High‐entropy sulfides (HESs) containing 5 equiatomic transition metals (M), with different M:S ratios, are prepared by a facile one‐step mechanochemical approach. Two new types of single‐phase HESs with pyrite (Pa‐3) and orthorhombic (Pnma) structures are obtained and demonstrate a homogeneously mixed solid solution. The straightforward synthesis method can easily tune the desired metal to sulfur ratio for HESs with different stoichiometries, by utilizing the respective metal sulfides, even pure metals, and sulfur as precursor chemicals. The structural details and solid solution nature of HESs are studied by X‐ray diffraction, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, electron energy loss spectroscopy, X‐ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, and Mössbauer spectroscopy. Since transition metal sulfides are a very versatile material class, here the application of HESs is presented as electrode materials for reversible electrochemical energy storage, in which the HESs show high specific capacities and excellent rate capabilities in secondary Li‐ion batteries.

P2-type layered oxides with the general Na-deficient composition Na _x TMO₂ (x < 1, TM: transition metal) are a promising class of cathode materials for sodium-ion batteries. The open Na⁺ transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates. However, a phase transition from P2 to O2 structure occurring above 4.2 V and metal dissolution at low potentials upon discharge results in rapid capacity degradation. In this work, we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation. Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry, Na_0.67(Mn_0.55Ni_0.21Co_0.24)O₂, Na_0.67(Mn_0.45Ni_0.18Co_0.24Ti_0.1Mg_0.03)O₂ and Na_0.67(Mn_0.45Ni_0.18Co_0.18Ti_0.1Mg_0.03Al_0.04Fe_0.02)O₂ with low, medium and high configurational entropy, respectively. The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V. Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly. Overall, the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.

With respect to efficient use of diminishing or harder to reach energy resources, the catalysis of processes that will otherwise require high overpotentials is a very important application in today's world. As a newly developed class of materials, high‐entropy sulfides (HESs) are promising electrocatalysts for a variety of different reactions. In this report, HESs containing five or six transition metals are synthesized in a one‐step mechanochemical process. Seven HESs of Pnma (M:S≈1:1) and three Pa‐3 (M:S = 1:2) structures are investigated as electrocatalysts for the oxygen evolution reaction (OER). The performances and properties of the HESs with different compositions and structures are compared with each other and with commercial IrO₂ as reference material, in terms of OER overpotential, Tafel slope, electrochemically active surface area, ionic conductivity, and durability. The structural and chemical properties of these HESs are determined by X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and energy‐dispersive X‐ray spectroscopy. Most of the HESs show excellent and promising performance as OER electrocatalysts under alkaline conditions, and outperform the reference OER catalyst IrO₂.

The rechargeable zinc–air battery is a clean technology for energy storage applications but is impeded by the slow kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during its cycling. Herein, a series of lanthanum cobaltate based perovskites are synthesised with the B-site cation deficiencies in the structure occupied by Ru substitution: LaCo_1−xRu_xO_3−δ (x = 0, 0.1, 0.2, 0.3 and 0.5). These compositions were designed to enhance the OER/ORR activities, which are two vital reactions for rechargeable Zn–air batteries. Powder X-ray diffraction analysis revealed that increasing the Ru substitution >20% (x > 0.2) alters the LaCoO₃ crystal structure from rhombohedral to orthorhombic. Photoelectron spectroscopy studies reveal that the surface oxygen vacancies increased in the Ru substituted catalyst, a property important for enhancing the OER/ORR efficiency. The LaCo_0.8Ru_0.2O_3−δ (LCRO82) catalyst exhibits promising electrocatalytic activities in both the OER and the ORR in 0.1 M KOH solution. Furthermore, the LCRO82 catalyst was evaluated as a cathode for rechargeable Zn–air battery applications displaying a high power density of 136 mW cm⁻² at a current density of 175 mA cm⁻² and a stable charge–discharge voltage gap of 0.78 V after 1440 cycles, with excellent cycling stability over 240 h.