A stable lithium-rich surface structure for lithium-rich layered cathode materials

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface.

[1]  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.

[2]  Y. Okamoto.  Ambivalent Effect of Oxygen Vacancies on Li2MnO3: A First-Principles Study , 2011 .

[3]  Byung Gon Kim,et al.  Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation. , 2015, Angewandte Chemie.

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

[5]  Jaephil Cho,et al.  A new type of protective surface layer for high-capacity Ni-based cathode materials: nanoscaled surface pillaring layer. , 2013, Nano letters.

[6]  M. Hirayama,et al.  Epitaxial growth and lithium ion conductivity of lithium-oxide garnet for an all solid-state battery electrolyte. , 2013, Dalton transactions.

[7]  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 .

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

[9]  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.

[10]  Erik J. Berg,et al.  Differential Electrochemical Mass Spectrometry Study of the Interface of xLi2MnO3·(1–x)LiMO2 (M = Ni, Co, and Mn) Material as a Positive Electrode in Li-Ion Batteries , 2014 .

[11]  Daan Frenkel,et al.  Suppression of crystal nucleation in polydisperse colloids due to increase of the surface free energy , 2001, Nature.

[12]  K Ramesha,et al.  Origin of voltage decay in high-capacity layered oxide electrodes. , 2015, Nature materials.

[13]  P. Biensan,et al.  Mechanisms Associated with the “Plateau” Observed at High Voltage for the Overlithiated Li1.12(Ni0.425Mn0.425Co0.15)0.88O2 System , 2008 .

[14]  Y. Koyama,et al.  First-principles study on lithium removal from Li2MnO3 , 2009 .

[15]  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.

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

[17]  Ya‐Xia Yin,et al.  Enhancing the Kinetics of Li‐Rich Cathode Materials through the Pinning Effects of Gradient Surface Na+ Doping , 2016 .

[18]  Kota Suzuki,et al.  Hetero-epitaxial growth of Li0.17La0.61TiO3 solid electrolyte on LiMn2O4 electrode for all solid-state batteries , 2014 .

[19]  Stephen J. Pennycook,et al.  High-resolution Z-contrast imaging of crystals , 1991 .

[20]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[21]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[22]  Min Gyu Kim,et al.  A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles. , 2015, Nano letters.

[23]  Feng Wu,et al.  Rod-like hierarchical nano/micro Li1.2Ni0.2Mn0.6O2 as high performance cathode materials for lithium-ion batteries , 2013 .

[24]  Jianming Zheng,et al.  Mitigating voltage fade in cathode materials by improving the atomic level uniformity of elemental distribution. , 2014, Nano letters.

[25]  Peter G. Bruce,et al.  Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries , 1996, Nature.

[26]  John T. Vaughey,et al.  Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: xLi2MnO3·(1 − x)LiMn0.333Ni0.333Co0.333O2 (0 ≤ x ≤ 0.7) , 2008 .

[27]  C. Delmas,et al.  Insight into the Atomic Structure of Cycled Lithium-Rich Layered Oxide Li1.20Mn0.54Co0.13Ni0.13O2 Using HAADF STEM and Electron Nanodiffraction , 2015 .

[28]  J. Dahn,et al.  The Effect of Co Substitution for Ni on the Structure and Electrochemical Behavior of T2 and O2 Structure Li2 / 3 [ Co x Ni1 / 3 − x Mn2 / 3 ] O 2 , 2001 .

[29]  Jaephil Cho,et al.  Countering Voltage Decay and Capacity Fading of Lithium‐Rich Cathode Material at 60 °C by Hybrid Surface Protection Layers , 2015 .

[30]  Lingyun Liu,et al.  A review of blended cathode materials for use in Li-ion batteries , 2014 .

[31]  Kazuhisa Tamura,et al.  Dynamic structural changes at LiMn2O4/electrolyte interface during lithium battery reaction. , 2010, Journal of the American Chemical Society.

[32]  Jie Xiao,et al.  Probing the Degradation Mechanism of Li2MnO3 Cathode for Li-Ion Batteries , 2015 .

[33]  J. E. Hilliard,et al.  Free Energy of a Nonuniform System. I. Interfacial Free Energy and Free Energy of a Nonuniform System. III. Nucleation in a Two‐Component Incompressible Fluid , 2013 .

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

[35]  J. E. Hilliard,et al.  Free Energy of a Nonuniform System. I. Interfacial Free Energy , 1958 .

[36]  Masao Yonemura,et al.  Room-temperature miscibility gap in LixFePO4 , 2006, Nature materials.

[37]  K. Amine,et al.  Conflicting roles of nickel in controlling cathode performance in lithium ion batteries. , 2012, Nano letters.

[38]  Tao Zheng,et al.  The elevated temperature performance of the LiMn2O4/C system: Failure and solutions , 1999 .

[39]  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 .

[40]  Meilin Liu,et al.  Nanoscale Surface Modification of Lithium-Rich Layered-Oxide Composite Cathodes for Suppressing Voltage Fade. , 2015, Angewandte Chemie.

[41]  Hidetaka Sawada,et al.  Visualization of Light Elements at Ultrahigh Resolution by STEM Annular Bright Field Microscopy , 2009, Microscopy and Microanalysis.

[42]  P. Novák,et al.  Ex situ and in situ Raman microscopic investigation of the differences between stoichiometric LiMO2 and high-energy xLi2MnO3·(1–x)LiMO2 (M = Ni, Co, Mn) , 2014 .

[43]  A. Manthiram,et al.  Calculations of Oxygen Stability in Lithium-Rich Layered Cathodes , 2012 .

[44]  Feng Wu,et al.  Spinel/Layered Heterostructured Cathode Material for High‐Capacity and High‐Rate Li‐Ion Batteries , 2013, Advanced materials.

[45]  John T. Vaughey,et al.  The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3 · (1 − x)LiMn0.5Ni0.5O2 electrodes , 2004 .

[46]  Yet-Ming Chiang,et al.  Electronically conductive phospho-olivines as lithium storage electrodes , 2002, Nature materials.

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

[48]  H. Sawada,et al.  Direct imaging of lithium atoms in LiV₂O₄ by spherical aberration-corrected electron microscopy. , 2010, Journal of electron microscopy.

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

[50]  Ning Li,et al.  Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries. , 2014, Nano letters.

[51]  Gerbrand Ceder,et al.  Layered-to-Spinel Phase Transition in Li x MnO2 , 2001 .

[52]  Gerbrand Ceder,et al.  Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries , 2014, Science.

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

[54]  Acknowledgements , 1992, Experimental Gerontology.

[55]  J. Colin,et al.  First evidence of manganese-nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries. , 2013, Nano letters.

[56]  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 .

[57]  M. Takano,et al.  Structure and charge/discharge characteristics of new layered oxides: Li1.8Ru0.6Fe0.6O3 and Li2IrO3 , 1997 .