Preparation and High-performance Lithium-ion Storage of Cobalt-free Perovskite High-entropy Oxide Anode Materials

doi:10.6023/A23020046

Abstract

High-entropy oxides (HEOs) have become increasingly popular as energy storage materials owing to their unique high-entropy effect, multi-principal synergy effect and customizable structure. In this study, a series of cobalt-free perovskite high-entropy oxide La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2M_0.2)O₃ (M=Cu, Mg, Zn) lithium-ion battery anode materials were successfully synthesized by solution combustion method using metal nitrate as the metal source and glycine as the fuel. The microstructure and electrochemical properties of the as-prepared powders were investigated. The results show that the as-prepared high- entropy oxides crystalize into single-phase perovskite structure with porous foam-like shape and chemical/microstructural homogeneity. Furthermore, the as-prepared HEOs introducing inactive element Mg or active element Cu possess similar electrochemical performance; while the La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃ electrode exhibits a highest reversible capacity (1014 mAh•g⁻¹ at 200 mA•g⁻¹ after 250 cycles), excellent cycling stability (450 mAh•g⁻¹ at 1000 mA•g⁻¹ and almost no capacity decay after 1000 cycles) and outstanding rate performance. Such excellent performance can be attributed to the addition of active element Zn, which can form Li-Zn alloy during the reduction process that makes the specific capacity increase significantly. Meanwhile, its higher specific surface area, mesoporous structure and abundant surface oxygen vacancies result in higher conductivity (0.14 S•cm⁻¹), increased larger lithium ion diffusion coefficient (2.1×10⁻¹² cm²•s⁻¹), and pseudo-capacitance contribution, thus significantly enhances the specific capacity and rate performance of the as-prepared material. Therefore, the introduction of electrochemically active metals, which can react with Li alloying, such as Zn, can improve the electrochemical performance, thereby providing ideas for designing cobalt-free HEOs with low-cost and excellent performance for energy storage.

Key words: lithium-ion battery anode material, high-entropy oxide, perovskite structure, alloying, pseudo-capacitance

Cite this article

Jia Yanggang, Chen Shijie, Shao Xia, Cheng Jie, Lin Na, Fang Daolai, Mao Aiqin, Li Canhua. Preparation and High-performance Lithium-ion Storage of Cobalt-free Perovskite High-entropy Oxide Anode Materials[J]. Acta Chimica Sinica, 2023, 81(5): 486-495.

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Fig. & Tab. 9

Figure 1. XRD patterns (a), N2 absorption-desorption isothermal curves, BJH pore size distribution of the samples (b) and SEM images (c~e) and energy dispersive spectroscopy (EDS) images (f) of 4MZn sample

Figure 2. XPS survey spectra of the samples (a), high resolution XPS spectrum of all elements of the samples (b~h) and four probes conductivity (i)

Figure 3. CV plots at 0.1 mV?s?1 sweep rate (a) and charge/discharge profiles (b) of 4MZn electrode, cycling performance and Coulomb efficiency at 200 mA?g?1 current density (c), rate performance (d), long cycle performance at 1000 mA?g?1 current density (e) and Nyquist plots (f) of as-prepared electrodes

Material	Materials synthesis	C-rate/ (mA•g⁻¹)	Cycle number	Capacity/ (mAh•g⁻¹)	Ref.
CoTiO₃	solvothermal	100	200	440	[42]
NdFeO₃	co-precipitation	100	450	475	[43]
HoFeO₃	co-precipitation	100	120	437	[44]
FeTiO₃	sol-gel and hydrothermal	50	200	515	[45]
LaCoO₃	electrospinning	200	200	646	[29]
[(Bi,Na)_1/5(La,Li)_1/5(Ce,K)_1/5(Ca_1/5Sr_1/5)]TiO₃	solid-state method	100	50	84	[47]
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Co_0.2)O₃	solid-state method	200	100	331	[18]
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Co_0.2)O₃	co-precipitation	200	150	772	[19]
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃	SCS	200	250	1014	This work
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃	SCS	1000	1000	450	This work

Table 1. Electrochemical performance of recently reported TMOs and HEOs anodes

Sample	R_s/Ω			R_ct/Ω			D_Li+/(10⁻¹⁴ cm²•s⁻¹)
Sample	Pristine	3rd	250th	Pristine	3rd	250th	Pristine	3rd	250th
4MCu	2.9	4.1	5.9	224	10.2	39.4	0.8	3.1	11.0
4MMg	5.4	4.5	5.0	364	31.9	45.4	1.7	6.7	27.8
4MZn	3.6	7.5	5.0	101	12.5	33.6	1.4	17.4	65.2

Table 2. Parameters of equivalent circuit diagrams of as-prepared electrodes after 0 cycle, 3 cycles and 250 cycles

Figure 4. Cyclic voltammetry (CV) curves of 4MZn electrode at different sweep rates (a), log(ip) vs. log(v) curves (b), separation of pseudocapacitive (blue region) and diffusion (red region) controlled contribution at 1.0 mV?s?1 (c) and contribution ratios of pseudocapacitive capacities at different scan rates (d) of the 4MZn electrode; contribution ratios of pseudocapacitive capacities at different scan rates (e), charge/discharge capacity curves during the GITT measurements (f) and lithium-ion diffusion coefficients during the charge/discharge process (g) of as-prepared electrodes

Figure 5. EIS spectra together with the equivalent circuit (a) and plots of Z' against ω?1/2 in the low frequency region (b) of 4MZn electrode after 0 cycle, 3 cycles and 250 cycles

Figure 6. SEM images of electrodes before and after cycling (the red area represents particle aggregation): (a, b) 4MCu, (c, d) 4MMg and (e, f) 4MZn

Figure 7. Ex-situ XRD patterns of 4MZn electrode

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