LixNi0.25Mn0.75Oy (0.5 ≤ x ≤ 2, 2 ≤ y ≤ 2.75) compounds for high-energy lithium-ion batteries

Manganese-rich and cobalt-free compounds of LixNi0.25Mn0.75Oy (0.5 ≤ x ≤ 2, 2 ≤ y ≤ 2.75) were investigated as the positive electrode materials for high energy lithium-ion batteries. Compounds with x = 0.5, 1, 1.25, 1.5, and 2 were prepared by a solid-state reaction from the same carbonate precursor, Ni0.25Mn0.75CO3, with an appropriate amount of Li2CO3. The structural and physical characteristics of these phases were determined by X-ray diffraction and scanning electron microscopy. With an increase of the lithium content, the LixNi0.25Mn0.75Oy evolved from a spinel (Fdm) structure (x = 0.5) to a mixed spinel-layered (Fdm and C2/c) structure (x = 1 and 1.25), to a more layered (Rm and C2/c) structure (x = 1.5 and 2). A similar structural trend was found for samples prepared from NiMn2O4–Mn2O3 mixed oxide, itself prepared by thermal decomposition of Ni0.25Mn0.75CO3carbonate precursor, to which appropriate amounts of Li2CO3 were added. An increase of the lithium content also affected the size of the primary particles and the roughness of the secondary particles, without any substantial change of their spherical morphology and packing densities. Further results showed that the electrochemical performance and safety characteristics of the LixNi0.25Mn0.75Oy materials were primarily governed by their structures.

[1]  Xiao‐Qing Yang,et al.  INVESTIGATION OF THE LOCAL STRUCTURE OF THE LINI0.5MN0.5O2 CATHODE MATERIAL DURING ELECTROCHEMICAL CYCLING BY X-RAY ABSORPTION AND NMR SPECTROSCOPY , 2002 .

[2]  Peter G. Bruce,et al.  Overcapacity of Li [ Ni x Li1 / 3 − 2x / 3Mn2 / 3 − x / 3 ] O 2 Electrodes , 2004 .

[3]  John B. Goodenough,et al.  Cathode materials: A personal perspective , 2007 .

[4]  Christopher S. Johnson,et al.  Electrochemical and Structural Properties of xLi2M‘O3·(1−x)LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M‘ = Ti, Mn, Zr; 0 ≤ x ⩽ 0.3) , 2004 .

[5]  W. H. Cloud CRYSTAL STRUCTURE AND FERRIMAGNETISM IN NiMnO$sub 3$ AND CoMnO$sub 3$ , 1958 .

[6]  M. Yoshio,et al.  In Situ XAFS Analysis of Li(Mn, M)2O4 (M=Cr, Co, Ni) 5V Cathode Materials for Lithium-Ion Secondary Batteries , 2001 .

[7]  K. Amine,et al.  Electrochemical and ex situ x-ray study of Li(Li{sub 0.2}Ni{sub 0.2}Mn{sub 0.6})O{sub 2} cathode material for Li secondary batteries. , 2003 .

[8]  Á. Caballero,et al.  Expanding the Rate Capabilities of the LiNi0.5Mn1.5O4 Spinel by Exploiting the Synergistic Effect Between Nano and Microparticles , 2005 .

[9]  J. Dahn,et al.  Lattice-gas model to understand voltage profiles of LiNi x Mn 2 − x O 4 / L i electrochemical cells , 1997 .

[10]  J. Dahn,et al.  Synthesis and Electrochemistry of LiNi x Mn2 − x O 4 , 1997 .

[11]  A. Feltz,et al.  Untersuchungen an elektronenleitenden Oxidsystemen. XXIII. Struktur und Eigenschaften stabiler Spinelle in den Reihen MzNiMn2−ZO4 (M=Li, Fe) , 1993 .

[12]  Christopher S. Johnson,et al.  Lithium-manganese-nickel-oxide electrodes with integrated layered-spinel structures for lithium batteries , 2007 .

[13]  Xiao-Zhen Liao,et al.  Electrochemical evaluation of composite cathodes base on blends of LiMn2O4 and LiNi0.8Co0.2O2 , 2001 .

[14]  Tsutomu Ohzuku,et al.  Synthesis and Characterization of LiAl1 / 4Ni3 / 4 O 2 ( R 3̄m ) for Lithium‐Ion (Shuttlecock) Batteries , 1995 .

[15]  Ying Shirley Meng,et al.  Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries , 2006, Science.

[16]  K. Zaghib,et al.  Dual active material composite cathode structures for Li-ion batteries , 2008 .

[17]  K. Amine,et al.  Comparative study of Li(Ni0.5-xMn0.5-xM2x')O2 (M' = Mg, Al, Co, Ni, Ti; x = 0, 0.025) cathode materials for rechargeable lithium batteries , 2003 .

[18]  I. Belharouak,et al.  Comparative study of different crystallographic structure of LiNi0.5Mn1.5O4−δ cathodes with wide operation voltage (2.0–5.0 V) , 2007 .

[19]  J. Dahn,et al.  Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries , 2001 .

[20]  Ilias Belharouak,et al.  Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2 , 2006 .

[21]  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.

[22]  T. Ohzuku,et al.  Electrochemistry and Structural Chemistry of LiNiO2 (R3̅m) for 4 Volt Secondary Lithium Cells , 1993 .

[23]  Ilias Belharouak,et al.  Advanced cathode materials for high-power applications , 2005 .

[24]  Doron Aurbach,et al.  The study of LiNi0.5Mn1.5O4 5-V cathodes for Li-ion batteries , 2005 .

[25]  J. Dahn,et al.  Thermal stability of LixCoO2, LixNiO2 and λ-MnO2 and consequences for the safety of Li-ion cells , 1994 .

[26]  S. Geller Structure of α-Mn2O3, (Mn0.983Fe0.017)2O3 and (Mn0.37Fe0.63)2O3 and relation to magnetic ordering , 1971 .

[27]  S. J. Kim,et al.  Nanocomposite electrode materials for high energy density rechargeable lithium batteries , 2007 .

[28]  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 .

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