Construction of Large Non-Localized π-Electron System for Enhanced Sodium-Ion Storage.

Organic electrode materials with the advantages of renewability, environment-friendliness, low cost, and high capacity have received widespread attention in recent years for sodium-ion batteries. However, small molecular organic materials suffer from issues such as low conductivity and the high dissolution rate in electrolytes. Herein, a phthalocyanine derivative (TPcDS) with a large non-localized π-electron system, obtained through thermodynamic polymerization of 4-aminophthalonitrile (AP) monomers, is designed to address these issues. According to the density function theory calculation, six sodium ions can be attracted by one polymer molecule, indicating a high theoretical capacity of 375 mA h g-1 . The TPcDS molecule realizes sodium storage through a non-localized π-electron system of phthalocyanine macrocycles. When employed as an anode material for sodium-ion batteries, the functional groups of phthalocyanine macrocycles, such as CN groups in TPcDS, experience obviously reversible structural variation upon discharge/charge. A high reversible capacity of 364 mAh g-1 is achieved at a current density of 0.05 A g-1 , and a charge capacity of as high as 246 mAh g-1 is still maintained after 500 cycles at 0.1 A g-1 . This work provides an effective strategy for the design and synthesis of new oligomeric organic electrode materials.