混合动力车用锂电池正极材料的制备和性能研究
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摘要
采用共沉淀法和高温固相烧结法制备了锂离子电池正极材料,研究了pH值和煅烧温度对前驱体物相组成、形貌、振实密度和元素组成以及对正极材料微结构和电化学性能的影响。结果表明,随着pH值从9升高至11,前驱体振实密度逐渐增大,适当的增加pH值有助于Mn的沉淀;随着煅烧温度的升高,I(003)/I(104)比值呈现先升高而后减小特征,在煅烧温度为850℃时取得I(003)/I(104)最大值,此时的正极材料中阳离子混排程度最小;随着煅烧温度升高,正极材料试样的颗粒尺寸不断增大,颗粒之间的团聚程度减小,充电容量逐渐减小,放电容量先增加而后减小,在煅烧温度为850℃时取得最大的放电容量和最佳的倍率性能。
The cathode materials of lithium ion batteries were prepared by coprecipitation and high temperature solid-phase sintering.The effects of pH value and calcining temperature on the phase composition,morphology,vibrational density and element composition of precursors,and the microstructures and electrochemical properties of the cathode materials were investigated.The results show that with the increase of pH value from 9 to 11,the density of the precursor is increased gradually,and the appropriate increase in pH value is helpful to the precipitation of Mn.With the increase of calcination temperature,the ratio of I(003)/I(104) increases first and then decreases.The maximum value of I(003)/I(104) can be obtained at the calcination temperature of 850 ℃,and the degree of cation mixing is the smallest at this time.With the increase of calcining temperature,the particle size of the positive material increases,the degree of agglomeration between particles decreases,the charging capacity gradually decreases,and the discharge capacity increases first and then decreases.The maximum discharge capacity and the best rate performance can be obtained at the calcining temperature of 850 ℃.
The cathode materials of lithium ion batteries were prepared by coprecipitation and high temperature solid-phase sintering.The effects of pH value and calcining temperature on the phase composition,morphology,vibrational density and element composition of precursors,and the microstructures and electrochemical properties of the cathode materials were investigated.The results show that with the increase of pH value from 9 to 11,the density of the precursor is increased gradually,and the appropriate increase in pH value is helpful to the precipitation of Mn.With the increase of calcination temperature,the ratio of I(003)/I(104) increases first and then decreases.The maximum value of I(003)/I(104) can be obtained at the calcination temperature of 850 ℃,and the degree of cation mixing is the smallest at this time.With the increase of calcining temperature,the particle size of the positive material increases,the degree of agglomeration between particles decreases,the charging capacity gradually decreases,and the discharge capacity increases first and then decreases.The maximum discharge capacity and the best rate performance can be obtained at the calcining temperature of 850 ℃.
引文
[1]冯耀华,李春雷,艾灵.锂离子电池正极材料LiNi0.8Co0.1Mn0.1O2的产业化工艺研究[J].现代化工,2018(9):1-6.
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[11]张新河,汤春微,马小林,等.富锂锰基Li1.2Mn0.54Ni0.13Co0.13O2正极材料的制备及电化学性能研究[J].电源技术,2017,41(11):1513-1515.
[12]陈伟,张华,张晓萍,等.锂离子电池正极材料LiMnBO3/C的合成及其电化学性能[J].中国有色金属学报,2018,28(3):565-571.
[2]梁有维,李世友,李春雷,等.锂离子电池富锂锰基正极材料的研究进展[J].化工新型材料,2018(8):46-50.
[3]候岩,李文升,樊勇利.锂离子电池正极材料LiNi0.80Co0.15Al0.05O2的研究进展[J].电源技术,2018,42(7):1072-1075.
[4]熊凡,张卫新,杨则恒,等.高比能量锂离子电池正极材料的研究进展[J].储能科学与技术,2018,7(4):607-617.
[5]Li J,Liu H,Xia J,et al.The impact of electrolyte additives and cycling voltage on the formation of a rocksalt surface layer in LiNi0.8Mn0.1Co0.1 electrodes[J].Journal of the Electrochemical Society,2016,164(4):655-665.
[6]Li L J,Li X H,Wang Z X,et al.Synthesis of LiNi0.8Co0.1Mn0.1O2 cathode material by chloride co-precipitation method[J].Transactions of Nonferrous Metals Society of China,2010,20(s1):279-282.
[7]陈巍,李新海,王志兴,等.共沉淀法制备LiNi0.8Co0.1Mn0.1O2过程中加料速度对其性能的影响[J].中国有色金属学报,2012,22(7):1956-1962.
[8]Gu Y J,Chen Y B,Liu H Q,et al.Structural characterization of layered LiNi0.85-xMnxCo0.15O2,with x=0,0.1,0.2 and 0.4 oxide electrodes for Li batteries[J].Journal of Alloys & Compounds,2011,509(30):7915-7921.
[9]Li X,Xie Z,Liu W,et al.Effects of fluorine doping on structure,surface chemistry,and electrochemical performance of LiNi0.8Co0.15Al0.05O2[J].Electrochimica Acta,2015,174:1122-1130.
[10]Liu W,Hua W,Zheng Z,et al.Facile synthesis of hierarchical porous Ni-rich LiNi 0.6Co0.2Mn0.2O2 cathode material with superior high-rate capability[J].Ionics,2016,22(10):1781-1790.
[11]张新河,汤春微,马小林,等.富锂锰基Li1.2Mn0.54Ni0.13Co0.13O2正极材料的制备及电化学性能研究[J].电源技术,2017,41(11):1513-1515.
[12]陈伟,张华,张晓萍,等.锂离子电池正极材料LiMnBO3/C的合成及其电化学性能[J].中国有色金属学报,2018,28(3):565-571.