The use of calcium (Ca) metal anodes in batteries is currently challenged by the development of a suitable solid electrolyte interface (SEI) that enables effective Ca2+ ion transport. Native calcium electrolytes produce a passivation layer on the surface of the calcium electrodes during cycling, causing a decrease in capacity during cycling and the need for large overpotentials. The use of a hybrid SEI is a strategy to mitigate the uncontrolled production of a passivation layer and reduce the overpotentials needed for the plating and stripping of calcium. Here, we report the development of a hybrid potassium (K)/Ca SEI layer investigated in symmetric Ca//Ca cell configurations. Using KPF6 salt in a ternary mixture of carbonate solvent (EC/EMC/DMC), Ca//Ca cells can be cycled up to 200 h at a capacity of 0.15 mAh/cm2 with a current density of 0.025 mA/cm2. The symmetrical cells consistently cycle at overpotentials of 1.8 V. Ex-situ X-ray diffraction (XRD) of cycled electrodes reveals plating and stripping of both calcium and potassium. Energy dispersive X-ray (EDX) maps confirm the plating of calcium and potassium during galvanostatic cycling. Scanning electron microscopy (SEM) cross-sectional views of the calcium electrodes reveal a continuous SEI layer formed over the calcium metal. XRD analysis reveals the SEI layer consists of K-based inorganics along with the identification of permanent and transient phases. FTIR outlines the parallel plating of both calcium and potassium at both regions of redox activity. Raman spectroscopy of the electrolyte reveals compositional changes over the course of cycling that promote increased plating and stripping. The results indicate that potassium electrolytes are a possible route for tuning the SEI to enable reversible calcium electrochemical cycling.

The dependence on lithium for rising global energy demand coupled with the scarcity of lithium necessitates the exploration of post-lithium strategies. Calcium-ion batteries are one such post-lithium strategy that can mitigate rising costs owing to calcium’s natural abundancy. A critical gap in this field is the lack of cathodes capable of intercalating calcium at high voltages and capacities while also retaining structural stability. The handful of candidates evaluated thus far have been plagued by low capacities and poor cycling performance due to intercalation–induced phase changes and instability. Transition metal oxide post–spinel–type materials have been identified as potential candidates for reversible Ca–ion storage owing to their crystal structures and high theoretical energy densities. However, experimental validation of these theoretical predictions remains largely unaddressed. In this work, post-spinel Calcium Iron Oxide (CaFe2O4) and Calcium Manganese Oxide (CaMn2O4) are explored as cathodes for calcium-ion batteries. The redox activity of each cathode is investigated using galvanostatic (GS) cycling while their structural stabilities are evaluated with X-ray diffraction (XRD) and scanning electron microscopy (SEM). The use of GS in tandem with XRD and SEM provides insights into the evolution of crystal structure with Ca–ion–transport within each cathode. Our results reveal that these post–spinel systems can cycle with a reversible capacity of 56 mAh/g, making them promising cathode candidates for Ca–ion batteries and warrant further investigation.