Symmetric six oxygen-coordinated Mn structural units (MnO₆) in MnO₂ with small Mn–O orbital overlap hamper electron transfer rates during energy storage. Herein, we report a novel bond angle modulation strategy to manipulate Mn–O orbital overlap in MnO₂ through the construction of Mn vacancies (MnO₂-V_Mn), aiming at expediting electron transfer, and thus enhancing energy storage performance. Both experimental and theoretical results disclose that the amplification of Mn–O–Mn bond angles exclusively augments the Mn (d_x²_-y²)-O (p_y) orbital overlap and triggers the electron redistribution in MnO₂-V_Mn, inducing an augmented Mn d_x²_-y² electron occupation. This heightened presence of active electrons in the Mn d_x²_-y² orbital paves the way for accelerating electron transfer and ion transfer in MnO₂-V_Mn. Notably, MnO₂-V_Mn delivers an improved specific capacitance of 425 F g⁻¹ at 1 A g⁻¹ and a superior rate capacity of 265 F g⁻¹ at 20 A g⁻¹. Furthermore, an asymmetric supercapacitor (MnO₂-V_Mn//AC ASC) was fabricated, exhibiting a high energy density of 64.3 Wh kg⁻¹ at a power density of 1000 W kg⁻¹. Furthermore, theoretical insights uncover the profound implications of metal–oxygen–metal bond angle regulation on interatomic orbital overlap modulation. These revelations illuminate pathways for the design of advanced energy storage materials.

_{MnO 2}中对称的六个氧配位Mn结构单元(MnO ₆ )具有小的Mn-O轨道重叠，阻碍了能量存储期间的电子转移速率。在此，我们报告了一种新颖的键角调制策略，通过构建Mn空位（MnO ₂ -V _{Mn ）来操纵MnO 2}中的Mn-O轨道重叠，旨在加速电子转移，从而提高储能性能。实验和理论结果都表明，Mn-O-Mn 键角的放大专门增强了 Mn ( d _x ² _{- y} ² )-O ( p _{y) 轨道重叠并触发 MnO 2} -V _Mn中的电子重新分布，从而诱导增强的 Mn d _x ² _{- y} ²电子占据。Mn d _x ² _{- y} ²轨道中活性电子的增加为加速MnO ₂ -V _Mn中的电子转移和离子转移铺平了道路。值得注意的是，MnO ₂ -V _Mn在 1 A g ^{-1下提供了 425 F g -1}的改进比电容，在 20 A g ^{-1下提供了 265 F g -1}的优异倍率容量。此外，制备了非对称超级电容器（MnO ₂ -V _{Mn //AC ASC），在1000 W kg} ^-1的功率密度下表现出64.3 Wh kg ^-1的高能量密度。此外，理论见解揭示了金属-氧-金属键角调节对原子间轨道重叠调制的深远影响。这些启示阐明了先进储能材料的设计途径。