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Unveiling the controversial mechanism of reversible Na storage in TiO2 nanotube arrays： Amorphous versus anatase TiO2

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Nano Research 2017年第8期10卷 2891-2903页

作者： Federico Bella Ana B. Munoz-Garcia Giuseppina Meligrana Andrea Lamberti Matteo Destro Michele Pavone Claudio Gerbaldi GAME Lab CHENERGY Group Department of Applied Science and Technology - DISAT Politecnico di Torino Corso Duca degli Abruzzi 24 10129 Torino Italy Department of Chemical Sciences University of Naples Fedefico II Via Cintia 21 University Campus of Monte Sant'Angelo 80126 Napoli Italy MPMNT Group Department of Applied Science and Technology - DISAT Politecnico di Torino Corso Duca degli Abruzzi 24 10129 Torino Italy LITHOPS S.r.l. Strada del Portone 61 10137 Torino Italy

Due to their inherent safety, low cost, and structural stability, TiO2 nanostructures represent a suitable choice as anode materials in sodiumion batteries. In the recent years, various hypotheses have been proposed regarding the actual mechanism of the reversible insertion of sodium ions in the TiO2 structure, and previous reports are often controversial in this respect. Interestingly, when tested as binder- and conducting additive-free electrodes in laboratory-scale sodium cells, amorphous and crystalline （anatase） TiO2 nanotubular arrays obtained by simple anodic oxidation exhibit peculiar and intrinsically different electrochemical responses. In particular, after the initial electrochemical activation, anatase TiO2 shows excellent rate capability and very stable long-term cycling performance with larger specific capacities, and thus a clearly superior response compared with the amorphous counterpart. To obtain deeper insight, the present materials are thoroughly characterized by scanning electron microscopy and ex situ X-ray diffraction, and the insertion of sodium ions in the TiO2 bulk phases is systematically modeled by density functional theory calculations. The present results may contribute to the development of more systematic screening approaches to identify suitable active materials for highly efficient sodium-based energy storage systems.

关键词： sodium battery TiO2 nanotube array anode modeling insertion mechanism

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