铁弹Zr0.92Y0.08O2对层状LiMnO2正极材料充放电循环行为的影响

doi:10.6023/A25030072

摘要/Abstract

具有正交结构的层状LiMnO₂ (LMO)是一种资源充足和廉价的锂离子电池锰基正极材料, 但存在着充放电循环稳定性差等难题. 针对层状LMO正极材料在充放电过程中循环稳定性很差的问题, 本工作采用湿化学法用钇稳定的二氧化锆(Zr_0.92Y_0.08O₂, 或YSZ)铁弹材料对 LMO粉体进行包覆改性, 以提高其充放电循环性能. X射线衍射(XRD)与透射电子显微镜(TEM)分析显示, YSZ为四方结构, 其尺寸分布在3~15 nm, 以薄层或颗粒包覆在LMO颗粒上, 形成了LMO@YSZ复合材料. 在200 mA•g⁻¹电流密度下循环300次, LMO@YSZ复合材料容量保持率为59%, 与纯LiMnO₂的36%相比, 明显抑制了其充放电比容量的衰减. 扫描电子显微镜(SEM)分析显示, LMO@YSZ复合材料电极片中的裂纹数量和开裂程度得到明显抑制. 而高分辨电子显微镜显示, 纳米尺寸YSZ存在着四方相的90°铁弹畴. 从实验结果得到推论, LMO@YSZ复合材料充放电循环性能的提高归因于裂纹减少或抑制, 这源于充放电过程中LiMnO₂正极材料与Zr_0.92Y_0.08O₂铁弹材料发生电化学-铁弹效应, YSZ的铁弹相变耗散了正极活性材料中的应力能, 有效抑制电极中的裂纹产生, 进而提高了LiMnO₂电极的充放电循环性能.

关键词: LiMnO₂, 钇稳定的二氧化锆, 正极材料, 铁弹材料, 锂离子电池

Layered LiMnO₂ (LMO) with an orthorhombic structure is an abundant and inexpensive manganese-based cathode material for lithium-ion batteries, but it suffers from challenges such as poor charge-discharge cycle stability. To address this issue, nanoscale Y-stabilized ZrO₂ (Zr_0.92Y_0.08O₂, YSZ) is coated on LiMnO₂ crystallites by a wet-chemical method to improve its charge-discharge cycle performance in this paper. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses show that YSZ in the synthesized material has a tetragonal structure with a size distribution of 3~15 nm, coating LMO particles as thin layers or particles to form LMO@YSZ nanocomposites. High resolution transmission electron microscope (HRTEM) analysis reveals the presence of 90° ferroelastic domains in the tetragonal phase within the nanoscale YSZ surrounding LMO particles. Charge-discharge tests demonstrate that the maximum discharge capacity is 192 mAh•g⁻¹ at a current density of 20 mA•g⁻¹. After 300 cycles at 200 mA•g⁻¹, the capacity of the LMO@YSZ composite remains at 59% of its maximum capacity, significantly suppressing the decay of charge-discharge specific capacity compared to 36% for pure LiMnO₂. Scanning electron microscope (SEM) observations reveal that after 300 charge-discharge cycles, the uncoated LMO electrode contains cracks approximately 700 nm wide and over 40 μm long, which interweave to form isolated "island-like" regions in the electrode. In contrast, cracks are hardly observable in the YSZ-coated electrode, with particles in close contact. The number of cracks in the LMO@YSZ composite electrode are significantly suppressed. Considering ferroelastic domains in YSZ of the composite, it is inferred that the improved charge-discharge cycle performance of the LMO@YSZ composite is attributed to reduced or inhibited cracking from the experimental results. This may originate from the electrochemical-ferroelastic coupling effect between the LMO cathode material and YSZ ferroelastic material during charge-discharge processes, delivering stress energy in LMO to YSZ. As a result, the ferroelastic behavior of YSZ dissipate the stress energy in the cathode material, effectively suppressing crack generation in the electrode without hindering electron and lithium-ion diﬀusion, thereby improving the charge-discharge cycle performance of the LiMnO₂ electrode.

Key words: LiMnO₂, Y-stabilized ZrO₂, cathode materials, ferroelastic materials, lithium-ion battery

引用此文

陆继承, 苟蕾, 刘小九, 樊小勇, 李东林. 铁弹Zr_0.92Y_0.08O₂对层状LiMnO₂正极材料充放电循环行为的影响[J]. 化学学报, 2025, 83(8): 844-852.

Jicheng Lu, Lei Gou, Xiaojiu Liu, Xiaoyong Fan, Donglin Li. Effect of Ferroelastic Zr_0.92Y_0.08O₂ on the Charge-Discharge Cycling Performances of the Layered LiMnO₂ Cathode Materials[J]. Acta Chimica Sinica, 2025, 83(8): 844-852.

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图/表 9

图1. (a)合成的LMO样品的XRD图谱; (b)在氩气气氛下600 ℃保温3 h合成的Zr0.92Y0.08O2粉末XRD图谱

Figure 1. (a) X-ray diffraction patterns of LMO samples; (b) XRD pattern of Zr0.92Y0.08O2 powder synthesized at 600 ℃ for 3 h under argon atmosphere

图2. LMO@1YSZ复合材料新鲜样品的透射电子显微镜照片. (a) TEM显示包覆层YSZ; (b) HR-TEM中YSZ四方相的铁弹畴、YSZ和LMO的晶格条纹

Figure 2. TEM images of as-synthesized LMO@1YSZ composite. (a) TEM showing YSZ coating layer on LMO particle; (b) HR-TEM showing ferroelastic domains and lattice strips corresponding to YSZ and LMO crystallites

图3. (a), (b)纯LMO和(c), (d) LMO@1YSZ样品在不同放大倍数下的SEM图

Figure 3. SEM images of (a), (b) pure LMO and (c), (d) LMO@1YSZ samples at different magnifications

图4. (a)纯LMO、LMO@1YSZ和LMO@3YSZ首次充放电曲线; (b)纯LMO、LMO@1YSZ和LMO@3YSZ第5周的充放电曲线; (c)纯LMO、LMO@1YSZ和LMO@3YSZ达到最大放电容量时的充放电曲线

Figure 4. (a) The initial charge and discharge curves of pure LMO, LMO@1YSZ and LMO@3YSZ; (b) Charge and discharge curves for the 5th cycle of pure LMO, LMO@1YSZ, and LMO@3YSZ; (c) Charge and discharge curves of pure LMO, LMO@1YSZ, and LMO@3YSZ at maximum discharge capacity

电极名称	初始充电比容量/ (mAh•g⁻¹)	初始放电比容量/ (mAh•g⁻¹)	库伦效率
LMO	350.60	138.17	39.40%
LMO@1YSZ	323.28	157.60	48.75%
LMO@3YSZ	321.62	113.13	35.17%

表1. 纯LMO、LMO@1YSZ和LMO@3YSZ电极首次充/放电比容量及其库伦效率

Table 1. Initial charge-discharge capacity and Coulomb efficiency of pure LMO, LMO@1YSZ and LMO@3YSZ electrode

图5. (a) LMO和(b) LMO@1YSZ的CV曲线图

Figure 5. (a) CV curves of LMO and (b) LMO@1YSZ

图6. 合成材料LMO、LMO@1YSZ和LMO@3YSZ的电化学性能. (a), (b)分别为材料在0.1C和1C循环性能; (c)~(e)分别为材料在200 mA•g−1时不同循环周次的充放电曲线; (f)为相应的30周和第300周的充放电曲线

Figure 6. Electrochemical properties of synthesized LMO, LMO@1YSZ, and LMO@3YSZ materials. (a), (b) Cycle performances at 0.1C and 1C; (c)~(e) charge-discharge curves at different cycles at 200 mA•g−1; (f) charge-discharge curves at 30th and 300th

图7. (a) LMO和(b) LMO@1YSZ为不同电流密度下的具有最大放电比容量的周次的充放电曲线图

Figure 7. Charge-discharge curves of the cycle with the maximum discharge capacity of (a) LMO@1YSZ and (b) LMO at different current densities

图8. (a), (c), (e) LMO和(b), (d), (f) LMO@1YSZ电极片在200 mA•g−1的电流密度下循环300周的SEM图

Figure 8. SEM images of (a), (c), (e) LMO and (b), (d), (f) LMO@1YSZ electrode pieces after cycling for 300th at a current density of 200 mA•g−1

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铁弹Zr_0.92Y_0.08O₂对层状LiMnO₂正极材料充放电循环行为的影响

Effect of Ferroelastic Zr_0.92Y_0.08O₂ on the Charge-Discharge Cycling Performances of the Layered LiMnO₂ Cathode Materials

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