Cu cation vacancies enhance the lithium storage performance of perovskite-type high-entropy oxides

doi:10.11949/0438-1157.20250292

Abstract

Abstract:

High-entropy oxides (HEOs) have attracted much attention in the field of energy storage due to their excellent cycle stability and high theoretical specific capacity, but their low intrinsic conductivity limits their application. In this study, the Cu content in La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Cu _x □_0.2-_x )O_3-_δ (x=0, 0.1 and 0.2) was systematically modulated to optimize cation/oxygen vacancies, synergistically improving the microstructure and electronic structure while stabilizing the perovskite framework. This optimization enhanced both electron/ion transport kinetics and electrochemical performance. The results demonstrate that La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Cu_0.1□_0.1)O_3-_δ exhibits outstanding high-rate lithium storage performance: a specific capacity of 1174.3 mAh·g^-1 after 250 cycles at 200 mA·g^-1, representing a 1.3-fold improvement over the x = 0.2 sample. Even at a high current density of 3000 mA·g^-1, it maintains a specific capacity of 200.1 mAh·g^-1 (49.6% capacity retention relative to 100 mA·g^-1), with a fourfold enhancement in rate capability. By strategically regulating cation/oxygen vacancy defects, this study effectively improves the electrochemical performance of perovskite-type HEOs, offering a novel design strategy for developing high-performance HEO anode materials.

Key words: cation vacancy, high-entropy perovskite oxides, nanomaterials, lithium-ion batteries anode materials, electrochemistry, kinetics

摘要：

高熵氧化物（HEOs）因其优异的循环稳定性和较高的理论比容量在储能领域备受关注，但其本征电导率较低限制了其应用。本研究通过调控La（Cr_0.2Fe_0.2Mn_0.2Ni_0.2Cu _x □_0.2-_x ）O_3-_δ （x=0、0.1和0.2）中Cu含量，优化阳离子/氧空位，在稳定钙钛矿结构的同时协同改善微观/电子结构，提升电子/离子传输速率，增强电化学性能。结果表明，La（Cr_0.2Fe_0.2Mn_0.2Ni_0.2Cu_0.1□_0.1）O_3-_δ 具有优异的高倍率储锂性能：200 mA·g^-1时循环250圈后比容量达1174.3 mAh·g^-1，较x=0.2的样品提升1.3倍；在3000 mA·g^-1高倍率下仍保持200.1 mAh·g^-1的比容量（容量保持率相较100 mA·g^-1时为49.6%），倍率性能提升4倍。本研究通过调控阳离子/氧空位缺陷，有效提升了钙钛矿型HEO的电化学性能，为开发高性能HEOs负极材料提供了新的设计策略。

关键词: 阳离子空位, 高熵钙钛矿氧化物, 纳米材料, 锂离子电池负极材料, 电化学, 动力学

CLC Number:

TM 912

Shibiao XU, Zhengbing WEI, Mengfan BAO, Yi CHENG, Yanggang JIA, Na LIN, Aiqin MAO. Cu cation vacancies enhance the lithium storage performance of perovskite-type high-entropy oxides[J]. CIESC Journal, 2025, 76(12): 6718-6728.

徐世彪, 韦正兵, 鲍梦凡, 程怡, 贾洋刚, 林娜, 冒爱琴. Cu阳离子空位提升钙钛矿型高熵氧化物储锂性能[J]. 化工学报, 2025, 76(12): 6718-6728.

Figures/Tables 8

Fig.1 (a) XRD patterns of the samples; (b)—(d) Rietveld refinement XRD patterns of the samples

Table 1 Lattice parameter of samples and the reliability factors of the Rietveld refinement

样品	晶胞参数					可靠性因子
样品	a/Å	b/Å	c/Å	α=β=γ/(°)	V_m/Å³	R_p/%	R_wp/%	χ²
Cu₀	3.897	3.897	3.897	90	59.12	9.18	7.01	3.74
Cu_0.1	3.892	3.892	3.892	90	58.99	7.63	5.74	2.79
Cu_0.2	3.894	3.894	3.894	90	59.05	7.75	5.88	3.13

Fig.2 N2 absorption-desorption isothermal curves and BJH pore size distribution of the samples (a); The metal element contents of the Cu0.1 and Cu0.2 samples measured by ICP (b);SEM patterns Cu0 (c), Cu0.1 (d) and Cu0.2 (e); EDS mapping patterns of Cu0.1 sample (f)

Table 2 BET surface areas， pore volume， average pore size and the most probable pore size of the samples

最可几

孔径/nm

Cu₀

Fig.3 XPS survry spectras(a); High resolution XPS spectrums of all elements of the samples (b)—(h); Four probes conductivity(i)

Table 3 Concentration ratio of cationic valence states in XPS and oxygen vacancy concentration

样品	阳离子价态浓度						O_V/%
样品	La³⁺	Cr³⁺	Fe²⁺/Fe³⁺	Mn³⁺/Mn⁴⁺	Ni²⁺/Ni³⁺	Cu⁺/Cu²⁺	O_V/%
Cu₀	1	1	46.1/53.9	53.5/46.5	54.2/45.8	0	27.6
Cu_0.1	1	1	53.6/46.4	55.8/44.2	54.9/45.1	42.4/57.6	41.2
Cu_0.2	1	1	52.3/47.7	54.8/45.2	61.5/38.5	54.9/45.1	27.4

Fig.4 CV curves at 0.1 mV·s-1 sweep rate (a) and charge/discharge profiles(b) and dQ/dV plots(c) at 200 mA·g-¹ of the Cu0.1 electrode; cycling performance/Coulombic efficiency (d) and rate performance of each electrode (e)

Fig.5 CV curves of Cu0.1 electrode at different scan rates (a); The relationship between lgip and lgv (b); Contribution ratios of pseudocapacitive capacities at different scan rates of the Cu0.1 electrode (c); Contribution ratios of the electrodes (d); The relationship between ip and v1/2(e); The b-value of pseudocapacitive and lithium-ion diffusion coefficient calculated from CV(f); Charge/discharge curves during the GITT test (g) and DLi+ during the charge/discharge process (h)

References 37

[1]	Anandkumar M, Trofimov E. Synthesis, properties, and applications of high-entropy oxide ceramics: current progress and future perspectives[J]. Journal of Alloys and Compounds, 2023, 960: 170690.
[2]	黄俊达, 朱宇辉, 冯煜, 等. 二次电池研究进展[J]. 物理化学学报, 2022, 38(12): 2208008.
	Huang J D, Zhu Y H, Feng Y, et al. Research progress on key materials and technologies for secondary batteries[J]. Acta Physico-Chimica Sinica, 2022, 38(12): 2208008.
[3]	Lim S, Kim J H, Yamada Y, et al. Improvement of rate capability by graphite foam anode for Li secondary batteries[J]. Journal of Power Sources, 2017, 355: 164-170.
[4]	Sarkar A, Velasco L, Wang D, et al. High entropy oxides for reversible energy storage[J]. Nature Communications, 2018, 9: 3400.
[5]	Chen G J, Li C W, Jia H M, et al. A novel approach for the composition design of high-entropy fluorite oxides with low thermal conductivity[J]. Journal of Advanced Ceramics, 2024, 13(9): 1369-1381.
[6]	Bai Y H, Li J R, Lu H, et al. Ultrafast high-temperature sintering of high-entropy oxides with refined microstructure and superior lithium-ion storage performance[J]. Journal of Advanced Ceramics, 2023, 12(10): 1857-1871.
[7]	Nguyen T X, Tsai C C, Patra J, et al. Co-free high entropy spinel oxide anode with controlled morphology and crystallinity for outstanding charge/discharge performance in lithium-ion batteries[J]. Chemical Engineering Journal, 2022, 430: 132658.
[8]	Patra J, Nguyen T X, Tsai C C, et al. Effects of elemental modulation on phase purity and electrochemical properties of Co-free high-entropy spinel oxide anodes for lithium-ion batteries[J]. Advanced Functional Materials, 2022, 32(17): 2110992.
[9]	Xiao B, Wu G, Wang T D, et al. High-entropy oxides as advanced anode materials for long-life lithium-ion batteries[J]. Nano Energy, 2022, 95: 106962.
[10]	Wang K, Hua W B, Huang X H, et al. Synergy of cations in high entropy oxide lithium ion battery anode[J]. Nature Communications, 2023, 14(1): 1487.
[11]	Luo X F, Patra J, Chuang W T, et al. Charge-discharge mechanism of high‐entropy Co-free spinel oxide toward Li⁺ storage examined using operando quick-scanning X-ray absorption spectroscopy[J]. Advanced Science, 2022, 9(21): 2201219.
[12]	Li Y N, Wang B B, Wang Y L, et al. Modulating crystal structure and lithium-ion storage performance of high-entropy oxide (CrMnFeCoNiZn)₃O₄ by single element extraction[J]. Composites Part B: Engineering, 2025, 294: 112175.
[13]	Gao P, Chen Z, Gong Y X, et al. The role of cation vacancies in electrode materials for enhanced electrochemical energy storage: synthesis, advanced characterization, and fundamentals[J]. Advanced Energy Materials, 2020, 10(14): 1903780.
[14]	Yan J H, Wang D, Zhang X Y, et al. A high-entropy perovskite titanate lithium-ion battery anode[J]. Journal of Materials Science, 2020, 55(16): 6942-6951.
[15]	Hou S S, Su L, Wang S, et al. Unlocking the origins of highly reversible lithium storage and stable cycling in a spinel high-entropy oxide anode for lithium-ion batteries[J]. Advanced Functional Materials, 2024, 34(4): 2307923.
[16]	张欣, 韩登宝, 陈小梅, 等. 钙钛矿材料制备中的溶剂配位效应[J]. 物理化学学报, 2021, 37(4): 2008055.
	Zhang X, Han D B, Chen X M, et al. Effects of solvent coordination on perovskite crystallization[J]. Acta Physico- Chimica Sinica, 2021, 37(4): 2008055.
[17]	Liu X F, Xing Y Y, Xu K, et al. Kinetically accelerated lithium storage in high‐entropy (LiMgCoNiCuZn)O enabled by oxygen vacancies[J]. Small, 2022, 18(18): 2200524.
[18]	Zhang R, Liu Z L, Gao T N, et al. A solvent‐polarity‐induced interface self‐assembly strategy towards mesoporous triazine‐based carbon materials[J]. Angewandte Chemie International Edition, 2021, 60(45): 24299-24305.
[19]	Feng D Y, Dong Y B, Zhang L L, et al. Holey lamellar high-entropy oxide as an ultra-high-activity heterogeneous catalyst for solvent-free aerobic oxidation of benzyl alcohol[J]. Angewandte Chemie International Edition, 2020, 59(44): 19503-19509.
[20]	Li X L, Lin Z F, Jin N, et al. Perovskite‐type SrVO₃as high‐performance anode materials for lithium-ion batteries[J]. Advanced Materials, 2022, 34(46): 2107262.
[21]	Yang Y, Zhu J W, Wang P Y, et al. NH₂-MIL-125 (Ti) derived flower-like fine TiO₂ nanoparticles implanted in N-doped porous carbon as an anode with high activity and long cycle life for lithium-ion batteries[J]. Acta Physico-Chimica Sinica, 2022, 38(6): 2106002.
[22]	Petrovičovà B, Xu W L, Musolino M G, et al. High-entropy spinel oxides produced via sol-gel and electrospinning and their evaluation as anodes in Li-ion batteries[J]. Applied Sciences, 2022, 12(12): 5965.
[23]	Howng W Y, Thorn R J. Investigation of the electronic structure of L a 1 - x ( M 2 + ) x C r O 3 , Cr₂O₃ and La₂O₃ by X-ray photoelectron spectroscopy[J]. Journal of Physics and Chemistry of Solids, 1980, 41(1): 75-81.
[24]	Jia Y G, Chen S J, Shao X, et al. Synergetic effect of lattice distortion and oxygen vacancies on high-rate lithium-ion storage in high-entropy perovskite oxides[J]. Journal of Advanced Ceramics, 2023, 12(6): 1214-1227.
[25]	Xiao B, Wu G, Wang T D, et al. Enhanced Li-ion diffusion and cycling stability of Ni-free high-entropy spinel oxide anodes with high-concentration oxygen vacancies[J]. ACS Applied Materials & Interfaces, 2023, 15(2): 2792-2803.
[26]	Tian K H, Duan C Q, Ma Q, et al. High-entropy chemistry stabilizing spinel oxide (CoNiZnXMnLi)₃O₄ (X = Fe, Cr) for high-performance anode of Li-ion batteries[J]. Rare Metals, 2022, 41(4): 1265-1275.
[27]	Wei S, Wan C C, Zhang L Y, et al. N-doped and oxygen vacancy-rich NiCo₂O₄ nanograss for supercapacitor electrode [J]. Chemical Engineering Journal, 2022, 429: 132242.
[28]	Nguyen T X, Patra J, Tsai C C, et al. Secondary-phase-induced charge-discharge performance enhancement of Co-free high entropy spinel oxide electrodes for Li-ion batteries[J]. Advanced Functional Materials, 2023, 33(30): 2300509.
[29]	冯炜程, 于景成, 杨溢澜, 等. 调控双钙钛矿中高熵组分促进高温析氧反应[J]. 物理化学学报, 2024, 40(6): 2306013.
	Feng W C, Yu J C, Yang Y L, et al. Regulating the high entropy component of double perovskite for high-temperature oxygen evolution reaction[J]. Acta Physico-Chimica Sinica, 2024, 40(6): 2306013.
[30]	Yang X D, Li F, Liu W, et al. Oxygen vacancy-induced spin polarization of tungsten oxide nanowires for efficient photocatalytic reduction and immobilization of uranium(Ⅵ) under simulated solar light[J]. Applied Catalysis B-Environmental, 2023, 324: 122202.
[31]	Duan C Q, Tian K H, Li X L, et al. New spinel high-entropy oxides (FeCoNiCrMnXLi)₃O₄(X= Cu, Mg, Zn) as the anode material for lithium-ion batteries[J]. Ceramics International, 2021, 47(22): 32025-32032.
[32]	杨毅, 闫崇, 黄佳琦. 锂电池中固体电解质界面研究进展[J]. 物理化学学报, 2021, 37(11): 62-74.
	Yang Y, Yan C, Huang J Q, et al. Research progress of solid electrolyte interphase in lithium batteries[J]. Acta Physico-Chimica Sinica, 2021, 37(11): 62-74.
[33]	Zhai F Y, Zhu X Y, Zhang W F, et al. Insight of the evolution of structure and energy storage mechanism of (FeCoNiCrMn)₃O₄ spinel high entropy oxide in life-cycle span as lithium-ion battery anode[J]. Journal of Power Sources, 2024, 603: 234418.
[34]	Kim H, Choi W, Yoon J, et al. Exploring anomalous charge storage in anode materials for next-generation Li rechargeable batteries[J]. Chemical Reviews, 2020, 120(14): 6934-6976.
[35]	Li X L, Lin Z F, Jin N, et al. Boosting the lithium-ion storage performance of perovskite Sr _x VO_3- _δ via Sr cation and O anion deficient engineering[J]. Chinese Science Bulletin, 2022, 67(22): 2305-2315.
[36]	Du W Q, Zheng Y Q, Liu X Y, et al. Oxygen-enriched vacancy spinel MFe₂O₄/carbon (M= Ni, Mn, Co) derived from metal-organic frameworks toward boosting lithium storage[J]. Chemical Engineering Journal, 2023, 451(2): 138626.
[37]	Lv H L, Wang X J, Yang Y, et al. RGO-coated MOF-derived In₂Se₃ as a high-performance anode for sodium-ion batteries[J]. Acta Physico-Chimica Sinica, 2023, 39(3): 2210014.