高性能无钴化钙钛矿型高熵氧化物负极材料的制备及储锂性能研究

doi:10.6023/A23020046

摘要/Abstract

高熵氧化物由于独特的高熵效应、多主元协同效应和可定制的结构, 作为能量存储材料受到广泛地关注. 本研究采用金属硝酸盐为金属源, 甘氨酸为燃料, 通过溶液燃烧法成功合成了一系列无钴的钙钛矿型高熵氧化物La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2M_0.2)O₃ (M=Cu, Mg, Zn)锂离子电池负极材料, 研究了粉体的微观结构和电化学性能. 结果表明: 所制备的钙钛矿型高熵氧化物La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2M_0.2)O₃均为单相钙钛矿结构, 形貌为多孔网状且各组成元素分布均匀, 其中引入非活性元素Mg或活性元素Cu的高熵氧化物电化学性能相近; 无钴化La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃电极具有最高的比容量(200 mA•g⁻¹电流密度下循环250圈后可逆比容量为1014 mAh•g⁻¹)、优异的循环稳定性(1000 mA•g⁻¹电流密度下循环1000圈后可逆比容量为450 mAh•g⁻¹且几乎没有容量衰减)以及卓越的倍率性能(100 mA•g⁻¹电流密度下可逆比容量为396 mAh•g⁻¹, 3000 mA•g⁻¹电流密度下可逆比容量为198 mAh•g⁻¹, 容量保持率为47.9%). 电化学性能提升主要归因于活性元素Zn的加入可以在还原过程中形成Li-Zn合金使得电极比容量明显增加; 同时较高的比表面积、介孔结构以及丰富的表面氧空位使其具有较高的电导率(0.14 S•cm⁻¹)、锂离子扩散系数(2.1×10⁻¹² cm²•s⁻¹)和较大的赝电容贡献率, 从而显著提升了材料的比容量和倍率性能. 因此, 引入能够与锂发生合金化反应的元素(如Zn)可以极大地提高电化学性能, 有利于为设计成本低廉、性能优异的无钴化高熵材料提供新的设计理念和思路.

关键词: 锂离子电池负极材料, 高熵氧化物, 钙钛矿结构, 合金化, 赝电容

High-entropy oxides (HEOs) have become increasingly popular as energy storage materials owing to their unique high-entropy effect, multi-principal synergy effect and customizable structure. In this study, a series of cobalt-free perovskite high-entropy oxide La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2M_0.2)O₃ (M=Cu, Mg, Zn) lithium-ion battery anode materials were successfully synthesized by solution combustion method using metal nitrate as the metal source and glycine as the fuel. The microstructure and electrochemical properties of the as-prepared powders were investigated. The results show that the as-prepared high- entropy oxides crystalize into single-phase perovskite structure with porous foam-like shape and chemical/microstructural homogeneity. Furthermore, the as-prepared HEOs introducing inactive element Mg or active element Cu possess similar electrochemical performance; while the La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃ electrode exhibits a highest reversible capacity (1014 mAh•g⁻¹ at 200 mA•g⁻¹ after 250 cycles), excellent cycling stability (450 mAh•g⁻¹ at 1000 mA•g⁻¹ and almost no capacity decay after 1000 cycles) and outstanding rate performance. Such excellent performance can be attributed to the addition of active element Zn, which can form Li-Zn alloy during the reduction process that makes the specific capacity increase significantly. Meanwhile, its higher specific surface area, mesoporous structure and abundant surface oxygen vacancies result in higher conductivity (0.14 S•cm⁻¹), increased larger lithium ion diffusion coefficient (2.1×10⁻¹² cm²•s⁻¹), and pseudo-capacitance contribution, thus significantly enhances the specific capacity and rate performance of the as-prepared material. Therefore, the introduction of electrochemically active metals, which can react with Li alloying, such as Zn, can improve the electrochemical performance, thereby providing ideas for designing cobalt-free HEOs with low-cost and excellent performance for energy storage.

Key words: lithium-ion battery anode material, high-entropy oxide, perovskite structure, alloying, pseudo-capacitance

引用此文

贾洋刚, 陈诗洁, 邵霞, 程婕, 林娜, 方道来, 冒爱琴, 李灿华. 高性能无钴化钙钛矿型高熵氧化物负极材料的制备及储锂性能研究[J]. 化学学报, 2023, 81(5): 486-495.

Yanggang Jia, Shijie Chen, Xia Shao, Jie Cheng, Na Lin, Daolai Fang, Aiqin Mao, Canhua Li. Preparation and High-performance Lithium-ion Storage of Cobalt-free Perovskite High-entropy Oxide Anode Materials[J]. Acta Chimica Sinica, 2023, 81(5): 486-495.

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图/表 9

图1. 样品的XRD图(a), N2吸脱附等温曲线及样品的Barrett-Joyner-Halenda (BJH)孔径分布(b), SEM图(c~e)和4MZn样品能谱分析(EDS)图(f)

Figure 1. XRD patterns (a), N2 absorption-desorption isothermal curves, BJH pore size distribution of the samples (b) and SEM images (c~e) and energy dispersive spectroscopy (EDS) images (f) of 4MZn sample

图2. 样品的XPS全谱图(a), 各元素的高分辨XPS光谱(b~h)和四探针电导率(i)

Figure 2. XPS survey spectra of the samples (a), high resolution XPS spectrum of all elements of the samples (b~h) and four probes conductivity (i)

图3. 4MZn电极在0.1 mV?s?1扫速下的循环伏安图(a)与充放电曲线图(b), 所制备的电极在200 mA?g?1电流密度下的循环性能和库伦效率(c), 倍率性能(d), 1000 mA?g?1电流密度下的长循环性能(e)和Nyquist图(f)

Figure 3. CV plots at 0.1 mV?s?1 sweep rate (a) and charge/discharge profiles (b) of 4MZn electrode, cycling performance and Coulomb efficiency at 200 mA?g?1 current density (c), rate performance (d), long cycle performance at 1000 mA?g?1 current density (e) and Nyquist plots (f) of as-prepared electrodes

Material	Materials synthesis	C-rate/ (mA•g⁻¹)	Cycle number	Capacity/ (mAh•g⁻¹)	Ref.
CoTiO₃	solvothermal	100	200	440	[42]
NdFeO₃	co-precipitation	100	450	475	[43]
HoFeO₃	co-precipitation	100	120	437	[44]
FeTiO₃	sol-gel and hydrothermal	50	200	515	[45]
LaCoO₃	electrospinning	200	200	646	[29]
[(Bi,Na)_1/5(La,Li)_1/5(Ce,K)_1/5(Ca_1/5Sr_1/5)]TiO₃	solid-state method	100	50	84	[47]
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Co_0.2)O₃	solid-state method	200	100	331	[18]
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Co_0.2)O₃	co-precipitation	200	150	772	[19]
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃	SCS	200	250	1014	This work
La(Cr_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)O₃	SCS	1000	1000	450	This work

表1. 近期报道的TMOs和HEOs负极的电化学性能

Table 1. Electrochemical performance of recently reported TMOs and HEOs anodes

Sample	R_s/Ω			R_ct/Ω			D_Li+/(10⁻¹⁴ cm²•s⁻¹)
Sample	Pristine	3rd	250th	Pristine	3rd	250th	Pristine	3rd	250th
4MCu	2.9	4.1	5.9	224	10.2	39.4	0.8	3.1	11.0
4MMg	5.4	4.5	5.0	364	31.9	45.4	1.7	6.7	27.8
4MZn	3.6	7.5	5.0	101	12.5	33.6	1.4	17.4	65.2

表2. 所制备的电极循环0, 3和250圈后的等效电路图参数

Table 2. Parameters of equivalent circuit diagrams of as-prepared electrodes after 0 cycle, 3 cycles and 250 cycles

图4. 4MZn电极在不同扫速下的CV曲线(a), log(ip)与log(v)的关系曲线(b), 1.0 mV?s?1时赝电容(蓝色区域)和扩散(红色区域)控制的贡献占比(c)和不同扫描速率下赝电容贡献率(d), 所制备的电极在不同扫描速率下赝电容贡献率汇总图(e), 恒电流间歇滴定技术测试过程中的充电/放电曲线(f)和充电/放电过程中的锂离子扩散系数(g)

Figure 4. Cyclic voltammetry (CV) curves of 4MZn electrode at different sweep rates (a), log(ip) vs. log(v) curves (b), separation of pseudocapacitive (blue region) and diffusion (red region) controlled contribution at 1.0 mV?s?1 (c) and contribution ratios of pseudocapacitive capacities at different scan rates (d) of the 4MZn electrode; contribution ratios of pseudocapacitive capacities at different scan rates (e), charge/discharge capacity curves during the GITT measurements (f) and lithium-ion diffusion coefficients during the charge/discharge process (g) of as-prepared electrodes

图5. 4MZn电极在循环0, 3和250圈后的电化学阻抗谱和等效电路(a)以及在低频区域ω?1/2与Z'的关系图(b)

Figure 5. EIS spectra together with the equivalent circuit (a) and plots of Z' against ω?1/2 in the low frequency region (b) of 4MZn electrode after 0 cycle, 3 cycles and 250 cycles

图6. 电极循环前后的SEM图(红色区域为颗粒团聚): (a, b) 4MCu, (c, d) 4MMg和(e, f) 4MZn

Figure 6. SEM images of electrodes before and after cycling (the red area represents particle aggregation): (a, b) 4MCu, (c, d) 4MMg and (e, f) 4MZn

图7. 4MZn电极的非原位XRD图

Figure 7. Ex-situ XRD patterns of 4MZn electrode

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