LiCoPO_4包覆的Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2锂离子电池正极材料:增强的库伦效率和循环性能
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摘要
LiCoPO_4包覆的Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2富锂正极材料是通过沉淀法制备的。包覆后的样品的首次库伦效率达到84.14%,在0.1C(1C=300mA/g)电流下放电比容量高达305.95mAh/g。特别是包覆后样品的循环性能得到极大的提升,1C倍率下100次循环后容量保持率为88.2%,远远高于未包覆样品的72.3%。这些电化学性能的提高主要归功于包覆层,包覆层不但增强了材料的结构稳定性,同时也有效保护了电极材料不受电解液的侵蚀并且提高了材料的锂离子迁移率。
LiCoPO_4 coated Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2 cathode materials were prepared by the precipitation method.The coated sample demonstrates high initial columbic efficiency of 84.14%and a large reversible capacity of 305.95 mAh/g at 0.1 C(1 C =300 mA/g).Especially,the coated sample demonstrates a better cycling performance,with capacity retention of 88.2% at 1Crate after 100 cycles,which is much better than that of72.3%in the pristine sample.The improved electrochemical properties have been ascribed to the LiCoPO_4 coating layer,which not only stabilizes the cathode structure,but also protects the Li-rich cathode material from side reaction with the electrolyte and increases the Li~+ migration rate at the cathode interface.
LiCoPO_4 coated Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2 cathode materials were prepared by the precipitation method.The coated sample demonstrates high initial columbic efficiency of 84.14%and a large reversible capacity of 305.95 mAh/g at 0.1 C(1 C =300 mA/g).Especially,the coated sample demonstrates a better cycling performance,with capacity retention of 88.2% at 1Crate after 100 cycles,which is much better than that of72.3%in the pristine sample.The improved electrochemical properties have been ascribed to the LiCoPO_4 coating layer,which not only stabilizes the cathode structure,but also protects the Li-rich cathode material from side reaction with the electrolyte and increases the Li~+ migration rate at the cathode interface.
引文
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[2]Chiang Y M.Building a better battery[J].Science,2010,330(6010):1485-1486.
[3]Gu M,Belharouak I,Genc A,et al.Conflicting roles of nickel in controlling cathode performance in lithium ion batteries[J].Nano Letters,2012,12(10):5186-5191.
[4]Johnson C S,Kim J S,Lefief C,et al.The significance of the Li2MnO3component in‘composite’xLi2MnO3·(1-x)LiMn0.5Ni0.5 O2 electrodes[J].Electrochemistry Communications,2004,6(10):1085-1091.
[5]Wei G Z,Xia L,Ke F S,et al.Crystal Habit-Tuned nanoplate material of Li[Li1/3–2x/3Nix Mn2/3-x/3]O2for highrate performance lithium-ion batteries[J].Advanced Materials,2010,22(39):4364-4367.
[6]Lu Z,Beaulieu L Y,Donaberger R A,et al.Synthesis,structure and electrochemical behavior of Li[NixLi1/3-2x/3Mn2/3-x/3]O2[J].Journal of the Electrochemical Society,2002,149(6):A778-A791.
[7]Kang S H,Sun Y K,Amine K.Electrochemical and ex situ X-Ray study of Li(Li0.2 Ni0.2 Mn0.6)O2 cathode material for Li secondary batteries[J].Electrochemical Solid State Letters,2003,6(9):A183-A186.
[8]Zhu Z Y,Zhu L W.Synthesis of layered cathode material0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 by an improved co-precipitation method for lithium-ion battery[J].Journal of Power Sources,2014,256(15):178-182.
[9]Oh P,Ko M,Myeong S,et al.A novel surface treatment method and new insight into discharge voltage deterioration for high-performance 0.4Li2 MnO3-0.6LiNi1/3Co1/3 Mn1/3O2 cathode materials[J].Advanced Energy Materials,2014,4(16):1400631-1400639.
[10]He F,Wang X Q,Du C Q,et al.The effect of samaria doped ceria coating on the performance of Li1.2 Ni0.13Co0.13Mn0.54O2 cathode material for lithium-ion battery[J].Electrochimica Acta,2015,153(11):484-491.
[11]Yang C,Zhang Q,Ding W X,et al.Improving the electrochemical performance of layered lithium-rich cathode materials by fabricating a spinel outer layer with Ni 3+[J].Journal of Materials Chemistry A,2015,3(14):7554-7559.
[12]Jin X,Xu Q J,Liu H M,et al.Excellent rate capability of Mg doped Li[Li0.2 Ni0.13 Co0.13 Mn0.54]O2cathode material for lithium-ion battery[J].Electrochimica Acta,2014,136(8):19-26.
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[16]Yamamoto S,Noguchi H,Zhao W.Improvement of cycling performance in Ti substituted 0.5Li2MnO3-0.5LiNi0.5Mn0.5O2through suppressing metal dissolution[J].Journal of Power Sources,2015,278(12):76-86.
[17]Du J Y,Shan Z Q,Zhu K L,et al.Improved electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2by doping with molybdenum for Lithium battery[J].Journal of Solid State Electrochemistry,2015,19(4):1037-1044.
[18]Li B,Li C,Cai J J,et al.In situ nano-coating on Li1.2Mn0.52Ni0.13Co0.13 O2 with a layered@spinel@coating layer heterostructure for lithium-ion batteries[J].Journal of Materials Chemistry A,2015,3(42):21290-21297.
[19]Zhao T L,Li L,Chen R J,et al.Design of surface protective layer of LiF/FeF3nanoparticles in Li-rich cathode for high-capacity Li-ion batteries[J].Nano Energy,2015,15(4):164-176.
[20]Xie Q L,Zhao C H,Hu Z B,et al.LaPO4-coated Li1.2Mn0.56Ni0.16Co0.08O2as a cathode material with enhanced coulombic efficiency and rate capability for lithium ion batteries[J].RSC Advances,2015,5(94):77324-77331.
[21]Liu Bing,Zhang Qian,He Shici,et al.Improved electrochemical properties of Li1.2 Ni0.18 Mn0.59Co0.03 O2 by surface modification with LiCoPO4[J].Electrochimica Acta,2011,56(9):6748-6751.
[22]Shi S J,Tu J P,Zhang Y D,et al.Morphology and electrochemical performance of Li[Li0.2Mn0.56Ni0.16Co0.08]O2cathode materials prepared with different metal sources[J].Electrochimica Acta,2013,109(11):828-834.
[23]Wu Y,Murugan A V,Manthiram A.Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes by AlPO4[J].Journal of Solid State Electrochemistry,2008,155(9):A635-A641.
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