Optimizing O3-Type Fe-Mn-Based Cathodes for Na-Ion Batteries: Unveiling the Synergistic Impact of Chemical Co-Substitution

• DOI: 10.1149/ma2024-01115mtgabs
• Publication Date: 2024-08-19T15:04:18Z
• Authors: Arindam Ghosh; Rashmi Hegde; Keshav Kumar; Premkumar Sengutt...
• Keywords: Substitution (logic)

Layered transition metal oxide-Na x MO 2 (M = metal) is the most widely explored class of cathode materials in lithium and sodium-ion batteries (LIBs SIBs). 1 The replacement expensive Co Ni with cheaper elements like Fe Mn appealing, which can reduce overall cost battery. Despite higher operating voltage 3+ /Fe 4+ large specific capacity /Mn , issues irreversible Fe-migration J. T. distortion are yet to be overcome. 2,3 To improve electrochemical performances layered oxide cathodes, various cationic substitutions (e.g., Li + Cu 2+ Mg Zn Ti ) partially substituted place M. 4–6 Along this line, search better Fe/Mn-based we selected an O3-type Na [Fe 0.50 ]O (NFMO) material co-substituted layer create a composition [Li y 0.50-x-y (NCLFMO) compared their performances.. Both crystallize rhombohedral structure Rietveld refinement TEM analyses suggest enhanced O-Na-O spacing after substitution. NFMO NCLFMO cathodes display 135 121 mAh g -1 potential window 4.0–2.0 V at 0.1 C rate, average (V avg 2.63 3.31 respectively, leads increased energy density 400 Wh kg for NCLFMO. 7 Following substitution, contributions become 20.2% 79.8%, instead 49.8% 50.2% NFMO. Clearly, it indicates pronounced redox activity suppressed redox. Chemical co-substitution significantly improves retention, retaining 98% its initial discharge 500 cycles, 52% Better rate capability, faster diffusion coefficient ions from GITT, reduced cell resistance impedance spectroscopy support In-situ XRD measurement reveals reversible O3-P3-O’3-P3-O3 phase ex-situ x-ray absorption analysis confirms prominent during charge-discharge cycling. More significantly, remains air-stable, properties exposure air 30 days. Finally, full precycled HC constructed, delivering 105 3.15 4.0-1.5 rate. In conclusion, (Li Cu)-co-substitution strategy performance Fe-Mn-based cathode, paving way developing commercialized SIBs. References Y. Hwang, S. Myung, K. Sun, Chem. Soc. Rev. 46, 3529–3614 (2017). Komaba, N. Yabuuchi, Nakayama, A. Ogata, Ishikawa I. Nakai, Inorg. 51 6211–6220 (2012). B. Mortemard De Boisse, H. Cheng, D. Carlier, Guignard, C. Pan, Bordère, Filimonov, Drathen, E. Suard, Wattiaux Delmas, Mater. A 3 10976–10989 (2015). L. Yang, X. Li, Liu, Xiong, Ma, P. Bai, W. Xu, Tang, Hu, Liu Chen, Am. 141 6680–6689 (2019). G. Singh, Tapia-Ruiz, Lopez Del Amo, U. Maitra, Somerville, R. Armstrong, Martinez Ilarduya, Rojo Bruce, 28 5087–5094 (2016). Wang, Piao, Guo, Manthiram, Ma Cao 5 8752–8761 Ghosh, Hegde, Kumar Senguttuvan, submitted(2023).