As for other multivalent systems, the interface between the calcium (Ca) metal anode and the electrolyte is of paramount importance for reversible plating/stripping. Here, we combined experimental and theoretical approaches...

While less mature than the Li-ion battery, technologies based on Na, K, Mg, and Ca are attracting more and more attention from the battery community. New material (cathode, anode, or electrolyte) testing for these post-Li systems commonly involves the use of an electrochemical setup called a half-cell in which metal counter and reference electrodes are used. Here we first describe the different issues that become critical when moving away from Li with respect to the cell hardware (cell design, current collector, separator, insulator) and the nature of the counter and reference electrodes. Workarounds are given, and a versatile setup is proposed to run reliable electrochemical tests for post-Li battery materials in general, in a broad range of electrolyte compositions.

Divalent-cation-based batteries are being considered as potential high energy density storage devices. The optimization of electrolytes for these technologies is, however, still largely lacking. Recent demonstration of the feasibility of Ca and Mg plating and stripping in the presence of a passivation layer or an artificial interphase has paved the way for more diverse electrolyte formulations. Here, we exhaustively evaluate several Ca-based electrolytes with different salts, solvents, and concentrations, via measuring physicochemical properties and using vibrational spectroscopy. Some comparisons with Mg-and Li-based electrolytes are made to highlight the unique properties of the Ca 2+ cation. The Ca-salt solubility is found to be a major issue, calling for development of new highly dissociative salts. Nonetheless, reasonable salt solubility and dissociation are achieved using bis(trifluoromethanesulfonyl)imide (TFSI), BF 4 , and triflate anion based electrolytes and high-permittivity solvents, such as ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (gBL), and N,N-dimethylformamide (DMF). The local Ca 2+ coordination is concentrationdependent and rather complex, possibly involving bidentate coordination and participation of the nitrogen atom of DMF. The ionicity and the degree of ion-pair formation are both investigated and found to be strongly dependent on the nature of the cation, solvent donicity, and salt concentration. The large ion−ion interaction energies of the contact ion pairs, confirmed by density functional theory (DFT) calculations, are expected to play a major role in the interfacial processes, and thus, we here provide electrolyte design strategies to engineer the cation solvation and possibly improve the power performance of divalent battery systems.

Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid–electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology.

The development of high energy density battery technologies based on divalent metals as the negative electrode is very appealing. Ca and Mg are especially interesting choices due to their combination of low standard reduction potential and natural abundance. One particular problem stalling the technological development of these batteries is the low efficiency of plating/stripping at the negative electrode, which relates to several factors that have not yet been looked at systematically; the nature/concentration of the electrolyte, which determines the mass transport of electro‐active species (cation complexes) toward the electrode; the possible presence of passivation layers, which may hinder ionic transport and hence limit electrodeposition; and the mechanisms behind the charge transfer leading to nucleation/growth of the metal. Different electrolytes are investigated for Mg and Ca, with the presence/absence of chlorides in the formulation playing a crucial role in the cation desolvation. From a R&D point‐of‐view, proper characterization alongside modeling is crucial to understand the phenomena determining the mechanisms of the plating/stripping processes. The state‐of‐the‐art is here presented together with a short perspective on the influence of the cation solvation also on the positive electrode and finally an attempt to define guidelines for future research in the field.

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Water-in-salt and water-in-bisalt electrolytes have recently attracted much attention due to their expanded electrochemical stability windows. The concentration limit of such electrolytes is constrained by the solubility of the lithium salts employed, ca. 21 m (mol kg–1) for LiTFSI (lithium bis­(trifluoromethanesulfonyl)­imide). By adding a second lithium salt, the total salt concentration can be increased, but the hydrogen evolution keeps limiting the application of such systems in batteries with low potential anodes. Herein we report a water-in-bisalt electrolyte with a record salt concentration (31.4 m LiTFSI + 7.9 m Li­[N­(CH3)2((CH2)3SO3)­((CH2)4SO3)]) in which the bulky anion completely prevents the crystallization, even at such low water contents. Although the hydrogen evolution reaction is not completely suppressed, the expanded electrochemical stability window allows for low potential reactions such as aluminum–lithium alloying. The high salt concentration favors the formation of a suitable passivation layer that can be further engineered by modifying the anion structure.

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