Li Huanhuan, Zhang Yu, Wu Yusheng, Hu Fang, You Junhua, Zhu Kai
School of Materials Science and Engineering, Shenyang University of Technology, Shenyang Key Laboratory of Advanced Energy Materials and Renewable Resources, Shenyang 110870, Liaoning, China.
School of Materials Science and Engineering, Shenyang University of Technology, Shenyang Key Laboratory of Advanced Energy Materials and Renewable Resources, Shenyang 110870, Liaoning, China.
J Colloid Interface Sci. 2025 Dec 15;700(Pt 3):138557. doi: 10.1016/j.jcis.2025.138557. Epub 2025 Jul 26.
Aqueous zinc-ion capacitors (ZICs) have garnered significant attention as safe and cost-effective alternatives to lithium-ion batteries. However, conventional carbon cathodes suffer from limited Zn adsorption capacity and sluggish charge transport, severely restricting their energy and power performance. Herein, we propose a scalable and cost-effective strategy to fabricate three-dimensional (3D) porous phosphorus-doped carbon (TPMC) with tunable graphitic domains, hierarchical porosity, and abundant active sites. The tailored microstructure features enlarged interlayer spacing, interconnected mesopores, and locally ordered graphitic regions, which together facilitate efficient Zn diffusion and fast electron transport. Besides, phosphorus doping and silica template introduce surface and edge defects, further enhancing electrochemical activity. As a result, the optimized TPMC electrode delivers a high specific capacity of 257 mAh g, an energy density of 244.1 Wh kg at a power density of 69.6 W kg, and excellent cycling stability with 94.9 % retention after 100,000 cycles. Both kinetic analysis and ex situ characterizations confirm that graphite domain modulation significantly accelerates interfacial charge transfer and enhances pseudocapacitive behavior, thereby promoting Zn adsorption/desorption. Moreover, the quasi-solid-state ZICs demonstrate high capacity, outstanding cycling stability with 95 % retention over 50,000 cycles, and excellent mechanical flexibility. This work provides new insights into the microstructural design of carbon materials and offers a promising strategy for developing advanced aqueous Zn-ion energy storage systems.
水系锌离子电容器（ZICs）作为锂离子电池安全且经济高效的替代品，已备受关注。然而，传统的碳阴极存在锌吸附容量有限和电荷传输缓慢的问题，严重限制了它们的能量和功率性能。在此，我们提出了一种可扩展且经济高效的策略，来制备具有可调石墨域、分级孔隙率和丰富活性位点的三维（3D）多孔磷掺杂碳（TPMC）。定制的微观结构具有扩大的层间距、相互连接的中孔和局部有序的石墨区域，这些共同促进了锌的高效扩散和快速电子传输。此外，磷掺杂和二氧化硅模板引入了表面和边缘缺陷，进一步增强了电化学活性。结果，优化后的TPMC电极具有257 mAh g的高比容量、在功率密度为69.6 W kg时244.1 Wh kg的能量密度，以及出色的循环稳定性，在100,000次循环后保留率为94.9%。动力学分析和非原位表征均证实，石墨域调制显著加速了界面电荷转移并增强了赝电容行为，从而促进了锌的吸附/脱附。此外，准固态ZICs表现出高容量、在50,000次循环中95%保留率的出色循环稳定性以及优异的机械柔韧性。这项工作为碳材料的微观结构设计提供了新的见解，并为开发先进的水系锌离子储能系统提供了一种有前景的策略。
