铕掺杂改善锂离子电池正极材料LiFePO4电化学性能研究

doi:10.19964/j.issn.1006-4990.2023-0520

Abstract

Abstract:

The olivine LiFePO₄ cathode material is widely used in the field of electric vehicles and energy storage due to its multiple advantages，however，its low temperature and rate performance are limited by poor electrical conductivity and sluggish lithium ions diffusion kinetics.Elemental doping is considered to be an effective strategy to improve the properties of cathode materials such as multiplicity and low temperature performance.Here，rare earth metal europium⁃doped LiFe_1-_x Eu _x PO₄/C cathode materials were synthesized by solid⁃phase method，and the effects of europium doping on the morphology，structure，and electrochemical properties of LiFePO₄were investigated.The results showed that europium doping could improve the electrochemical properties of LiFePO₄/C.The LiFe_0.97Eu_0.03PO₄/C showed the best rate，low temperature and cycling performance，with its discharge capacity of 95.1 mA·h/g at high rate of 20C（57.7% enhancement compared with that of LiFePO₄/C），discharge capacity of 81.5 mA·h/g（73.8% enhancement compared with that of LiFePO₄/C） at low temperature of -20 ℃，and capacity retention rate of 96.43%（26.2% enhancement compared with that of LiFePO₄/C） after 200 cycles at 1C.X-ray diffraction（XRD） and scanning electron microscopy（SEM） results showed that the europium doping could increase the cell volume of LiFePO₄ and decrease the binding energy between Li and O atoms，which could improve the diffusion rate of lithium ions.Electrochemical alternating impedance（EIS） test results showed that LiFe_0.97Eu_0.03PO₄/C exhibited the lowest charge transfer resistance，and the highest lithium ion diffusion coefficient that was two orders of magnitude higher than that of the undoped LiFePO₄/C，which explained its excellent rate，low⁃temperature and cycling performance.

Key words: LiFePO₄, lithium?ion batteries, europium doping, rate, cycling

CLC Number:

TM911

XUE Shan, LIU Lu, DAI Jiansheng, LI Qing, FENG Ze, LI Yineng. Study on electrochemical properties of europium⁃doped LiFePO₄ cathode material for lithium⁃ion battery[J]. Inorganic Chemicals Industry, 2024, 56(8): 67-73.

Figures/Tables 8

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Table 1

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Table 3

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样品	a/Å	b/Å	c/Å	V/Å³	平均Li—O键长/Å
纯LiFePO₄/C	10.333	6.010	4.695	291.57	2.137
LiFe_0.99Eu_0.01PO₄/C	10.338	6.011	4.697	291.880	2.146
LiFe_0.97Eu_0.03PO₄/C	10.343	6.014	4.703	292.540	2.148
LiFe_0.95Eu_0.05PO₄/C	10.334	6.009	4.698	291.732	2.143
LiFePO₄标准卡片	10.334	6.010	4.693	291.470

样品	w（Fe）/ %	w（Li）/ %	w（P）/ %	w（Eu）/10^-6	w（C）/ %	电阻率/（Ω·cm）
LiFePO₄/C	34.86	4.54	19.56	0	1.18	24.2
LiFe_0.99Eu_0.01PO₄/C	34.78	4.48	19.53	860	1.15	23.6
LiFe_0.97Eu_0.03PO₄/C	34.44	4.46	19.52	2 531	1.17	23.4
LiFe_0.95Eu_0.05PO₄/C	34.05	4.49	19.55	4 472	1.17	23.8

样品	R_b/Ω	R_ct/Ω	R_sei/Ω	δ	D_Li/（cm²·s^-1）
LiFePO₄/C	3.89	132.4		25.8	4.57×10^-15
LiFe_0.99Eu_0.01PO₄/C	3.71	70.3		11.5	5.41×10^-14
LiFe_0.97Eu_0.03PO₄/C	3.38	80.77		5.20	1.12×10^-13
LiFe_0.95Eu_0.05PO₄/C	3.27	96.44	85.82	16.4	2.47×10^-14

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Study on electrochemical properties of europium⁃doped LiFePO₄ cathode material for lithium⁃ion battery

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Study on electrochemical properties of europium⁃doped LiFePO4 cathode material for lithium⁃ion battery