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Publication Type : Journal Article
Publisher : ACS Applied Energy MaterialsACS Applied Energy Materials, American Chemical Society
Source : ACS Applied Energy MaterialsACS Applied Energy Materials, American Chemical Society, Volume 3, Issue 9, p.8716 - 8724 (2020)
Url : https://doi.org/10.1021/acsaem.0c01268
Campus : Coimbatore
School : School of Engineering
Department : Sciences
Year : 2020
Abstract : The cation-disordered lithium metal oxides display interesting electrochemical behavior quite distinct from the conventional cation-ordered layered structures. Comprehending the structure–property relations in these cation-disordered oxides is still in the preliminary stage. Herein, we report evidence of structural instabilities upon mechanical milling and electrochemical cycling of Li4FeMoO6. Remarkably, even under normal ball-milling conditions, the material becomes atomically disordered/the long-range order is severely affected. X-ray and electron diffraction studies reveal that pristine cationic disordered Li4FeMoO6 adopts the C2/m structure with stacking faults, whereas upon ball milling, a biphasic structure comprising a cubic phase (Fm3̅m + R3̅m) develops. With increasing milling time, these phases still coexist but as nanoscale domains (<5 nm); the 3 h ball-milled sample shows almost a 90.4% cubic (Fm3̅m) phase. Concomitant to ball milling, a dramatic improvement in charge–discharge capacities is also observed. The prepared sample Li4FeMoO6 showed a modest discharge capacity of 140 mA h g–1, whereas the 3 h ball-milled sample showed a discharge capacity of 359 mA h g–1, reaching 91.5% of its theoretical capacity. This unusual observation is a result of Li-ion percolation pathways (0-TM channels) introduced by the milling process.The cation-disordered lithium metal oxides display interesting electrochemical behavior quite distinct from the conventional cation-ordered layered structures. Comprehending the structure–property relations in these cation-disordered oxides is still in the preliminary stage. Herein, we report evidence of structural instabilities upon mechanical milling and electrochemical cycling of Li4FeMoO6. Remarkably, even under normal ball-milling conditions, the material becomes atomically disordered/the long-range order is severely affected. X-ray and electron diffraction studies reveal that pristine cationic disordered Li4FeMoO6 adopts the C2/m structure with stacking faults, whereas upon ball milling, a biphasic structure comprising a cubic phase (Fm3̅m + R3̅m) develops. With increasing milling time, these phases still coexist but as nanoscale domains (<5 nm); the 3 h ball-milled sample shows almost a 90.4% cubic (Fm3̅m) phase. Concomitant to ball milling, a dramatic improvement in charge–discharge capacities is also observed. The prepared sample Li4FeMoO6 showed a modest discharge capacity of 140 mA h g–1, whereas the 3 h ball-milled sample showed a discharge capacity of 359 mA h g–1, reaching 91.5% of its theoretical capacity. This unusual observation is a result of Li-ion percolation pathways (0-TM channels) introduced by the milling process.
Cite this Research Publication : D. Bosubabu, Ette, P. Masthanaia, Dr. A. K. Nanda Kumar, Arulraj, A., and Ramesha, K., “Proliferation of Atomic Shuffling through Mechanical Stress on Cationic Disorder Li4FeMoO6 as a Cathode Material for a Lithium-Ion Battery”, ACS Applied Energy MaterialsACS Applied Energy Materials, vol. 3, no. 9, pp. 8716 - 8724, 2020.