分散的LiMn6对Li1.17Ni0.17Fe0.17Mn0.49O2层状正极材料结构稳定性及氧化机理的影响研究

doi:10.6023/A24120377

化学学报 ›› 2025, Vol. 83 ›› Issue (4): 369-376.DOI: 10.6023/A24120377 上一篇下一篇

研究论文

分散的LiMn₆对Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂层状正极材料结构稳定性及氧化机理的影响研究

张旭^a^,^b, 郭鑫^a^,^c, 张纪阳^a, 刘继洪^a, 祝佳鹏^a, 黄超洋^a, 黎明^a, 贾桂霄^a^,^*(), 安胜利^a^,^b

a 内蒙古科技大学材料科学与工程学院内蒙古自治区先进陶瓷材料与器件重点实验室轻稀土资源绿色提取与高效利用教育部重点实验室(内蒙古科技大学) 包头 014010
b 内蒙古科技大学稀土产业学院包头 014010
c 贵州大学省部共建公共大数据国家重点实验室贵阳 550025

投稿日期:2024-12-21 发布日期:2025-03-03
基金资助:
国家自然科学基金(52262039); 内蒙古自治区自然科学基金(2024FX19); 内蒙古自治区直属高校基本科研业务费资助

Influence Research of Decentralized LiMn₆ on Structural Stability and Oxidation Mechanism of Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂ Layered Cathode Materials

Xu Zhang^a^,^b, Xin Guo^a^,^c, Jiyang Zhang^a, Jihong Liu^a, Jiapeng Zhu^a, Chaoyang Huang^a, Ming Li^a, Guixiao Jia^a(), Shengli An^a^,^b

a School of Materials Science and Engineering, Inner Mongolia University of Science and Technology, Inner Mongolia Key Laboratory of Advanced Ceramic Material and Devices, Key Laboratory of Green Extraction & Efficient Utilization of Light Rare-Earth Resources Inner Mongolia University of Science and Technology, Ministry of Education, Baotou 014010, China
b School of Rare Earth Industry, Inner Mongolia University of Science and Technology, Baotou 014010, China
c State Key Laboratory of Public Big Data, Guizhou University, Guiyang 550025, China

Received:2024-12-21 Published:2025-03-03
Contact: * E-mail: guixiao.jia@163.com; Tel.: 13015151366
Supported by:
National Natural Science Foundation of China(52262039); Inner Mongolia Autonomous Region Natural Science Foundation Program(2024FX19); Basic research expenses of universities directly under the Inner Mongolia Autonomous Region

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摘要/Abstract

富锂层状氧化物(LLOs)是下一代高容量锂离子电池正极材料的有利竞争者. 然而, LLOs材料常掺杂的Co元素不仅价格昂高, 且环境有害. 因此, 本工作使用价格便宜、环境友好的Fe元素代替Co, 构建了具有聚集和分散LiMn₆的Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂体系. 使用密度泛函理论(DFT)计算方法对体系结构、氧化过程、氧释放焓、过渡金属离子迁移及Fe掺杂作用等进行了研究. 研究发现, 掺杂的Fe激活了更多的氧参与电荷补偿, 分散的LiMn₆抑制了由Fe引起的Jahn-Teller效应畸变、氧的释放和Mn⁴⁺的迁移, 进而稳定了结构. 特别需要指出的是不同环境O的活性不同, 线性Li-O-Li中O是主要氧化还原中心, 主导氧化还原反应; 其次Fe-O-Li中O也参与氧化, LiTMO₂相O前期参与氧化, LiTMO₂与Li₂MnO₃相的边界O后期参与氧化. 本工作为设计无Co且结构稳定容量高的锂离子电池富锂层状正极材料提供了新的见解.

关键词: 分散LiMn₆, Fe掺杂, Jahn-Teller效应, Mn⁴⁺的迁移, 第一性原理计算

Lithium-rich layered oxides (LLOs) are a favorable competitor for the next generation of high-capacity lithium-ion battery cathode materials. However, the doped Co in LLOs materials is not only expensive, but also harmful to the environment. Furthermore, in LLOs cathodes, the aggregation of Li₂MnO₃ domains and lattice oxygen release lead to severe capacity/voltage degradation, ultimately impeding their commercial viability. Therefore, in this work, we substituted environmentally friendly and cost-effective Fe for Co, and designed two structural models—local distribution (LD) and delocalized distribution (DD) in the Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂ system. A spin-polarized generalized gradient approximation (GGA) method with the PBE (Perdew-Burke-Ernzerhof) exchange-correlation functional was explored. A 2×2×1 supercell with a total of 96 atoms, namely Li₂₈Fe₄Ni₄Mn₁₂O₄₈ is selected. We systematically investigated geometrical and electronic structures of DD and LD systems, oxidation processes, oxygen release enthalpy, transition metal ion migration and the role of Fe using density functional theory (DFT) calculations. It was found that the doped Fe activates more interfacial oxygen ions to participate to the charge compensation and disperses oxygen oxidation, thereby sharing the oxidation pressure of oxygen in the Li-O-Li configuration, which would be beneficial for suppressing the release of lattice oxygen. The dispersed LiMn₆ in the Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂ system inhibits the Jahn-Teller distortion caused by Fe and the migration of Mn⁴⁺ ions, thus stabilizing the structures. Oxygen in the linear Li-O-Li structure serves as the primary redox center, driving the redox reactions. Additionally, oxygen in Fe-O-Li-based systems also participates in the oxidation process. Specifically, the oxygen in the LiTMO₂ phase contributes to the early-stage oxidation, while oxygen at the interface between the LiTMO₂ and Li₂MnO₃ phases plays a role in the later stages of oxidation. This work provides new insights into the design of lithium-rich layered cathode materials without Co and with the high structural stability and the high capacity for lithium-ion batteries.

Key words: disperse LiMn₆, Fe doping, Jahn-Teller effect, migration of Mn⁴⁺, first principles calculations

引用此文

张旭, 郭鑫, 张纪阳, 刘继洪, 祝佳鹏, 黄超洋, 黎明, 贾桂霄, 安胜利. 分散的LiMn₆对Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂层状正极材料结构稳定性及氧化机理的影响研究[J]. 化学学报, 2025, 83(4): 369-376.

Xu Zhang, Xin Guo, Jiyang Zhang, Jihong Liu, Jiapeng Zhu, Chaoyang Huang, Ming Li, Guixiao Jia, Shengli An. Influence Research of Decentralized LiMn₆ on Structural Stability and Oxidation Mechanism of Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂ Layered Cathode Materials[J]. Acta Chimica Sinica, 2025, 83(4): 369-376.

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图/表 5

图1. LD体系Ni—O键长(a1)和Fe—O键长(b1); DD体系Ni—O键长(a2)和Fe—O键长(b2); Li28-xNi4Fe4Mn12O48中FeO6在x=20时的配位结构, 蓝色和绿色虚线框分别对应最长和最短键长(c); 氧的4种配位结构以及配位结构数, 黑色虚线框表示线性Li-O-Li结构(d); LD和DD体系的氧释放焓(e)

Figure 1. Ni—O bond lengths (a1, a2) and Fe—O bond lengths (b1, b2) in LD and DD systems; coordination structures of FeO6 at x=20 in Li28-xNi4Fe4Mn12O48, where the blue and green dashed boxes correspond to the longest and shortest bonds respectively (c); four types of coordination structures of the oxygen center and their numbers, where the black dashed box represents the linear Li-O-Li structure (d); oxygen release enthalpy (e) of LD and DD systems

图2. Li28-xNi4Fe4Mn12O48中LD (a1)与DD (a2)体系在脱锂数x=18、20、22和24时最稳定迁移方式结构及能垒图(b), 其中图(a)中红色虚线圆圈表示迁移的Mn4+离子, 箭头方向和末端分别表示迁移的方向和位置

Figure 2. (b) The most stable migration structures and their energy barriers (b) of LD (a1) and DD (a2) systems at x=18, 20, 22 and 24 in Li28-xNi4Fe4Mn12O48, where the red dashed circle in figure (a) represents the migrating Mn4+ ion, and the arrow direction and end indicate the direction and position of Mn4+ ion migration respectively

图3. Li28-xNi4Fe4Mn12O48中LD (a1)与DD (a2)体系氧的PDOS随脱锂量x的变化, 右侧红色框为能量–0.3 eV到0 eV的放大图, 对应分子式Li1.17Ni0.17Fe0.17Mn0.49O2积分面积为1时的能量范围

Figure 3. PDOS evolution of O for LD (a1) and DD (a2) as x in Li28-xNi4Fe4Mn12O48, the red box on the right provides an enlarged figure of the energy range from –0.3 eV to 0 eV with the integral area of 1 of DOS for the Li1.17Ni0.17Fe0.17Mn0.49O2 formula

图4. Li28-xNi4Fe4Mn12O48中LD (a1, b1)和DD (a2, b2)体系脱锂量x=12, 16和22时局域电荷密度图. 其中红色虚线圆圈表示过渡金属层脱去的锂

Figure 4. Local charge density of LD (a1, b1) and DD (a2, b2) systems at x=12, 16 and 22 as x in Li28-xNi4Fe4Mn12O48. The red dotted circles represent removed Li from the transition metal layer

图5. Li1.17Ni0.17Fe0.17Mn0.49O2体系的LD (a1)和DD (a2)结构模型, 不同元素的颜色如图左上角, 且本文所有图元素表示均如此

Figure 5. LD (a1) and DD (a2) structure models in Li1.17Ni0.17Fe0.17Mn0.49O2, the colors of the different elements are shown at the upper left corner in figure and this is used in all figures

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分散的LiMn₆对Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂层状正极材料结构稳定性及氧化机理的影响研究

Influence Research of Decentralized LiMn₆ on Structural Stability and Oxidation Mechanism of Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂ Layered Cathode Materials

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