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    Rechargeable Ca-Ion Batteries: A New Energy Storage System
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    † § †Chemical Sciences and Engineering Division, ‡X-ray Sciences Division, and §Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    *E-mail: [email protected]
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    Chemistry of Materials

    Cite this: Chem. Mater. 2015, 27, 24, 8442–8447
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    https://doi.org/10.1021/acs.chemmater.5b04027
    Published November 24, 2015
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    Abstract

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    As new uses for larger scale energy storage systems are realized, new chemistries that are less expensive or have higher energy density are needed. While lithium-ion systems have been well studied, the availability of new energy storage chemistries opens up the possibilities for more diverse strategies and uses. One potential path to achieving this goal is to explore chemistries where a multivalent ion such as Ca2+ or Mg2+ is the active species. Herein, we demonstrate this concept for a Ca-ion system utilizing manganese hexacyanoferrate (MFCN) as the cathode to intercalate Ca reversibly in a dry nonaqueous electrolyte. Through characterization via X-ray absorption near-edge spectroscopy, it is determined that only the manganese changes oxidation state during cycling with Ca. X-ray diffraction indicates the MFCN maintains its crystallinity during cycling, with only minor structural changes associated with expansion and contraction. Furthermore, we have demonstrated the first rechargeable Ca-ion battery utilizing MFCN as the cathode and elemental tin as the anode.

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    • SEM of as-synthesized MFCN, ferrocene calibration, Sn CV vs Ca, and EDX of MFCN after cycling vs Sn anode (PDF)

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    Cite this: Chem. Mater. 2015, 27, 24, 8442–8447
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