Phosphate Species up to 70% Mass Ratio for Enhanced Pseudocapacitive Properties

The emerging phosphate species on the surface or near‐surface of electrode materials are versatile and have an intriguing ability for dramatically enhanced electrochemical performance. Unfortunately, the distribution/dispersion of phosphate species still keeps at levels on the exterior not within the interior surface of materials, and the micro‐/nanoscale tuning is commonly rarely concerned and its function remains poorly understood. Herein, for the first time, well‐dispersed phosphate species up to 70% mass ratio implanted within Ni‐doped CoP nanowire matrix are presented via an efficient low‐temperature phosphorization strategy. The resultant nanohybrids possess kinetics‐favorable open frameworks with abundant mesopores and a high degree covalency in the chemical bonds, thus leading to rapid mass transport/charge transfer and enhanced redox reaction kinetics. Remarkably, the phosphate species feature superwettability toward water and strong affinity for OH− in the electrolyte, evidenced by the shortened distance and reduced adsorption energy between the OH− and the nuclear Co atoms on the nanohybrids as revealed by density functional theory calculations. As such, the nanohybrids exhibit an ultrahigh specific capacity of 250 mAh g−1 even at 50 A g−1. This work presents a deeper understanding of the dispersion and role of phosphate species for supercapacitors and other energy‐related storage/conversion devices.