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Effect of Na-ion doping on the improved electrochemical performances of olivine structured LiNi1/3Mn1/3Co1/3PO4 for Li-ion hybrid capacitors

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Abstract

Olivine structured materials (LiMPO4; M = Fe, Mn, Co, Ni) are promising for energy storage applications due to their appreciable electrochemical performance, stability, safety, and cost-effectiveness. However, the poor electronic and Li-ion conductivity is the primary drawback of such materials. Therefore, in the present study, the monovalent larger Na+ ion (0.098 nm) is doped in the Li+ (0.076 nm) site of LiNi1/3Mn1/3Co1/3PO4 using the sol–gel method to facilitate the smooth flow of Li+ ions during intercalation/de-intercalation by increasing unit cell volume. The X-ray diffraction pattern reveals that Li1-xNaxNi1/3Mn1/3Co1/3PO4 (x = 0, 0.025, 0.05, 0.1, and 0.15) are orthorhombic structures with the Pnma space group. The slight peak shift of the (311) plane towards lower degrees infers the increased d-spacing. The high-resolution transmission electron microscopic image corroborates that the prepared Li0.95Na0.05Ni1/3Mn1/3Co1/3PO4 particles are in size range of 150–200 nm. The EDX mapping confirms the uniform distribution of transition metals throughout the system. The observed redox peaks in the cyclic voltammogram suggest the Faradaic behavior of the electrodes in 1 M LiOH electrolyte. The calculated specific capacity of Li0.95Na0.05Ni1/3Mn1/3Co1/3PO4 is 117 C g−1 (32.4 mAh g−1) at 5 A g−1. The charge transfer resistance of Li0.95Na0.05Ni1/3Mn1/3Co1/3PO4 is substantially lower than the pristine LiNi1/3Mn1/3Co1/3PO4 electrode infers the higher ionic conductivity. The Li0.95Na0.05Ni1/3Mn1/3Co1/3PO4 || AC device delivered an energy density of 11.7 Wh kg−1 with a power density of 2400 W kg−1 @ 3 A g−1 and has appreciable stability over 2000 cycles.

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Funding

One of the authors, Dr.RKS would like to thank Tamil Nadu State Council for Higher Education (RGP/2019–20/BU/HECP-0008) for providing financial assistance to carry out this research work. The authors also acknowledge the HRTEM facility, Central Instrumentation Center (CIC), Bharathiar University, supported by the DST-PURSE Phase-II program.

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Authors and Affiliations

  1. Energy Storage and Conversion Devices Laboratory, Department of Physics, Bharathiar University, Coimbatore, 641 046, India

    M. Ganeshbabu, N. Prasanna Naga Puneeth & R. Kalai Selvan

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  1. M. Ganeshbabu
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  2. N. Prasanna Naga Puneeth
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  3. R. Kalai Selvan
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Contributions

M.Ganeshbabu: Conceptualization, Data curation, Formal analysis, Methodology, Investigation, Writing –original draft.

N.Prasanna Naga Puneeth: Investigation.

R.Kalai Selvan: Conceptualization, Formal analysis, Writing – reviewing and editing, Supervision, Funding acquisition.

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Correspondence to R. Kalai Selvan.

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Ganeshbabu, M., Puneeth, N.P.N. & Selvan, R.K. Effect of Na-ion doping on the improved electrochemical performances of olivine structured LiNi1/3Mn1/3Co1/3PO4 for Li-ion hybrid capacitors. Ionics 30, 1669–1676 (2024). https://doi.org/10.1007/s11581-024-05377-9

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