Boosting the Lithium-Ion Transport Kinetics of Sn-Based Coordination Polymers through Ligand Aromaticity Manipulation

Tin-based compounds are promising anode materials for lithium-ion batteries owing to their low charge/discharge voltage and high theoretical capacity but are plagued by both huge volume expansion during cycling and complex synthetic procedures. Constructing a coordination network between Sn and the lithium-active organic matrix can effectively relieve the volume expansion and increase the lithium storage active site utilization. Herein, we report a facile method to prepare two one-dimensional Sn-based coordination polymers [Sn(Hcta)](n) (1) and [Sn(Hbtc)](n) (2) (H(3)cta = 1,3,5-cyclohexanetricarboxylic acid, H(3)btc = 1,3,5-benzenetricarboxylic acid) for lithium storage, which differ only in the aromaticity of the ligand. 2 with an aromatic ligand provided a reversible capacity of 833 mAh g(-1) at 200 mA g(-1) over 160 cycles, higher than that of 1 without an aromatic ligand due to the quick charge transfer. The reversible lithium storage reactions of metal centers and organic ligands and the volume expansion rate of Sn-based coordination polymers during cycling were studied by detailed characterization and density functional theory (DFT) calculations. This research revealed that the structural factor of ligand aromaticity in these Sn-based coordination polymers boosted the utilization of active sites and rapid charge transfer, offering a coordination chemistry strategy for the design and synthesis of advanced anode materials.

Automated summary

Tin-based coordination polymers with aromatic ligands showed enhanced reversible capacity and quick charge transfer, making them promising anode materials for lithium-ion batteries. The construction of a coordination network between Sn and the lithium-active organic matrix effectively relieved the volume expansion and increased the lithium storage active site utilization.