K+掺杂尖晶石型（Co0.2Cr0.2Fe0.2Mn0.2Ni0.2）3O4高熵氧化物负极材料制备与储锂性能研究

doi:10.11949/0438-1157.20221116

化工学报 ›› 2022, Vol. 73 ›› Issue (12): 5625-5637.DOI: 10.11949/0438-1157.20221116

• 材料化学工程与纳米技术 • 上一篇下一篇

K⁺掺杂尖晶石型（Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2）₃O₄高熵氧化物负极材料制备与储锂性能研究

王朋朋(), 贾洋刚, 邵霞, 程婕, 冒爱琴(), 檀杰, 方道来

安徽工业大学材料科学与工程学院，先进金属材料绿色制备与表面技术教育部重点实验室，安徽马鞍山 243032

收稿日期:2022-08-08 修回日期:2022-11-01 出版日期:2022-12-05 发布日期:2023-01-17
通讯作者: 冒爱琴
作者简介:王朋朋（1995—），男，硕士研究生，wang_pengpeng2022@163.com
基金资助:
安徽省自然科学基金项目(2008085ME125);先进金属材料绿色制备与表面技术教育部重点实验室主任基金项目(GFST2022ZR08);安徽省高校自然科学研究重点项目(KJ2020A0268)

Preparation and lithium storage performance of K⁺-doped spinel (Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)₃O₄ high-entropy oxide anode materials

Pengpeng WANG(), Yanggang JIA, Xia SHAO, Jie CHENG, Aiqin MAO(), Jie TAN, Daolai FANG

Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, School of Materials Science and Engineering, Anhui University of Technology, Ma’anshan 243032, Anhui, China

Received:2022-08-08 Revised:2022-11-01 Online:2022-12-05 Published:2023-01-17
Contact: Aiqin MAO

摘要/Abstract

摘要：

通过溶液燃烧法成功合成了一系列非活性K⁺掺杂的尖晶石型 (K _x CoCrFeMnNi)_3/(5+_x₎O₄(x=0，0.5，1，1.5)高熵氧化物锂离子电池负极材料，系统研究了K⁺掺杂对结构和储锂性能的影响。结果表明：随着K⁺掺杂量的增加，均可制备出具有单一尖晶石结构的纳米晶粉体材料，其中等摩尔K⁺掺杂的 (K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄高熵氧化物负极材料具有最高的比容量、优异的循环稳定性和倍率性能。(K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄电极在200 mA·g^-1电流密度下，首次放电比容量为1295 mA·h·g^-1（首次库仑效率78%）；随着循环的进行，可逆比容量先降低后增加，循环150次可逆比容量增加至1505 mA·h·g^-1；即使在1000 mA·g^-1大电流密度下循环500次后仍具有1402 mA·h·g^-1的可逆比容量（均高于理论比容量898 mA·h·g^-1）。低价非活性K⁺的掺杂由于电荷补偿效应使晶格常数降低，但高构型熵稳定的晶体结构提高了循环稳定性；丰富的表面氧空位、较小的晶粒尺寸和介孔结构，增加了赝电容贡献率和电子/离子传输能力，从而显著提升了材料的比容量和倍率性能。

关键词: 锂离子电池负极材料, 非活性K⁺掺杂, 高熵氧化物, 尖晶石结构, 纳米材料, 电化学, 动力学

Abstract:

A series of inactive K⁺-doped spinel-type (K _x CoCrFeMnNi)_3/(5+_x₎O₄ (x=0, 0.5, 1, 1.5) high-entropy oxides lithium-ion battery anode materials were successfully synthesized by solution combustion method, and the effects of K⁺ doping on the structure and lithium storage performance were systematically investigated. The results show that all the synthesized nanocrystalline powders are crystallized as single spinel structure with the increase of K⁺ doping. Among them, the equimolar K⁺-doped (K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄ high-entropy oxide anode material has the highest specific capacity, excellent cycling stability and rate capability. The initial specific discharge capacity of (K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄ is 1295 mA·h·g^-1 at the current density of 200 mA·g^-1 with columbic efficiency of 78%. The specific capacity decreases first and then increases as the cycle proceeds, and after 150 cycles the reversible specific capacity increases to 1505 mA·h·g^-1. Even at a high current density of 1000 mA·g^-1, it still has a reversible specific capacity of 1402 mA·h·g^-1 after 500 cycles, which is much higher than the theoretical specific capacity of 898 mA·h·g^-1. Although the doping of low-valent inactive K⁺ decreases the lattice constant due to the charge compensation effect, entropy-stabilized crystal structure improves the cycling stability, and the abundant surface oxygen vacancies, small grain size and mesoporous structure are beneficial to improve the pseudocapacitive contribution and electron/ion diffusion ability, which significantly improve the specific capacity and rate performance of the as-synthesized (K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄ anode material.

Key words: lithium-ion batteries anode materials, inactive K⁺ doping, high-entropy oxide, spinel structure, nanomaterials, electrochemistry, kinetics

中图分类号:

TQ 152

王朋朋, 贾洋刚, 邵霞, 程婕, 冒爱琴, 檀杰, 方道来. K⁺掺杂尖晶石型（Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2）₃O₄高熵氧化物负极材料制备与储锂性能研究[J]. 化工学报, 2022, 73(12): 5625-5637.

Pengpeng WANG, Yanggang JIA, Xia SHAO, Jie CHENG, Aiqin MAO, Jie TAN, Daolai FANG. Preparation and lithium storage performance of K⁺-doped spinel (Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)₃O₄ high-entropy oxide anode materials[J]. CIESC Journal, 2022, 73(12): 5625-5637.

图/表 11

图1 样品的XRD谱图(a)和局部放大图(b)

Fig.1 XRD patterns (a) and enlarged patterns (b) of the samples

图2 样品K1的HRTEM图(a)，选区电子衍射图(b)，不同放大倍数SEM图[(c)，(d)]，元素EDS图(e)

Fig.2 High-resolution TEM image (a), selected area electron diffraction (SAED) pattern (b), SEM images at different magnifications [(c),(d)] and EDS mapping images (e) of K1 sample

图3 (K x CoCrFeMnNi)3/(5+x)O4海绵状粉体合成过程

Fig.3 Illustration of preparation of (K x CoCrFeMnNi)3/(5+x)O4 sponge-like powder

图4 样品K1的N2吸/脱附等温线和BJH孔径分布

Fig.4 Nitrogen adsorption/desorption isotherms and the BJH pore diameter distribution (inset) of K1 sample

表1 样品的BET比表面积、孔体积、平均孔径和最可几孔径

Table 1 BET surface area， pore volume， average pore size and the most probable pore size of the samples

样品	比表面积/ (m²·g^-1)	孔体积/ (cm³·g^-1)	平均孔径/nm	最可几孔径/nm
K₀	26.31	0.14	21.45	2.77
K_0.5	38.69	0.18	18.83	2.78
K₁	22.28	0.08	14.17	3.06
K_1.5	42.35	0.14	13.39	2.58

图5 样品的XPS全谱图(a)，各元素精细谱图[(b)~(h)]，拉曼光谱(i)，四探针电导率(j)

Fig.5 XPS survey spectra (a), high-resolution XPS spectrum of all elements [(b)—(h)] and Raman spectra (i) and four-probes conductivity (j) of the samples

图6 各电极在不同电流密度下的循环性能[(a)，(c)]和阶梯倍率性能(b)；K1电极的循环伏安图(d)和容量电压曲线(e)

Fig.6 Cycling performance at different current density [(a), (c)] and stepped rate capability (b) of the electrodes； CV curves (d) and charge-discharge profiles (e) of K1 electrode

图7 K1电极循环前(a)和150次后(b)SEM图，循环150次后HRTEM图(c)，循环150次前后XRD谱图(d)

Fig.7 SEM images before cycling (a) and after 150 cycles (b), HRTEM image after 150 cycles (c) and XRD patterns before cycling and after 150 cycles (d) of K1 electrode

图8 电极的阻抗谱(a)和Z'-ω-1/2关系(b)

Fig.8 Nyquist plots (a) and Z'-ω-1/2 relation (b) of the electrodes

表2 电极循环前和循环150次后的等效电路图参数

Table 2 Parameters of equivalent circuit diagrams of the electrodes before and after 150 cycles

Samples	R_s/Ω		R_ct/Ω		$D L i +$ /(10^-20 cm²·s^-1)
Samples	Before	After	Before	After	Before	After
K₀	6.7	4.2	284	156	32.1	29.0
K_0.5	4.1	5.4	246	125	13.2	86.3
K₁	5.3	4.8	228	102	38.5	257.3
K_1.5	7.4	5.5	265	134	17.0	45.4

表2 电极循环前和循环150次后的等效电路图参数

Table 2 Parameters of equivalent circuit diagrams of the electrodes before and after 150 cycles

Samples	R_s/Ω		R_ct/Ω		$D L i +$ /(10^-20 cm²·s^-1)
Samples	Before	After	Before	After	Before	After
K₀	6.7	4.2	284	156	32.1	29.0
K_0.5	4.1	5.4	246	125	13.2	86.3
K₁	5.3	4.8	228	102	38.5	257.3
K_1.5	7.4	5.5	265	134	17.0	45.4

图9 K1电极在不同扫速下的CV曲线(a)，lgip-lgv关系(b)，0.1 mV·s-1扫速下的赝电容（阴影区域）贡献(c)；各电极在不同扫速下的赝电容贡献(d)

Fig.9 CV curves at different scan rates (a), lgip-lgv relation (b) and pseudocapacitive (shaded region) contribution at 0.1 mV·s-1 scan rate (c) of K1 electrode; pseudocapacitive contribution at different scan rates of the electrodes (d)

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K⁺掺杂尖晶石型（Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2）₃O₄高熵氧化物负极材料制备与储锂性能研究

Preparation and lithium storage performance of K⁺-doped spinel (Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)₃O₄ high-entropy oxide anode materials

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