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Structure and reversible lithium intercalation in a new P ' 3-phase: Na2/3Mn1-yFeyO2 (y=0, 1/3, 2/3)

  作者 YONCHEVA M; STOYANOVA R; ZHECHEVA E; KUZMANOVA E; SENDOVAVASSILEVA M; NIHTIANOVA D; CARTIER D; GUIGNARD M; DELMAS C  
  选自 期刊  Journal of Materials Chemistry;  卷期  2012年22-44;  页码  23418-23427  
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[摘要]In this contribution, new data on the reversible Li+ intercalation in iron substituted sodium manganates are provided. Novel Na2/3Mn1-yFeyO2 (y = 0, 1/3 and 2/3) compounds with a P'3-type structure are prepared from freeze-dried citrate precursors at 500 degrees C. A new structural element is the development of three-layer oxygen stacking contrary to the well-known P2-type Na2/3MnO2 with a two-layer sequence. The effect of Fe additives on the structure of Na2/3MnO2 was examined by XRD powder diffraction and TEM analysis. The oxidation state and the distribution of transition metal ions in Na2/3Mn1-yFeyO2 were analysed using electron paramagnetic resonance spectroscopy. The lithium intercalation in Na2/3Mn1-yFeyO2 was investigated in two-electrode lithium cells of the type Li vertical bar LiPF6 (EC:DMC)vertical bar Na2/3Mn1-yFeyO2. The stability of the layered phases during lithium intercalation was studied by ex situ Raman spectroscopy. It was found that the intermediate Na2/3Mn1-yFeyO2 composition is able to intercalate Li+ reversibly in high amounts. Details of the structure and its stability during the Li+ intercalation are discussed.

 
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