Preparation of Sn-doped NaNi1/3Fe1/3Mn1/3-x Sn x O2 cathode materials and their electrochemical performance

doi:10.19799/j.cnki.2095-4239.2022.0061

Abstract

Abstract:

The O3-type NaNi_1/3Fe_1/3Mn_1/3O₂ materials have been considered as the most promising cathode materials for high-energy density layered sodium-ion batteries owing to their high capacity and structural stability. However, its poor cycling stability and rate performance as a layered oxide material limit its practical application. In this study, NaNi_1/3Fe_1/3Mn_1/3-_x Sn _x O₂ cathode materials with different Sn-doping ratios were synthesized using a simple solid-phase method to improve the electrochemical performance. The analysis results revealed that optimized Sn doping retained the O3 layered structure with R3m space group. In addition, the NaNi_1/3Fe_1/3Mn_1/3-0.02Sn_0.02O₂ material exhibited the best comprehensive electrochemical performance. Mn, which was partially substituted by Sn, could increase the interlayer spacing, enhance the Na⁺ diffusion ability, and reduce lattice-structure damage caused by the Na⁺ insertion/extraction process. Moreover, Sn doping could shrink the length of the TM—O bond, thus enhancing the structural stability of the transition-metal layer. The transmission electron microscopy images showed that Sn-doped cathodes possess more perfectly layered lattice structure, which inhibited lattice distortion. Sn-replaced Mn could improve the redox reversibility of the cathode materials and possibly reduce the loss of favorable phase transition P phase. The NaNi_1/3Fe_1/3Mn_1/3-0.02Sn_0.02O₂ material exhibited the best comprehensive electrochemical performance in which 139.1 mAh/g of initial specific discharge capacity at 0.2 C was achieved. Excellent rate performance was also achieved, as evidenced by the 110.5 mAh/g of specific discharge capacity at 8 C rate and 80.1% capacity retention after 200 cycles in the voltage range of 2-4 V. This work demonstrated the Sn mechanism, which is very important in designing cathode materials with higher rate performance and cyclability.

Key words: sodium ion battery, NaNi_1/3Fe_1/3Mn_1/3O₂ materials, Sn-doped, layered transition metal oxides

CLC Number:

TQ 152

ZHANG Haoran, CHE Haiying, GUO Kaiqiang, SHEN Zhan, ZHANG Yunlong, CHEN Hangda, ZHOU Huang, LIAO Jianping, LIU Haimei, MA Zifeng. Preparation of Sn-doped NaNi_1/3Fe_1/3Mn_1/3-_x Sn _x O₂ cathode materials and their electrochemical performance[J]. Energy Storage Science and Technology, 2022, 11(6): 1874-1882.

Figures/Tables 6

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Table 1

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Table 2

References 31

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Sample	a/Å	c/Å	TM—O/Å	Na—O/Å	Rwp/%
NFM	2.933	16.15	2.061	2.333	10.9
NFMS2	3.01	16.298	2.032	2.406	11.94

Sample	R_s/Ω	R_f/Ω	R_ct/Ω
NFM	9.63	153.7	485．7
NFM-200	25	424.4	292.6
NFMS2	10.7	159.2	175.3
NFMS2-200	14.5	215.3	129.8

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Preparation of Sn-doped NaNi_1/3Fe_1/3Mn_1/3-_x Sn _x O₂ cathode materials and their electrochemical performance

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