<strong>Zn</strong>含量对岩盐型高熵氧化物储锂性能的影响

doi:10.11901/1005.3093.2023.567

材料研究学报

2024, Vol. 38

Issue (7): 508-518 DOI: 10.11901/1005.3093.2023.567

研究论文

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Zn含量对岩盐型高熵氧化物储锂性能的影响

陈诗洁¹, 鲍梦凡¹, 林娜¹, 杨海琴¹, 冒爱琴¹^,²(

)

^1.安徽工业大学材料科学与工程学院先进陶瓷研究中心马鞍山 243032
^2.先进金属材料绿色制备与表面技术教育部重点实验室马鞍山 243032

Effect of Zn Content on Lithium Storage Properties of Rock Salt Type High Entropy Oxides

CHEN Shijie¹, BAO Mengfan¹, LIN Na¹, YANG Haiqin¹, MAO Aiqin¹^,²(

)

^1.Advanced Ceramics Research Center, School of Materials Science and Engineering, Anhui University of Technology, Ma'anshan 243032, China
^2.Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Ma'anshan 243032, China

引用本文:

陈诗洁, 鲍梦凡, 林娜, 杨海琴, 冒爱琴. Zn含量对岩盐型高熵氧化物储锂性能的影响[J]. 材料研究学报, 2024, 38(7): 508-518.
Shijie CHEN, Mengfan BAO, Na LIN, Haiqin YANG, Aiqin MAO. Effect of Zn Content on Lithium Storage Properties of Rock Salt Type High Entropy Oxides[J]. Chinese Journal of Materials Research, 2024, 38(7): 508-518.

全文: PDF(11106 KB) HTML

摘要:

用溶液燃烧法制备不同Zn含量的岩盐型高熵氧化物(Co_0.22Cu_0.22Mg_0.22Ni_0.22Zn_0.12)O、(Co_0.2Cu_0.2Mg_0.2-Ni_0.2Zn_0.2)O和(Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O，研究了Zn离子浓度对其电化学性能的影响。结果表明：随着Zn含量的提高这类电极材料的电化学性能随之提高。(Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O电极具有优异的电化学性能，其原因是较高的晶格畸变和氧空位浓度使其本征电导率和锂离子扩散系数略微提高。电流密度为200 mA·g^-1时这种材料的初始放电比容量(777.06 mAh·g^-1)和循环稳定性(循环150圈后容量保持率接近100%)最高，电流密度为3000 mA·g^-1时比容量为140.2 mAh·g^-1时其倍率性能优异，即使电流密度为1000 mA·g^-1其循环150圈 (比容量198.1 mAh·g^-1)也表现出最高的循环稳定性。(Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O电极优异的电化学性能和循环稳定性，可归因于Zn元素在氧化还原反应中完全转化，含量较高的Zn提供了更多的容量，适当的氧空位浓度和晶格畸变程度为锂离子传输提供了更多的通道。

关键词 ：无机非金属材料, 锂离子电池, 不同Zn含量, 岩盐型高熵氧化物, 晶格畸变, 协同作用

Abstract：

Rock salt-type high entropy oxide (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O as anode material for lithium-ion battery has attracted widespread attention due to its unique synergistic effect of multiple elements. Zn and part of Co elements provide the main source of electrode capacities, while MgO stabilizes the crystal structure, Ni, Cu, and the reduced residual Co may form a 3-dimensional network to enhance the conductivities of the oxide. In this study, a series of rock salt-type high entropy oxides (Co_0.22Cu_0.22Mg_0.22Ni_0.22Zn_0.12)O,(Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O and (Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O with different Zn contents were prepared by solution combustion method, while the effect of Zn ion concentration on the electrochemical performance of rock salt-type HEOs was also assessed. The results suggest that with the increasing Zn content, the electrochemical performance of the electrode material was enhanced. Although the (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O electrode exhibits a higher lattice distortion and oxygen vacancy concentration, resulting in a slightly higher intrinsic conductivity and lithium ion diffusion coefficient, however, the (Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O electrode showed the most excellent electrochemical performance with the highest initial discharge specific capacity (777.06 mAh·g^-1) and cycling stability (capacity retention rate nearly 100% after 150 cycles) at 200 mA·g^-1, as well as excellent rate performance (specific capacity of 140.2 mAh·g^-1 at 3000 mA·g^-1), and it even shows the best cycling stability after 150 cycles at a high current density of 1000 mAh·g^-1 (specific capacity of 198.1 mAh·g^-1). The excellent electrochemical performance of the (Co_0.18Cu_0.18Mg_0.18-Ni_0.18Zn_0.28)O electrode may be attributed to the complete conversion of Zn element during the redox reaction. The higher Zn content is beneficial to increase capacities, while the appropriate oxygen vacancy concentration and lattice distortion may provide more channels for Li ion migration, thus resulting in higher cycle stability of the electrode.

Key words： inorganic non-metallic materials lithium-ion battery different Zn contents rocksalt type high-entropy oxide lattice distortion synergistic effect

收稿日期: 2023-11-22

ZTFLH:

TM912

基金资助: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(GFST2022ZR08);安徽省高校自然科学研究重点项目(2023AH051104)

通讯作者: 冒爱琴，副教授，maoaiqinmaq@163.com，研究方向为高熵材料的制备及在能量储存中的应用研究

Corresponding author: MAO Aiqin, Tel: 13855599146, E-mail: maoaiqinmaq@163.com

作者简介: 陈诗洁，女，1999年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2023.567 或 https://www.cjmr.org/CN/Y2024/V38/I7/508

图1 样品的XRD谱和局部放大谱

图2 Zn0.28样品的SEM照片和EDS mapping图、三种样品的N2吸脱附等温曲线和BJH孔径分布

表1 样品的BET比表面积(SBET)、BJH吸附孔体积(VBJH)、平均孔径(Daver)和最可几孔径(Dmost)

图3 样品的XPS、Co、Cu、Ni、O的高分辨XPS谱和电导率

表2 根据XPS分析结果计算出的Co和Cu元素的价态分布和平均化合价

图4 Zn0.12、Zn0.2和Zn0.28电极在0.1 mV·s-1扫速下的循环伏安曲线、充放电曲线、不同电流密度下的循环性能和倍率性能

图5 三电极在200 mA·g-1下循环前和循环150次后的SEM照片

图6 Zn0.28电极在不同扫速下的CV曲线、lg(ip)与lg(v)的关系曲线、1 mV·s-1时的赝电容(蓝色区域)和扩散控制(红色区域)贡献的占比、三电极在不同扫描速率下的赝电容贡献率汇总图、恒电流间歇滴定技术(GITT)测试过程中的充放电曲线以及充放电过程中锂离子的扩散系数

图7 Zn0.28电极首次(a, b)和第三次(c, d)循环过程中的原位阻抗；三电极的初始阻抗(e)及对应低频区的ω-1/2与Z′的关系图(i)；电极在循环前、3和100次后的电化学阻抗谱和等效电路：Zn0.12 (f), Zn 0.2 (g)，Zn0.28 (h)以及相对应低频区的ω-1/2与Z′的关系图(j~l)

Samples	R_s / Ω			R_ct / Ω			D $L i +$ / 10^-21 cm²·s^-1
Samples	Pristine	3rd	100th	Pristine	3rd	100th	Pristine	3rd	100th
Zn0.12	4.4	5.2	6.1	338.0	26.8	31.8	14.9	2.1	14.8
Zn0.2	8.3	6.0	8.6	248.0	42.0	14.9	10.4	2.5	20.4
Zn0.28	5.6	4.3	6.4	283.7	8.1	26.9	17.3	2.5	10.8

表3 所制备的电极循环前和循环3、100圈后的等效电路图参数和锂离子扩散系数的计算值

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