A comparative study on the oxidation state of lattice oxygen among Li1.14Ni0.136Co0.136Mn0.544O2, Li2MnO3, LiNi0.5Co0.2Mn0.3O2 and LiCoO2 for the initial charge–discharge

The Li-rich layered oxides are attractive electrode materials due to their high reversible specific capacity (>250 mA h g−1); however, the origin of their abnormal capacity is still ambiguous. In order to elucidate this curious anomaly, we compare the lattice oxygen oxidation states among the Li-rich layered oxide Li1.14Ni0.136Co0.136Mn0.544O2, Li2MnO3 and LiNi0.5Co0.2Mn0.3O2, the two components in Li-rich layered oxides, and the most common layered oxide LiCoO2 before and after initial charge–discharge. For simplicity, we employ chemical treatments of NO2BF4 and LiI acetonitrile solutions to simulate the electrochemical delithiation and lithiation processes. X-ray photoelectron spectroscopy (XPS) studies reveal that part of lattice oxygen in Li1.14Ni0.136Co0.136Mn0.544O2 and Li2MnO3 undergoes a reversible redox process (possibly O2− ↔ O22−), while this does not occur in LiNi0.5Co0.2Mn0.3O2 and LiCoO2. This indicates that the extra capacity of Li-rich layered oxides can be attributed to the reversible redox processes of oxygen in the Li2MnO3 component. Thermogravimetric analysis (TGA) further suggests that the formed O22− species in the delithiated Li1.14Ni0.136Co0.136Mn0.544O2 can decompose into O2 at about 210 °C. This phenomenon demonstrates a competitive relationship between extra capacity and thermal stability, which presents a big challenge for the practical applications of these materials.

[1]  Zhaoping Liu,et al.  Surface structural conversion and electrochemical enhancement by heat treatment of chemical pre-delithiation processed lithium-rich layered cathode material , 2014 .

[2]  B. Polzin,et al.  Functioning Mechanism of AlF3 Coating on the Li- and Mn-Rich Cathode Materials , 2014 .

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

[4]  D. Aurbach,et al.  Phase Transitions in Li2MnO3 Electrodes at Various States-of-Charge , 2014 .

[5]  K Ramesha,et al.  Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. , 2013, Nature materials.

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

[7]  Haoshen Zhou,et al.  Direct atomic-resolution observation of two phases in the Li(1.2)Mn(0.567)Ni(0.166)Co(0.067)O2 cathode material for lithium-ion batteries. , 2013, Angewandte Chemie.

[8]  K. Amine,et al.  Nanoscale Phase Separation, Cation Ordering, and Surface Chemistry in Pristine Li1.2Ni0.2Mn0.6O2 for Li-Ion Batteries , 2013 .

[9]  Marie-Liesse Doublet,et al.  High Performance Li2Ru1–yMnyO3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding , 2013 .

[10]  Lijun Wu,et al.  Combining In Situ Synchrotron X‐Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium‐Ion Batteries , 2013 .

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

[12]  M. Whittingham,et al.  Oxygen and transition metal involvement in the charge compensation mechanism of LiNi1/3Mn1/3Co1/3O2 cathodes , 2012 .

[13]  Haoshen Zhou,et al.  Initial Coulombic efficiency improvement of the Li1.2Mn0.567Ni0.166Co0.067O2 lithium-rich material by ruthenium substitution for manganese , 2012 .

[14]  C. Delmas,et al.  Li1.20Mn0.54Co0.13Ni0.13O2 with Different Particle Sizes as Attractive Positive Electrode Materials for Lithium-Ion Batteries: Insights into Their Structure , 2012 .

[15]  Zhaoping Liu,et al.  The structure, morphology, and electrochemical properties of Li1+xNi1/6Co1/6Mn4/6O2.25+x/2 (0.1 ≤ x ≤ 0.7) cathode materials , 2012 .

[16]  Yuichi Sato,et al.  In situ X-ray absorption spectroscopic study of Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2 , 2011 .

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

[18]  Tsutomu Ohzuku,et al.  High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries: toward rechargeable capacity more than 300 mA h g−1 , 2011 .

[19]  Lijun Wu,et al.  A new in situ synchrotron X-ray diffraction technique to study the chemical delithiation of LiFePO4. , 2011, Chemical communications.

[20]  Xiangming He,et al.  Synthesis and characterization of LiNi0.6Mn0.4―xCoxO2 as cathode materials for Li-ion batteries , 2009 .

[21]  M. Armand,et al.  Building better batteries , 2008, Nature.

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

[23]  Y. Takeda,et al.  Effect of CO2 on layered Li1+zNi1−x−yCoxMyO2 (M = Al, Mn) cathode materials for lithium ion batteries , 2007 .

[24]  M. Langell,et al.  Surface properties of LiCoO2, LiNiO2 and LiNi1−xCoxO2 , 2007 .

[25]  Michael Holzapfel,et al.  Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. , 2006, Journal of the American Chemical Society.

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

[27]  C. Julien,et al.  XPS and Raman spectroscopic characterization of LiMn2O4 spinels , 2005 .

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

[29]  Y. Ein‐Eli,et al.  In situ synchrotron X-ray studies on copper–nickel 5 V Mn oxide spinel cathodes for Li-ion batteries , 2004 .

[30]  Yong Yang,et al.  Origin of deterioration for LiNiO2 cathode material during storage in air , 2004 .

[31]  Min Gyu Kim,et al.  Synthesis and electrochemical properties of nanocrystalline Li[NixLi(1−2x)/3Mn(2−x)/3]O2 prepared by a simple combustion method , 2004 .

[32]  N. Kosova,et al.  Electronic state of cobalt and oxygen ions in stoichiometric and nonstoichiometric Li1+xCoO2 before and after delithiation according to XPS and DRS , 2003 .

[33]  W. Crone,et al.  Surface characterization of NiTi modified by plasma source ion implantation , 2002 .

[34]  Richard T. Haasch,et al.  Surface Characterization of Electrodes from High Power Lithium-Ion Batteries , 2002 .

[35]  D. D. MacNeil,et al.  Layered Cathode Materials Li [ Ni x Li ( 1 / 3 − 2x / 3 ) Mn ( 2 / 3 − x / 3 ) ] O 2 for Lithium-Ion Batteries , 2001 .

[36]  S. Rhee,et al.  Chemical vapor deposition of nickel oxide films from Ni(C5H5)2/O2 , 2001 .

[37]  Sai-Cheong Chung,et al.  Optimized LiFePO4 for Lithium Battery Cathodes , 2001 .

[38]  Byungwoo Park,et al.  Novel LiCoO2 Cathode Material with Al2O3 Coating for a Li Ion Cell , 2000 .

[39]  Albert Frederick Carley,et al.  The formation and characterisation of Ni3+ — an X-ray photoelectron spectroscopic investigation of potassium-doped Ni(110)–O , 1999 .

[40]  C. Julien,et al.  Characterization and Electrochemical Studies of LiMn2O4 Cathode Materials Prepared by Combustion Method , 1999 .

[41]  P. Ross,et al.  The Reaction of Lithium with Dimethyl Carbonate and Diethyl Carbonate in Ultrahigh Vacuum Studied by X-ray Photoemission Spectroscopy , 1999 .

[42]  A. Davidson,et al.  Spectroscopic Studies of Nickel(II) and Nickel(III) Species Generated upon Thermal Treatments of Nickel/Ceria-Supported Materials , 1996 .

[43]  A. Manthiram,et al.  Chemical Extraction of Lithium from Layered LiCoO2 , 1996 .

[44]  J. Tarascon,et al.  THE SPINEL PHASE OF LIMN2O4 AS A CATHODE IN SECONDARY LITHIUM CELLS , 1991 .

[45]  J. Tarascon,et al.  Li Metal‐Free Rechargeable Batteries Based on Li1 + x Mn2 O 4 Cathodes ( 0 ≤ x ≤ 1 ) and Carbon Anodes , 1991 .

[46]  Francis J. DiSalvo,et al.  Powerful oxidizing agents for the oxidative deintercalation of lithium from transition-metal oxides , 1989 .

[47]  S. Kikkawa,et al.  Deintercalated NaCoO2 and LiCoO2 , 1986 .

[48]  Chongmin Wang,et al.  Insights into the Phase Formation Mechanism of [0.5Li2MnO3·0.5LiNi0.5Mn0.5O2] Battery Materials , 2014 .

[49]  Ji‐Guang Zhang,et al.  Electrochemical Kinetics and Performance of Layered Composite Cathode Material Li(Li0.2Ni0.2Mn0.6)O2 , 2013 .

[50]  Hui Li,et al.  High-capacity Li(Ni0.5Co0.2Mn0.3)O2 lithium-ion battery cathode synthesized using a green chelating agent , 2013, Journal of Solid State Electrochemistry.

[51]  C. Delmas,et al.  Reversible Oxygen Participation to the Redox Processes Revealed for Li1.20Mn0.54Co0.13Ni0.13O2 , 2013 .