Preparation and High-rate Lithium-ion Storage of Hollow Sphere Perovskite High-entropy Oxides Assisted by Deep Eutectic Solvents

doi:10.6023/A23100465

Abstract

In recent years, high-entropy oxides (HEOs) have attracted much attention as high-performance anode materials for lithium-ion batteries (LIBs) due to their four effects. In this study, lattice distortions and oxygen vacancies are modulated through morphology and defect modulation strategies. Perovskite-type La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃, La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃, and La(Na_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃ HEO nanocrystalline powders are synthesized through solid state reaction method assisted by deep eutectic solvents using metal nitrate as the metal source, glucose and urea as the deep eutectic solvents. The results show that the as-prepared HEOs exhibit a single perovskite phase which are hollow spherical porous structure with chemical and microstructure homogeneity. The lithium-ion storage performance shows that the La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃ electrode possesses the highest specific capacity (reversible specific capacity of 410.0 mAh•g⁻¹ for 100 cycles at 200 mA•g⁻¹) as well as the outstanding rate performance (342 mAh•g⁻¹ at 100 mA•g⁻¹ and 169.43 mAh•g⁻¹ at 3000 mA•g⁻¹ with a capacity retention rate of 49.4%). Although La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃ exhibts a smaller D_Li+, the appropriate lattice distortions, oxygen vacancies and higher specific area give it a higher conductivity (0.072 S•cm⁻¹) as well as a lower electrochemical impedance, thereby leading to the improved specific capacity and rate performance. This work provides new design concepts and ideas for developing advanced anode materials for high-performance LIBs.

Key words: anode materials, perovskite high-entropy oxides, dope, defect engineering, lithium-ion storage

Cite this article

Mengfan Bao, Shijie Chen, Xia Shao, Huijuan Deng, Aiqin Mao, Jie Tan. Preparation and High-rate Lithium-ion Storage of Hollow Sphere Perovskite High-entropy Oxides Assisted by Deep Eutectic Solvents[J]. Acta Chimica Sinica, 2024, 82(3): 303-313.

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Fig. & Tab. 9

Figure 1. XRD patterns of HEO, Li-HEO and Na-HEO samples (a); Rietveld refined XRD patterns for (b) HEO; (c) Li-HEO; (d) Na-HEO

Figure 2. SEM images of different magnifications for (a1, b1) HEO; (a2, b2) Li-HEO; (a3, b3) Na-HEO; (c) EDS Mapping for elements of (c1) HEO; (c2) Li-HEO; (c3) Na-HEO

Figure 3. N2 adsorption-desorption isotherms and pore size distributions for (a1, b1) HEO; (a2, b2) Li-HEO; (a3, b3) Na-HEO

Sample	S_BET/(m²•g⁻¹)	D_aver/nm	D_most/nm
HEO	13.79	21.34	2.34
Li-HEO	23.74	26.91	2.86
Na-HEO	19.46	19.47	3.10

Table 1. BET specific surface area (SBET), average pore diameter (Daver) and the most probable pore diameter (Dmost)

Figure 4. XPS survey spectra of samples (a), and high resolution XPS spectra of all elements (b~i)

Figure 5. CV curves, charge/discharge profiles and dQ/dV plots for the first three cycles of the three electrodes: (a1, b1, c1) HEO, (a2, b2, c2) Li-HEO, (a3, b3, c3) Na-HEO; Cyclic performance and Coulomb efficiency at 200 mA?g?1 (d) and rate performance (e) for three electrodes and La(Co0.4Fe0.6)O3 electrode

Figure 6. SEM images of different magnifications for Li-HEO before (a1, b1) and after 80 cycles of rate performance (a2, b2)

Figure 7. Four-probe conductivity for three electrodes (a) and initial impedance plots (b); Impedance plots before and after cycling and straight-line plots of ω1/2 versus Z' for three electrodes: (c1, d1) HEO; (c2, d2) Li-HEO and (c3, d3) Na-HEO; Charge/discharge capacity curves during the GITT measurements (e) and lithium-ion diffusion coefficients during the charge/discharge process of as-prepared electrodes (f)

Figure 8. CV curves of HEO, Li-HEO and Na-HEO electrodes (a1, a2, a3) at different sweeping rates; (b1, b2, b3) lg(ip) versus lg(v); (c1, c2, c3) Percentage contribution of pseudocapacitance at 1.0 mV?s?1; (d1, d2, d3) Contribution ratios of pseudocapacitance at different scan rates

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