Yang Jun, Hou Wenxiu, Ye Lingqian, Hou Guoyu, Yan Chao, Zhang Yu
School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu, 212003, China.
School of Mechanical and Power Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Small. 2024 Jan;20(2):e2305386. doi: 10.1002/smll.202305386. Epub 2023 Sep 5.
The significant attraction toward aqueous proton batteries (APBs) is attributable to their expedited kinetics, elevated safety profile, and economical feasibility. Nevertheless, their practical implement is significantly blocked by the unsatisfactory energy density due to the limited cathode materials. Herein, vanadium hexacyanoferrate Prussian blue analog (VOHCF) is introduced as a potentially favorable cathode material for APBs. The findings demonstrate that this VOHCF electrode exhibits a notable reversible capacity of 102.7 mAh g and exceptional cycling stability, with 95.4% capacity retention over 10 000 cycles at 10 A g . It is noteworthy that this is the detailed instance of VOHCF being proposed as a cathode for APBs. Combining the in situ characterization techniques and theoretical simulations, the origins of excellent proton storage performance are revealed as the multiple redox mechanisms with double active centers of ─C≡N group and V═O bond in VOHCF as well as the robust structure stability. A proton full cell with excellent performance is further achieved by coupling the VOHCF cathode and diquinoxalino[2,3-a:2',3'-c] phenazine (HATN) anode, demonstrating the great potential of VOHCF in practical applications. This work could provide fundamental understanding to the development of feasible cathode materials for proton storage device.
水系质子电池（APB）具有显著吸引力，这归因于其快速的动力学、更高的安全性和经济可行性。然而，由于阴极材料有限，其能量密度不尽人意，严重阻碍了它们的实际应用。在此，六氰合铁酸钒普鲁士蓝类似物（VOHCF）被引入作为APB潜在的优良阴极材料。研究结果表明，这种VOHCF电极展现出102.7 mAh g的显著可逆容量和出色的循环稳定性，在10 A g的电流密度下10000次循环后容量保持率为95.4%。值得注意的是，这是首次详细报道将VOHCF用作APB阴极的实例。结合原位表征技术和理论模拟，揭示了优异的质子存储性能源于VOHCF中─C≡N基团和V═O键双活性中心的多重氧化还原机制以及强大的结构稳定性。通过将VOHCF阴极与二喹喔啉并[2,3-a:2',3'-c]吩嗪（HATN）阳极耦合，进一步实现了性能优异的质子全电池，证明了VOHCF在实际应用中的巨大潜力。这项工作可为开发可行的质子存储装置阴极材料提供基础认识。
