热处理时间对高压正极材料LiNi_(0.5)Mn_(1.5)O_4的电化学性能影响
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摘要
以硝酸锂、硝酸镍和醋酸锰为原材料采用溶液蒸干法合成LiNi_(0.5)Mn_(1.5)O_4正极材料,将前驱体在400℃空气气氛中煅烧4h以分解硝酸盐和醋酸盐后,在800℃氧气氛围中分别煅烧4h、6h、8h和10h制备对比样品。测试数据显示通过XRD、SEM表征及材料电化学性能比较得出烧结时间为10h、煅烧温度为800℃时合成的样品电化学性能最好。在电化学循环伏安测试结果中显示采用不同热处理时间所制备的材料均具有4.7V和4.0V两个放电平台,可说明制备材料属于Fd-3m空间群尖晶石结构。不同倍率下的循环性能随着样品热处理时间的延长放电比容量呈增大趋势,10h样品0.5C首次放电比容量为121.7mAh g~(-1)。
LiNi_(0.5)Mn_(1.5)O_4 cathode material was synthesized with lithium nitrate,nickel nitrate and manganese acetate as raw materials by solution evaporation-drying method.The precursor was calcined in 400℃atmospheres for 4 hours to decompose nitrate and acetate,and then calcined in800℃ oxygen atmospheres for 4,6,8 and 10 hours to prepare contrast samples.The test data show that the samples synthesized at 10 hsintering time and 800℃ calcination temperature had the best electrochemical performance by XRD,SEM characterization and electrochemical performance comparison.The electrochemical cyclic voltammetry results show that the materials prepared by different heat treatment time have two discharge platforms of 4.7 V and 4.0 V,which indicates that the prepared materials belong to the spinel structure of Fd-3 mspace group.The cycling performance at different rate increases with the prolongation of heat treatment time,and the first discharge capacity of 0.5 Csample at 10 his 121.7 mAh g~(-1).
LiNi_(0.5)Mn_(1.5)O_4 cathode material was synthesized with lithium nitrate,nickel nitrate and manganese acetate as raw materials by solution evaporation-drying method.The precursor was calcined in 400℃atmospheres for 4 hours to decompose nitrate and acetate,and then calcined in800℃ oxygen atmospheres for 4,6,8 and 10 hours to prepare contrast samples.The test data show that the samples synthesized at 10 hsintering time and 800℃ calcination temperature had the best electrochemical performance by XRD,SEM characterization and electrochemical performance comparison.The electrochemical cyclic voltammetry results show that the materials prepared by different heat treatment time have two discharge platforms of 4.7 V and 4.0 V,which indicates that the prepared materials belong to the spinel structure of Fd-3 mspace group.The cycling performance at different rate increases with the prolongation of heat treatment time,and the first discharge capacity of 0.5 Csample at 10 his 121.7 mAh g~(-1).
引文
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[2]LIU G Q,WANG Y J,LI W,et al.Synthesis and electrochemical performance of LiNi0.5Mn1.5O4spinel compound[J].Electrochemical Acta,2005,50:1965-1968.
[3]OH ZU KU T,ARIYOSHI K,Y AMAMOTO S,Synthesis and Characterization of Li[Ni1/2Mn3/2]O4by Two-step Solid State Reaction[J].Journal of American Ceramic Society,2002,110(5):501-505.
[4]KIM J H,MYUNG S T,SUN Y K.Molten Salt Synthesis of LiNi0.5Mn1.5O4Spinel for 5VClass Cathode Material of Li-ion Secondary Battery[J].Eletrochemical Acta,2004,49(2):219-227.
[5]LEE Y S,SUN Y K,OTA S,et al.Preparation and characterization of nano-crystalline LiNi0.5 Mn1.5O4for 5Vcathode material by composite carbonate process[J].E-lectrochemistry Communication,2002,4(12):989-994.
[6]DONG Y C,WANG Z B.Synthesis and electrochemical properties of LiNi0.5Mn1.5O4as material for lithium ion batteries[J].RSC Adances,2012,10.
[7]PIECZONKA N P W,LIU Z,LU P,et al.Understanding transition-metal dissolution behavior in LiNi0.5Mn1.5O4high-voltage spinel for lithium ion batteries[J].The Journal of Physical Chemistry C,2013,117(31):15947-15957.
[8]KUNDURACI M,AMATUCCI G G.Synthesis and Characterization of Nanostructured 4.7VLixMn1.5Ni0.5O4Spinels for High-Power Lithium-Ion Batteries[J].Journal of The Electrochemical Society,2006,153(7):A1345-A1352.
[9]AMDOUNI N.,ZAGHIB K,GENDRON F.et al.Magnetic properties of LiNi0.5 Mn1.5O4 spinels prepared by wet chemical methods[J].Journal of Magnetism and Magnetic Materials.2007,309:100-105P.
[10]AMDOUNI N.,ZAGHIB K.,GENDRON F.et al.Structure and insertion properties of disordered and ordered LiNi0.5Mn1.5O4spinel prepared by wet chemistry[J].Ionics.2006,12:117-126P.
[11]YUAN X,Yi H,WANG Z B,et al.Study on LixNi0.5Mn1.5O4(x=0.8,0.9,1,1.1and 1.2)High-voltage Cathode for Lithium-Ion Batteries[J].Ionics,2018.
[12]LEE Y S,SHIN W K,KANMAN A G,et al.Improvement of the Cycling Performance and Thermal Stability of Lithium-Ion Cells by Double-Layer Coating of Cathode Materials with Al2O3 Nanoparticles and Conductive Polymer[J].ACS applied materials&interfaces.2015,7(25):13944-13951.
[13]张若楠,尖晶石型锰酸锂电极材料的制备及镍钴掺杂改性研究[D].哈尔滨:哈尔滨工业大学,2006,14-19.
[14]ZHANG Y,WANG Z B,YU F D,et al.Studies on stability and capacity for long-life cycle performance of Li(Ni0.5Co0.2Mn0.3)O2by Mo modification for lithium-ion battery[J].Journal of Power Sources,2017,358:1-12.
[15]BEN L,YU H,CHEN B,et al.Unusual Spinel-toLayered Transformation in LiMn2O4 Cathode Explained by Electrochemical and Thermal Stability Investigation[J].ACS Applied Materials&Interfaces,2017,9(40):35463.
[16]TANG C Y,LEUNG K,HAASCH R T,et al.LiMn2O4surface chemistry evolution during cycling revealed by in situ Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy[J].ACS Applied Materials&Interfaces,2017,9(39):33968.
[17]YUAN X,WANG Z B,ZHENG L,et al.Investigation on spinel LiNi0.5 Mn1.5O4 synthesized by MnCO3 prepared under different conditions for lithium-ion batteries[J].Chemistry Select,2017,2:4325-4331.
[18]SARAVANAN K,JARRY A,KOSECKI R,et al.A study of room-temperature LiNi0.5Mn1.5O4solid solutions[J].Scientific Reports,2015,5(1).
[19]LUO W.Effect of morphology on the physical and electrochemical properties of the high-voltage spinel cathode LiNi0.5Mn1.5O4[J].Journal of Alloys and Compounds,2015,636:24-28.
[20]LAI F,ZHANG X,WANG H,et al.Three-Dimension Hierarchical Al2O3 Nanosheets Wrapped LiMn2O4 with Enhanced Cycling Stability as Cathode Material for Lithium Ion Batteries[J].ACS Applied Materials&Interfaces.2016,8(33):21656-21665.
[21]SANTHANAM R,RAMBABU B.Research progress in high voltage spinel LiNi0.5Mn1.5O4 material[J].J.Power Sources,2010,195(17):5442-5451.
[22]YUAN X,WANG Z B,ZHENG L,et al.Investigation on preparation and performance of spinel LiNi0.5 Mn1.5O4with different microstructures for lithium-ion batteries[J].Scientific Reports,2015,5:13299.