Self‐reporting and Biodegradable Thermosetting Solid Polymer Electrolyte

Abstract To date, significant efforts have been dedicated to improve their ionic conductivity, thermal stability, and mechanical strength of solid polymer electrolytes (SPEs). However, direct monitoring of physical and chemical changes in SPEs is still lacking. Moreover, existing thermosetting SPEs are hardly degradable. Herein, by overcoming the limitation predicted by Flory theory, self‐reporting and biodegradable thermosetting hyperbranched poly(β‐amino ester)‐based SPEs (HPAE‐SPEs) are reported. HPAE is successfully synthesized through a well‐controlled “A2+B4” Michael addition strategy and then crosslinked it in situ to produce HPAE‐SPEs. The multiple tertiary aliphatic amines at the branching sites confer multicolour luminescence to HPAE‐SPEs, enabling direct observation of its physical and chemical damage. After use, HPAE‐SPEs can be rapidly hydrolysed into non‐hazardous β‐amino acids and polyols via self‐catalysis. Optimized HPAE‐SPE exhibits an ionic conductivity of 1.3×10 −4 S/cm at 60 °C, a Na + transference number ( ) of 0.67, a highly stable sodium plating‐stripping behaviour and a low overpotential of ≈190 mV. This study establishes a new paradigm for developing SPEs by engineering multifunctional polymers. The self‐reporting and biodegradable properties would greatly expand the scope of applications for SPEs.