高功率型异质结构尖晶石/层状正极材料LiNi1/3Co1/3Mn1/3O2制备及电化学性能研究Preparation and Electrochemical Performance of Heterostructured Spinel/Layered LiNi1/3Co1/3Mn1/3O2 Cathodes for High Power Lithium-Ion Batteries
郑卓,吴振国,唐艳,杨秀山
摘要(Abstract):
采用草酸盐共沉淀法制备了一系列(x=0.1、0.2、0.3、0.4、0.5)异质结构的尖晶石/层状复合正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2。借助X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)、电化学阻抗谱(EIS)和恒电流充放电测试等表征手段对材料的晶体结构、微观形貌和电化学性能进行了系统研究。结果表明,x=0.2的材料具有最佳的高倍率性能和长循环稳定性。在2.7~4.5 V,1C下循环100次后(1 C=180 m A?g~(-1)),放电比容量为144 m Ah?g-1,容量保持率为92%;在10 C时的放电比容量仍能达到126 m Ah?g~(-1),相比于原始LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料的放电比容量(73 m Ah?g~(-1))有较大提高。此外,该材料的储能能力也非常突出,在0.1和10 C时的比能量密度分别为733.44和437.21 W×h?kg~(-1)。
关键词(KeyWords): LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2;异质尖晶石/层状结构;电化学性能;锂离子电池
基金项目(Foundation): 国家自然科学基金(21506133)
作者(Author): 郑卓,吴振国,唐艳,杨秀山
参考文献(References):
- [1]Dunn B,Kamath H,Tarascon J M.Electrical energy storage for the grid:a battery of choices[J].Science,2011,334(6058):928-935.
- [2]Tarascon J M,Armand M.Issues and challenges facing rechargeable lithium batteries[J].Nature,2001,414(6861):359-367.
- [3]Manthiram A,Murugan A V,Sarkar A,et al.Nanostructured electrode materials for electrochemical energy storage and conversion[J].Energy&Environmental Science,2008,1(6):621-638.
- [4]Hua W B,Guo X D,Zheng Z,et al.Uncovering a facile large-scale synthesis of Li Ni1/3Co1/3Mn1/3O2 nanoflowers for high power lithium-ion batteries[J].Journal of Power Sources,2015,275:200-206.
- [5]XIA Shu-biao(夏书标),ZHANG Ying-jie(张英杰),DONG Peng(董鹏),et al.Solid synthesis of Li Ni0.80Co0.15Al0.05O2 cathode with fine-sized materials and its structure and electrochemical properties(高倍率性能锂离子电池Li[Ni1/3Co1/3Mn1/3]O2正极材料的制备及其电化学性能)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2015,29(2):425-431.
- [6]Xu Z L,Xiao L L,Wang F,et al.Effects of precursor,synthesis time and synthesis temperature on the physical and electrochemical properties of Li(Ni1-x-y Cox Mny)O2 cathode materials[J].Journal of Power Sources,2014,248:180-189.
- [7]ZHANG Ji-bin(张继斌),HUA Wei-bo(滑纬博),ZHENG Zhuo(郑卓),et al.Preparation and electrochemical performance of Li Ni1/3Co1/3Mn1/3O2 cathode material for high-rate lithium-ion batteries(高倍率性能锂离子电池Li[Ni1/3Co1/3Mn1/3]O2正极材料的制备及其电化学性能)[J].Acta Physico-Chimica Sinica(物理化学学报),2015,31(5):905-912.
- [8]WANG Hai-yan(王海燕),TANG Ai-dong(唐爱东),HUANG Ke-long(黄可龙),et al.Preparation and rate capability study of Li Ni1/3Co1/3Mn1/3O2 as cathode material(Li Ni1/3Co1/3Mn1/3O2正极材料的制备与倍率性能研究)[J].Chinese Journal of Inorganic Chemistry(无机化学学报),2008,24(4):593-599.
- [9]Xia Q B,Zhao X F,Xu M Q,et al.A Li-rich layered@spinel@carbon heterostructured cathode material for high capacity and high rate lithium-ion batteries fabricated via an in situ synchronous carbonization-reduction method[J].Journal of Materials Chemistry A,2015,3(7):3995-4003.
- [10]Song B H,Liu H W,Liu Z W,et al.High rate capability caused by surface cubic spinels in Li-rich layer-structured cathodes for Li-ion batteries[J].Scientific Reports,2013,3:3094.
- [11]Wu F,Li N,Su Y F,et al.Spinel/layered heterostructured cathode material for high-capacity and high-rate Li-ion batteries[J].Advanced Materials,2013,25(27):3722-3726.
- [12]Zheng Z,Hua W B,Yu C,et al.Heterogeneous intergrowth x Li1.5Ni0.25Mn0.75O2.5?(1-x)Li0.5Ni0.25Mn0.75O2(0≤x≤1)composites:synergistic effect on electrochemical performance[J].Dalton Transactions,2015,44(32):14255-14264.
- [13]Amine K,Liu J,Belharouak I,et al.Advanced cathode materials for high-power applications[J].Journal of Power Sources,2005,146(1-2):111-115.
- [14]Santhanam R,Rambabu B.Research progress in high voltage spinel Li Ni0.5Mn1.5O4 material[J].Journal of Power Sources,2010,195(17):5442-5451.
- [15]Li J,Xiong S,Liu Y,et al.Uniform Li Ni1/3Co1/3Mn1/3O2 hollow microspheres:designed synthesis,topotactical structural transformation and their enhanced electrochemical performance[J].Nano Energy,2013,2(6):1249-1260.
- [16]Idemoto Y,Narai H,Koura N.Crystal structure and cathode performance dependence on oxygen content of Li Mn1.5Ni0.5O4 as a cathode material for secondary lithium batteries[J].Journal of Power Sources,2003,119-121(6):125-129.
- [17]CHEN Ming-zhe(陈明哲),GUO Xiao-dong(郭孝东),ZHONG Ben-he(钟本和),et al.High energy density spinel Li Cr0.2Ni0.4Mn1.4O4cathode material prepared by spray pyrolysis method(喷雾热解制备高能量密度尖晶石Li Cr0.2Ni0.4Mn1.4O4正极材料)[J].Journal of Inorganic Materials(无机材料学报),2014,29(9):917-923.
- [18]Park S H,Oh S W,Kang S H,et al.Comparative study of different crystallographic structure of Li Ni0.5Mn1.5O4-δcathodes with wide operation voltage(2.0~5.0 V)[J].Electrochimica Acta,2007,52(25):7226-7230.
- [19]Xiao J,Chen X,Sushko P V,et al.High-performance Li Ni0.5Mn1.5O4 spinel controlled by Mn3+concentration and site disorder[J].Advanced Materials,2012,24(16):2109-2116.
- [20]Zheng J,Xiao J,Yu X,et al.Enhanced Li+ion transport in Li Ni0.5Mn1.5O4 through control of site disorder[J].Physical Chemistry Chemical Physics,2012,14(39):13515-13521.
- [21]Zhu Z,Yan H,Zhang D,et al.Preparation of 4.7 V cathode material Li Ni0.5Mn1.5O4 by an oxalic acid-pretreated solid-state method for lithium-ion secondary battery[J].Journal of Power Sources,2013,224:13-19.
- [22]Shaju K M,Bruce P G.Macroporous Li Ni1/3Co1/3Mn1/3O2:a high-power and high-energy cathode for rechargeable lithium batteries[J].Advanced Materials,2006,18(17):2330-2334.
- [23]Li Q,Li G S,Fu C C,et al.K+-doped Li1.2Mn0.54Co0.13Ni0.13O2:a novel cathode material with an enhanced cycling sability for lithium-ion batteries[J].Acs Applied Materials&Interfaces,2014,6(13):10330-10341.
- [24]Li B H,Han C P,He Y B,et al.Facile synthesis of Li4Ti5O12/C composite with super rate performance[J].Energy&Environmental Science,2012,5(11):9595-9602.
- [25]Wang L,Zhao J,He X,et al.Electrochemical impedance spectroscopy(EIS)study of Li Ni1/3Co1/3Mn1/3O2 for Li-ion batteries[J].International Journal of Electrochemical Science,2012,7(1):345-353.