Effect of amorphous FePO4 coating on structure and electrochemical performance of Li1.2Ni0.13Co0.13Mn0.54O2 as cathode material for Li-ion batteries

Abstract Lithium-rich layered cathode Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 is synthesized by a co-precipitation method followed by high-temperature treatment and surface coated with different amount of amorphous FePO 4 . The microstructure and electrochemical performance of the as-prepared cathode materials are investigated systematically. It is demonstrated that the Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 particles are uniformly coated with amorphous FePO 4 . With proper amount of amorphous FePO 4 coating layer, significant improvements in discharge capacity, initial Coulombic efficiency, rate capability, cycle performance, and thermal stability are achieved at room temperature. Specifically, the 3 wt.% FePO 4 -coated cathode exhibits the highest discharge specific capacities (271.7 mAh g −1 at C/20), improved initial Coulombic efficiency (85.1%), and best cyclability (discharge capacity of 202.6 mAh g −1 at C/2 after 100 cycles), while the 1 wt.% FePO 4 -coated cathode displays the best rate capability (194.3 mAh g −1 at 1 C rate and 167.9 mAh g −1 at 2 C rate). The charge–discharge curves and electrochemical impedance spectra reveal that the improved electrochemical performances are due to the suppression of both the oxygen vacancy elimination at the end of the first charge and side reactions of the cathode with the electrolyte, as well as the decrease in charge transfer polarization by the FePO 4 coating layer.

[1]  D. Aurbach,et al.  A review of advanced and practical lithium battery materials , 2011 .

[2]  Ilias Belharouak,et al.  Growth mechanism of Ni0.3Mn0.7CO3 precursor for high capacity Li-ion battery cathodes , 2011 .

[3]  Yongyao Xia,et al.  Highly ordered three-dimensional macroporous FePO4 as cathode materials for lithium–ion batteries , 2008 .

[4]  Zhanxu Yang,et al.  Effect of FePO4 coating on electrochemical and safety performance of LiCoO2 as cathode material for Li-ion batteries , 2008 .

[5]  Ying Bai,et al.  Enhanced cycling stability of LiMn2O4 cathode by amorphous FePO4 coating , 2011 .

[6]  A. Manthiram,et al.  Functional surface modifications of a high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode , 2010 .

[7]  Min Gyu Kim,et al.  Amorphous FePO4 as 3 V cathode material for lithium secondary batteries , 2002 .

[8]  Xi‐Wen Du,et al.  Enhanced electrochemical performance of LiFePO4 cathode with in-situ chemical vapor deposition synthesized carbon nanotubes as conductor , 2012 .

[9]  Khalil Amine,et al.  Symmetric cell approach and impedance spectroscopy of high power lithium-ion batteries , 2001 .

[10]  Xugeng Guo,et al.  The effects of TiO2 coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery , 2008 .

[11]  A. Manthiram,et al.  High capacity double-layer surface modified Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode with improved rate capability , 2009 .

[12]  A. Manthiram,et al.  Understanding structural defects in lithium-rich layered oxide cathodes , 2012 .

[13]  Marshall C. Smart,et al.  Electrochemical Behavior of Layered Solid Solution Li2MnO3−LiMO2 (M = Ni, Mn, Co) Li-Ion Cathodes with and without Alumina Coatings , 2011 .

[14]  Miss A.O. Penney (b) , 1974, The New Yale Book of Quotations.

[15]  J. Goodenough Challenges for Rechargeable Li Batteries , 2010 .

[16]  Paulo J. Ferreira,et al.  Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution , 2011 .

[17]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[18]  Jiangfeng Qian,et al.  Improved electrochemical performances of nanocrystalline Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for Li-ion batteries , 2012 .

[19]  Christopher M Wolverton,et al.  Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries , 2012 .

[20]  Young‐Jun Kim,et al.  Effect of aluminum fluoride coating on the electrochemical and thermal properties of 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2 composite material , 2012 .

[21]  Weifeng Zhang,et al.  Improved cycling performance of 5 V spinel LiMn1.5Ni0.5O4 by amorphous FePO4 coating , 2012 .

[22]  Shinichi Komaba,et al.  Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2. , 2011, Journal of the American Chemical Society.

[23]  A. Manthiram,et al.  Understanding the Improvement in the Electrochemical Properties of Surface Modified 5 V Limn1.42Ni0.42Co0.16O4 Spinel Cathodes in Lithium-ion Cells , 2009 .

[24]  Zhaoping Liu,et al.  Electrochemical properties of 0.6Li[Li1/3Mn2/3]O2–0.4LiNixMnyCo1−x−yO2 cathode materials for lithium-ion batteries , 2012 .

[25]  Chong Seung Yoon,et al.  Nanostructured high-energy cathode materials for advanced lithium batteries. , 2012, Nature materials.

[26]  Zhaoqi Sun,et al.  Enhanced Electrochemical Performance of Li [ Li0.2Ni0.2Mn0.6 ] O2 Modified by Manganese Oxide Coating for Lithium-Ion Batteries , 2011 .

[27]  Arumugam Manthiram,et al.  Surface Modification of High Capacity Layered Li [ Li0.2Mn0.54Ni0.13Co0.13 ] O2 Cathodes by AlPO4 , 2008 .

[28]  Arumugam Manthiram,et al.  High Capacity, Surface-Modified Layered Li [ Li ( 1 − x ) ∕ 3Mn ( 2 − x ) ∕ 3Nix ∕ 3Cox ∕ 3 ] O2 Cathodes with Low Irreversible Capacity Loss , 2006 .

[29]  A. Manthiram,et al.  Structural stability of chemically delithiated layered (1 − z)Li[Li1/3Mn2/3]O2–zLi[Mn0.5−yNi0.5−yCo2y]O2 solid solution cathodes , 2008 .

[30]  Bruno Scrosati,et al.  The Role of AlF3 Coatings in Improving Electrochemical Cycling of Li‐Enriched Nickel‐Manganese Oxide Electrodes for Li‐Ion Batteries , 2012, Advanced materials.

[31]  J. Yamaki,et al.  Cathode properties of amorphous and crystalline FePO4 , 2005 .

[32]  A. Manivannan,et al.  Electrochemical and Structural Investigations on ZnO Treated 0.5 Li2MnO3-0.5LiMn0.5Ni0.5O2 Layered Composite Cathode Material for Lithium Ion Battery , 2012 .

[33]  John T. Vaughey,et al.  Li{sub2}MnO{sub3}-stabilized LiMO{sub2} (M=Mn, Ni, Co) electrodes for high energy lithium-ion batteries , 2007 .

[34]  Jiangfeng Ni,et al.  A modified ZrO2-coating process to improve electrochemical performance of Li(Ni1/3Co1/3Mn1/3)O2 , 2009 .

[35]  Joong-Kee Lee,et al.  Effects of ZnO coating on electrochemical performance and thermal stability of LiCoO2 as cathode material for lithium-ion batteries , 2010 .

[36]  Jisuk Kim,et al.  Controlled Nanoparticle Metal Phosphates (Metal = Al , Fe, Ce, and Sr) Coatings on LiCoO2 Cathode Materials , 2005 .

[37]  John T. Vaughey,et al.  Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries , 2005 .

[38]  Yunhui Huang,et al.  Significant Improved Electrochemical Performance of Spinel LiMn2O4 Promoted by FePO4 Incorporation , 2011 .

[39]  S. Ye,et al.  Surface nitridation of Li-rich layered Li(Li0.17Ni0.25Mn0.58)O2 oxide as cathode material for lithium-ion battery , 2012 .

[40]  Min Gyu Kim,et al.  Structural Characterization of the Surface-Modified Li x Ni0.9Co0.1O2 Cathode Materials by MPO4 Coating (M = Al , Ce, SrH, and Fe) for Li-Ion Cells , 2006 .