Polyimide covalent organic framework (PI-COF) materials
that can
realize intrinsic redox reactions by changing the charge state of
their electroactive sites are considered as emerging electrode materials
for rechargeable devices. However, the highly crystalline PI-COFs
with hierarchical porosity are less reported due to the rapid reaction
between monomers and the poor reversibility of the polyimidization
reaction. Here, we developed a water-assistant synthetic strategy
to adjust the reaction rate of polyimidization, and PI-COF (COFTPDA‑PMDA) with
kgm
topology
consisting of dual active centers of N,N,N′,N′-tetrakis(4-aminophenyl)-1,4-benzenediamine
(TPDA) and pyromellitic dianhydride (PMDA) ligands was successfully
synthesized with high crystallinity and porosity. The COFTPDA‑PMDA possesses hierarchical micro-/mesoporous channels with the largest
surface area (2669 m2/g) in PI-COFs, which can promote
the Li+ ions and bulky bis(trifluoromethanesulfonyl)imide
(TFSI–) ions in organic electrolyte to sufficiently
interact with the dual active sites on COF skeleton to increase the
specific capacity of cathode materials. As a cathode material for
lithium-ion batteries, COFTPDA‑PMDA@50%CNT which
integrated high surface area and dual active center of COFTPDA‑PMDA with carbon nanotubes via π–π interactions gave
a high initial charge capacity of 233 mAh/g (0.5 A/g) and maintains
at 80 mAh/g even at a high current density of 5.0 A/g after 1800 cycles.