Ho掺杂诱导NCM622局域电子重构抑制阳离子混排的改性机制研究

doi:10.11949/0438-1157.20250291

化工学报 ›› 2025, Vol. 76 ›› Issue (7): 3733-3741.DOI: 10.11949/0438-1157.20250291

• 材料化学工程与纳米技术 • 上一篇下一篇

Ho掺杂诱导NCM622局域电子重构抑制阳离子混排的改性机制研究

李欣然¹(), 常龙娇¹(), 罗绍华²^,³, 李永兵¹, 杨瑞芬¹, 侯增磊¹, 邹杰¹

^1.渤海大学化学与材料工程学院，辽宁锦州 121013
^2.东北大学材料科学与工程学院，辽宁沈阳 110819
^3.东北大学秦皇岛分校资源与材料学院，河北秦皇岛 066099

收稿日期:2025-03-24 修回日期:2025-04-07 出版日期:2025-07-25 发布日期:2025-08-13
通讯作者: 常龙娇
作者简介:李欣然（2002—），男，硕士研究生，2908358672@qq.com
基金资助:
国家自然科学基金项目(51804035);国家自然科学基金项目(52104307);辽宁省教育厅项目(JYTM20231612);秦皇岛东北大学电介质与电解质功能材料河北省重点实验室项目(HKDEFM2023201);河北省电介质与电解质功能材料重点实验室绩效补贴资金(22567627H)

Modification mechanism of Ho doped NCM622 induced local electron remodeling to inhibit cationic mixing

Xinran LI¹(), Longjiao CHANG¹(), Shaohua LUO²^,³, Yongbing LI¹, Ruifen YANG¹, Zenglei HOU¹, Jie ZOU¹

^1.School of Chemical and Material Engineering, Bohai University, Jinzhou 121013, Liaoning, China
^2.School of Material Science and Engineering, Northeastern University, Shenyang 110819, Liaoning, China
^3.College of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066099, Hebei, China

Received:2025-03-24 Revised:2025-04-07 Online:2025-07-25 Published:2025-08-13
Contact: Longjiao CHANG

摘要/Abstract

摘要：

LiNi_0.6Co_0.2Mn_0.2O₂（NCM622）为锂离子电池高镍正极材料，镍含量为其带来了更高的比容量，同时具有一定的热稳定性，但材料充放电过程中存在的镍锂混排现象抑制了其比容量的进一步增加且影响晶格稳定性。为了缓解这种现象以得到更高性能的NCM622材料，用镧系元素钬（Ho）掺杂进行改性，Ho元素具备高能级的d、f层电子，能够显著增加材料内部的电子离域程度，抑制镍锂混排，通过降低电荷集中程度提高晶格稳定性。Ho掺杂NCM622能够达到196.82 mAh·g^-1的放电比容量，并且在多次充放电循环下仍有92.6%的容量保持率。最后通过循环前后微观结构的变化与第一性原理计算探讨了Ho掺杂的具体改性机理，可为锂离子电池稀土掺杂的研究提供参考。

关键词: 锂离子电池, 正极材料, 电化学, 优化, 再生能源

Abstract:

LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) is a high nickel cathode material for lithium-ion batteries. The nickel content brings higher specific capacity and certain thermal stability. However, the nickel-lithium mixing phenomenon in the charge-discharge process of the material inhibits the further increase of its specific capacity and affects the lattice stability. In order to alleviate this phenomenon to obtain higher-performance NCM622 materials, the lanthanide element Ho is doped for modification. The Ho element has high-energy d and f-layer electrons, which can significantly increase the degree of electron delocalization inside the material, inhibit nickel-lithium mixing, and improve lattice stability by reducing charge concentration. Compared with the pure phase material, Ho-doped NCM622 can achieve a discharge specific capacity of 196.82 mAh·g^-1, and still has a retention rate of 92.6% after multiple charge-discharge cycles. Finally, the specific modification mechanism of Ho doping was discussed through the change of microstructure before and after cycling and first-principles calculation, which has certain guiding significance for rare earth doping of lithium ion battery.

Key words: lithium-ion battery, cathode material, electrochemistry, optimization, renewable energy

中图分类号:

TQ 028.8

李欣然, 常龙娇, 罗绍华, 李永兵, 杨瑞芬, 侯增磊, 邹杰. Ho掺杂诱导NCM622局域电子重构抑制阳离子混排的改性机制研究[J]. 化工学报, 2025, 76(7): 3733-3741.

Xinran LI, Longjiao CHANG, Shaohua LUO, Yongbing LI, Ruifen YANG, Zenglei HOU, Jie ZOU. Modification mechanism of Ho doped NCM622 induced local electron remodeling to inhibit cationic mixing[J]. CIESC Journal, 2025, 76(7): 3733-3741.

图/表 8

图1 NCM622制备流程

Fig.1 NCM622 preparation flow

图2 (a)纯相与Ho掺杂样品的XRD衍射谱图；(b)XRD局部放大图；(c)两种材料的SEM图

Fig.2 (a) XRD patterns of pure phase and Ho-doped samples; (b) Local amplified XRD patterns; (c) SEM images of the two materials

图3 (a)纯相与Ho掺杂样品的XRD精修图；(b)两种材料的晶体结构以及晶胞参数

Fig.3 (a) XRD refinement of pure phase and Ho-doped samples; (b) Crystal structure and unit cell parameters of the two materials

图4 (a)纯相与Ho掺杂样品的首次充放电曲线；(b)倍率性能；(c) 0.1C充放电倍率下的长循环性能；(d)电化学阻抗曲线

Fig.4 (a) The first charge-discharge curves of pure phase and Ho-doped samples; (b) Rate performance; (c) Long cycle performance at 0.1C charge-discharge rate; (d)Electrochemical impedance curve

图5 (a)纯相与Ho掺杂样品循环后的XRD衍射谱图；(b)循环后两者的SEM图；(c)Ho掺杂NCM622的TEM图与对应区域的FFT

Fig.5 (a) XRD patterns of pure phase and Ho-doped samples after cycling; (b) SEM images of the two samples after cycles;(c) TEM image of Ho-doped NCM622 and the FFT of the corresponding region

图6 NCM622改性机理

Fig.6 Mechanism of NCM622 modification

图7 Ho掺杂的NCM622的(a)能带结构和(b)分波态密度

Fig.7 (a) The band structure and (b) partial density of states of Ho-doped NCM622

表1 不同稀土掺杂的NCM622性能比较

Table 1 Comparison of properties of NCM622 doped with different rare earths

材料	比容量/(mAh·g^-1)	文献
LiNi_0.55Co_0.2Mn_0.2Ho_0.05O₂	196.82	本文
LiNi_0.595Co_0.2Mn_0.2Nd_0.005O₂	160.1	[35]
LiNi_0.59Co_0.2Mn_0.2La_0.01O₂	151.8	[35]
LiNi_0.595Co_0.2Mn_0.2Eu_0.005O₂	153.1	[35]
LiNi_0.6Co_0.2Mn_0.2O₂-1/24Ce doped	248	[30]

参考文献 35

[1]	Cao W P, Yan J T, Zhang P, et al. Cerium-doped lithium-rich Li_1.2Mn_0.56Ni_0.11Co_0.13O₂ as cathode with high performance for lithium-ion batteries[J]. Ionics, 2022, 28(10): 4515-4526.
[2]	Zheng Z Y, Zhou J, Zhu Y S. Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning[J]. Chemical Society Reviews, 2024, 53(6): 3134-3166.
[3]	Jiang P, Van Fan Y, Klemeš J J. Impacts of COVID-19 on energy demand and consumption: challenges, lessons and emerging opportunities[J]. Applied Energy, 2021, 285: 116441.
[4]	Zhang C, Chou S, Guo Z, et al. Beyond lithium-ion batteries[J]. Advanced Functional Materials, 2024, 34(5): 2308001.
[5]	Chan K H, Liu H T, Azimi G. Synthesis of a nickel-rich LiNi_0.6Mn_0.2Co_0.2O₂ cathode material utilizing the supercritical carbonation process[J]. Industrial & Engineering Chemistry Research, 2023, 62(10): 4271-4280.
[6]	Soloy A, Flahaut D, Ledeuil J B, et al. Unraveling the morphological dependency of the LiNi_0.6Mn_0.2Co_0.2O₂ layered oxide reactivity in Li-ion batteries[J]. ACS Applied Energy Materials, 2022, 5(7): 8669-8685.
[7]	Klein S, Bärmann P, Fromm O, et al. Prospects and limitations of single-crystal cathode materials to overcome cross-talk phenomena in high-voltage lithium ion cells[J]. Journal of Materials Chemistry A, 2021, 9(12): 7546-7555.
[8]	Ling J, Karuppiah C, Krishnan S G, et al. Phosphate polyanion materials as high-voltage lithium-ion battery cathode: a review[J]. Energy & Fuels, 2021, 35(13): 10428-10450.
[9]	Kong Y L, Yuan L X, Liao Y Q, et al. Efficient separation and selective Li recycling of spent LiFePO₄ cathode[J]. Energy Materials, 2023, 3(6): 300053.
[10]	Jiang X M, Chen Y J, Meng X K, et al. The impact of electrode with carbon materials on safety performance of lithium-ion batteries: a review[J]. Carbon, 2022, 191: 448-470.
[11]	Román-Ramírez L A, Marco J. Design of experiments applied to lithium-ion batteries: a literature review[J]. Applied Energy, 2022, 320: 119305.
[12]	Sheng L, Yang K, Chen J, et al. A protophilic MOF enables Ni-rich lithium-battery stable cycling in a high water/acid content[J]. Advanced Materials, 2023, 35(25): 2212292.
[13]	Yu Z Z, Zhao G Q, Ji F L, et al. Collaboratively enhancing electrochemical properties of LiNi_0.83Co_0.11Mn_0.06O₂ through doping and coating of quadrivalent elements[J]. Rare Metals, 2023, 42(12): 4103-4114.
[14]	Miyaoka Y, Sato T, Oguro Y, et al. A practical and sustainable Ni/Co-free high-energy electrode material: nanostructured LiMnO₂ [J]. ACS Central Science, 2024, 10(9): 1718-1732.
[15]	Ramadan R A. Internet of things dataset for home renewable energy management[J]. Data in Brief, 2024, 53: 110166.
[16]	Zheng Z Y, Zhou J, Zhu Y S. Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning[J]. Chemical Society Reviews, 2024, 53(6): 3134-3166.
[17]	Lenus S, Thakur P, Megha, et al. Lithium transfer dynamics and storage capacity/cyclability properties of Ni and Ru dual-doped two-dimensional FePS₃ nanoflakes[J]. Materials Research Bulletin, 2024, 176: 112837.
[18]	Zheng H N, Peng S, Liang S Z, et al. Progress and challenges of Ni-rich layered cathodes for all-solid-state lithium batteries[J]. Advanced Functional Materials, 2025, 35(16): 2418274.
[19]	Akhilash M, Salini P S, John B, et al. Surface modification on nickel rich cathode materials for lithium-ion cells: a mini review[J]. The Chemical Record, 2023, 23(11): e202300132.
[20]	Wang Z, Li L, Heo H, et al. Synthesis and characterization of core-shell high-nickel cobalt-free layered LiNi_0.95Mg_0.02Al_0.03O₂@Li₂ZrO₃ cathode for high-performance lithium ion batteries[J]. Journal of Colloid and Interface Science, 2024, 666: 424-433.
[21]	Kumar D, Ramesha K. Comprehensive study of Ti and Ta co-doping in Ni-rich cathode material LiNi_0.8Mn_0.1Co_0.1O₂ towards improving the electrochemical performance[J]. ChemPhysChem, 2024, 25(13): e202400064.
[22]	Yang X R, Huang Y X, Li J H, et al. Understanding of working mechanism of lithium difluoro(oxalato) borate in Li\|\|NCM85 battery with enhanced cyclic stability[J]. Energy Materials, 2023, 3: 300029.
[23]	Chu B B, Xu R Y, Li G X, et al. Simultaneous B/W dual coating on ultra-high nickel single crystal cathode material for lithium-ion batteries[J]. Journal of Power Sources, 2023, 577: 233260.
[24]	Lei H L, Peng M, Liu J, et al. Boron & nitrogen synergistically enhance the performance of LiNi_0.6Co_0.1Mn_0.3O₂ [J]. Journal of Alloys and Compounds, 2023, 959: 170522.
[25]	Chen Y G, Tian H L, Cai Y J, et al. Preparing Li₆V₃(PO₄)₅ cathode with boron-doped carbon layer as a cathode material for lithium-ion batteries[J]. Energy Technology, 2024, 12(7): 2301537.
[26]	Ren X X, Wang G R, Chen T L, et al. A surface-bulk integrated strategy of Ti doping and LaTiO₃ coating achieves highly reversible anionic redox and fast-charging cyclability in cobalt-free lithium-rich layered oxides[J]. Advanced Functional Materials, 2025, 35(22): 2422482.
[27]	Yu Z Z, Tong Q L, Cheng Y, et al. Enabling 4.6 V LiNi_0.6Co_0.2Mn_0.2O₂ cathodes with excellent structural stability: combining surface LiLaO₂ self-assembly and subsurface La-pillar engineering[J]. Energy Materials, 2022, 2(5): 37.
[28]	Shen Y B, Zhang X Y, Wang L C, et al. A universal multifunctional rare earth oxide coating to stabilize high-voltage lithium layered oxide cathodes[J]. Energy Storage Materials, 2023, 56: 155-164.
[29]	Li D J, Yang P H, Deng Q, et al. Stabilizing Ni-rich single-crystalline LiNi_0.83Co_0.07Mn_0.10O₂ cathodes using Ce/Gd co-doped high-entropy composite surfaces[J]. Angewandte Chemie International Edition, 2024, 63(10): e202318042.
[30]	Chang L J, Hou Z L, Yang W, et al. The theory guides the doping of rare earth elements in the bulk phase of LiNi_0.6Co_0.2Mn_0.2O₂ to reach the theoretical limit of energy density[J]. Journal of Colloid and Interface Science, 2025, 682: 340-352.
[31]	Sun Y B, Chang C K, Zheng J N. Doping effects on ternary cathode materials for lithium-ion batteries: a review[J]. ChemPhysChem, 2024, 25(17): e202300966.
[32]	Yu X K, Scipioni R, Xu Y B, et al. Beneficial effects of La_0.5Sr_0.5CoO₃ coatings on thin-film LiMn₂O₄ cathodes for lithium ion batteries[J]. Advanced Sustainable Systems, 2023, 7(9): 2300137.
[33]	Mei Y, Liu J X, Cui T, et al. Defect chemistry in high-voltage cathode materials for lithium-ion batteries[J]. Advanced Materials, DOI: 10.1002/adma.202411311 .
[34]	Bae J H, Hwang K, Kim J, et al. Enhanced electrochemical performance of Ni-rich cathode for lithium ion batteries under elevated cut-off voltage (4.5 V): elongated cycle stability of cathode by relaxed mechanical stress in the presence of internal porous layer[J]. Journal of Electroanalytical Chemistry, 2024, 957: 118123.
[35]	Zybert M, Ronduda H, Dąbrowska K, et al. Suppressing Ni/Li disordering in LiNi_0.6Mn_0.2Co_0.2O₂ cathode material for Li-ion batteries by rare earth element doping[J]. Energy Reports, 2022, 8: 3995-4005.

Ho掺杂诱导NCM622局域电子重构抑制阳离子混排的改性机制研究

Modification mechanism of Ho doped NCM622 induced local electron remodeling to inhibit cationic mixing

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