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)具有较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(High-entropy, 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0.1C(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、55 ℃和4.3 V条件下的放电比容量达到281 mAh·g^-1, 在0.5C、25 ℃和4.5 V条件下的放电比容量最高达194 mAh·g^-1。这种材料具有良好的层状结构, 微观上表现为纳米级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 appears drawbacks such as severe cation disorder, poor cycling performance and insecurity at high temperatures and high cut-off voltages. In this study, a high-entropy (HE) doping modification strategy was introduced into a 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 0.1C (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, 55 ℃ and 4.3 V, the discharge capacity reaches 281 mAh·g^-1, while at 0.5C, 25 ℃ and 4.5 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 microscale and a smaller total impedance. This work significantly improves 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, 2026, 41(2): 193-200.

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, 2026, 41(2): 193-200.

图/表 7

图1 HE-NCM-sc与LE-NCM-sc的XRD图谱

Fig. 1 XRD patterns of HE-NCM-sc and LE-NCM-sc (b) (003); (c) (006)/(012); (d) (018)/(110)

图2 (a)前驱体与(b) HE-NCM-sc材料的SEM照片

Fig. 2 SEM images of (a) precursor and (b) HE-NCM-sc

图3 HE-NCM-sc的SEM照片及EDS元素分布图

Fig. 3 SEM image and EDS elemental mappings of HE-NCM-sc

图4 HE-NCM-sc的XPS刻蚀谱图

Fig. 4 In-depth XPS etching spectra of HE-NCM-sc

图5 HE-NCM-sc的(a) STEM、(b) TEM和(c) HRTEM照片

Fig. 5 (a) STEM, (b) TEM, and (c) HRTEM images of HE-NCM-sc

图6 HE-NCM-sc与LE-NCM-sc电池的电化学性能

Fig. 6 Electrochemical performance of HE-NCM-sc and LE-NCM-sc cells (a) Rate performance; (b) Cycling performance at 0.1C; (c) Initial charging and discharging curves at 0.1C; (d) Cycling performance at 0.5C within the voltage range of 2.8−4.5 V; (e) Cycling performance at 0.5C and 55 ℃; (f) EIS spectra

图7 HE-NCM-sc的CV曲线

Fig. 7 CV curve of HE-NCM-sc

参考文献 33

[1]	MAO M, JI X, WANG Q, et al. Anion-enrichment interface enables high-voltage anode-free lithium metal batteries. Nature Communications, 2023, 14: 1082. DOI PMID
[2]	朱亮, 严长青, 倪涛来. 锂离子电池预锂化技术的研究现状. 电池, 2018, 48(3): 206.
[3]	李鹏飞, 李威, 许春阳, 等. 锂离子电池三元正极材料掺杂改性研究进展. 郑州大学学报(理学版), 2024, 56(5): 80.
[4]	YANG T, ZHANG K, ZUO Y, et al. Ultrahigh-nickel layered cathode with cycling stability for sustainable lithium-ion batteries. Nature Sustainability, 2024, 7(9): 1204. DOI
[5]	TAN S, SHADIKE Z, LI J, et al. Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V. Nature Energy, 2022, 7(6): 484. DOI
[6]	CAO L, CHU M, LI Y, et al. In situ-constructed multifunctional composite anode with ultralong-life toward advanced lithium- metal batteries. Advanced Materials, 2024, 36(41): 2406034. DOI URL
[7]	ZHANG R, WANG C, ZOU P, et al. Compositionally complex doping for zero-strain zero-cobalt layered cathodes. Nature, 2022, 610(7930): 67. DOI
[8]	DOU S. Review and prospect of layered lithium nickel manganese oxide as cathode materials for Li-ion batteries. Journal of Solid State Electrochemistry, 2013, 17: 911. DOI URL
[9]	QIN L, YU H, JIANG X, et al. All-dry solid-phase synthesis of single-crystalline Ni-rich ternary cathodes for lithium-ion batteries. Science China Materials, 2024, 67(2): 650. DOI
[10]	LI H, LI J, ZAKER N, et al. Synthesis of single crystal LiNi_0.88Co_0.09Al_0.03O₂ with a two-step lithiation method. Journal of the Electrochemical Society, 2019, 166(10): A1956.
[11]	PANG P, TAN X, WANG Z, et al. Crack-free single-crystal LiNi_0.83Co_0.10Mn_0.07O₂ as cycling/thermal stable cathode materials for high-voltage lithium-ion batteries. Electrochimica Acta, 2021, 365: 137380. DOI URL
[12]	SONG J, HUANG L, YANG G, et al. Solid-state approach for synthesizing single crystal LiN_i0.8Co_0.1Mn_0.1O₂ cathode of lithium-ion batteries. Journal of Alloys and Compounds, 2023, 946: 169358. DOI URL
[13]	LEE S H, SIM S J, JIN B S, et al. High performance well-developed single crystal LiNi_0.91Co_0.06Mn_0.03O₂ cathode via LiCl-NaCl flux method. Materials Letters, 2020, 270: 127615. DOI URL
[14]	ZHOU W, HUANG H, LIU X, et al. Perspective on the preparation methods of single crystalline high nickel oxide cathode materials. Advanced Energy Materials, 2023, 13(32): 2300378. DOI URL
[15]	YU B, WANG Y, LI J, et al. Recent advances on low-Co and Co-free high entropy layered oxide cathodes for lithium-ion batteries. Nanotechnology, 2023, 34(45): 452501. DOI
[16]	GAO H, LI J, ZHANG F, et al. Revealing the potential and challenges of high-entropy layered cathodes for sodium-based energy storage. Advanced Energy Materials, 2024, 14(20): 2304529. DOI URL
[17]	BÉRARDAN D, FRANGER S, MEENA A K, et al. Room temperature lithium superionic conductivity in high entropy oxides. Journal of Materials Chemistry A, 2016, 4(24): 9536. DOI URL
[18]	XU Z, CHEN X, FAN W, et al. High-entropy rock-salt surface layer stabilizes the ultrahigh-Ni single-crystal cathode. ACS Nano, 2024, 18(49): 33706. DOI URL
[19]	SARKAR A, VELASCO L, WANG D, et al. High entropy oxides for reversible energy storage. Nature Communications, 2018, 9: 3400. DOI PMID
[20]	TAN X, ZHANG Y, XU S, et al. High-entropy surface complex stabilized LiCoO₂ cathode. Advanced Energy Materials, 2023, 13(24): 2300147. DOI URL
[21]	ZHAO C, WANG C, LIU X, et al. Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating. Nature Energy, 2024, 9(3): 345. DOI
[22]	SONG J, NING F, ZUO Y, et al. Entropy stabilization strategy for enhancing the local structural adaptability of Li-rich cathode materials. Advanced Materials, 2023, 35(7): 2208726.
[23]	LIU S, LIU F, ZHAO S, et al. A high-entropy engineering on sustainable anionic redox Mn-based cathode with retardant stress for high-rate sodium-ion batteries. Angewandte Chemie International Edition, 2025, 64(10): e202421089. DOI URL
[24]	ZHOU J, HU J, ZHOU X, et al. High-entropy doping for high-performance zero-cobalt high-nickel layered cathode materials. Energy & Environmental Science, 2025, 18(1): 347.
[25]	STURMAN J, YIM C H, BARANOVA E A, et al. Communication- design of LiNi_0.2Mn_0.2Co_0.2Fe_0.2Ti_0.2O₂ as a high-entropy cathode for lithium-ion batteries guided by machine learning. Journal of the Electrochemical Society, 2021, 168(5): 050541. DOI
[26]	XU J, YOU J, WU Y, et al. Building an entropy-assisted enhanced surface on ultrahigh nickel cathodes to improve electrochemical stability. Journal of Colloid and Interface Science, 2025, 682: 961. DOI PMID
[27]	ZENG C, FAN F, ZHENG R, et al. Structure and charge regulation strategy enabling superior cycling stability of Ni-rich cathode materials. ACS Applied Materials & Interfaces, 2024, 16(9): 11377.
[28]	REN J, LIU Z, TANG Y, et al. Enhancing electrochemical performance of nickel-rich NCM cathode material through Nb modification across a wide temperature range. Journal of Power Sources, 2024, 606: 234522. DOI URL
[29]	HUANG L, ZHU J, LIU J, et al. Emerging high-entropy strategy: a booster to the development of cathode materials for power batteries. Journal of Advanced Ceramics, 2024, 13(8): 1093. DOI URL
[30]	LI L, RAN Q, HAO S, et al. Dual functions of zirconium metaphosphate modified high-nickel layered oxide cathode material with enhanced electrochemical performance. Journal of Colloid and Interface Science, 2022, 615: 554. DOI PMID
[31]	YANG S, FAN Q, SHI Z, et al. Superior stability secured by a four-phase cathode electrolyte interface on a Ni-rich cathode for lithium ion batteries. ACS Applied Materials & Interfaces, 2019, 11(40): 36742.
[32]	LI X, ZHANG K, WANG M, et al. Dual functions of zirconium modification on improving the electrochemical performance of Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂. Sustainable Energy & Fuels, 2018, 2(2): 413.
[33]	SUN G, ZHUANG S, JIANG S, et al. Elevating cycle stability of Ni-rich NCM811 cathode via single-crystallization integrating dual-modification strategy for lithium-ion batteries. Journal of Alloys and Compounds, 2024, 976: 173097. DOI URL