Department of Chemistry, Shahid Beheshti University, G. C., 1983963113, Evin, Tehran, Iran.
Nanoscale. 2023 Jul 6;15(26):11115-11130. doi: 10.1039/d3nr01734f.
Transition metal phosphides (TMPs) demonstrate excellent potential for supercapacitor electrode materials owing to their good theoretical capacity and great electrical conductivity. The electrochemical features of the electrode materials based on monometallic or bimetallic phosphides are not desirable or satisfactory due to their low rate performance, unfavorable energy density, and short durability. One practical solution to overcome the above problems is to bring in heteroatoms to the structure of the bimetallic materials to create trimetallic phosphides. In this work, brand-new MnNiCoP yolk-shell spheres assembled with nanosheets are synthesized in a facile self-templated way using greatly uniform co-glycerate spheres as sacrificial templates, followed by a phosphorization process. Because of the existence of plenty of oxidation-reduction active sites, great surface area (SA) with mesoporous pathways, high electrical conductivity, and synergistic effect of Mn, Ni, and Co atoms, the fabricated MnNiCoP@NiF electrode demonstrates a considerably increased electrochemical efficiency compared with the bimetallic phosphide MnCoP@NiF electrode. Noticeably, the MnNiCoP@NiF electrode exhibits a great specific capacity of 291.24 mA h g at an applied current density of 1 Ag, 80% capacity retention at an applied current density of 20 Ag, and 91.3% capacity retention after 14 000 cycles. In addition, a hybrid supercapacitor device with a brand-new positive electrode (MnNiCoP@NiF) and an appropriate negative electrode (AC@NiF) demonstrates an energy density of 57.03 W h kg with a power density of 799.98 W kg, plus superb cyclability with 88.41% of the primary capacitance after 14 000 cycles.
过渡金属磷化物（TMPs）由于其良好的理论容量和高导电性，在超级电容器电极材料方面表现出优异的潜力。由于其低倍率性能、不利的能量密度和短的循环寿命，基于单金属或双金属磷化物的电极材料的电化学性能并不理想或令人满意。克服上述问题的一种实用方法是在双金属材料的结构中引入杂原子来制造三金属磷化物。在这项工作中，采用简便的自模板法，以高度均匀的共甘油酸酯球为牺牲模板，通过磷化过程合成了全新的 MnNiCoP 蛋黄壳球组装的纳米片。由于存在大量的氧化还原活性位点、大的比表面积（SA）和介孔通道、高导电性以及 Mn、Ni 和 Co 原子的协同效应，与双金属磷化物 MnCoP@NiF 电极相比，所制备的 MnNiCoP@NiF 电极表现出相当大的电化学效率提高。值得注意的是，MnNiCoP@NiF 电极在 1 A g 的应用电流密度下具有 291.24 mA h g 的大比容量，在 20 A g 的应用电流密度下保持 80%的容量，在 14000 次循环后保持 91.3%的容量。此外，具有全新正极（MnNiCoP@NiF）和合适负极（AC@NiF）的混合超级电容器装置具有 57.03 W h kg 的能量密度和 799.98 W kg 的功率密度，在 14000 次循环后具有 88.41%的初始电容的出色循环稳定性。
