Two Birds One Stone: Graphene Assisted Reaction Kinetics and Ionic Conductivity in Phthalocyanine-Based Covalent...

This work reports a covalent organic framework composite structure (PMDA-NiPc-G), incorporating multiple-active carbonyls and graphene on the basis of the combination of phthalocyanine (NiPc(NH₂ )₄ ) containing a large π-conjugated system and pyromellitic dianhydride (PMDA) as the anode of lithium-ion batteries. Meanwhile, graphene is used as a dispersion medium to reduce the accumulation of bulk covalent organic frameworks (COFs) to obtain COFs with small-volume and few-layers, shortening the ion migration path and improving the diffusion rate of lithium ions in the two dimensional (2D) grid layered structure. PMDA-NiPc-G showed a lithium-ion diffusion coefficient (D_Li ⁺ ) of 3.04 × 10^-10 cm² s^-1 which is 3.6 times to that of its bulk form (0.84 × 10^-10 cm² s^-1 ). Remarkably, this enables a large reversible capacity of 1290 mAh g^-1 can be achieved after 300 cycles and almost no capacity fading in the next 300 cycles at 100 mA g^-1 . At a high areal capacity loading of ≈3 mAh cm^-2 , full batteries assembled with LiNi_0.8 Co_0.1 Mn_0.1 O₂ (NCM-811) and LiFePO₄ (LFP) cathodes showed 60.2% and 74.7% capacity retention at 1 C for 200 cycles. Astonishingly, the PMDA-NiPc-G/NCM-811 full battery exhibits ≈100% capacity retention after cycling at 0.2 C. Aided by the analysis of kinetic behavior of lithium storage and theoretical calculations, the capacity-enhancing mechanism and lithium storage mechanism of covalent organic frameworks are revealed. This work may lead to more research on designable, multifunctional COFs for electrochemical energy storage.