Chemically Recyclable Conjugated Polymer and One‐Shot Preparation of Thermally Stable and Efficient Bulk‐Heterojunction from Recycled Monomer

Recyclable conjugated polymers are important for realizing eco‐friendly electronics with advantages of solution processability and flexibility. A recyclable conjugated polymer, PY‐TIP is developed, of which a key monomer is successfully extracted via a mild depolymerization process and is reused for the synthesis of novel conjugated polymers. One‐shot preparation of polymer acceptor and its bulk‐heterojunction (BHJ) is demonstrated from the recycled monomer, Y5‐TA, for the first time and the resulting BHJ film shows optimal nanoscale morphology for efficient charge generation and transport. As a result, the solar cells prepared using the BHJ film show a higher efficiency of 13.08% and much improved thermal and mechanical stability compared with those based on the small molecular acceptor. These results are important in that the various polymers can be prepared from the recycled monomer in a solid state without organic solvents and purification step and this strategy is effective for improving the thermal and mechanical stability of the BHJ film as well as achieving high photovoltaic performance. PY‐TIP is exemplary in that it can reproduce its monomer which can be used to synthesize conjugated polymers with novel chemical structures and physical properties. This work provides a design guideline for developing recyclable conjugated polymers with dynamic covalent bonds. Recyclable conjugated polymer is developed and gives the recycled monomer via a mild depolymerization process. The recycled monomer utilizes for the network acceptor polymer through one‐shot preparation and the solar cells utilizing the BHJ achieved higher power conversion efficiency of 13.08% with higher thermal and mechanical stability than small molecular acceptor‐based BHJs.