Ni2+掺杂改性对LiMn0.75Fe0.25PO4正极材料电化学性能的影响

doi:10.6023/A25020060

摘要/Abstract

相较于磷酸铁锂, 磷酸铁锰锂LiMn₁₋_xFe_xPO₄ (LMFP, 0<x<1)可提供更高的放电电压, 然而其低电子、离子电导率和Jahn-Teller晶格畸变导致了低可逆容量和短循环寿命. 本工作使用溶剂热合成工艺, 将物质的量比例为1%的Ni²⁺掺入到LiMn_0.75Fe_0.25PO₄正极材料. 结果表明Ni²⁺的掺入可导致Li—O键的伸长, 拓宽Li⁺传输通道, 从而有利于Li⁺的脱出和嵌入, 提高了材料的放电比容量和倍率性能. 同时掺入的Ni²⁺缩短了Mn/Fe—O键的平均键长, 增强了其结合能, 进而抑制了Jahn-Teller晶格畸变, 改善了材料的结构和循环稳定性. 与未掺杂的LiMn_0.75Fe_0.25PO₄相比, Ni²⁺掺杂后的LiMn_0.75Fe_0.24Ni_0.01PO₄具有较低的电荷转移电阻和较高Li⁺扩散系数. 在0.1 C倍率下, 其放电比容量从未掺杂的136 mAh•g⁻¹上升到147 mAh•g⁻¹, 且在0.5 C下循环150圈后, 容量保持率仍有88.2%. 因此, Ni²⁺掺杂策略可被视为一种有潜力且有效的改性手段, 用于实现LMFP的快速充放电和长循环.

关键词: 锂离子电池, LiMn_0.75Fe_0.25PO₄, 离子掺杂, 倍率性能, 循环稳定性

Compared with lithium iron phosphate, lithium iron manganese phosphate LiMn₁₋_xFe_xPO₄ (LMFP, 0<x<1) has a higher discharge voltage. However, its low electronic and ionic conductivities, along with Jahn-Teller lattice distortion, result in low reversible capacity and short cycle life of LMFP. In this study, the solvothermal synthesis process is used to incorporate Ni²⁺ with a molar ratio of 1% into the LiMn_0.75Fe_0.25PO₄ cathode material. The effects of Ni²⁺ doping on the structure and electrochemical performance of LiMn_0.75Fe_0.25PO₄ were systematically investigated. Results of X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy confirm the successful incorporation of Ni²⁺ ions into the crystal lattice of LiMn_0.75Fe_0.25PO₄. In addition, Rietveld refinement results of XRD data indicate that the incorporation of Ni²⁺ leads to the elongation of the Li—O bonds and widening of the Li⁺ transport channels. Consequently, this is conducive to the extraction and insertion of Li⁺, improving the discharge specific capacity and rate performance of the material. Moreover, the incorporated Ni²⁺ shortens the average bond lengths of the Mn—O and Fe—O bonds, suppresses the Jahn-Teller lattice distortion, and improves the structure and cycling stability of the material. Furthermore, cyclic voltammetry tests reveal that Ni²⁺ doping could reduce the degree of polarization of the material and enhance the reversibility of the reaction. Analysis of electrochemical impedance spectroscopy reveals that, compared with undoped LiMn_0.75Fe_0.25PO₄, LiMn_0.75Fe_0.24Ni_0.01PO₄ exhibits a lower charge-transfer resistance and a higher lithium-ion diffusion coefficient. At a rate of 0.1 C, its discharge specific capacity has been increased from 136 mAh•g⁻¹ of the undoped material to 147 mAh•g⁻¹. The capacity retention rate is still 88.2% after 150 cycles at a rate of 0.5 C. Therefore, the Ni²⁺ doping strategy can be regarded as a promising and effective modification method for achieving rapid charge and discharge and long cycle of LMFP.

Key words: lithium ion battery, LiMn_0.75Fe_0.25PO₄, ion doping, rate performance, cycling stability

引用此文

薛兰, 刘爽, 章硕, 伽龙. Ni²⁺掺杂改性对LiMn_0.75Fe_0.25PO₄正极材料电化学性能的影响[J]. 化学学报, 2025, 83(8): 853-860.

Lan Xue, Shuang Liu, Shuo Zhang, Long Qie. Effect of Ni²⁺ Doping Modification on the Electrochemical Performance of LiMn_0.75Fe_0.25PO₄ Cathode Material[J]. Acta Chimica Sinica, 2025, 83(8): 853-860.

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图/表 10

图1. (a) LMFP31和LMFP31-Ni的XRD图谱; (b) LMFP31和LMFP31-Ni在34°~37°范围的XRD局部放大图; (c) LMFP31和(d) LMFP31-Ni的XRD精修图谱

Figure 1. (a) XRD patterns and (b) local amplification of XRD at 34°~37° of LMFP31 and LMFP31-Ni. Rietveld refinement patterns of (c) LMFP31 and (d) LMFP31-Ni

Sample	a/nm	b/nm	c/nm	V/nm³
LMFP31	1.0429	0.6085	0.4741	0.3009
LMFP31-Ni	1.0422	0.6080	0.4737	0.3002

表1. LMFP31和LMFP31-Ni的XRD精修结果

Table 1. The results of XRD refinement of LMFP31 and LMFP31-Ni

Sample	Bond length/nm
Sample	Li—O(1)	Li—O(2)	Li—O(3)
LMFP31	0.2237	0.2118	0.2132
LMFP31-Ni	0.2238	0.2120	0.2136

表2. Li—O键的键长变化

Table 3. Changes in bond length of Li—O bonds

图2. (a) LMFP31和LMFP31-Ni的拉曼光谱; (b) LMFP31和LMFP31-Ni的FT-IR光谱

Figure 2. (a) Raman spectra of LMFP31 and LMFP31-Ni, (b) FT-IR spectra of LMFP31 and LMFP31-Ni

图3. (a) LMFP31和(b) LMFP31-Ni的SEM图, (c) LMFP31-Ni的元素面扫描图

Figure 3. SEM images of (a) LMFP31 and (b) LMFP31-Ni, (c) EDS maps of LMFP31-Ni

图4. LMFP31的微观结构分析: (a) HRTEM图, (b)区域Ⅰ的放大图, (c)区域Ⅰ的FFT图, (d) iFFT线性剖面图; LMFP31-Ni的微观结构分析: (e) HRTEM图, (f)区域Ⅱ的放大图, (g)区域Ⅱ的FFT图, (h) iFFT线性剖面图

Figure 4. Microstructural analysis of LMFP31: (a) HRTEM image, (b) magnified view of area I, (c) FFT pattern of area I, (d) iFFT line profile; Microstructural analysis of LMFP31-Ni: (e) HRTEM image, (f) magnified view of area II, (g) FFT pattern of area II, (h) iFFT line profile

图5. LMFP31-Ni的XPS图谱: (a)全谱, (b) Fe 2p高分辨图谱, (c) Mn 2p高分辨图谱, (d) Ni 2p高分辨图谱

Figure 5. XPS spectra of LMFP31-Ni: (a) full spectrum, (b) high resolution spectrum of Fe 2p, (c) high resolution spectrum of Mn 2p, (d) high resolution spectrum of Ni 2p

图6. LMFP半电池的电化学性能: (a) LMFP31和(b) LMFP31-Ni在不同倍率下的首圈充放电曲线; LMFP31和LMFP31-Ni的(c)倍率性能和(d)循环稳定性

Figure 6. Electrochemical performance of LMFP half-cell: The first cycle charge and discharge curves at different rates of (a) LMFP31 and (b) LMFP31-Ni. (c) Rate performance and (d) cycling stability of LMFP31 and LMFP31-Ni

图7. LMFP半电池的动力学表征: (a) LMFP31和LMFP31-Ni半电池的CV曲线, (b)氧化还原峰间电压差, (c)等效电路和拟合后的奈奎斯特图, (d)低频区Z'与ω−1/2的线性拟合关系

Figure 7. Kinetic characterization of LMFP half-cells: (a) CV curves of LMFP31 and LMFP31-Ni half-cell, (b) voltage difference between redox peak, (c) EIS spectra and the equivalent circuit, (d) the linear fitting relationship between Z' and ω−1/2 in the low frequency region of EIS

Sample	R_ct/Ω	D_Li⁺/(×10⁻¹² cm²•s⁻¹)
LMFP31	128.1	3.3
LMFP31-Ni	57.3	5.2

表3. LMFP31和LMFP31-Ni的EIS测试结果

Table 3. EIS test results of LMFP31 and LMFP31-Ni

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Ni²⁺掺杂改性对LiMn_0.75Fe_0.25PO₄正极材料电化学性能的影响

Effect of Ni²⁺ Doping Modification on the Electrochemical Performance of LiMn_0.75Fe_0.25PO₄ Cathode Material

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