Holding ultralong cycle life and superior rate capability with high specific capacity is an inevitable requirement for the practical applications of transition metal compounds battery-type supercapacitor electrode materials. In this paper, a novel class of transition metal phosphide (TMP) nanostructures evenly bonded on N/P co-doped graphene nanotubes (N/P-GNTs@b-TMP) is firstly built via one-step in-situ growth procedure. The N, P elements as substitutions of C in GNTs skeleton introduce rich electronic centers, further change the surface electronic structures of the skeleton, inducing the TMPs to anchor the surface of N/P-GNTs through metal-N and metal-P bonds, which is demonstrated by the characterizations and Density functional theory (DFT) calculation. The unique chemical bonding can not only reinforce the integration of the hybrid electrode materials during durable cycling, but also generate the typical internal electric field and greatly reduce the free energy of the reaction system, endowing a superior rate capacity and easy redox process relating to high specific capacity. Moreover, ex-situ impedance and capacitive/diffusion control analysis suggest the fast ions diffusion behavior and reaction kinetics. Benefiting from the unique architecture, the achieved N/P-GNTs@b-NiCoP positive electrode possesses high specific capacity of 250 mAh g⁻¹ (1800 F g⁻¹) at 2 A g⁻¹ and 166 mAh g⁻¹ (1200 F g⁻¹) at 50 A g⁻¹. Meanwhile, the N/P-GNTs@b-Fe₂NiP and N/P-GNTs@b-FeCoP negative electrodes constructed by the same approach can also own a high specific capacity of 151.9, 159.7 mAh g⁻¹ (547, 575 F g⁻¹) at 1A g⁻¹ and 63.6, 73.6 mAh g⁻¹ (229, 265 F g⁻¹) at 50 A g⁻¹, respectively. More significantly, they all can present ∼90% capacity retention after 75000 cycles, which can be comparable to all of the reported transition metal compound electrodes even commercial carbonaceous materials. In addition, an asymmetric supercapacitor (ASC) using the achieved N/P-GNTs@b-NiCoP as electrode expresses a remarkable energy density of 77.8 Wh kg⁻¹ and cycling stability. This work provides an innovative structural design strategy for obtaining battery-type supercapacitor electrode materials with commercial application prospects.

保持超长的循环寿命和高比容量的优异倍率性能是过渡金属化合物电池型超级电容器电极材料实际应用的必然要求。本文首次通过一步原位构建了一类新型的均匀键合在N/P共掺杂石墨烯纳米管上的过渡金属磷化物（TMP）纳米结构（N/P-GNTs@b-TMP）。成长过程。N、P元素作为GNTs骨架中C的替代物引入丰富的电子中心，进一步改变骨架的表面电子结构，诱导TMPs通过金属-N和金属-P键锚定N/P-GNTs表面，表征和密度泛函理论 (DFT) 计算证明了这一点。独特的化学键合不仅可以增强混合电极材料在耐久循环过程中的整合，还可以产生典型的内电场，大大降低反应体系的自由能，赋予了优异的倍率容量和容易的氧化还原过程。具体容量。此外，异地阻抗和电容/扩散控制分析表明快速离子扩散行为和反应动力学。得益于独特的结构，所获得的 N/P-GNTs@b-NiCoP 正极在² A g ^-1和 166 mAh ^{g -1} ( 1200 F g ^-1 ) 在 50 A g ^-1。同时，采用相同方法构建的N/P-GNTs@b-Fe ₂ NiP和N/P-GNTs@b-FeCoP负极也可以拥有151.9, 159.7 mAh g ^-1 (547, 575 F g ^-1 ) 在 1A g ^-1和 63.6, 73.6 mAh g ^-1 (229, 265 F g^-1 ) 分别在 50 A g ^-1下。更重要的是，它们在 75000 次循环后都可以保持 90% 的容量保持率，这可以与所有报道的过渡金属化合物电极甚至商业碳质材料相媲美。此外，使用所获得的 N/P-GNTs@b-NiCoP 作为电极的非对称超级电容器 (ASC) 表现出 77.8 Wh kg ^-1的显着能量密度和循环稳定性。该工作为获得具有商业应用前景的电池型超级电容器电极材料提供了一种创新的结构设计策略。