Vanadium trioxide (V2O3) has emerged as one of the promising candidates for fiber‐shaped supercapacitors. However, irreversible redox behavior during prolonged cycling process has been commonly reported due to the intrinsically distorted VO6 octahedron in V2O3, which inevitably compromises its electrochemical capacitance. Herein, a strategy to simultaneously mitigate the distortion in VO6 octahedron and optimization of electronic structure in V2O3 is proposed by studying a Mo‐doped V2O3 modified stainless steel wire (Mo‐V2O3@SSW). The introduction of Mo dopants effectively tunes the V–O local environment, resulting in a substantial alleviation of the distortion in VO6 octahedron. The as‐prepared Mo‐V2O3 with a more regular VO6 octahedron exhibits highly reversible redox behavior, with negligible structural change after 10 000 cycles. Moreover, it is found that doping Mo into V2O3 leads to V 3d band broadening, which generates more electronic states around Fermi level, thereby significantly accelerating the electron transfer during redox processes. Consequently, Mo‐V2O3@SSW attains a capacitance of 774.4 mF cm−2 at 0.4 mA cm−2, with a capacitance retention of 85.49% after 10 000 cycles. And the integration of Mo‐V2O3@SSW supercapacitors, further showcases its strong applicability in wearable technologies. The comprehensive understanding of the structural–activity/stability relationship in this study offers a novel paradigm for developing flexible high‐performing supercapacitors.

中文翻译：

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高性能柔性超级电容器中同时减轻 VO6 八面体畸变和 V2O3 中的能带展宽


三氧化二钒（V2O3）已成为纤维状超级电容器的有前途的候选者之一。然而，由于 V2O3 中 VO6 八面体本质上扭曲，长时间循环过程中的不可逆氧化还原行为已被普遍报道，这不可避免地损害了其电化学电容。在此，通过研究Mo掺杂V2O3改性不锈钢丝（Mo-V2O3@SSW），提出了一种同时减轻VO6八面体变形和优化V2O3电子结构的策略。 Mo掺杂剂的引入有效地调节了V-O局域环境，从而大大减轻了VO6八面体的畸变。所制备的具有更规则的 VO6 八面体的 Mo-V2O3 表现出高度可逆的氧化还原行为，10000 次循环后结构变化可以忽略不计。此外，研究发现，将Mo掺杂到V2O3中会导致V 3d带展宽，从而在费米能级附近产生更多电子态，从而显着加速氧化还原过程中的电子转移。因此，Mo-V2O3@SSW在0.4 mA cm−2下获得了774.4 mF cm−2的电容，10 000次循环后电容保持率为85.49%。而Mo-V2O3@SSW超级电容器的集成，进一步展示了其在可穿戴技术中的强大适用性。本研究对结构-活性/稳定性关系的全面理解为开发柔性高性能超级电容器提供了新的范例。