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Study on electrochemical properties of europium⁃doped LiFePO4 cathode material for lithium⁃ion battery
Received date: 2023-11-02
Online published: 2024-09-26
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 LiFe1-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 LiFePO4 were investigated.The results showed that europium doping could improve the electrochemical properties of LiFePO4/C.The LiFe0.97Eu0.03PO4/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 LiFe0.97Eu0.03PO4/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
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 . DOI: 10.19964/j.issn.1006-4990.2023-0520
1 | HUANG Jinwang, ZHANG Bo, ZHANG Shipeng,et al.Ultra?fine nano-Mg(OH)2 electrodeposited in flexible confined space and its enhancement of the performance of LiFePO4 lithium?ion batteries[J].Advanced Functional Materials,2023,33(44):2307215. |
2 | 王甲泰,赵段,马莲花,等.锂离子电池正极材料磷酸铁锂的研究进展[J].无机盐工业,2020,52(4):18-22. |
WANG Jiatai, ZHAO Duan, MA Lianhua,et al.Research progress of LiFePO4 cathode materials for Li-ion battery[J].Inorganic Chemicals Industry,2020,52(4):18-22. | |
3 | LING J, KARUPPIAH C, KRISHNAN S G,et al.Phosphate polyanion materials as high?voltage lithium?ion battery cathode:A review[J].Energy & Fuels,2021,35(13):10428-10450. |
4 | KITTNER N, LILL F, KAMMEN D M.Energy storage deployment and innovation for the clean energy transition[J].Nature Energy,2017,2(9):17125. |
5 | LI Yilin, FAN Ziqiang, PENG Zhijian,et al.Metal?organic framework?derived LiFePO4/C composites for lithium storage:In situ construction,effective exploitation,and targeted restoration[J].EcoMat,2023,5(12):e12415. |
6 | XU Wenhan, LI Yanwei, YAO Jinhuan,et al.LiFePO4/rGO composite prepared from the leaching liquor of jarosite residue as a cathode material for lithium?ion batteries[J].Journal of Alloys and Compounds,2023,952:170105. |
7 | MENG Dehai, DUAN Haozhi, WU Shijie,et al.Lithium iron phosphate with high?rate capability synthesized through hydrothermal reaction in low Li concentration solution[J].Journal of Alloys and Compounds,2023,967:171570. |
8 | 潘晓晓,庄树新,孙雨晴,等.动力型磷酸铁锂正极材料改性的研究进展[J].无机盐工业,2023,55(6):18-26. |
PAN Xiaoxiao, ZHUANG Shuxin, SUN Yuqing,et al.Research progress of modified-LiFePO4 as cathode materials for lithium ion batteries[J].Inorganic Chemicals Industry,2023,55(6):18-26. | |
9 | LIU Yulong, LIU Jian, WANG Jiajun,et al.Formation of size?dependent and conductive phase on lithium iron phosphate during carbon coating[J].Nature Communications,2018,9:929. |
10 | MO Runwei, LI Fan, TAN Xinyi,et al.High?quality mesoporous graphene particles as high?energy and fast?charging anodes |
for lithium?ion batteries[J].Nature Communications,2019,10: 1474. | |
11 | 张婷,林森,于建国.磷酸铁锂正极材料的制备及性能强化研究进展[J].无机盐工业,2021,53(6):31-40. |
ZHANG Ting, LIN Sen, YU Jianguo.Research progress in synthesis and performance enhancement of LiFePO4 cathode materi? | |
als[J].Inorganic Chemicals Industry,2021,53(6):31-40. | |
12 | LI Fan, TAO Ran, TAN Xinyi,et al.Graphite?embedded lithium iron phosphate for high?power?energy cathodes[J].Nano Letters,2021,21(6):2572-2579. |
13 | 张贵萍,闫筱炎,王兵,等.长寿命循环的磷酸铁锂电池及材料、工艺[J].储能科学与技术,2023,12(7):2134-2140. |
ZHANG Guiping, YAN Xiaoyan, WANG Bing,et al.Long life lithium iron phosphate battery and its materials and process[J].Energy Storage Science and Technology,2023,12(7):2134-2140. | |
14 | TAO Ran, LI Fan, LU Xing,et al.High?conductivity?dispersibility graphene made by catalytic exfoliation of graphite for lithium?ion battery[J].Advanced Functional Materials,2021,31(6):2007630. |
15 | LAMA B, SMIRNOVA A L, PAUDEL T R.Enhanced Li-ion diffusivity of LiFePO4 by Ru doping:Ab initio and machine learning force field results[J].ACS Applied Energy Materials,2023,6(20):10424-10431. |
16 | ZHANG Yin, ALARCO J A, NERKAR J Y,et al.Observation of preferential cation doping on the surface of LiFePO4 particles and its effect on properties[J].ACS Applied Energy Materials,2020,3(9):9158-9167. |
17 | LIU Xingzhong, ZHANG Yue, MENG Yanshuang,et al.Influence mechanism of Mg2+ doping on electrochemical properties of LiFePO4 cathode materials[J].ACS Applied Energy Materials,2022,5(7):8452-8459. |
18 | ZHANG Baofeng, MA Xiaoning, HOU Wenqiang,et al.Revealing the ultrahigh rate performance of the La and Ce co?doping LiFePO4 composite[J].ACS Applied Energy Materials,2022,5(12):14712-14719. |
19 | SHEN Chaoqi, LIN Wei, HU Heshan,et al.The electronic and geometric structure modifications of LiFePO4 with vanadium doping to achieve ultrafast discharging capability:The experimental and theoretical investigations[J].Journal of Alloys and Compounds,2023,936:168035. |
20 | TIAN Zhe, ZHOU Zhufa, LIU Shanshan,et al.Enhanced properties of olivine LiFePO4/graphene co?doped with Nb5+ and Ti4+ by a sol-gel method[J].Solid State Ionics,2015,278:186-191. |
21 | ZHANG Baofeng, XU Youlong, WANG Jie,et al.Lanthanum and cerium co?doped LiFePO4:Morphology,electrochemical performance and kinetic study from -30-+50 ℃[J].Electrochimica Acta,2019,322:134686. |
22 | CONG Jun, LUO Shaohua, LI Pengyu,et al.Excellent electrochemical performance europium?doped LiFePO4 cathode material derived from acid?washed iron red[J].Ionics,2023,29(11):4527-4535. |
23 | XU Yan, ZHAO Minshou, SUN Bin.Doping supervalent rare earth ion in LiFePO4/C through hydrothermal method[J].Solid State Ionics,2016,291:14-19. |
24 | ZHAO Nannan, LI Yongsheng, ZHI Xiaoke,et al.Effect of Ce3+ doping on the properties of LiFePO4 cathode material[J].Journal of Rare Earths,2016,34(2):174-180. |
25 | TENG Tao, XIAO Li, SHEN Li,et al.Effect of Nb doping at Fe site on the cycling stability and rate capability of LiFePO4 for lithium?ion batteries[J].Vacuum,2022,203:111306. |
26 | 凌仕刚,许洁茹,李泓.锂电池研究中的EIS实验测量和分析方法[J].储能科学与技术,2018,7(4):732-749. |
LING Shigang, XU Jieru, LI Hong.Experimental measurement and analysis methods of electrochemical impedance spectroscopy for lithium batteries[J].Energy Storage Science and Technology,2018,7(4):732-749. |
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