Anionic Hofmeister Effect Regulated Conductivity in Polyelectrolyte Hydrogels for High‐Performance Supercapacitor

Abstract The Hofmeister effect not only affects the stability and solubility of protein colloids but also has specific effects on the polymer molecules. Here, the impact of the Hofmeister effect on the electrochemical properties of polyelectrolyte hydrogels at room temperature and subzero temperature studied for the first time. Polyelectrolyte hydrogels exhibit an anti‐polyelectrolyte effect in low concentrations of ammonium salt, while they exhibit an obvious Hofmeister effect in high concentrations of ammonium salt. Kosmotropic ions demonstrate strong interaction with water molecules or polymer chains, resulting in the reduction of conductivity of polyelectrolyte hydrogels. However, chaotropic ions exhibit weak interactions with water molecules or molecular chains, leading to an increase in conductivity. The Hofmeister effect has a more significant effect on the polyzwitterion electrolyte. The conductivity of polyzwitterion hydrogel soaked in chaotropic ion is up to 6.2 mS cm ‐1 at −40 °C. The supercapacitor assembled by polyzwitterion electrolytes maintains a capacitance retention rate of 85% and ≈100% coulomb efficiency after 15 000 cycles at −40 °C. This study elucidates the influence of the Hofmeister effect on conductivity in polyelectrolytes and expands the regulatory approach for improving the performance of energy storage devices.