Eletrical modulation of glass transtion in polyelectrolyte complexes

The phase transition between glassy and rubbery states substantially alters the physical properties of polymers. Conventional control of this transition relies on thermal processes, which are inherently slow and lack spatial selectivity. In this work, we demonstrate an electrically induced glass transition in a polyelectrolyte complex (PEC) confined between two oppositely charged ionoelastomers (IEs). Upon applying an external bias, mobile counter-ions within the IEs are reversibly injected into or extracted from the PEC, thereby modulating its viscoelastic state in accordance with the time–temperature–salt superposition (TTSS) relationship. The resulting voltage-driven transition occurs at low potentials (~1 V) and produces pronounced, reversible changes in ionic conductivity. This electrically mediated switching establishes a new operational paradigm for ionic diodes—one governed by kinetic control rather than thermodynamic equilibrium.