Organic-acid-assisted fabrication of low-cost Li-rich cathode material (Li[Li1/6Fe1/6Ni1/6Mn1/2]O2) for lithium-ion battery.

A novel Li-rich cathode Li[Li1/6Fe1/6Ni1/6Mn1/2]O2 (0.4Li2MnO3-0.6LiFe1/3Ni1/3Mn1/3O2) was synthesized by a sol-gel method, which uses citric acid (SC), tartaric acid (ST), or adipic acid (SA) as a chelating agent. The structural, morphological, and electrochemical properties of the prepared samples were characterized by various methods. X-ray diffraction showed that single-phase materials are formed mainly with typical α-NaFeO2 layered structure (R3̅m), and the SC sample has the lowest Li/Ni cation disorder. The morphological study indicated homogeneous primary particles in good distribution size (100 nm) with small aggregates. The Fe, Ni, and Mn valences were determined by X-ray absorption near-edge structure analysis. In coin cell tests, the initial reversible discharge capacity of an SA electrode was 289.7 mAh g(-1) at the 0.1C rate in the 1.5-4.8 V voltage range, while an SC electrode showed a better cycling stability with relatively high capacity retention. At the 2C rate, the SC electrode can deliver a discharge capacity of 150 mAh g(-1) after 50 cycles. Differential capacity vs voltage curves were employed to further investigate the electrochemical reactions and the structural change process during cycling. This low-cost, Fe-based compound prepared by the sol-gel method has the potential to be used as the high capacity cathode material for Li-ion batteries.

[1]  Y. Nitta,et al.  Fe content effects on electrochemical properties of Fe-substituted Li2MnO3 positive electrode material , 2010 .

[2]  Tsutomu Ohzuku,et al.  Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell , 1990 .

[3]  Yun Zhang,et al.  The electrochemical properties of Fe- and Ni-cosubstituted Li2MnO3 via combustion method , 2013, Journal of Solid State Electrochemistry.

[4]  T. Akita,et al.  Participation of Oxygen in Charge/Discharge Reactions in Li1.2Mn0.4Fe0.4O2: Evidence of Removal/Reinsertion of Oxide Ions , 2011 .

[5]  Haijun Yu,et al.  High-Energy Cathode Materials (Li2MnO3-LiMO2) for Lithium-Ion Batteries. , 2013, The journal of physical chemistry letters.

[6]  J. Paulsen,et al.  Novel Lithium‐Ion Cathode Materials Based on Layered Manganese Oxides , 2001 .

[7]  Jianjun Li,et al.  Synthesis and characterization of Li(Li0.23Mn0.47Fe0.2Ni0.1)O2 cathode material for Li-ion batteries , 2013 .

[8]  M. Tabuchi,et al.  Synthesis of high-capacity Ti- and/or Fe-substituted Li2MnO3 positive electrode materials with high initial cycle efficiency by application of the carbothermal reduction method , 2013 .

[9]  M. Shikano,et al.  Material design concept for Fe-substituted Li2MnO3-based positive electrodes , 2007 .

[10]  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 .

[11]  T. Ohzuku,et al.  Layered Lithium Insertion Material of LiCo1/3Ni1/3Mn1/3O2 for Lithium-Ion Batteries , 2001 .

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

[13]  Jun Lu,et al.  The effect of chromium substitution on improving electrochemical performance of low-cost Fe–Mn based Li-rich layered oxide as cathode material for lithium-ion batteries , 2014 .

[14]  She-huang Wu,et al.  Preparation of α-LiFeO2-based cathode materials by an ionic exchange method , 2007 .

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

[16]  Tsutomu Ohzuku,et al.  Electrochemistry of manganese dioxide in lithium nonaqueous cell. I: X-ray diffractional study on the reduction of electrolytic manganese dioxide , 1990 .

[17]  K. Kang,et al.  Electrochemical performance of cobalt free, Li1.2(Mn0.32Ni0.32Fe0.16)O2 cathodes for lithium batteries , 2012 .

[18]  Alain Mauger,et al.  Minimization of the cation mixing in Li1+x(NMC)1-xO2 as cathode material , 2010 .

[19]  H. Sakaebe,et al.  Synthesis, Cation Distribution, and Electrochemical Properties of Fe-Substituted Li2MnO3 as a Novel 4 V Positive Electrode Material , 2002 .

[20]  K. Amine,et al.  Nanoarchitecture Multi‐Structural Cathode Materials for High Capacity Lithium Batteries , 2013 .

[21]  Jeremy Barker,et al.  Cathode materials for lithium rocking chair batteries , 1996 .

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

[23]  S. Franger,et al.  Insights into the electrochemical activity of nanosized α-LiFeO2 , 2008 .

[24]  Liquan Chen,et al.  Effect of Co Content on Rate Performance of LiMn0.5 − x Co2x Ni0.5 − x O 2 Cathode Materials for Lithium-Ion Batteries , 2004 .

[25]  M. Tabuchi,et al.  Synthesis and electrochemical characterization of Fe and Ni substituted Li2MnO3—An effective means to use Fe for constructing “Co-free” Li2MnO3 based positive electrode material , 2011 .

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

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

[28]  C. Pérez-Vicente,et al.  Cation distribution and chemical deintercalation of Li1-xNi1+xO2 , 1990 .

[29]  H. Sakaebe,et al.  Preparation of lithium manganese oxides containing iron , 2001 .

[30]  Li Li,et al.  Structural and Electrochemical Study of Al2O3 and TiO2 Coated Li1.2Ni0.13Mn0.54Co0.13O2 Cathode Material Using ALD , 2013 .

[31]  Jianjun Li,et al.  Recent Advances in the LiFeO2-based Materials for Li-ion Batteries , 2011, International Journal of Electrochemical Science.

[32]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .