower-like spherical α-Ni(OH)₂ by phosphating and carbon encapsulation processes. When used as a sodium-ion batteries anode material, the NiP₂@rGO composite shows an excellent cycling performance (117 mA h g⁻¹ at 10 A g⁻¹ after 8000 cycles). The outstanding electrochemical performance of NiP₂@rGO is ascribed to the synergistic effect of the rGO and NiP₂. The rGO wrapped on the NiP₂ nanoparticles build a conductive way, improving ionic and electronic conductivity. The effective combination of NiP₂ nanoparticles with graphene greatly reduces the aggregation and pulverization of NiP₂ nanoparticles during the discharge/charge process. This study may shed light on the construction of high-performance anode materials for sodium-ion batteries and to other electrode materials.     

介孔碳/石墨烯复合材料的制备及其醌类改性电容性能

首先利用硬模板法制备出介孔碳/石墨烯复合材料,然后向复合材料中引入具有赝电容活性的醌类分子进一步增大材料的电容性能。研究结果表明,负载30%（w/w）叔丁基氢醌的介孔碳/石墨烯复合材料具有最佳的电容性能,在电流密度为0.5 A·g^-1时,比电容值为355 F·g^-1;当电流密度高达30 A·g^-1时,其比电容值高达226 F·g^-1,比电容保持率为64%,表现出良好的速率特性。