高镍单晶层状三元正极材料的高熵策略掺杂改性研究

doi:10.15541/jim20250085

摘要/Abstract

摘要： 高镍三元正极材料LiNi_xCo_yMn_1-_x_-_yO₂ (NCM, x≥0.8) 具有很高的能量密度和优异的放电性能,是发展前景较好的一类锂离子电池正极材料,但也面临着阳离子混排严重、高温和高截止电压下循环性能和安全性不佳等瓶颈。本研究将高熵(HE)掺杂改性策略引入高镍低钴的LiNi_0.86Co_0.04Mn_0.1O₂正极材料,采用高温固相反应法合成了一种高镍单晶层状三元正极材料。在0.5C(1C=180 mA·g^-1)倍率和25 ℃条件下,改性后的材料具有197 mAh·g^-1的可逆放电比容量,能在高温环境和高截止电压下表现出很好的放电性能,在0.5C、4.30 V和55 ℃条件下的放电比容量达到281 mAh·g^-1,在0.5C、25 ℃和4.50 V条件下的放电比容量最高达194 mAh·g^-1。这种材料具有很好的层状结构,微观上表现为纳米级的一次颗粒的均匀排布,具有更小的总阻抗。本工作显著提升了高镍三元正极材料在高温环境和高截止电压下的循环性能及安全性能,为三元材料的去钴化、高镍化和实用化提供了一种很好的改性方法。

关键词: 高熵, 单晶, 高镍低钴, 三元正极材料

Abstract: LiNi_xCo_yMn_1-_x_-_yO₂ (NCM, x≥0.8), a promising cathode material for lithium-ion batteries, possesses high energy density and excellent discharge performance. However, it also faces challenges such as severe cation disorder, poor cycling performance and safety at high temperatures and high cut-off voltages. In this study, a high-entropy (HE) doping modification strategy was introduced into the high-nickel and low-cobalt LiNi_0.86Co_0.04Mn_0.1O₂ cathode material, and a high-nickel single-crystal layered ternary cathode material was synthesized by a high-temperature solid-state reaction method. The results show that at 0.5C (1C=180 mA·g^-1)and 25 ℃, the battery equipped with modified material has a reversible discharge capacity of 197 mAh·g^-1 and exhibits excellent discharge performance at high temperatures and high cut-off voltages. At 0.5C, 4.30 V and 55 ℃, the discharge capacity reaches 281 mAh·g^-1, and at 0.5C, 25 ℃ and 4.50 V, the discharge capacity is as high as 194 mAh·g^-1. This material has a good layered structure with a uniform arrangement of nanoscale primary particles at the microscale and a smaller total impedance. This work significantly improves the cycling performance and safety of high-nickel ternary cathode materials at high temperatures and high cut-off voltages, providing a good modification method for the cobalt-free, high-nickel and practical application of ternary materials.

Key words: high-entropy, single crystal, high nickel and low cobalt, ternary cathode material

中图分类号:

O646

侯佳兵, 胡强, 崔久治, 黄云迪, 王心蕊, 刘兴泉. 高镍单晶层状三元正极材料的高熵策略掺杂改性研究[J]. 无机材料学报, DOI: 10.15541/jim20250085.

HOU Jiabing, HU Qiang, CUI Jiuzhi, HUANG Yundi, WANG Xinrui, LIU Xingquan. High-entropy Doping Modification of High-nickel Single-crystal Layered Ternary Cathode Material[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250085.

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