ZrO2包覆高镍LiNi0.8Co0.1Mn0.1O2正极材料提高其循环稳定性的作用机理

doi:10.3866/PKU.WHXB202005062

物理化学学报 >> 2021, Vol. 37 >> Issue (3): 2005062.doi: 10.3866/PKU.WHXB202005062

ZrO₂包覆高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料提高其循环稳定性的作用机理

苏岳锋¹^,², 张其雨¹^,², 陈来¹^,²^,*(), 包丽颖¹, 卢赟¹^,², 陈实¹, 吴锋¹^,²^,*()

¹ 北京理工大学材料学院，环境科学与工程北京市重点实验室，北京 100081
² 北京理工大学重庆创新中心，重庆 401120

收稿日期:2020-05-25 录用日期:2020-06-08 发布日期:2020-06-12
通讯作者: 陈来,吴锋 E-mail:chenlai144@sina.com;wufeng863@vip.sina.com
基金资助:
国家重点研发项目(2016YFB0100301);国家自然科学基金(21875022);国家自然科学基金(51802020);国家自然科学基金(U1664255);北京理工大学重庆创新中心科技创新计划项目(2020CX5100006);北京理工大学“青年教师学术启动计划”项目和中国科学技术协会青年人才托举计划(2018QNRC001)

Effects of ZrO₂ Coating on Ni-Rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathodes with Enhanced Cycle Stabilities

Yuefeng Su¹^,², Qiyu Zhang¹^,², Lai Chen¹^,²^,*(), Liying Bao¹, Yun Lu¹^,², Shi Chen¹, Feng Wu¹^,²^,*()

¹ School of Materials Science and Engineering, Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
² Beijing Institute of Technology Chongqing Innovation Center, Chongqing 401120, China

Received:2020-05-25 Accepted:2020-06-08 Published:2020-06-12
Contact: Lai Chen,Feng Wu E-mail:chenlai144@sina.com;wufeng863@vip.sina.com
About author:Email: wufeng863@vip.sina.com (F.W.)
Email: chenlai144@sina.com (L.C.)
Supported by:
the National Key R&D Program of China(2016YFB0100301);the National Natural Science Foundation of China(21875022);the National Natural Science Foundation of China(51802020);the National Natural Science Foundation of China(U1664255);the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center, China(2020CX5100006);the Beijing Institute of Technology Research Fund Program for Young Scholars, and the Young Elite Scientists Sponsorship Program by CAST, China(2018QNRC001)

摘要/Abstract

摘要：

高镍三元材料作为一种锂离子电池正极材料，因其较高的放电比容量而得到科学界和工业界的广泛关注。研究表明，高镍三元材料的比容量与材料中的Ni含量呈正相关，但Ni含量的增加也会加剧循环过程中的界面副反应，材料表面释氧以及结构转变等问题。本文采用ZrO₂包覆LiNi_0.8Co_0.1Mn_0.1O₂材料，利用X射线衍射证明，在高温处理下ZrO₂包覆物中的Zr⁴⁺会掺杂进LiNi_0.8Co_0.1Mn_0.1O₂材料表面晶格中，使得X射线衍射谱中的(003)衍射峰左移。电化学测试证明在4.3和4.5 V的截止电压下，改性最优的材料在1C循环100周后容量保持率分别从84.89%和75.60%提高到97.61%和81.37%，同时发现循环稳定性的提升主要来自材料表面的Zr⁴⁺掺杂。X射线光电子能谱证明Zr⁴⁺表层掺杂后材料的Ni化合价由Ni³⁺向Ni²⁺转变，透射电子显微镜观察到Zr⁴⁺的表层掺杂使得材料表面的层状结构发生重构，从而稳定了材料体相结构，提高了材料整体的循环稳定性。

关键词: 锂离子电池, LiNi_0.8Co_0.1Mn_0.1O₂, 正极材料, ZrO₂包覆, Zr⁴⁺掺杂, 表层结构重构

Abstract:

With the development of electric vehicles (EVs) and hybrid electric vehicles (HEVs), the demand for lithium ion power batteries with high energy density and long cycle life has continuously increased in the recent years. According to the "Made in China 2025" plan, the energy densities of lithium ion batteries need to reach 300 Wh·kg^-1 in 2020. Due to their high discharge capacities and work voltages, Ni-rich layered materials have attracted considerable attention from the science and industry fields as one of the most promising cathodes to achieve high energy density. According to previous reports, the discharge capacities of Ni-rich cathodes were positively correlated to their Ni content. However, the increased Ni content can aggravate the side reactions between the cathode and electrolyte, induce O loss, and trigger structural transformation from the surface to bulk. In this study, ZrO₂ was coated on LiNi_0.8Co_0.1Mn_0.1O₂ with a simple wet chemical method to improve its cycle performance. The scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) demonstrated that Zr was only detected in the ZrO₂-coated samples and was mainly distributed at the surface of the secondary particles of the LiNi_0.8Co_0.1Mn_0.1O₂ cathodes. The X-ray diffraction (XRD) indicated that Zr⁴⁺ in ZrO₂ migrated into the layered surface structure of LiNi_0.8Co_0.1Mn_0.1O₂ based on the shift of the (003) peak to a lower angle, which was considered as a lattice expansion along the c axis. Under the cut-off voltage of 4.3 and 4.5 V, the capacity retentions of the LiNi_0.8Co_0.1Mn_0.1O₂ cathodes improved from 84.89 to 97.61% and 75.60 to 81.37%, respectively, after 100 cycles at 1C. This was mainly attributed to the doped Zr⁴⁺ in surface structure as opposed to the ZrO₂ coating. The X-ray photoelectron spectroscopy (XPS) indicated that the Ni³⁺ at the surface of LiNi_0.8Co_0.1Mn_0.1O₂ was reduced to Ni²⁺ after the Zr⁴⁺ surface doping due to charge balance. Rietveld refinement also indicated that the Li⁺/Ni²⁺ cation disordering improved after the Zr⁴⁺ in ZrO₂ doped into NCM surface structure. The raised cation disordering may be triggered by the increased content of Ni²⁺ and their migration into Li layers due to the similar ion radius of Li⁺ (0.076 nm) and Ni²⁺ (0.069 nm). A structure-reconstructed layer at the surface of LiNi_0.8Co_0.1Mn_0.1O₂ was formed after the Zr⁴⁺ doping, which had been confirmed by transmission electron microscope (TEM). It was determined that this structure-reconstructed layer can hinder the side reactions at the interface and stabilize the bulk structure during cycles; thus, the cycle stability of LiNi_0.8Co_0.1Mn_0.1O₂ material was improved.

Key words: Lithium ion battery, LiNi_0.8Co_0.1Mn_0.1O₂, Cathode material, ZrO₂ coating, Zr⁴⁺ doping, Surface structural reconstruction

苏岳锋, 张其雨, 陈来, 包丽颖, 卢赟, 陈实, 吴锋. ZrO₂包覆高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料提高其循环稳定性的作用机理[J]. 物理化学学报, 2021, 37(3), 2005062. doi: 10.3866/PKU.WHXB202005062

Yuefeng Su, Qiyu Zhang, Lai Chen, Liying Bao, Yun Lu, Shi Chen, Feng Wu. Effects of ZrO₂ Coating on Ni-Rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathodes with Enhanced Cycle Stabilities[J]. Acta Phys. -Chim. Sin. 2021, 37(3), 2005062. doi: 10.3866/PKU.WHXB202005062

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202005062

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I3/2005062

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Sample	a/nm	c/nm	Unit volume/nm³	c/a	R_wp/%	Cation disordering/%
Zr-0	0.28719	1.42021	0.11714	4.945	11.35	2.87
Zr-2	0.28721	1.42026	0.11716	4.944	11.17	3.65

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ZrO₂包覆高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料提高其循环稳定性的作用机理

Effects of ZrO₂ Coating on Ni-Rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathodes with Enhanced Cycle Stabilities

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