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Defect‐engineering is a viable strategy to improve the activity of nanocatalysts for the oxygen evolution reaction (OER), whose slow kinetics still strongly limits the broad market penetration of electrochemical water splitting as a sustainable technology for large‐scale hydrogen production. High‐entropy spinel oxides (HESOs) are in focus due to their great potential as low‐cost OER electrocatalysts. In this work, electrospun HESO nanofibers (NFs), based on (Cr,Mn,Fe,Co,Ni), (Cr,Mn,Fe,Co,Zn) and (Cr,Mn,Fe,Ni,Zn) combinations, with granular architecture and oxygen‐deficient surface are produced by calcination at low temperature (600 or 500 °C), characterized by a combination of benchtop analytical techniques and evaluated as electrocatalysts for OER in alkaline medium. The variation of HESO composition and calcination temperature produces complex and interdependent changes in the morphology of the fibers, crystallinity and inversion degree of the spinel oxide, concentration of the oxygen‐vacancies, cation distribution in the lattice, which mirror on different electrochemical properties of the fibers. The best electrocatalytic performance (overpotential and Tafel slope at 10 mA cm−2: 360 mV and 41 mV dec−1, respectively) pertains to (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4 NFs calcined at 500 °C and results from the lower outer 3d‐electron number, eg filling closer to its optimal value and higher occupation of 16d sites by the most redox‐active species. [ABSTRACT FROM AUTHOR]

New high voltage and high capacity storage systems are needed to sustain the increasing energy demand set by the portable electronics and auto­motive fields. Due to their good electrochemical performance, lithium-transition metal-phosphates (LiMPO4) seem to be very attractive as cathode materials for lithium secondary batteries. Here the synthesis and the characterization of five high voltage cathodes for lithium batteries, based on lithium-iron, lithium-nickel, lithium-cobalt phosphates are described. The effect of differing degrees of cobalt and nickel doping on structure, morphology, and the electrochemical properties of the different materials is thoroughly studied. Transition metal atoms in these materials are found to be vicariant within the olivine crystal structure; however, the lattice parameters and cell volume can be modulated by varying the nickel/cobalt ratio during the synthesis. High performance battery prototypes in terms of voltage (>4.0 V), specific capacity (125 mAh g−1), specific energy (560 mWh g−1), and cyclic life (>150 cycles) are also demonstrated. [ABSTRACT FROM AUTHOR]