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P2-type Na0.67Ni0.33−x Cu x Mn0.67O2 as new high-voltage cathode materials for sodium-ion batteries

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Abstract

P2-Na0.67Ni0.33−x Cu x Mn0.67O2 (x = 0, 0.02, 0.04, 0.06, 0.08) cathode materials have been synthesized via acetate decomposition method. The elementary composition and crystal structure of the powders are studied in detail using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and X-ray diffraction (XRD). XRD results demonstrate that Cu2+ ions have been incorporated into the crystal structure successfully and the P2-type structure remains unchanged after substitution. According to XPS data, Cu substitution does not change the valence states of Ni and Mn, whose predominant oxidation states in Na-Ni-Mn-O structure remains +2 and +4. The introduction of Cu2+ can effectively suppress P2-O2 phase transformation when charging to 4.5 V, and significantly improve rate performance and cyclic stability compared to the undoped material. The P2-Na0.67Ni0.27Cu0.06Mn0.67O2 sample can deliver an initial discharge capacity of 211.6 mAh g−1 at 10 mAh g−1 between 1.5 and 4.5 V, and a capacity retention of 93.9% after 10 cycles. Moreover, it can also deliver a discharge capacity of 115.2 mAh g−1 at 100 mAh g−1. In addition, electrochemical impedance spectroscopy (EIS) reveals that P2-Na0.67Ni0.27Cu0.06Mn0.67O2 cathode exhibits a higher electronic conductivity and faster sodium ion diffusion velocity than that of undoped sample. These results show that P2-Na0.67Ni0.27Cu0.06Mn0.67O2 is a promising high-voltage cathode material for sodium-ion batteries.

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Authors and Affiliations

  1. School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, 300130, People’s Republic of China

    Sen Chen, Enshan Han, Lingzhi Zhu, Bin Liu, Guangquan Zhang & Min Lu

  2. National Key Lab of Power Sources, Tianjin Institute of Power Sources, Tianjin, 300384, China

    Sen Chen & Han Xu

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  1. Sen Chen
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  2. Enshan Han
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  3. Han Xu
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  4. Lingzhi Zhu
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  5. Bin Liu
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  6. Guangquan Zhang
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  7. Min Lu
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Correspondence to Sen Chen or Han Xu.

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Chen, S., Han, E., Xu, H. et al. P2-type Na0.67Ni0.33−x Cu x Mn0.67O2 as new high-voltage cathode materials for sodium-ion batteries. Ionics 23, 3057–3066 (2017). https://doi.org/10.1007/s11581-017-2122-x

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