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Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage



Calcium-ion batteries (CIBs) are attractive candidates for energy storage because Ca2+ has low polarization and a reduction potential (−2.87 V versus standard hydrogen electrode, SHE) close to that of Li+ (−3.04 V versus SHE), promising a wide voltage window for a full battery. However, their development is limited by difficulties such as the lack of proper cathode/anode materials for reversible Ca2+ intercalation/de-intercalation, low working voltages (<2 V), low cycling stability, and especially poor room-temperature performance. Here, we report a CIB that can work stably at room temperature in a new cell configuration using graphite as the cathode and tin foils as the anode as well as the current collector. This CIB operates on a highly reversible electrochemical reaction that combines hexafluorophosphate intercalation/de-intercalation at the cathode and a Ca-involved alloying/de-alloying reaction at the anode. An optimized CIB exhibits a working voltage of up to 4.45 V with capacity retention of 95% after 350 cycles.

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Fig. 1: Configuration and reaction mechanism of a CIB.
Fig. 2: Electrochemical and mechanical reversibility of the Sn anode.
Fig. 3: Electrochemical performance of a CIB.

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The authors thank Nanzhong Wu and Lei Shi for data analysis and in situ stress measurements. The authors acknowledge financial support from the National Natural Science Foundation of China (grant no. 51302238), Shenzhen Peacock Plan (KQJSCX20170331161244761 and KQTD2016112915051055), the Natural Science Foundation of Guangdong Province (no. 2017A030310482), Shenzhen Science and Technology Planning Project (JCYJ20160122143155757, JSGG20160301173854530, JSGG20160301155933051, JSGG20160229202951528, JCYJ20170307171232348, JCYJ20170307172850024 and JSGG20170413153302942), Guangdong Engineering Technology Research Center Foundation (no. 20151487), Shenzhen Engineering Laboratory Foundation (no. 20151837), and the Scientific Equipment Project of the Chinese Academy of Sciences (GJHS20170314161200165, yz201440).

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Authors and Affiliations



Y.B.T. and H.-M.C. conceived and designed the experiments. M.W. and S.Q.Z. performed electrochemical experiments. C.L.J. conducted in situ stress measurements. M.W. and S.Q.Z. conducted XRD, Raman, XPS and SEM measurements. X.H.S. conducted simulation work. Y.B.T., M.W., C.L.J., X.H.S. and H.-M.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Yongbing Tang or Hui-Ming Cheng.

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Wang, M., Jiang, C., Zhang, S. et al. Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage. Nature Chem 10, 667–672 (2018).

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