低共熔溶剂辅助制备空心球状钙钛矿型高熵氧化物及高倍率储锂性能

doi:10.6023/A23100465

摘要/Abstract

近年来高熵氧化物因其独特的四大效应, 作为高性能的锂离子电池(LIBs)负极材料受到广泛关注. 本研究借助于形貌和缺陷调控策略调控晶格畸变和氧空位, 以金属硝酸盐为金属源, 葡萄糖和尿素为低共熔溶剂, 采用基于低共熔溶剂辅助的固相反应法制备了La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃以及Li、Na元素掺杂的La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃和La(Na_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃钙钛矿型高熵氧化物纳米晶粉体. 测试结果表明: 所制备的高熵氧化物均为单相钙钛矿结构, 其形貌为具有介孔结构的空心球状且各组成元素分布均匀. 储锂性能表明: La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃电极展示了最高的比容量(电流密度200 mA•g⁻¹下循环100圈的可逆比容量为410.0 mAh•g⁻¹)和优异的倍率性能(100 mA•g⁻¹电流密度下可逆比容量为342 mAh•g⁻¹, 3000 mA•g⁻¹电流密度下可逆比容量为169.43 mAh•g⁻¹, 容量保持率为49.4%). 虽然La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃具有略小的D_Li⁺, 但适当的晶格畸变、氧空位和较高的比表面积使其具有更高的电导率(0.072 S•cm⁻¹)以及更小的阻抗, 从而显著提升了材料的比容量和倍率性能. 该项工作为开发出高性能LIBs的先进负极材料提供了新的设计理念和思路.

关键词: 负极材料, 钙钛矿型高熵氧化物, 掺杂, 缺陷工程, 储锂性能

In recent years, high-entropy oxides (HEOs) have attracted much attention as high-performance anode materials for lithium-ion batteries (LIBs) due to their four effects. In this study, lattice distortions and oxygen vacancies are modulated through morphology and defect modulation strategies. Perovskite-type La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃, La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃, and La(Na_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃ HEO nanocrystalline powders are synthesized through solid state reaction method assisted by deep eutectic solvents using metal nitrate as the metal source, glucose and urea as the deep eutectic solvents. The results show that the as-prepared HEOs exhibit a single perovskite phase which are hollow spherical porous structure with chemical and microstructure homogeneity. The lithium-ion storage performance shows that the La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃ electrode possesses the highest specific capacity (reversible specific capacity of 410.0 mAh•g⁻¹ for 100 cycles at 200 mA•g⁻¹) as well as the outstanding rate performance (342 mAh•g⁻¹ at 100 mA•g⁻¹ and 169.43 mAh•g⁻¹ at 3000 mA•g⁻¹ with a capacity retention rate of 49.4%). Although La(Li_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)O₃ exhibts a smaller D_Li+, the appropriate lattice distortions, oxygen vacancies and higher specific area give it a higher conductivity (0.072 S•cm⁻¹) as well as a lower electrochemical impedance, thereby leading to the improved specific capacity and rate performance. This work provides new design concepts and ideas for developing advanced anode materials for high-performance LIBs.

Key words: anode materials, perovskite high-entropy oxides, dope, defect engineering, lithium-ion storage

引用此文

鲍梦凡, 陈诗洁, 邵霞, 邓慧娟, 冒爱琴, 檀杰. 低共熔溶剂辅助制备空心球状钙钛矿型高熵氧化物及高倍率储锂性能[J]. 化学学报, 2024, 82(3): 303-313.

Mengfan Bao, Shijie Chen, Xia Shao, Huijuan Deng, Aiqin Mao, Jie Tan. Preparation and High-rate Lithium-ion Storage of Hollow Sphere Perovskite High-entropy Oxides Assisted by Deep Eutectic Solvents[J]. Acta Chimica Sinica, 2024, 82(3): 303-313.

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图/表 9

图1. HEO、Li-HEO和Na-HEO样品的XRD图谱(a); 三电极材料的XRD精修图: (b) HEO; (c) Li-HEO; (d) Na-HEO

Figure 1. XRD patterns of HEO, Li-HEO and Na-HEO samples (a); Rietveld refined XRD patterns for (b) HEO; (c) Li-HEO; (d) Na-HEO

图2. 不同放大倍数SEM图: (a1, b1) HEO; (a2, b2) Li-HEO; (a3, b3) Na-HEO; (c)元素EDS Mapping图: (c1) HEO; (c2) Li-HEO; (c3) Na-HEO

Figure 2. SEM images of different magnifications for (a1, b1) HEO; (a2, b2) Li-HEO; (a3, b3) Na-HEO; (c) EDS Mapping for elements of (c1) HEO; (c2) Li-HEO; (c3) Na-HEO

图3. N2吸附-脱附等温曲线和孔径分布图: (a1, b1) HEO; (a2, b2) Li-HEO; (a3, b3) Na-HEO

Figure 3. N2 adsorption-desorption isotherms and pore size distributions for (a1, b1) HEO; (a2, b2) Li-HEO; (a3, b3) Na-HEO

Sample	S_BET/(m²•g⁻¹)	D_aver/nm	D_most/nm
HEO	13.79	21.34	2.34
Li-HEO	23.74	26.91	2.86
Na-HEO	19.46	19.47	3.10

表1. HEOs的比表面积(SBET)、平均孔径(Daver)和最可几孔径(Dmost)

Table 1. BET specific surface area (SBET), average pore diameter (Daver) and the most probable pore diameter (Dmost)

图4. 样品的XPS全谱图(a)和各元素的高分辨XPS光谱(b~i)

Figure 4. XPS survey spectra of samples (a), and high resolution XPS spectra of all elements (b~i)

图5. 三电极前3圈的CV曲线、充放电曲线和微分容量曲线: (a1, b1, c1) HEO, (a2, b2, c2) Li-HEO, (a3, b3, c3) Na-HEO; 三电极与La(Co0.4Fe0.6)O3电极在200 mA?g?1的循环性能和库伦效率(d)和倍率性能(e)

Figure 5. CV curves, charge/discharge profiles and dQ/dV plots for the first three cycles of the three electrodes: (a1, b1, c1) HEO, (a2, b2, c2) Li-HEO, (a3, b3, c3) Na-HEO; Cyclic performance and Coulomb efficiency at 200 mA?g?1 (d) and rate performance (e) for three electrodes and La(Co0.4Fe0.6)O3 electrode

图6. Li-HEO在倍率性能循环前(a1, b1)和循环80圈后(a2, b2)的SEM

Figure 6. SEM images of different magnifications for Li-HEO before (a1, b1) and after 80 cycles of rate performance (a2, b2)

图7. 三电极的四探针电导率(a)和初始阻抗图(b); 三电极循环前后的阻抗图和ω1/2与Z'的线性关系图: (c1, d1) HEO; (c2, d2) Li-HEO和(c3, d3) Na-HEO; GITT测试过程中的充电/放电曲线(e)和充电/放电过程中的锂离子扩散系数(f)

Figure 7. Four-probe conductivity for three electrodes (a) and initial impedance plots (b); Impedance plots before and after cycling and straight-line plots of ω1/2 versus Z' for three electrodes: (c1, d1) HEO; (c2, d2) Li-HEO and (c3, d3) Na-HEO; Charge/discharge capacity curves during the GITT measurements (e) and lithium-ion diffusion coefficients during the charge/discharge process of as-prepared electrodes (f)

图8. HEO、Li-HEO与Na-HEO电极(a1, a2, a3)不同扫速下的CV曲线; (b1, b2, b3) lg(ip)与lg(v)的关系曲线; (c1, c2, c3) 在1.0 mV?s?1时赝电容的贡献比; (d1, d2, d3) 在不同扫描速率下赝电容的贡献率

Figure 8. CV curves of HEO, Li-HEO and Na-HEO electrodes (a1, a2, a3) at different sweeping rates; (b1, b2, b3) lg(ip) versus lg(v); (c1, c2, c3) Percentage contribution of pseudocapacitance at 1.0 mV?s?1; (d1, d2, d3) Contribution ratios of pseudocapacitance at different scan rates

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