Cu阳离子空位提升钙钛矿型高熵氧化物储锂性能

doi:10.11949/0438-1157.20250292

化工学报 ›› 2025, Vol. 76 ›› Issue (12): 6718-6728.DOI: 10.11949/0438-1157.20250292

• 材料化学工程与纳米技术 • 上一篇下一篇

Cu阳离子空位提升钙钛矿型高熵氧化物储锂性能

徐世彪¹(), 韦正兵¹, 鲍梦凡¹, 程怡¹, 贾洋刚¹, 林娜¹, 冒爱琴¹^,²()

^1.安徽工业大学材料科学与工程学院，先进陶瓷研究中心，安徽马鞍山 243032
^2.安徽工业大学，氢电高效转化与固态存储安徽省重点实验室，安徽马鞍山 243032

收稿日期:2025-03-24 修回日期:2025-05-11 出版日期:2025-12-31 发布日期:2026-01-23
通讯作者: 冒爱琴
作者简介:徐世彪（2000—），男，硕士研究生，xushibiao002@163.com
基金资助:
安徽省高校自然科学研究重点项目(2023AH051104);氢电高效转化与固态存储安徽省重点实验室开放基金(ECSSHE2024KF05)

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

Shibiao XU¹(), Zhengbing WEI¹, Mengfan BAO¹, Yi CHENG¹, Yanggang JIA¹, Na LIN¹, Aiqin MAO¹^,²()

^1.Advanced Ceramics Research Center, School of Materials Science and Engineering, Anhui University of Technology, Ma’anshan 243032, Anhui, China
^2.Anhui Province Key Laboratory of Efficient Conversion and Solid-State Storage of Hydrogen & Electricity, Anhui University of Technology, Ma’anshan 243032, Anhui, China

Received:2025-03-24 Revised:2025-05-11 Online:2025-12-31 Published:2026-01-23
Contact: Aiqin MAO

摘要/Abstract

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

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

中图分类号:

TM 912

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.

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.

图/表 8

图1 (a)各样品的XRD谱图；(b）~（d)各样品的Rietveld精修图谱

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

表1 样品的晶胞参数和精修的可靠性因子

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

图2 N2吸/脱附等温曲线及BJH孔径分布(a)；ICP测量的Cu0.2和Cu0.1样品中金属元素的摩尔比(b)；Cu0(c)、Cu0.1(d)和Cu0.2(e)的SEM图；Cu0.1样品的EDS mapping图(f)

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)

表2 样品的BET比表面积、孔体积、平均孔径和最可几孔径

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

图3 XPS测量光谱(a)；样品中所有元素的高分辨率XPS光谱(b）~（h)；四探针电导率(i)

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

表3 XPS中阳离子价态浓度比及氧空位浓度

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

图4 Cu0.1电极在0.1 mV·s-1描扫速率下的CV图(a)、在200 mA·g-1下的充放电曲线图(b)以及微分容量曲线(c)；各电极在200 mA·g-1下的循环性能/库仑效率(d)和倍率性能(e)

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)

图5 Cu0.1电极在不同扫速下的CV曲线(a)；lgip与lgv的关系曲线(b)；Cu0.1电极不同扫描速率下的赝电容贡献率(c)；各电极不同扫描速率下的赝电容贡献率(d)；ip与v1/2的关系图(e)；赝电容b值和循环伏安法DLi+(f)；GITT测试过程中的充电/放电曲线(g)和充电/放电过程中的DLi+(h)

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)

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Cu阳离子空位提升钙钛矿型高熵氧化物储锂性能

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

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