The design and development of energy storage device with high energy/power density has become a research hotspot. Zinc-ion hybrid capacitors (ZHCs) are considered as one of the most promising candidates. However, the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material. In this study, a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide (P-CNT/rGO) aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design. The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera, expanded interlayer spacing, and enhanced pseudocapacitance behavior, thus leading to significantly enhanced specific capacitance and superb ions transport performance. The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life. In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs. Furthermore, the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations. This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.

高能量/功率密度的储能装置的设计与开发已成为研究热点。锌离子混合电容器（ZHC）被认为是最有前途的候选者之一。然而，由于正极材料不理想，ZHCs在高功率密度下能量密度低，阻碍了其应用。在这项研究中，通过CNT插入和P掺杂改性的协同改性策略与3D多孔设计相结合，合成了一种新型3D磷掺杂碳纳米管/还原氧化石墨烯（P-CNT/rGO）气凝胶阴极。所获得的 P-CNT/rGO 气凝胶阴极表现出显着增加的表面积、扩大的层间距和增强的赝电容行为，从而导致显着增强的比电容和优异的离子传输性能。基于 P-CNT/rGO 阴极的组装 ZHC 可在 80 kW/kg 的极高功率密度下提供 42.2 Wh/kg 的卓越能量密度和出色的循环寿命。通过深入的动力学分析来证明 ZHC 具有增强的赝电容行为和卓越的功率输出能力。此外，通过系统的异位表征揭示了P-CNT/rGO阴极上电解质离子的物理和化学吸附/解吸的反应机制。这项工作可以为开发用于高能量/功率密度 ZHC 的先进石墨烯基阴极提供有价值的参考。