Sodium-ion batteries have promising potential in large-scale electric storage applications due to their low cost, environmental friendliness, and similar working principles to lithium-ion batteries. O3-type layered oxides are used as a cathode material that determines the energy density of SIBs and stand out from other cathodes due to their high capacity and ease of synthesis. However, the migration of Na+ between octahedral positions in the O3 phase must overcome a large energy barrier, which results in complex reaction phase transitions and rapid capacity decay. Therefore, the Na+ de-intercalation behavior and the structural evolution of O3-type structure should be explored before developing high-performance cathodes. Herein, we systematically investigated the electrochemical properties, Na+ transport kinetics, and phase transition mechanism of O3-NaNi0.4Fe0.2Mn0.4O2 (O3-NFM). The O3-NFM cathode delivered a capacity about 201.9 mAh/g (corresponding to 0.84 mol of Na+ extraction) when charged to 4.3 V. After the cut-off voltage is set to 4.0 V, O3-NFM can achieve a stable reversible cycle. The improved cycling performance between 2.0 V and 4.0 V can be ascribed to the reversible transformation of O3-P3/O3-P3-P3/O3-O3 structural evolution, as determined by in situ X-ray diffraction. A fast kinetics of the Na+ diffusion in the O3 structure was revealed by cyclic voltammetry and galvanostatic intermittent titration technique techniques, which contributes to a good rate performance. This work provides a theoretical basis for investigating the structure modification and material design based on O3-NFM cathodes.
ZHOU Ya′nan. Understanding the Na+ transport kinetics and phase transition mechanism of O3-NaNi0.4Fe0.2Mn0.4O2 cathode materials[J]. Energy Storage Science and Technology, 2023, 12(4): 1011-1017
Fig. 1
The structure, morphology and surface valence characterization of NFM: (a) Rietveld refinement against XRD patterns of NFM; (b) Crystal structures view along c axis; (c) SEM image; XPS spectra of Ni 2p (d), Fe 2p (e) and Mn 2p(f)
Table 1
表1
表1XRD精修得到的O3-NFM晶体学数据
Table 1 Structural parameters and atomic position of O3-NFM from Rietveld refinement
图3
(a) NFM在不同扫速下的CV曲线；(b) 对应的峰电流 Ip 对扫速的平方根 V1/2 的线性拟合；(c) 单步GITT过程示意图；(d) 由GITT拟合得到的电压极化及欧姆极化
Fig. 3
(a) Cyclic voltammograms of NFM under different sweep rates; (b) Peak current Ip as a function of square root of scan rate V1/2; (c) Schematic illustration of single-step GITT process; (d) Corresponding voltage polarization and ohmic polarization from the GITT plots
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