Rechargeable calcium batteries possess attractive features for sustainable energy-storage solutions owing to their high theoretical energy densities, safety aspects and abundant natural resources. However, divalent Ca-ions and reactive Ca metal strongly interact with cathode materials and non-aqueous electrolyte solutions, leading to high charge-transfer barriers at the electrode-electrolyte interface and consequently low electrochemical performance. Here, we demonstrate the feasibility and elucidate the electrochemical properties of calcium-tin (Ca–Sn) alloy anodes for Ca-ion chemistries. Crystallographic and microstructural characterizations reveal that Sn formed from electrochemically dealloying the Ca–Sn alloy possesses unique properties, and that this in-situ formed Sn undergoes subsequent reversible calciation/decalciation as CaSn3. As demonstration of the suitability of Ca–Sn alloys as anodes for Ca-ion batteries, we assemble coin cells with an organic cathode (1,4-polyanthraquinone) in an electrolyte of 0.25 M calcium tetrakis(hexafluoroisopropyloxy)borate in dimethoxyethane. These electrochemical cells are charged/discharged for 5000 cycles at 260 mA g−1, retaining a capacity of 78 mAh g−1 with respect to the organic cathode. The discovery of new class of Ca–Sn alloy anodes opens a promising avenue towards viable high-performance Ca-ion batteries.

Porphyrin complexes have been widely studied as promising electrode material in diverse energy storage systems and chemistries. However, like other organic electrodes, porphyrins often suffer from low conductivity and, consequently, require a significant amount (typically 40 %) of electrochemically inactive conductive carbon that occupies volume and mass without storing energy. In this study, we investigate [5,10,15,20 tetrakis(4‐aminophenyl)‐porphyrin] (TAPP) and its metal complexes as redox‐active cathode materials to address the aforementioned issues. The lithium‐ion cells prepared with a high content of CuTAPP active material (70 wt %) demonstrate a stable discharge capacity of ∼120 mAh/g when cycling with a constant current density of 1000 mA/g. The material also showed superior rate capability, e. g., ∼60 mAh/g at 8 A/g. The results of DFT calculations and experimental analysis indicate that the degree of planarity of the metalloporphyrins directly correlates to their cycling stability. Moreover, the contribution from the central metal redox during the cycling is found to be the reason for the significantly higher performance of the Cu‐complex compared to the metal‐free complex. The findings of this study show a general approach for facing common conductivity challenges of organic electrodes and open up a pathway for practical application of organics electrode materials in energy storage application.

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