类金属磷掺杂调控高熵氧化物本征缺陷: 协同提升结构稳定性与反应动力学

doi:10.6023/A26050161

摘要/Abstract

高熵氧化物(HEO)因具有高熵效应、多主元协同效应和可调组成, 在锂离子电池负极材料领域展现出良好的应用前景. 然而, 尖晶石型高熵氧化物在储锂过程中仍存在电子/离子传输动力学缓慢等问题, 限制了其电化学性能的进一步提升. 采用类金属P掺杂策略, 通过溶液燃烧法制备了尖晶石型HEO [P_x(Co_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)_1－_x]₃O₄ (x=0, 0.05, 0.10, 0.15, 0.2, 记为Px-HEO), 并研究了P掺杂对材料结构、缺陷特征及储锂性能的影响. 结果表明, P掺杂形成的P—O及P—O—M共价键促进了氧空位生成, 并通过电荷补偿使部分Mn^3＋转化为Mn^4＋, 有效减弱Jahn-Teller效应, 提升了结构稳定性. 其中, P0.1-HEO样品具有较高的比表面积(60.85 m²•g^－1)和丰富的表面氧空位(50.1%), 显著改善了电子/离子传输动力学. P0.1-HEO电极在200 mA•g^－1下循环250圈后仍保持1711 mAh•g^－1的可逆容量, 在3000 mA•g^－1下仍可提供385 mAh•g^－1的可逆容量. 该研究为通过类金属P掺杂协同优化高熵氧化物的结构稳定性和储锂性能提供了实验基础.

关键词: 高熵氧化物, 磷掺杂, 氧空位, 结构稳定性, 反应动力学

High-entropy oxides (HEOs) have attracted considerable attention as promising anode materials for lithium-ion batteries (LIBs) owing to their high-entropy effect, multicomponent synergistic effect, and highly tunable compositions. However, spinel-structured HEOs still suffer from sluggish electron/ion transport kinetics during lithiation and delithiation, which limits their further electrochemical performance enhancement. In this work, a metalloid phosphorus (P) doping strategy was employed to synthesize spinel-structured [P_x(Co_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)_1－_x]₃O₄ (x=0, 0.05, 0.10, 0.15, 0.2, denoted as Px-HEO) via a solution combustion synthesis (SCS) method, and the effects of P doping on the crystal structure, defect characteristics, and lithium-storage properties were systematically investigated. The results demonstrate that the formation of covalent P—O and P—O—M bonds promotes the generation of oxygen vacancies and induces the partial conversion of Mn^3＋ to Mn^4＋ through charge compensation, thereby effectively suppressing the Jahn-Teller effect and enhancing the structural stability of the spinel framework. Among all samples, P0.1-HEO exhibits a relatively high specific surface area (60.85 m²• g^－1) and abundant surface oxygen vacancies (50.1%), which significantly accelerate electron/ion transport kinetics. As a result, the P0.1-HEO electrode delivers a high reversible capacity of 1711 mAh•g^－1 after 250 cycles at 200 mA•g^－1 and retains a reversible capacity of 385 mAh•g^－1 even at a high current density of 3000 mA•g^－1. This study provides an experimental basis for synergistically optimizing the structural stability and lithium-storage performance of high-entropy oxide anodes through metalloid P doping.

Key words: high-entropy oxide, phosphorus doping, oxygen vacancy, structural stability, reaction kinetics

引用此文

徐世彪, 潘美伊, 韦正兵, 尹飞龙, 鲍梦凡, 胡倩倩, 孙君豪, 林娜, 冒爱琴. 类金属磷掺杂调控高熵氧化物本征缺陷: 协同提升结构稳定性与反应动力学[J]. 化学学报, 2026, 84(10): 1579-1590.

Shibiao Xu, Meiyi Pan, Zhengbing Wei, Feilong Yin, Mengfan Bao, Qianqian Hu, Junhao Sun, Na Lin, Aiqin Mao. Metalloid Phosphorus Doping-regulated Intrinsic Defect Engineering in High-entropy Oxides: Synergistically Enhanced Structural Stability and Reaction Kinetics[J]. Acta Chimica Sinica, 2026, 84(10): 1579-1590.

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图/表 11

图1. (a)各样品XRD图谱、(b)所制备样品的平均晶粒尺寸和晶胞参数及(c~f) Rietveld精修图

Figure 1. (a) XRD patterns of the samples, (b) average crystallite size and lattice constants of synthesized samples, and (c~f) rietveld-refined XRD patterns

Sample	Average crystallite size/nm	Crystal lattice parameter
Sample	Average crystallite size/nm	a/nm	α/(°)	V_m/nm³	R_p	R_wp	χ²
P0-HEO	28.6	0.8365	90	0.58533	2.60	3.29	1.18
P0.05-HEO	13.6	0.8345	90	0.58114	1.67	1.23	1.52
P0.1-HEO	12.4	0.8321	90	0.57614	2.07	1.58	2.50
P0.15-HEO	10.1	0.8364	90	0.58512	1.71	1.32	1.74

表1. 平均晶粒尺寸和Rietveld精修参数

Table 1. Average crystallite size and the rietveld refinement parameters

图2. 样品(a~c) P0-HEO和(d~f) P0.1-HEO的不同放大倍数的SEM图, (g) P0.1-HEO相应元素EDS元素面分布图, P0.1-HEO对应的(h) TEM图像、(i)高分辨TEM图像和(j)选区电子衍射图

Figure 2. SEM images of the samples of (a~c) P0-HEO and (d~f) P0.1-HEO at different magnifications, (g) corresponding EDS elemental mapping of P0.1-HEO, and (h) TEM image, (i) HRTEM image and (j) SAED pattern of P0.1-HEO

图3. N2吸/脱附等温线及其孔径分布图: (a) P0-HEO, (b) P0.05-HEO, (c) P0.1-HEO, (d) P0.15-HEO样品

Figure 3. N2 adsorption-desorption isotherms and pore diameter distribution of as-synthesized samples: (a) P0-HEO, (b) P0.05-HEO, (c) P0.1-HEO, (d) P0.15-HEO samples

Samples	S_BET/(m²•g^－1)	V_BJH/(cm³•g^－1)	D_aver./nm	D_most/nm
P0-HEO	11.31	0.06	19.74	2.59
P0.05-HEO	89.18	0.24	10.82	2.56
P0.1-HEO	60.85	0.14	9.48	2.57
P0.15-HEO	31.27	0.11	13.52	2.60

表2. 比表面积(SBET)、BJH吸附累积孔隙体积(VBJH)、平均孔径(Daver.) 和最可几孔径(Dmost)

Table 2. Specific surface areas (SBET), BJH adsorption cumulative pore volumes (VBJH), average pore diameters (Daver.) and the most probable pore diameter (Dmost)

图4. (a~g)所制备样品各元素的高分辨XPS谱图及(h)各样品的EPR光谱图

Figure 4. (a~g) High-resolution XPS spectra of synthesized samples and (h) EPR spectra of synthesized samples

Samples	Co^2＋/Co^3＋	Fe^2＋/Fe^3＋	Mn^3＋/Mn^4＋	Ni^2＋/Ni^3＋	O_V/(O_V＋O_L)
P0-HEO	32.9/67.1	47.5/52.5	54.3/45.7	54.9/45.1	25.8%
P0.1-HEO	44.1/55.9	54.9/45.1	40.8/59.2	55.3/44.7	50.1%

表3. 金属阳离子价态与氧空位浓度的XPS定量分析结果

Table 3. Metal cation states and OV concentrations derived from XPS

图5. (a~c) P0-HEO和(d~f) P0.1-HEO电极前3圈的CV曲线、充放电曲线和微分容量曲线、(g)四种电极在200 mA•g－1下的循环性能和库伦效率、(h)倍率性能和(i) 1000 mA•g－1下的长循环性能

Figure 5. CV curves, charge/discharge profiles and dQ/dV plots for the first three cycles of (a~c) P0-HEO and (d~f) P0.1-HEO, (g) the cycling stability and coulombic efficiency at 200 mA•g－1, (h) rate capability, and (i) prolonged cycling behavior at 1000 mA•g－1 of synthesized electrodes

图6. (a)四种电极的四探针电导率、(b)循环前阻抗图、(c) ω－1/2与Z'的线性关系图、(d) P0.1-HEO电极不同扫速下的CV曲线、(e) lg ip与lg v的关系曲线、(f) 1.0 mV•s－1时赝电容的贡献比、(g)不同扫描速率下赝电容的贡献率、(h) GITT测试过程中的充电/放电曲线及(i)充电/放电过程中的锂离子扩散系数

Figure 6. (a) Four-probe conductivity, (b) initial impedance plots, (c) straight-line plots of ω-1/2 versus Z′ for four electrodes, (d) CV curves of P0.1-HEO at different scan rates, (e) lg ip versus lg v, (f) percentage contribution of pseudocapacitance at 1.0 mV•s－1, (g) contribution ratios of all electrodes at different scan rates, (h) charge/discharge capacity curves during the GITT measurements, and (i) lithium-ion diffusion coefficients during the charge/discharge process of as-prepared electrodes

图7. (a) P0.1-HEO电极在不同电位下的非原位XRD图谱、(b) P0.1-HEO电极在不同循环圈数下的微分容量(dQ/dV)曲线及(c, d)循环过程中(dQ/dV)的二维分布图[颜色标尺由蓝(低值)至红(高值)表示强度变化]

Figure 7. (a) Ex situ XRD patterns of the P0.1-HEO electrode at different potentials, (b) differential capacity (dQ/dV) curves of the P0.1-HEO electrode at various cycle numbers, and (c, d) two-dimensional distribution maps of dQ/dV during cycling [the color scale ranges from blue (low intensity) to red (high intensity)]

图8. P0.1-HEO电极在(a~c)循环前和(d~f)在200 mA•g−1下循环250圈的表面与截面的SEM图、(g) P0.1-HEO电极循环250圈后的mapping及(h, i) P0.1-HEO电极循环250圈后的原位阻抗谱

Figure 8. Surface and cross-sectional SEM images of the P0.1-HEO electrode (a~c) before cycling and (d~f) after 250 cycles at 200 mA•g－1, (g) the elemental mapping of the P0.1-HEO electrode after 250 cycles, and (h, i) in situ EIS of the P0.1-HEO electrode after 250 cycles

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