Ion-conductive hydrogels have received great attention due to their significant potential in flexible electronics. However, achieving hydrogels that simultaneously possess high ionic conductivity and stability under varying humidity conditions remains a challenge, limiting their practical applications. Herein, we propose a thermally controlled chemical cross-linking strategy to prepare an elastic and conductive hydrogel (ECH) of poly(vinyl alcohol) (PVA) with high content of H₂SO₄. The covalent cross-links formed effectively tackle the instability issue in high humidity of physically cross-linked PVA/H₂SO₄ hydrogels with high ionic conductivity, which were previously developed via the polymer-in-salt strategy. We systematically investigated the reaction conditions and clarified the methods to optimize the hydroxyl dehydration of PVA, resulting in excellent mechanical properties and ion conductivity simultaneously. The ECH demonstrates impressive ionic conductivity (up to 392 ± 49 mS cm^-¹) and elasticity (over 80% resilience upon stretching and compression after being equilibrated at various humidity levels for 24 days). Thanks to the excellent water retention of the high H₂SO₄ content, the ECH maintains an ionic conductivity exceeding 210 mS cm^-1 for over 420 days at 50% relative humidity (RH) and retains over 100 mS cm^-1 even after 3 days under extremely dry conditions (7% RH). These remarkable properties make the ECH an ideal candidate for applications requiring reliable ionic conductivity in diverse environmental conditions. Additionally, we demonstrated that the ECH can function as a stretchable Joule heater with high conformability for heating up objects with curved surfaces. The heating rate could reach a fast rate of ∼12 °C s^-1 even when a human-safe alternating current voltage is below 36 V, attributed to the high ionic conductivity. We believe that the high performance and ease of fabrication make our hydrogels a promising candidate for use as electrolytes in flexible energy storage devices, electrolyte gates in electrochemical transistors, and artificial skin, which often face long-term stability challenges under varying humidity conditions.

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