Effect of Ni2+ Doping Modification on the Electrochemical Performance of LiMn0.75Fe0.25PO4 Cathode Material

doi:10.6023/A25020060

Abstract

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

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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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Fig. & Tab. 10

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

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

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

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

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

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

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

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

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

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