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Title: Synthesis, characterization, and electrochemical cycling behavior of the Ru-doped spinel, Li[Mn2-xRux]O4 (x=0, 0.1, and 0.25)
Authors: Reddy, M.V. 
Manoharan, S.S.
John, J.
Singh, B.
Subba Rao, G.V. 
Chowdari, B.V.R. 
Issue Date: 2009
Citation: Reddy, M.V., Manoharan, S.S., John, J., Singh, B., Subba Rao, G.V., Chowdari, B.V.R. (2009). Synthesis, characterization, and electrochemical cycling behavior of the Ru-doped spinel, Li[Mn2-xRux]O4 (x=0, 0.1, and 0.25). Journal of the Electrochemical Society 156 (8) : A652-A660. ScholarBank@NUS Repository.
Abstract: Pure and Ru-doped Li[Mn2-xRux]O4 (x=0.1 and 0.25) spinel compounds are prepared by the high temperature solid-state reaction and characterized by X-ray diffraction (XRD), scanning electron microscopy, Brunauer, Emmett, and Teller surface area, density, IR, Raman spectroscopy, and X-ray absorption spectroscopy. XRD studies show single-phase compounds with the cubic spinel structure and a decrease in (Mn-O) and an increase in (Li-O) bond lengths on Ru doping. The electrochemical cycling behavior of Li[Mn2-xRux]O4 is examined by galvanostatic cycling and cyclic voltammetry (CV). The CV shows that the Mn 3+Mn4+ couple lies in the range from ∼4.0 to ∼4.2 V and the spinel-to-double-hexagonal (S-DH) transition at ∼4.5 V in agreement with results in the literature. The Ru4+ Ru5+ redox couple operates at ∼4.3 V vs Li in the spinel structure. The S-DH phase transition is suppressed on Ru doping. Charge-discharge cycling, up to 25 or 40 cycles, in the voltage ranges 3.5-4.3 and 3.5-4.6 V vs Li at 0.14C rate gave initial charge capacities ranging from 118 to 139 mAh g-1 for various x. Compositions with x=0.1 and 0.25 showed smaller initial capacity loss and smaller capacity fading during cycling as compared to x=0. For x=0.25 in the voltage range 3.5-4.6 V and 2-25 cycles, the capacity fade is only 9% thereby showing the beneficial effect of Ru doping, by way of suppression of S-DH transition, participation of Ru-redox couple, and better electronic conductivity of the compound during cycling, in comparison to pure Li Mn2 O4. © 2009 The Electrochemical Society.
Source Title: Journal of the Electrochemical Society
ISSN: 00134651
DOI: 10.1149/1.3139013
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