Chain structure-dependent electrochemical performance of polyimide cathode materials for lithium-ion batteries

Organic polyimides have received an ever-growing interest in lithium-ion batteries based on the reversible anion stabilization mechanism of redox-active carbonyl groups due to their high theoretical capacities, resource sustainability, and diverse chain structures. Herein, four linear polyimides with different chain structures were synthesized by a facile and green hydrothermal method. The chain structure-electrochemical performance relationship was explored by regulating active anhydride units and diamine linkers. The incorporation of flexible linkers between redox-active anhydrides results in the facile movement of polyimide chains and the formation of porous networks with abundant active sites. In contrast, rigid aromatic linkers with strong pi-pi conjugation tend to assemble into the orderly-stacked sheets, enabling the efficient electron transfer. When used as the battery cathode, 1,4,5,8-naphthalenetetracarboxylic dianhydride-based polyimide with a relatively flexible linker delivers the largest specific capacity. Such a polyimide also demonstrates the high cycling stability with a capacity retention up to 52% over 10000 cycles. In contrast, pyromellitic dianhydride-based polyimide with a benzene-enriched linker exhibits the lowest capacity and poor rate capability due to its densely-stacked sheets and limited exposure of active groups. The chain structure-dependent performance relationship of polyimides would offer new insights into the rational design of high-performance organic electrodes for the next-generation batteries.

Automated summary

Organic polyimides have drawn increasing attention in lithium-ion batteries due to their high theoretical capacities, resource sustainability, and diverse chain structures, which utilize the reversible anion stabilization mechanism of redox-active carbonyl groups. By adjusting the active anhydride units and diamine linkers, the relationship between chain structure and electrochemical performance was explored. The incorporation of flexible linkers facilitates the movement of polyimide chains, forming porous networks with abundant active sites and enhancing capacity and cycling stability; in contrast, rigid aromatic linkers lead to orderly-stacked sheets that affect capacity and rate capability.