Underlying Mechanisms of the Synergistic Role of Li₂MnO₃ and LiNi_{1/3}Co_{1/3}Mn_{1/3}O₂ in High-Mn, Li-Rich Oxides

dc.contributor.ORCID0000-0003-2698-7774 (Cho, K)en_US
dc.contributor.authorLim, J. -Men_US
dc.contributor.authorKim, D.en_US
dc.contributor.authorPark, M. -Sen_US
dc.contributor.authorCho, M.en_US
dc.contributor.authorCho, Kyeongjaeen_US
dc.date.accessioned2018-06-01T15:07:53Z
dc.date.available2018-06-01T15:07:53Z
dc.date.created2016-03-18
dc.descriptionIncludes supplementary materialen_US
dc.description.abstractFor large-scale energy storage applications requiring high energy density, the development of Li-rich oxides with enhanced cyclic stabilities during high-voltage operations and large specific capacities is required. In this regard, high-Mn, Li-rich oxides (HMLOs; xLi₂MnO₃3 (1 - x)LiNi_{1/3}Co_{1/3}Mn_{1/3}O₂ at x > 0.5) warrant an in-depth study because of their good cyclic performance at high operating voltages and potentially large specific capacities. Here, to understand the synergistic effects and enhanced cyclic stability of HMLOs, mechanically blended HMLO (m-HMLO) and chemically bonded HMLO (c-HMLO) were prepared and investigated. c-HMLO exhibits relatively high reaction voltages, large specific capacities, and enhanced cyclic stabilities (∼99%) at a high operating voltage (∼4.8 V vs. Li/Li⁺) compared with m-HMLO. First-principles calculations with electronic structure analysis were performed using an atomic model developed by Rietveld refinement using as-synthesised c-HMLO. The redox mechanisms of Ni, Co, and Mn ions were determined via the partial density of states of the ground states predicted using the cluster expansion method, which elucidates that LiNi_{1/3}Co_{1/3}Mn_{1/3}O₂ stabilises the transition metal (TM) layer of Li₁MnO₃ and separates Li delithiation potentials in Li₁MnO₃ in the HMLO. Kinetic analyses including electronic structures revealed that the interlayer migration of TMs from the TM layer to the Li layer depends on the crystal field stabilisation. Thus, TMs with reduced character in the tetrahedral sites than the octahedral sites owing to the effects of crystal field stabilisation, such as Ni ions, in HMLOs would face a higher interlayer migration barrier, impeding phase transformation into spinel phases. Furthermore, Cu ions could constitute a doping source for HMLOs to improve the material's cyclic stability through this mechanism. These characteristics may be widely applied to explain experimental phenomena and improve the properties of cathode materials for Li-ion batteries.en_US
dc.description.sponsorship"This study was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean Government (MEST) (2012R1A3A2048841) and the New & Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20152020105420)."en_US
dc.identifier.bibliographicCitationLim, J. -M, D. Kim, M. -S Park, M. Cho, et al. 2016. "Underlying mechanisms of the synergistic role of Li₂MnO₃ and LiNi_{1/3}Co_{1/3}Mn_{1/3}O₂ in high-Mn, Li-rich oxides." Physical Chemistry Chemical Physics 18(16), doi: 10.1039/C6CP00088Fen_US
dc.identifier.issn1463-9076en_US
dc.identifier.issue16en_US
dc.identifier.urihttp://hdl.handle.net/10735.1/5809
dc.identifier.volume18en_US
dc.language.isoenen_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.urihttp://dx.doi.org/10.1039/c6cp00088fen_US
dc.rights©2016 The Owner Societies. All Rights Reserved.en_US
dc.source.journalPhysical Chemistry Chemical Physicsen_US
dc.subjectCrystal field theoryen_US
dc.subjectPhase transformations (Statistical physics)en_US
dc.subjectLithium ion batteriesen_US
dc.subjectManganese oxidesen_US
dc.subjectLithium compoundsen_US
dc.titleUnderlying Mechanisms of the Synergistic Role of Li₂MnO₃ and LiNi_{1/3}Co_{1/3}Mn_{1/3}O₂ in High-Mn, Li-Rich Oxidesen_US
dc.type.genrearticleen_US

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