多孔碳锚定磷酸钒锂修饰高镍正极材料的研究

doi:10.6023/A26050167

摘要/Abstract

高镍三元正极材料以其较高的能量密度优势成为锂离子电池正极材料的重要发展方向. 但界面副反应、阳离子混排及微裂纹产生等一系列问题制约着高镍正极材料的应用进展. 为此, 本研究利用生物基多孔碳锚定磷酸钒锂的复合涂层修饰高镍正极材料LiNi_0.83Co_0.12Mn_0.05O₂, 改善其界面稳定性. 结果表明, 磷酸钒锂稳定的三维结构和高的锂离子迁移速率不仅提供了良好的物理隔离效果, 抑制了界面副反应, 也为锂离子迁移提供了快速通道. 同时, 多孔碳优异的导电性能也为涂层构建了高效的电子传输网络, 显著改善了电极材料的电化学性能. 复合涂层修饰的高镍正极材料在不同倍率下容量保持率均高于未改性材料; 在1 C下循环200圈后, 容量保持率提升了12.3%, 放电中值电压差ΔV减小了0.123 V.

关键词: 锂离子电池, 高镍正极, 磷酸钒锂, 多孔碳, 复合涂层

High-nickel ternary cathode materials, known for their high energy density, have become an important direction for the development of cathode materials in lithium-ion batteries. However, their high nickel content increases surface activity, leading to side reactions. Moreover, a series of issues such as cation mixing and microcrack generation also restrict the development of high-nickel cathode materials. To address these issues, this study employs a composite coating of bio-based porous carbon anchored with lithium vanadium phosphate (LVP@PC) to modify the high-nickel cathode material LiNi_0.83Co_0.12Mn_0.05O₂ (NCM83), thereby improving its interfacial stability. The results show that the stable three-dimensional olivine structure and high lithium-ion migration rate of lithium vanadium phosphate not only provide effective physical isolation, suppressing interfacial side reactions, but also offer fast channels for lithium-ion migration at the interface. Combined with the high electrical conductivity of porous carbon, the LVP@PC composite coating constructs an efficient hybrid conductive network for electrons and ions, significantly enhancing the kinetic performance of the electrode reaction. The results indicate that the electrochemical performance of the high-nickel cathode material is optimized through multiple synergistic effects. After 200 cycles at 1 C, the specific discharge capacity retention of the modified sample is increased by 12.3%. The charge-discharge platforms under different cycle numbers are more stable, and the voltage difference of the discharge median voltage is reduced, indicating weakened polarization. In rate capability tests, as the rate gradually increases from 0.1 C to 5 C, the specific discharge capacity still reaches approximately 180 mAh•g^-1. Observation of the electrodes after galvanostatic charge-discharge cycling tests via scanning electron microscopy reveals that the surface of the NCM83 electrode modified with the lithium vanadium phosphate@porous carbon composite coating is smooth and exhibits tight connections, whereas the surface of the unmodified NCM83 electrode shows cracking textures. This demonstrates that the lithium vanadium phosphate@porous carbon composite coating can inhibit the generation of microcracks and slow their propagation.

Key words: lithium-ion battery, high-nickel cathode, lithium vanadium phosphate, porous carbon, composite coating

引用此文

杨帆, 陈兴杰, 梁硕, 余涛, 吴朝明, 赖春艳. 多孔碳锚定磷酸钒锂修饰高镍正极材料的研究[J]. 化学学报, 2026, 84(10): 1601-1609.

Fan Yang, Xingjie Chen, Shuo Liang, Tao Yu, Zhaoming Wu, Chunyan Lai. Study on Porous Carbon-Anchored Lithium Vanadium Phosphate Modified High-Nickel Cathode Materials[J]. Acta Chimica Sinica, 2026, 84(10): 1601-1609.

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图/表 6

图1. (a~f) LVP@PC复合结构的SEM及EDS图; PC的(g) SEM图和(h) TEM图

Figure 1. (a~f) SEM and EDS images of LVP@PC composite structure; (g) SEM image and (h) TEM image of PC

图2. (a) NCM83, (b) 0.5%LVP@PC-NCM83, (c) 1.0%LVP@PC-NCM83, (d) 1.5%LVP@PC-NCM83, (e) 2.0%LVP@PC-NCM83的SEM图和(f) 1.0%LVP@PC-NCM83的EDS图; (g) NCM83, (h) 1.0%LVP@PC-NCM83的透射电镜(TEM)图

Figure 2. The SEM images of (a) NCM83, (b) 0.5% LVP@PC-NCM83, (c) 1.0%LVP@PC-NCM83, (d) 1.5%LVP@PC-NCM83, (e) 2.0%LVP@PC-NCM83, and (f) the EDS image of 1.0%LVP@PC-NCM83; TEM images of (g) NCM83 and (h) 1.0% LVP@PC-NCM83

图3. (a) NCM83、0.5%LVP@PC-NCM83、1.0%LVP@PC-NCM83、1.5%LVP@PC-NCM83、2.0%LVP@PC-NCM83的XRD图谱; (b) LVP@PC的XRD图; (c) NCM83、1.0%LVP@PC-NCM83的XPS全谱图; (d) 1.0%LVP@PC-NCM83的V 2p精细谱; (e) NCM83和(f) 1.0%LVP@PC-NCM83的Ni 2p精细谱; (g) NCM83和(h) 1.0%LVP@PC-NCM83的O 1s精细谱

Figure 3. (a) XRD patterns of samples NCM83, 0.5%LVP@PC-NCM83, 1.0%LVP@PC-NCM83, 1.5%LVP@PC-NCM83 and 2.0%LVP@PC-NCM83; (b) XRD pattern of LVP@PC; (c) XPS survey spectra of NCM83 and 1.0%LVP@PC-NCM83; (d) V 2p high-resolution spectrum of 1.0%LVP@PC-NCM83; Ni 2p high-resolution spectrum of (e) NCM83 and (f) 1.0%LVP@PC-NCM83; O 1s high-resolution spectrum of (g) NCM83 and (h) 1.0%LVP@PC-NCM83

图4. NCM83、0.5%LVP@PC-NCM83、1.0%LVP@PC-NCM83、1.5%LVP@PC-NCM83和2.0%LVP@PC-NCM83的(a)倍率图, (b)循环图和(f)阻抗图; (c) NCM83和1.0%LVP@PC-NCM83的中值电压图; (d) NCM83, (e) 1.0%LVP@PC-NCM83不同循环圈数的充放电曲线图; NCM83, 1.0%PC-NCM83, 1.0%LVP-NCM83和1.0%LVP@PC-NCM83的(g)倍率性能图, (h)循环图和(i)阻抗图

Figure 4. (a) Rate capability plots, (b) cycling plots and (f) impedance plots of NCM83, 0.5%LVP@PC-NCM83, 1.0%LVP@PC-NCM83, 1.5%LVP@PC-NCM83 and 2.0%LVP@PC-NCM83; (c) Median voltage plots of NCM83 and 1.0%LVP@PC-NCM83; Charge-discharge curves of (d) NCM83 and (e) 1.0%LVP@PC-NCM83 at different cycle numbers; (g) Rate capability plots, (h) cycling plots and (i) impedance plots of NCM83, 1.0%PC-NCM83, 1.0%LVP-NCM83 and 1.0%LVP@PC-NCM83

图5. (a) NCM83、(b) 1.0%LVP@PC-NCM83的CV图; (c) NCM83, (d) 1.0%LVP@PC-NCM83的GITT测试图; NCM83和1.0%LVP@PC-NCM83在(e)充电期间和(f)放电期间的Log D

Figure 5. CV curves of (a) NCM83 and (b) 1.0%LVP@PC-NCM83; GITT plots of (c) NCM83 and (d) 1.0%LVP@PC-NCM83; Log D of NCM83 and 1.0%LVP@PC-NCM83 during (e) charging and (f) discharging

图6. (a) NCM83、(b) 1.0%LVP@PC-NCM83循环前后的SEM形貌; NCM83和1.0%LVP@PC-NCM83循环前后的(c) XRD图、(d)放电曲线; (e) NCM83、(f) 1.0%LVP@PC-NCM83循环前后的Williamson-Hall分析图

Figure 6. SEM morphology of (a) NCM83 and (b) 1.0%LVP@PC-NCM83 before and after cycling; (c) XRD patterns and (d) discharge curves of NCM83 and 1.0% LVP@PC-NCM83 before and after cycling; Williamson-Hall analysis plots before and after cycling of (e) NCM83 and (f) 1.0% LVP@PC-NCM83

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