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Electrochemistry and structure of the cobalt-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode

Journal Article


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Abstract


  • The development of cathode materials with high capacity and cycle stability is essential to emerging electric-vehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wet-chemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b). We find Ni2+/Ni3+/Ni4+ to be the active redox-center of the cathode with lithiation/delithiation occurring via a solid-solution reaction where the lattice responds approximately linearly with cycling, differing to that observed for iso-structural commercial cathodes with a lower level of cation mixing. The composite cathode has ∼75% active material and delivers an initial discharge-capacity of ∼103 mA h g-1 with a reasonable capacity retention of ∼84.4% after 100 cycles. Notably, the electrochemically-active component possesses a capacity of ∼139 mA h g-1, approaching that of the commercialized LiCoO2 and Li(Ni1/3Mn1/3Co1/3)O2 materials. Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ∼80% less change in its stacking-axis than for LiCoO2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials.

Publication Date


  • 2014

Citation


  • Pang, W., Kalluri, S., Peterson, V. K., Dou, S. Xue. & Guo, Z. (2014). Electrochemistry and structure of the cobalt-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode. Physical Chemistry Chemical Physics, 16 (46), 25377-25385.

Scopus Eid


  • 2-s2.0-84908610786

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4163&context=eispapers

Ro Metadata Url


  • http://ro.uow.edu.au/eispapers/3147

Has Global Citation Frequency


Number Of Pages


  • 8

Start Page


  • 25377

End Page


  • 25385

Volume


  • 16

Issue


  • 46

Place Of Publication


  • United Kingdom

Abstract


  • The development of cathode materials with high capacity and cycle stability is essential to emerging electric-vehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wet-chemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b). We find Ni2+/Ni3+/Ni4+ to be the active redox-center of the cathode with lithiation/delithiation occurring via a solid-solution reaction where the lattice responds approximately linearly with cycling, differing to that observed for iso-structural commercial cathodes with a lower level of cation mixing. The composite cathode has ∼75% active material and delivers an initial discharge-capacity of ∼103 mA h g-1 with a reasonable capacity retention of ∼84.4% after 100 cycles. Notably, the electrochemically-active component possesses a capacity of ∼139 mA h g-1, approaching that of the commercialized LiCoO2 and Li(Ni1/3Mn1/3Co1/3)O2 materials. Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ∼80% less change in its stacking-axis than for LiCoO2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials.

Publication Date


  • 2014

Citation


  • Pang, W., Kalluri, S., Peterson, V. K., Dou, S. Xue. & Guo, Z. (2014). Electrochemistry and structure of the cobalt-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode. Physical Chemistry Chemical Physics, 16 (46), 25377-25385.

Scopus Eid


  • 2-s2.0-84908610786

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4163&context=eispapers

Ro Metadata Url


  • http://ro.uow.edu.au/eispapers/3147

Has Global Citation Frequency


Number Of Pages


  • 8

Start Page


  • 25377

End Page


  • 25385

Volume


  • 16

Issue


  • 46

Place Of Publication


  • United Kingdom