Nanoscale Surface Modification of Lithium-Rich Layered-Oxide Composite Cathodes for Suppressing Voltage Fade.

Lithium-rich layered oxides are promising cathode materials for lithium-ion batteries and exhibit a high reversible capacity exceeding 250 mAh g(-1) . However, voltage fade is the major problem that needs to be overcome before they can find practical applications. Here, Li1.2 Mn0.54 Ni0.13 Co0.13 O2 (LLMO) oxides are subjected to nanoscale LiFePO4 (LFP) surface modification. The resulting materials combine the advantages of both bulk doping and surface coating as the LLMO crystal structure is stabilized through cationic doping, and the LLMO cathode materials are protected from corrosion induced by organic electrolytes. An LLMO cathode modified with 5 wt % LFP (LLMO-LFP5) demonstrated suppressed voltage fade and a discharge capacity of 282.8 mAh g(-1) at 0.1 C with a capacity retention of 98.1 % after 120 cycles. Moreover, the nanoscale LFP layers incorporated into the LLMO surfaces can effectively maintain the lithium-ion and charge transport channels, and the LLMO-LFP5 cathode demonstrated an excellent rate capacity.

[1]  Chenghao Yang,et al.  Surfactants assisted synthesis and electrochemical properties of nano-LiFePO4/C cathode materials for low temperature applications , 2015 .

[2]  I. Bloom,et al.  Effects of cycling temperatures on the voltage fade phenomenon in 0.5Li2MnO3·0.5LiNi0.375Mn0.375Co0.25O2 cathodes , 2015 .

[3]  Zhenhua Wang,et al.  A design strategy of large grain lithium-rich layered oxides for lithium-ion batteries cathode , 2015 .

[4]  Dean J. Miller,et al.  Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach , 2014, Nature Communications.

[5]  Shifei Kang,et al.  Preparation and Electrochemical Performance of Yttrium-doped Li[Li0.20Mn0.534Ni0.133Co0.133]O2 as Cathode Material for Lithium-Ion Batteries , 2014 .

[6]  Piero Pianetta,et al.  Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling , 2014, Nano letters.

[7]  Xueling Gao,et al.  Surface modification of Li(Li0.17Ni0.2Co0.05Mn0.58)O2 with CeO2 as cathode material for Li-ion batteries , 2014 .

[8]  Zhaoping Liu,et al.  Enhanced electrochemical performance with surface coating by reactive magnetron sputtering on lithium-rich layered oxide electrodes. , 2014, ACS applied materials & interfaces.

[9]  Xueping Gao,et al.  PO43− polyanion-doping for stabilizing Li-rich layered oxides as cathode materials for advanced lithium-ion batteries , 2014 .

[10]  Ling Huang,et al.  Facile synthesis of the Li-rich layered oxide Li1.23Ni0.09Co0.12Mn0.56O2 with superior lithium storage performance and new insights into structural transformation of the layered oxide material during charge-discharge cycle: in situ XRD characterization. , 2014, ACS applied materials & interfaces.

[11]  Ilias Belharouak,et al.  Effect of interface modifications on voltage fade in 0.5Li2MnO3.0.5LiNi0.375Mn0.375Co0.25O2 cathode materials , 2014 .

[12]  F. Kang,et al.  Enhanced oxygen reducibility of 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2 cathode material with mild acid treatment , 2014 .

[13]  E. Han,et al.  The effect of MgO coating on Li1.17Mn0.48Ni0.23Co0.12O2 cathode material for lithium ion batteries , 2014 .

[14]  B. Hwang,et al.  Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material, Li[Ni(x)Li((1-2x)/3)Mn((2-x)/3)]O2 (0 ≤ x ≤ 0.5). , 2014, Journal of the American Chemical Society.

[15]  Ying Wang,et al.  Atomic layer deposition of epitaxial ZrO2 coating on LiMn2O4 nanoparticles for high-rate lithium ion batteries at elevated temperature , 2013 .

[16]  Kevin G. Gallagher,et al.  Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes , 2013 .

[17]  Ji‐Guang Zhang,et al.  Corrosion/fragmentation of layered composite cathode and related capacity/voltage fading during cycling process. , 2013, Nano letters.

[18]  Jagjit Nanda,et al.  Solid electrolyte coated high voltage layered–layered lithium-rich composite cathode: Li1.2Mn0.525Ni0.175Co0.1O2 , 2013 .

[19]  Jianming Zheng,et al.  Formation of the spinel phase in the layered composite cathode used in Li-ion batteries. , 2012, ACS nano.

[20]  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.

[21]  Miaofang Chi,et al.  Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study , 2011 .

[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]  Cheol-Woo W. Yi,et al.  Improved electrochemical performance of AlPO4-coated LiMn1.5Ni0.5O4 electrode for lithium-ion batteries , 2010 .

[24]  J. Goodenough,et al.  Challenges for Rechargeable Li Batteries , 2010 .

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

[26]  Y. S. Lee,et al.  Structural and electrochemical study of Li[CrxLi(1−x)/3Mn2(1−x)/3]O2 (0 ≤ x ≤ 0.328) cathode materials , 2008 .

[27]  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 .

[28]  Gil-Ho Kim,et al.  Synthesis of spherical Li[Ni(1/3−z)Co(1/3−z)Mn(1/3−z)Mgz]O2 as positive electrode material for lithium-ion battery , 2006 .

[29]  Yang‐Kook Sun,et al.  Synthesis and electrochemical properties of layered Li[Li0.15Ni(0.275−x/2)AlxMn(0.575−x/2)]O2 materials prepared by sol–gel method , 2003 .

[30]  T. Osaka,et al.  Preparation and electrochemical properties of Zn-doped LiNi0.8Co0.2O2 , 2002 .

[31]  G. Fey,et al.  Preparation and characterization of LiNi0.7Co0.2Ti0.05M0.05O2 (M=Mg, Al and Zn) systems as cathode materials for lithium batteries , 2002 .

[32]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.