In view of the burgeoning demand for energy storage stemming largely from the growing renewable energy sector, the prospects of high (>300 °C), intermediate (100–200 °C) and room temperature (25–60 °C) battery systems are encouraging. Metal sulfur batteries are an attractive choice since the sulfur cathode is abundant and offers an extremely high theoretical capacity of 1672 mA h g⁻¹ upon complete discharge. Sodium also has high natural abundance and a respectable electrochemical reduction potential (−2.71 V vs. standard hydrogen electrode). Combining these two abundant elements as raw materials in an energy storage context leads to the sodium–sulfur battery (NaS). This review focuses solely on the progress, prospects and challenges of the high and intermediate temperature NaS secondary batteries (HT and IT NaS) as a whole. The already established HT NaS can be further improved in terms of energy density and safety record. The IT NaS takes advantage of the lower operating temperature to lower manufacturing and potentially operating costs whilst creating a safer environment. A thorough technical discussion on the building blocks of these two battery systems is discussed here, including electrolyte, separators, cell configuration, electrochemical reactions that take place under the different operating conditions and ways to monitor and comprehend the physicochemical and electrochemical processes under these temperatures. Furthermore, a brief summary of the work conducted on the room temperature (RT) NaS system is given seeking to couple the knowledge in this field with the one at elevated temperatures. Finally, future perspectives are discussed along with ways to effectively handle the technical challenges presented for this electrochemical energy storage system.

The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented. Atomic layer deposition (ALD) is adopted because it enables the synthesis of CoPi films with cobalt-to-phosphorous ratios between 1.4 and 1.9. It is shown that the pristine chemical composition of the CoPi film strongly influences its OER activity in the early stages of the activation process as well as after prolonged exposure to the electrolyte. The best performing CoPi catalyst, displaying a current density of 3.9 mA cm^–2 at 1.8 V versus reversible hydrogen electrode and a Tafel slope of 155 mV/dec at pH 8.0, is selected for an in-depth study of the evolution of its electrochemical properties, chemical composition, and electrochemical active surface area (ECSA) during the activation process. Upon the increase of the number of CV cycles, the OER performance increases, in parallel with the development of a noncatalytic wave in the CV scan, which points out to the reversible oxidation of Co²⁺ species to Co³⁺ species. X-ray photoelectron spectroscopy and Rutherford backscattering measurements indicate that phosphorous progressively leaches out the CoPi film bulk upon prolonged exposure to the electrolyte. In parallel, the ECSA of the films increases by up to a factor of 40, depending on the initial stoichiometry. The ECSA of the activated CoPi films shows a universal linear correlation with the OER activity for the whole range of CoPi chemical composition. It can be concluded that the adoption of ALD in CoPi-based electrocatalysis enables, next to the well-established control over film growth and properties, to disclose the mechanisms behind the CoPi electrocatalyst activation.