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W-Doped LiMn0.6Fe0.4PO4/C as a High-Performance Cathode
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J
李
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F
刘
DOI：10.3390/batteries12080281.png)
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Abstract
En 中文
The inferior electronic conductivity, sluggish bulk Li+ transport, and Jahn–Teller distortion intrinsic to Mn3+ collectively impede the practical application of LiMn0.6Fe0.4PO4 (LMFP) as a high-performance cathode for lithium-ion batteries. Herein, a series of W-doped Li(Mn0.6Fe0.4)1−xWxPO4/C (x = 0, 0.005, 0.010, 0.015) cathode materials were synthesized via spray-drying combined with carbothermal reduction. Rietveld refinement indicated decreases in the fitted lattice parameters and unit-cell volume with increasing nominal W content, and no crystalline secondary phases were detected within the laboratory XRD detection limit. Although the structural evolution is consistent with W incorporation, direct determination of the occupation site requires further local structural characterization. X-ray photoelectron spectroscopy indicated that the detectable near-surface W species are predominantly present as W6+, and the semi-quantitative Mn 2p peak-area fitting showed that the fitted relative Mn3+ contribution decreased from 70.4% in LMFP-0 to 58.3% in LMFP-2. The optimal composition (LMFP-2, x = 0.010) delivers an initial discharge capacity of 160.2 mAh g−1 at 0.1 C, retains 98.1% capacity after 100 cycles at 1 C, and achieves 126.3 mAh g−1 at 5 C. Electrochemical impedance spectroscopy reveals that LMFP-2 possesses the lowest charge-transfer resistance (195.4 Ω) and the highest Li+ diffusion coefficient (5.3 × 10−15 cm2 s−1). These improvements may be attributed to the synergistic effects of enhanced bulk electronic conductivity, accelerated Li+ diffusion kinetics, and improved structural stability induced by moderate W incorporation. This work establishes W doping as a viable compositional engineering strategy for olivine-based cathode materials.
Keywords:
lithium-ion battery
lithium manganese iron phosphate
tungsten doping
cathode material
Jahn–Teller effect
electrochemical kinetics
olivine structure
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4.8
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1.8K
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