Co-Assembly of Polyoxometalates and Porphyrins as Anode for High-Performance Lithium-Ion Batteries

Polyoxometalates (POMs) have been considered one of the most promising anode candidates for lithium-ion batteries (LIBs) in virtue of their high theoretical capacity and reversible multielectron redox properties. However, the poor intrinsic electronic conductivity, low specific surface area, and high solubility in organic electrolytes hinder their widespread applications in LIBs. Herein, a novel hybrid nanomaterial is synthesized by co-assembling POMs and porphyrins (PMo₁₂/CoTPyP) through a facile solvothermal method. The POM clusters are stabilized by porphyrin units through electrostatic interactions, which simultaneously realize the uniform dispersion of POMs and porphyrin units. Benefiting from the generated sub-1 nm channels for fast ion transport and the synergistic effect between evenly distributed PMo₁₂ clusters and high-conductive CoTPyP units, the LIB based on the optimized PMo₁₂/CoTPyP anode exhibits significantly improved Li⁺ storage capability as well as superior rate and cycling performance. The results of density functional theory simulations further reveal that the co-assembly of PMo₁₂ and CoTPyP can accelerate the mobility of Li⁺ and electrons, which in turn promotes the enhancement of LIBs performance. This work paves a strategy for synthesizing POMs-based anode materials with simultaneously high dispersibility, redox activity, and stability.