Mondal Sanjoy, Yoshida Takefumi, Maji Subrata, Ariga Katsuhiko, Higuchi Masayoshi
Electronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Japan.
World Premier International Research Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Japan.
ACS Appl Mater Interfaces. 2020 Apr 8;12(14):16342-16349. doi: 10.1021/acsami.9b23123. Epub 2020 Mar 27.
The use of metallo-supramolecular polymer (MSP) as a thin-film-based redox supercapacitor electrode material is reported for the first time. Fe(II)- and Ru(II)-based MSPs (polyFe and polyRu, respectively) were synthesized by complexation of appropriate metal salts with 4',4″-(1,4-phenylene)bis-2,2':6',2″-terpyridine, and thin films of these polymers were prepared by spray coating onto an indium tin oxide glass substrate. A study of the energy storage performances of the polyFe and polyRu films in a nonaqueous electrolyte system revealed volumetric capacitances of ∼62.6 ± 3 F/cm for polyFe and 98.5 ± 7 F/cm for polyRu at a current density of 2 A/cm. To improve the energy storage performance over a wider potential range, asymmetric supercapacitor (ASC) displays were fabricated with suitable combinations of the MSPs as cathodic materials and Prussian blue as the anodic counter material in a sandwich configuration with a transparent polymeric ion gel as the electrolyte. The fabricated ASCs showed a maximum volumetric energy density (∼10-18 mW h/cm) that was higher than that of lithium thin-film batteries and a power density (7 W/cm) comparable to that of conventional electrolyte capacitors, with superb cyclic stability for 10 000 cycles. To demonstrate the practical use of the MSP, the illumination of a light-emitting diode bulb was powered by a laboratory-made device. This work should inspire the development of high-performance thin-film flexible supercapacitors based on MSPs as active cathodic materials.
首次报道了将金属超分子聚合物(MSP)用作基于薄膜的氧化还原超级电容器电极材料。通过将适当的金属盐与4',4″-(1,4-亚苯基)双-2,2':6',2″-三联吡啶络合,合成了基于Fe(II)和Ru(II)的MSP(分别为聚铁和聚钌),并通过喷涂在氧化铟锡玻璃基板上制备了这些聚合物的薄膜。对聚铁和聚钌薄膜在非水电解质系统中的储能性能研究表明,在电流密度为2 A/cm时,聚铁的体积电容约为62.6±3 F/cm³,聚钌的体积电容为98.5±7 F/cm³。为了在更宽的电位范围内提高储能性能,采用合适的MSP组合作为阴极材料,普鲁士蓝作为阳极对电极材料,以透明聚合物离子凝胶作为电解质,制成三明治结构的不对称超级电容器(ASC)。所制备的ASC显示出最大体积能量密度(约10-18 mW h/cm³)高于锂薄膜电池,功率密度(7 W/cm)与传统电解质电容器相当,具有出色的10000次循环稳定性。为了证明MSP的实际应用,用实验室自制的装置为发光二极管灯泡供电。这项工作将激发基于MSP作为活性阴极材料的高性能薄膜柔性超级电容器的发展。