Flexible ion-conductive materials exhibit intriguing advantages for applications in flexible electronic devices. Currently, the further enhancement of their conductivity within environmental limitations is an urgent demand for the development of flexible electronic devices, yet remains as a great challenge. Herein, we report a “dual-acid” strategy, via the encapsulation of two acids, H₃PW₁₂O₄₀ (HPW) and NH₂SO₃H (SA), with synergistic interaction into poly(vinyl alcohol)-glycerol (PVA-Gly) hydrogel, to achieve polyoxometalate(POM)-based flexible materials with superionic conductivity under various environmental conditions. As a representative example, the prepared PVA-Gly/HPW-SA-20% hydrogel presents an ultrahigh proton conductivity ranging from −30 °C (3.33×10⁻² S cm⁻¹) to room temperature (2.78×10⁻¹ S cm⁻¹) under ambient humidity. Moreover, the PVA-Gly/HPW-SA-20% hydrogel exhibits remarkable advantages in anti-freezing, mechanical flexibility and self-adhesiveness, making it a promising multifunctional electrolyte for flexible electronic devices. Both experimental results and molecular dynamics (MD) simulations jointly demonstrate that SA bridges HPW clusters to form a dense proton transport pathway induced by multiple electrostatic and hydrogen bonding interactions between SA and HPW counterparts, which contributes to the high-level proton conductivity of the PVA-Gly/HPW-SA-20% hydrogel. This work provides new insights into the design of POM-based flexible materials with superionic conductivity.

柔性离子导电材料在柔性电子设备中的应用表现出令人着迷的优势。目前，在环境限制下进一步提高其导电性是柔性电子器件发展的迫切需求，但仍然是一个巨大的挑战。在此，我们报告了一种“双酸”策略，通过封装两种酸，H ₃ PW ₁₂ O ₄₀ (HPW) 和 NH ₂ SO ₃ H (SA)与聚(乙烯醇)-甘油(PVA-Gly)水凝胶的协同相互作用，在超离子导电率下实现基于多金属氧酸盐(POM)的柔性材料各种环境条件。作为一个代表性的例子，所制备的PVA-Gly/HPW-SA-20%水凝胶呈现出-30 °C (3.33×10 ⁻² S cm ⁻¹ )范围内的超高质子电导率环境湿度下至室温（2.78×10 ⁻¹ S cm ⁻¹ ）。此外，PVA-Gly/HPW-SA-20%水凝胶在抗冻性、机械柔韧性和自粘性方面表现出显着的优势，使其成为一种有前途的柔性电子器件多功能电解质。实验结果和分子动力学（MD）模拟共同证明，SA 桥接 HPW 簇，形成由 SA 和 HPW 对应物之间的多重静电和氢键相互作用诱导的致密质子传输路径，这有助于 PVA 的高水平质子电导率-Gly/HPW-SA-20% 水凝胶。这项工作为具有超离子导电性的 POM 柔性材料的设计提供了新的见解。