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

Nature Chemistryvolume 10pages667672 (2018) | Download Citation

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Abstract

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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References

  1. 1.

    Lin, M.-C. et al. An ultrafast rechargeable aluminium-ion battery. Nature 520, 324–328 (2015).

  2. 2.

    Ponrouch, A., Frontera, C., Bardé, F. & Palacin, M. Towards a calcium-based rechargeable battery. Nat. Mater. 15, 169–173 (2016).

  3. 3.

    Larcher, D. & Tarascon, J.-M. Towards greener and more sustainable batteries for electrical energy storage. Nat. Chem. 7, 19–29 (2015).

  4. 4.

    Shterenberg, I., Salama, M., Gofer, Y., Levi, E. & Aurbach, D. The challenge of developing rechargeable magnesium batteries. MRS Bull. 39, 453–460 (2014).

  5. 5.

    Wang, R. Y., Wessells, C. D., Huggins, R. A. & Cui, Y. Highly reversible open framework nanoscale electrodes for divalent ion batteries. Nano Lett. 13, 5748–5752 (2013).

  6. 6.

    Wang, R. Y. et al. Reversible multivalent (monovalent, divalent, trivalent) ion insertion in open framework materials. Adv. Energy Mater. 5, 1401869 (2015).

  7. 7.

    Arroyo-de Dompablo, M. E. et al. A joint computational and experimental evaluation of CaMn2O4 polymorphs as cathode materials for Ca ion batteries. Chem. Mater. 28, 6886–6893 (2016).

  8. 8.

    Lipson, A. L. et al. Rechargeable Ca-ion batteries: a new energy storage system. Chem. Mater. 27, 8442–8447 (2015).

  9. 9.

    Aurbach, D., Skaletsky, R. & Gofer, Y. The electrochemical behavior of calcium electrodes in a few organic electrolytes. J. Electrochem. Soc. 138, 3536–3545 (1991).

  10. 10.

    Ouchi, T., Kim, H., Spatocco, B. L. & Sadoway, D. R. Calcium-based multi-element chemistry for grid-scale electrochemical energy storage. Nat. Commun. 7, 10999 (2016).

  11. 11.

    Gogotsi, Y. & Simon, P. True performance metrics in electrochemical energy storage. Science 334, 917–918 (2011).

  12. 12.

    Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nat. Mater. 7, 845–854 (2008).

  13. 13.

    Bai, S. Y., Liu, X. Z., Zhu, K., Wu, S. C. & Zhou, H. S. Metal–organic framework-based separator for lithium-sulfur batteries. Nat. Energy 1, 16094 (2016).

  14. 14.

    Kim, J. H. et al. Stabilization of insoluble discharge products by facile aniline modification for high performance Li–S batteries. Adv. Energy Mater. 5, 1500268 (2015).

  15. 15.

    Seel, J. & Dahn, J. Electrochemical intercalation of PF6 into graphite. J. Electrochem. Soc. 147, 892–898 (2000).

  16. 16.

    Placke, T. et al. Influence of graphite characteristics on the electrochemical intercalation of bis(trifluoromethanesulfonyl) imide anions into a graphite-based cathode. J. Electrochem. Soc. 160, A1979–A1991 (2013).

  17. 17.

    Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4418 (2004).

  18. 18.

    Sheng, M., Zhang, F., Ji, B., Tong, X. & Tang, Y. A novel tin‐graphite dual‐ion battery based on sodium‐ion electrolyte with high energy density. Adv. Energy Mater. 7, 1601963 (2017).

  19. 19.

    Lee, Y., Lee, J., Kim, H., Kang, K. & Choi, N.-S. Highly stable linear carbonate-containing electrolytes with fluoroethylene carbonate for high-performance cathodes in sodium-ion batteries. J. Power Sources 320, 49–58 (2016).

  20. 20.

    Fan, H., Qi, L. & Wang, H. Hexafluorophosphate anion intercalation into graphite electrode from methyl propionate. Solid State Ion. 300, 169–174 (2017).

  21. 21.

    Jain, A. et al. Commentary: The Materials Project. A materials genome approach to accelerating materials innovation. Appl. Mater. 1, 011002 (2013).

  22. 22.

    Schechter, A., Aurbach, D. & Cohen, H. X-ray photoelectron spectroscopy study of surface films formed on Li electrodes freshly prepared in alkyl carbonate solutions. Langmuir 15, 3334–3342 (1999).

  23. 23.

    Borg, R. & Dienes, G. J. An Introduction to Solid State Diffusion (Academic, San Diego, 1988).

  24. 24.

    Stoney, G. G. The tension of metallic films deposited by electrolysis. Proc. R. Soc. Lond. 82, 40–43 (1909).

  25. 25.

    Zhang, S. Nanostructured Thin Films and Coatings: Mechanical Properties 1 (CRC, Boca Raton, 2010).

  26. 26.

    Fang, L. & Chowdari, B. Sn–Ca amorphous alloy as anode for lithium ion battery. J. Power Sources 97, 181–184 (2001).

  27. 27.

    Noel, M. & Santhanam, R. Electrochemistry of graphite intercalation compounds. J. Power Sources 72, 53–65 (1998).

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Acknowledgements

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).

Author information

Affiliations

  1. Functional Thin Films Research Center, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen, China

    • Meng Wang
    • , Chunlei Jiang
    • , Songquan Zhang
    • , Xiaohe Song
    •  & Yongbing Tang
  2. Tsinghua-Berkeley Shenzhen Institute, Tsinghua University, Shenzhen, China

    • Hui-Ming Cheng
  3. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

    • Hui-Ming Cheng

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Contributions

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.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Yongbing Tang or Hui-Ming Cheng.

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DOI

https://doi.org/10.1038/s41557-018-0045-4