2D Conductive Metal-Organic Frameworks Based on Tetraoxa[8]circulenes as Promising Cathode for Aqueous Zinc Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) are the new generation electrochemical energy storage systems. Recently, two-dimensional conductive metal-organic frameworks (2D c-MOFs) are attractive to serve as cathode materials of ZIBs due to their compositional diversity, abundant active sites, and excellent conductivity. Despite the growing interest in 2D c-MOFs, their application prospects are still to be explored. Herein, a tetraoxa[8]circulene (TOC) derivative with unique electronic structure and interesting redox-active property are synthesized to construct c-MOFs. A series of novel 2D c-MOFs (Cu-TOC, Zn-TOC and Mn-TOC) with different conductivities and packing modes are obtained by combining the linker tetraoxa[8]circulenes-2,3,5,6,8,9,11,12-octaol (8OH-TOC) and corresponding metal ions. Three c-MOFs all exhibit typical semiconducting properties, and Cu-TOC exhibits the highest electrical conductivity of 0.2 S cm-1 among them. Furthermore, their electrochemical performance as cathode materials for ZIBs have been investigated. They all performed high reversible capacity, decent cycle stability and excellent rate capability. This work reveals the key insights into the electrochemical application potential of 2D c-MOFs and advances their development as cathode materials in ZIBs.

The Increasing Number of Electron Reservoirs in Nonporous, High-Conducting Coordination Polymers Cux BHT (x = 3, 4, and 5, BHT = Benzenehexathiol) for Improved Faradaic Capacitance.

Although asymmetric supercapacitors (ASCs) can achieve high energy density, the lifespan and power density are severely suppressed due to the low conductivity of using pseudocapacitive or battery-type electrode materials. Recently, nonporous conductive coordination polymers (c-CPs) have sparked interests in supercapacitors. However, their performance is expected to be limited by the nonporous features, low specific surface area and absence of ion-diffusion channels. Here, it is demonstrated that the capacity of nonporous CPs will be significantly enhanced by maximizing the number of faradaic redox sites in their structures through a comparative investigation on three highly conductive nonporous c-CPs, Cux BHT(x = 3, 4, 5.5). They show excellent capacitance of 312.1 F g-1 (374.5 C g-1 ) (Cu3 BHT), 186.7 F g-1 (224.0 C g-1 ) (Cu4 BHT) and 89.2 F g-1 (107.0 C g-1 ) (Cu5.5 BHT) at 0.5 A g-1 in a sequence related to the number of electron storage units in structures and outstanding rate performance and cycle stability. Furthermore, the constructed Cu3 BHT//MnO2 ASC device exhibits capacity retention of 92% (after 1500 cycles at 3 A g-1 ) and delivers a high energy density of 39.1 Wh kg-1 at power density of 549.6 W kg-1 within a large working potential window of 0-2.2 V.