Organic compounds exhibit great potential as sustainable,
tailorable,
and environmentally friendly electrode materials for rechargeable
batteries. However, the intrinsic defects of organic electrodes, including
solubility, low ionic conductivity, and restricted electroactivity
sites, will inevitably decrease the cycling life and capacity. We
herein designed and prepared nanostructured porous polymers (NPP)
with a simple one-pot method to overcome the above defects. Theoretical
calculations and experimental results demonstrate that the as-synthesized
NPP exhibited low volume expansion, molecular–structural distortion,
and a gradual function activation process during cycling, thus exhibiting
superior, high, and durable lithium storage. The gradual molecular
distortion during the lithium storage processes provides more redox-active
sites for Li storage, increasing the Li-storage capacity. Ex situ
spectrum studies reveal the redox reaction mechanism of Li storage
and demonstrate a gradual activation process during the repeated charging/discharging
until the full storage of 18 Li ions is achieved. Additionally, a
real-time observation on the NPP anode by in situ transmission electron
microscope reveals a slight volume expansion during the repeating
lithiation and delithiation processes, ensuring its structural integrity
during cycling. This quantitative work for high-durability lithium
storage could be of immediate benefit for designing organic electrode
materials.