The design of power supply systems for wearable applications requires both flexibility and durability. Thermoelectrochemical cells (TECs) with large Seebeck coefficient can efficiently convert low-grade heat into electricity, thus having attracted considerable attention in recent years. Utilizing hydrogel electrolyte essentially addresses the electrolyte leakage and complicated packaging issues existing in conventional liquid-based TECs, which well satisfies the need for flexibility. Whereas, the concern of mechanical robustness to ensure stable energy output remains yet to be addressed. Herein, a flexible quasi-solid-state TEC is proposed based on the rational design of a hydrogel electrolyte, of which the thermogalvanic effect and mechanical robustness are simultaneously regulated via the multivalent ions of a redox couple. The introduced redox ions not only endow the hydrogel with excellent heat-to-electricity conversion capability, but also act as ionic crosslinks to afford a dual-crosslinked structure, resulting in reversible bonds for effective energy dissipation. The optimized TEC exhibits a high Seebeck coefficient of 1.43 mV K⁻¹ and a significantly improved fracture toughness of 3555 J m⁻², thereby can maintain a stable thermoelectrochemical performance against various harsh mechanical stimuli. This study reveals the high potential of the quasi-solid-state TEC as a flexible and durable energy supply system for wearable applications.

可穿戴应用的电源系统设计需要灵活性和耐用性。具有大塞贝克系数的热电化学电池（TEC）可以有效地将低品位热量转化为电能，因此近年来引起了广泛关注。使用水凝胶电解质从本质上解决了传统液基TEC存在的电解质泄漏和复杂封装问题，很好地满足了灵活性的需求。然而，确保稳定能量输出的机械鲁棒性问题仍有待解决。在此，基于水凝胶电解质的合理设计，提出了一种柔性准固态 TEC，其热电效应和机械鲁棒性通过氧化还原对的多价离子同时调节。引入的氧化还原离子不仅赋予水凝胶优异的热电转换能力，而且作为离子交联剂提供双交联结构，产生可逆键以有效耗能。优化后的 TEC 表现出 1.43 mV K 的高塞贝克系数^-1和显着提高的断裂韧性3555 J m ^-2，从而可以在各种苛刻的机械刺激下保持稳定的热电化学性能。这项研究揭示了准固态 TEC 作为可穿戴应用的灵活耐用的能源供应系统的巨大潜力。