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Title: Electrochemical behavior of [(Mn(Bpy))(VO{sub 3}){sub 2}]≈(H{sub 2}O){sub 1.24} and [(Mn(Bpy){sub 0.5})(VO{sub 3}){sub 2}]≈(H{sub 2}O){sub 0.62} inorganic–organic Brannerites in lithium and sodium cells

The performance of MnV{sub 2}O{sub 6} (MnV) and its [(Mn(Bpy))(VO{sub 3}){sub 2}]≈(H{sub 2}O){sub 1.16} (MnBpy) and [(Mn(Bpy){sub 0.5})(VO{sub 3}){sub 2}]≈(H{sub 2}O){sub 0.62}(MnBpy0.5) hybrid derivative compounds was investigated against sodium and lithium counter electrodes. For MnV{sub 2}O{sub 6} stable capacities of 850 mAh/g were achieved in lithium cells, the best value reported so far. The whole capacity is ascribed to a conversion reaction in which the amorphization of the compounds takes place. No significant differences in the capacities for the inorganic compound and the hybrid ones were observed. Interestingly, the potential hysteresis decreases in the hybrid compounds. The difference between Li and Na cell capacity most probably comes from the difference of standard potential of the two redox couples Li{sup +}/Li and Na{sup +}/Na of about ca. 0.3 V leading to an incomplete conversion reaction and thus lowers capacity in the case of Na cells. The Raman and IR ex-situ experiments after cycling indicate that the bipyridine organic ligands are completely decomposed during the electrochemical testing. The IR studies in MnV inorganic and MnBpy and MnBpy0.5 hybrid electrodes after the electrochemical cycling, suggest that the SEI formation and bipyridine degradation give rise to different aliphatic compounds. - Graphical abstract: The electrochemicalmore » performance of [(Mn(Bpy))(VO{sub 3}){sub 2}]≈(H{sub 2}O){sub 1.16} and [(Mn(Bpy){sub 0.5})(VO{sub 3}){sub 2}]≈(H{sub 2}O){sub 0.62} against sodium and lithium counter electrodes give rise to the structural collapse of the initial compounds. The IR and Raman studies show that the Bpy organic ligand is completely decomposed during the during the electrochemical testing. However, after the amorphization stable capacities as high as 850 mAh/g for lithium cells were achieved. - Highlights: • We test the lithium and sodium insertion in hybrid brannerites. • Capacities as large as 850 mAh/g were obtained for the Li cells. • The capacity and good cycling is ascribed to a conversion reaction of the electrodes. • The Bpy molecule of the hybrid compounds is degraded during the first reduction. • The decomposition products of the Bpy ligand reduce the potential hysteresis.« less
Authors:
 [1] ;  [2] ;  [2] ;  [1] ;  [1]
  1. Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain)
  2. Institut de Ciència de Materials de Barcelona (CSIC) Campus UAB, E-08193, Bellaterra, Catalonia (Spain)
Publication Date:
OSTI Identifier:
22334168
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 212; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; BIPYRIDINES; BRANNERITE; DECOMPOSITION; ELECTRODES; HYSTERESIS; INFRARED SPECTRA; LIGANDS; LITHIUM; LITHIUM IONS; MOLECULES; SODIUM