Transition-Metal-Triggered High-Efficiency Lithium Ion Storage via Coordination Interactions with Redox-Active...

Coordination polymers (CPs) have powerful competence as anode materials for lithium-ion batteries (LIBs) owing to their structural diversity, tunable functionality, and facile and mild synthetic conditions. Here, we show that two isostructural one-dimensional croconate-based CPs, namely, [M(C₅O₅)(H₂O)₃]_n (M = Mn for 1 and Co for 2; C₅O₅^2- = croconate dianion), can work as high-performance electrode materials for rechargeable LIBs. By means of the coordination between the redox-active transition metal ion and the ligand, the anode materials were stable in the electrolyte and showed high capacities, impressive rate capabilities, and excellent cycling performance during the discharging/charging processes. The chain-based supramolecular structures of the CPs also make them stand out from a crowd of porous three-dimensional molecular materials due to their free channels between the chains for lithium ion diffusion. When tested in a voltage window of 0.01-2.4 V at 100 mA g^-1, CPs 1 and 2 demonstrated high discharge specific capacities of 729 and 741 mA h g^-1, respectively. The synergistical redox reactions on both metal centers and the organic moieties play a crucial role in the high electrochemical performance of CPs 1 and 2. After undergoing elevated discharging/charging rates to 2 A g^-1, the electrodes could finally recover their capabilities as those in the initial stage when the current rate was back to 100 mA g^-1, indicating excellent rate performance and outstanding cycling stabilities of the materials.