Phase Transitions in Li2MnO3 Electrodes at Various States-of-Charge

Amalraj, S. Francis; Burlaka, Luba; Julien, C.; Mauger, A.; Kovacheva, D.; Talianker, M.; Markovsky, Boris; Aurbach, Doron

doi:10.1016/j.electacta.2014.01.051

Cited by 56 publications

(41 citation statements)

References 41 publications

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“…The Raman spectra for the pristine Li 2 MnO 3 cathode material, shown in Fig. 3a, exhibits nine resolved peaks at 248, 309, 323, 368, 414, 431, 487, 559 and 607 cm −1 , which are in good agreement with those reported by Amalraj et al [23]. According to their theoretical calculations, the monoclinic Li 2 MnO 3 oxide with C 2h 3 spectroscopic symmetry is predicted to show 10 Raman-active modes with 4A g + 6B g species.…”

Section: Raman Scatteringsupporting

confidence: 88%

Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3

Torres-Castro

Shojan

Julien

et al. 2015

Materials Science and Engineering: B

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a b s t r a c tLi 2 MnO 3 is known to be electrochemically inactive due to Mn in tetravalent oxidation state. Several compositions such as Li 2 MnO 3 , Li 1.5 Al 0.17 MnO 3 , Li 1.0 Al 0.33 MnO 3 and Li 0.5 Al 0.5 MnO 3 were synthesized by a sol-gel Pechini method. All the samples were characterized with XRD, Raman, XPS, SEM, Tap density and BET analyzer. XRD patterns indicated the presence of monoclinic phase for pristine Li 2 MnO 3 and mixed monoclinic/spinel phases (Li 2 − x Mn 1 − y Al x + y O 3 + z ) for Al-substituted Li 2 MnO 3 compounds. The Al substitution seems to occur both at Li and Mn sites, which could explain the presence of spinel phase. XPS analysis for Mn 2p orbital reveals a significant decrease in binding energy for Li 1.0 Al 0.33 MnO 3 and Li 0.5 Al 0.5 MnO 3 compounds. Cyclic voltammetry, charge/discharge cycles and electrochemical impedance spectroscopy were also performed. A discharge capacity of 24 mAh g −1 for Li 2 MnO 3 , 68 mAh g −1 for Li 1.5 Al 0.17 MnO 3 , 58 mAh g −1 for Li 1.0 Al 0.33 MnO 3 and 74 mAh g −1 for Li 0.5 Al 0.5 MnO 3 were obtained. Aluminum substitutions increased the formation of spinel phase which is responsible for cycling.Published by Elsevier B.V.

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Section: Raman Scatteringsupporting

confidence: 88%

Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3

Torres-Castro

Shojan

Julien

et al. 2015

Materials Science and Engineering: B

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“…The previous studies reported the appearance of the diffraction peaks attributable to cubic/tetragonal spinel phases for the charged samples. 24,25 Some diffraction peaks observed in the present study (Sp. #5) are close in position to those for Li-poor cubic spinel Liδ~0.05Mn2O4 (λ-MnO2, Fig.…”

mentioning

confidence: 52%

“…Some studies reported weak diffraction peaks attributable to spinel structure in the partially delithiated Li2MnO3. 24,25 Recent advances in scanning transmission electron microscopy (STEM) techniques have offered a chance to gain the atomic column images for the delithiated/relithiated electrode materials. [26][27][28] the Mn migration from the TM layer to the Li layer in Li2MnO3 charged to 4.8 V in the initial cycle, which was considered as a direct evidence of the formation of spinel-like domain during delithiation.…”

Section: Introductionmentioning

confidence: 99%

Direct observation of layered-to-spinel phase transformation in Li₂MnO₃ and the spinel structure stabilised after the activation process

et al. 2017

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“…But it is unexpected to notice that the Mn migrated out of the lithium layer when discharged to 2.0 V by comparing the line profiles from lithium layer in Li 2 MnO 3 with different charge/discharge state, implying that migration of Mn is reversible at shallow delithiation/relithiation. This is in sharp contrast with irreversible migration of Mn resulting in a structure with spinel‐like features in Li 2 MnO 3 . However, direct imaging of atomic structure indicated that Mn has high mobility in Li 2 MnO 3 .…”

Section: Migration Of Transition Metal Ionsmentioning

confidence: 99%

Atomic‐Scale Structure Evolution in a Quasi‐Equilibrated Electrochemical Process of Electrode Materials for Rechargeable Batteries

Xiao

et al. 2015

Advanced Materials

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Lithium-ion batteries have proven to be extremely attractive candidates for applications in portable electronics, electric vehicles, and smart grid in terms of energy density, power density, and service life. Further performance optimization to satisfy ever-increasing demands on energy storage of such applications is highly desired. In most of cases, the kinetics and stability of electrode materials are strongly correlated to the transport and storage behaviors of lithium ions in the lattice of the host. Therefore, information about structural evolution of electrode materials at an atomic scale is always helpful to explain the electrochemical performances of batteries at a macroscale. The annular-bright-field (ABF) imaging in aberration-corrected scanning transmission electron microscopy (STEM) allows simultaneous imaging of light and heavy elements, providing an unprecedented opportunity to probe the nearly equilibrated local structure of electrode materials after electrochemical cycling at atomic resolution. Recent progress toward unraveling the atomic-scale structure of selected electrode materials with different charge and/or discharge state to extend the current understanding of electrochemical reaction mechanism with the ABF and high angle annular dark field STEM imaging is presented here. Future research on the relationship between atomic-level structure evolution and microscopic reaction mechanisms of electrode materials for rechargeable batteries is envisaged.

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Phase Transitions in Li2MnO3 Electrodes at Various States-of-Charge

Cited by 56 publications

References 41 publications

Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3

Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3

Direct observation of layered-to-spinel phase transformation in Li₂MnO₃ and the spinel structure stabilised after the activation process

Atomic‐Scale Structure Evolution in a Quasi‐Equilibrated Electrochemical Process of Electrode Materials for Rechargeable Batteries

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Phase Transitions in Li2MnO3 Electrodes at Various States-of-Charge

Cited by 56 publications

References 41 publications

Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3

Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3

Direct observation of layered-to-spinel phase transformation in Li2MnO3 and the spinel structure stabilised after the activation process

Atomic‐Scale Structure Evolution in a Quasi‐Equilibrated Electrochemical Process of Electrode Materials for Rechargeable Batteries

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Direct observation of layered-to-spinel phase transformation in Li₂MnO₃ and the spinel structure stabilised after the activation process