Metal ion-induced capacitance modulation in near-isostructural complexes-derived electrochromic coordination polymers

Abstract

Coordination polymers and metal–organic frameworks have attracted immense attention across different fields of science as materials with numerous functional applications. Herein, we report the use of coordination polymers obtained from near-isostructural metal (Mn2+, Fe2+, and Co2+) bipyridine complexes as electrode materials in a symmetric supercapacitor test cell. The variation in the central metal ion (Mn2+ vs. Fe2+ vs. Co2+) in these nearly identical coordination complexes was found to dictate the capacitive performance of the coordination polymers obtained via Pd(II) cross-linking. The central metal ion not only influences the porosity, Brunauer–Emmett–Teller (BET) surface area (6.5 (Mn), 10.4 (Fe), and 29.7 (Co) m2/g), and the areal capacitance, but also the performance parameters such as the cycling stability and charge–discharge kinetics as well as the charge transfer mechanism. A 3:4:5 ratio for the areal capacitance values (9.1 (Mn), 12.2 (Fe), and 15.4 (Co) mF cm−2 at a scan rate of 5 mV/s) corroborates the modulative effect of the metal center. The cycling stabilities of these coordination polymers also followed the same order. At higher current densities (<0.50 mA cm−2), the supercapacitors fabricated from the Mn-coordination polymer were found to charge and discharge at faster rates, whereas those fabricated from Fe- or Co-coordination polymers continued to discharge at similar rates, indicating similar pore volumes for the latter as confirmed by BET surface area measurements. Although the materials used in this study resulted in modest capacitive performance, the possibilities to enhance their surface area and crystallinity is envisaged to result in the development of new, multifunctional non-carbon electrode materials with efficient electrochemical storage characteristics and tunable electro-optical properties.