氟掺杂诱导岩盐型高熵氧化物本征缺陷调控及其储锂性能优化

doi:10.6023/A25040107

摘要/Abstract

高熵氧化物因其灵活的组分设计和多组元之间的协同效应, 被认为是锂离子电池最具有潜力的负极材料之一. 然而其较低的本征电子/离子电导率严重限制其在锂离子电池存储中的动力学行为, 高熵氧化物负极材料存在倍率性能低、循环稳定性差的现状. 本研究以岩盐型(Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O为研究基础, 采用溶液燃烧法, 通过高电负性阴离子F^－掺杂策略, 调控晶格畸变和氧空位等本征缺陷, 成功制备了具有单一岩盐结构的F^－掺杂(Co_0.2Cu_0.2Mg_0.2- Ni_0.2Zn_0.2)O_1－_xF_x (x=0, 0.05, 0.1)高熵氧化物锂离子电池负极材料. 测试结果表明: (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O_0.95F_0.05负极材料展示了卓越的倍率性能和优异的循环稳定性, 200 mA•g^－1下循环150圈后比容量高达389.5 mAh•g^－1; 电流密度至1000 mA•g^－1循环150圈后比容量仍高达233.4 mAh•g^－1, 较未掺杂的样品提升56%, 且容量保持率依然高达93.1%. 其优异的电化学性能归因于: 适量的F^－掺杂提升了电极材料的比表面积和表面Cu^＋含量, 导致晶格畸变降低和氧空位增加, 优化的质构、适度的晶格畸变和氧空位, 不仅提供了更多的电化学反应活性位点和传输通道, 而且还强化了表面赝电容特性, 极大促进了电子和离子的传输动力学.

关键词: 锂离子电池负极材料, 岩盐型高熵氧化物, 阴离子掺杂, 晶格畸变, 氧空位

High-entropy oxides (HEOs) have emerged as one of the most promising anode materials for lithium-ion batteries due to their flexible compositional design and synergistic effects among multiple components. However, their practical application is severely hindered by inferior intrinsic electronic/ionic conductivity, which leads to poor rate capability and cycling stability in lithium storage systems. In this study, we developed a fluorine anion doping strategy to regulate intrinsic defects including lattice distortion and oxygen vacancies in rock-salt type (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O through solution combustion synthesis. This approach successfully fabricated single-phase F-doped (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O_1－_xF_x (x=0, 0.05, 0.1) HEO anode materials. Electrochemical evaluations demonstrate that the (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O_0.95F_0.05 anode exhibits exceptional rate performance and cycling stability, delivering a high specific capacity of 389.5 mAh•g^－1 after 150 cycles at 200 mA•g^－1. Even under high current density of 1000 mA•g^－1, it maintains 233.4 mAh•g^－1after 150 cycles with 93.1% capacity retention, representing a 56% improvement compared to undoped counterparts. The enhanced electrochemical performance originates from optimized material characteristics induced by appropriate F^－ doping: increased specific surface area, elevated surface Cu^＋ content, reduced lattice distortion, and controlled oxygen vacancies. These structural modifications not only provide additional active sites and ion transport pathways but also enhance surface pseudocapacitive behavior, thereby significantly improving both electronic and ionic transport kinetics.

Key words: lithium-ion battery anode material, rock salt-type high-entropy oxide, anion doping, lattice distortion, oxygen vacancy

引用此文

韦正兵, 鲍梦凡, 徐世彪, 程怡, 陈诗洁, 林娜, 冒爱琴. 氟掺杂诱导岩盐型高熵氧化物本征缺陷调控及其储锂性能优化[J]. 化学学报, 2025, 83(8): 868-877.

Zhengbing Wei, Mengfan Bao, Shibiao Xu, Yi Cheng, Shijie Chen, Na Lin, Aiqin Mao. Fluorine Doping-Induced Intrinsic Defect Modulation in Rock-Salt-Type High-Entropy Oxide for Lithium Storage Performance Optimization[J]. Acta Chimica Sinica, 2025, 83(8): 868-877.

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图/表 9

图1. 样品的XRD图和局部放大图(a), 以及HEO (b)、HEO-F0.05 (c)和HEO-F0.1 (d)的Rietveld XRD精修图

Figure 1. XRD spectra and local magnification spectra of as-synthesized samples (a), and the Rietveld refined XRD patterns of HEO (b), HEO-F0.05 (c) and HEO-F0.1 (d)

Sample	a/nm	b/nm	c/nm	V/nm³	R_wp	R_p
HEO	0.42389	0.42389	0.42389	0.07617	5.35%	3.92%
HEO-F0.05	0.42369	0.42369	0.42369	0.07606	3.49%	2.46%
HEO-F0.1	0.42351	0.42351	0.42351	0.07596	3.67%	2.62%

表1. 三组样品的晶胞参数和精修因子

Table 1. The lattice constants and refinement factors of as-synthesized three samples

图2. 样品HEO (a1,b1,c1)、HEO-F0.05 (a2,b2,c3)和HEO-F0.1 (a3,b3,c3)不同放大倍数的SEM图和EDS mapping图及样品HEO (d1,e1,f1)和HEO-F0.05 (d2,e2,f2)的TEM图(插图为SAED花样)、HR-TEM(插图为IFFT图像)和晶格条纹线扫描强度分布曲线

Figure 2. SEM images (different magnifications) and EDS elemental maps of HEO (a1,b1,c1), HEO-F0.05 (a2,b2,c2), and HEO-F0.1 (a3,b3,c3). TEM images (with insets showing SAED patterns), HR-TEM images (with insets showing IFFT images), and line scan intensity distribution curves of lattice fringes for samples HEO (d1,e1,f1) and HEO-F0.05 (d2,e2,f2)

Sample	S_BET/(m²•g^－1)	V_BJH/(cm³•g^－1)	D_aver./nm	D_most/nm
HEO	7.564	0.022	11.474	3.278
HEO-F0.05	18.810	0.016	3.399	3.092
HEO-F0.1	9.200	0.018	11.740	3.290

表2. 样品的质构参数

Table 2. Textural characteristics of as-synthesized samples

图3. 样品HEO (a, d)、HEO-F0.05 (b, e)和HEO-F0.1 (c, f)的N2吸脱附等温曲线和孔径分布图

Figure 3. The N2 adsorption-desorption isotherms and pore size distributions of as-synthesized HEO (a, d), HEO-F0.05 (b, e), and HEO-F0.1 (c, f) samples

图4. 样品的XPS全谱图(a), Co 2p (b)、Cu 2p (c)、Ni 2p (d)、O 1s (e)的高分辨率XPS谱及不同元素价态分布比例(f)、电导率(g)、UV-Vis光谱(h)及[F(R∞)•hν]1/n与hν关系曲线(i)

Figure 4. The XPS survey spectrum of the sample (a), high-resolution XPS spectra of Co 2p (b), Cu 2p (c), Ni 2p (d), and O 1s (e), valence state distribution ratios of different elements (f), electrical conductivity (g), UV-Vis spectrum (h), and the plot of [F(R∞)•hν]1/n versus hν (i)

图5. HEO、HEO-F0.05、HEO-F0.1电极在0.1 mV•s－1扫速下的CV曲线(a~c)、充放电曲线(d~f); 不同电流密度下的循环性能以及倍率性能(g~i)

Figure 5. Cyclic voltammetry curves (a~c), charge-discharge curves (d~f) and cycling behaviour at different current densities and multiplication behaviour (g~i) of HEO, HEO-F0.05 and HEO-F0.1 electrodes at 0.1 mV•s－1

图6. 三种电极首次充放电过程中的原位阻抗(a~f); HEO-F0.05第二圈(g)和第三圈(h)放电过程中的原位阻抗以及循环不同圈数的阻抗谱(i); 循环前的电化学阻抗谱及等效电路图(j); 三电极恒电流间歇滴定技术(GITT)曲线(k)以及充放电过程中锂离子的扩散系数(l)

Figure 6. In-situ impedance during the first charge-discharge of three electrodes (a~f); in-situ impedance of HEO-F0.05 during 2nd (g) and 3rd (h) discharge and impedance spectra after cycling (i); electrochemical impedance spectra and equivalent circuit before cycling (j); galvanostatic intermittent titration technique (GITT) curves (k) and Li⁺ diffusion coefficients during charge-discharge (l) for three electrodes

图7. HEO、HEO-F0.05、HEO-F0.1电极不同扫速下的CV曲线(a~c); lg(ip)与lg(v)的关系曲线(d~f); 1.0 mV•s－1时赝电容的贡献率(g~i); 在不同扫描速率下赝电容的贡献率(j~l)

Figure 7. CV curves of HEO, HEO-F0.05 and HEO-F0.1 electrodes at different sweeping rates (a~c); lg(ip) versus lg(v) (d~f); Percentage contribution of pseudocapacitance at 1.0 mV•s－1 (g~i); Contribution ratios of pseudocapacitance at different scan rates (j~l)

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