Electrochemical behavior of [{Mn(Bpy)}(VO3)2]≈(H2O)1.24 and [{Mn(Bpy)0.5}(VO3)2]≈(H2O)0.62 inorganic–organic Brannerites in lithium and sodium cells

• Published in: Journal of solid state chemistry 2014-04, Vol.212, p.92-98
• Main Authors: Fernández de Luis, Roberto, Ponrouch, Alexandre, Rosa Palacín, M., Karmele Urtiaga, M., Arriortua, María I.
• Format: Article
• Language: English
• Subjects: Applied sciences; Chemistry; Conversion reaction; Direct energy conversion and energy accumulation; Electrical engineering. Electrical power engineering; Electrical power engineering; Electrochemical conversion: primary and secondary batteries, fuel cells; Electrochemistry; Electrode materials; Electrodes: preparations and properties; Exact sciences and technology; General and physical chemistry; Hybrid materials; Infrared spectroscopy; Lithium batteries; Sodium batteries
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2014.01.013

The performance of MnV2O6 (MnV) and its [{Mn(Bpy)}(VO3)2]≈(H2O)1.16 (MnBpy) and [{Mn(Bpy)0.5}(VO3)2]≈(H2O)0.62(MnBpy0.5) hybrid derivative compounds was investigated against sodium and lithium counter electrodes. For MnV2O6 stable capacities of 850mAh/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+/Li and Na+/Na of about ca. 0.3V 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. The electrochemical performance of [{Mn(Bpy)}(VO3)2]≈(H2O)1.16 and [{Mn(Bpy)0.5}(VO3)2]≈(H2O)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 850mAh/g for lithium cells were achieved. [Display omitted] •We test the lithium and sodium insertion in hybrid brannerites.•Capacities as large as 850mAh/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.