In:
ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2014-04, No. 4 ( 2014-06-10), p. 662-662
Abstract:
Metal fluorides/oxides (MF x /M x O y ) are promising electrode candidates for lithium-ion batteries (LIBs) that operate via conversion reactions. 1 These conversion-type reactions are associated with much higher energy densities as compared with the reactions based on intercalation chemistry that are typically used in commercially available LIBs. These metal salts (MF x /M x O y ) can also exhibit significant additional reversible capacity beyond the theoretical estimate based on the maximum electron transfer from available redox metal centers. 2 3 4 5 6 However, the difficulty in characterizing structures at the nano-scale, particularly at buried interfaces, has meant that the mechanism accounting for the additional capacity remains unclear. This study employs high-resolution multinuclear ( 1 H, 6 Li/ 7 Li, 17 O, 19 F) multidimensional solid-state NMR techniques, complemented by real-time detection using X-ray based methods in order to characterize two model systems, RuO 2 and TiF 3 . The results illustrate the origin of additional capacities found in metal oxides/fluorides used as electrodes in LIBs. 7 Changes in the long-range structure and valence of Ruthenium in the RuO 2 /Li battery system as a function of the state of charge have been followed by real-time high-resolution X-ray diffraction and absorption techniques. Variations in short-range atomic distances were probed with pair distribution function analysis and near edge X-ray absorption fine structure refinement. In-situ X-ray based techniques prove to be valuable in illustrating the reaction mechanism of the classic conversion reactions (xLi + RuO 2 = Li x RuO 2 , Li x RuO 2 + (1-x) Li = LiRuO 2 , and LiRuO 2 + 3Li = Ru + 2Li 2 O), yet provide little information regarding the cause of additional capacities in the low voltage region ( 〈 0.8 V). A comprehensive solid-state NMR characterization protocol has been developed to identify and quantify all the chemical phases formed over the whole electrochemical process. In particular, NMR results have shown that in the RuO 2 /Li system a major contribution to the extra capacity is due to the generation of LiOH and its subsequent reversible combination with extra Li to form Li 2 O and LiH (Figure). First-principles calculations have been employed to examine various mechanisms for additional Li storage in the RuO 2 /Li system. To generalize the findings from the RuO 2 /Li system, a similar study has been conducted on TiF 3 /Li batteries. This study shows that the additional capacity seen in TiF 3 /Li batteries is also mainly from the reversible formation of solid-electrolyte-interphase (SEI), likely catalyzed by Ti metal nanoparticles. In addition, the homogeneous distribution of transition metal nanoparticles within the LiF matrix facilitates reversible extraction of Li from LiF. This study illustrates the characterization of the source of additional capacities in metal oxide (RuO 2 ) and metal fluoride (TiF 3 ) conversion-type electrodes for LIBs and provides a comprehensive understanding of the chemical phases and the spatial distribution of these phases at the electrode and electrolyte interface. This study also demonstrates a solid-state NMR protocol with which to study the amorphous SEI that exists in essentially all battery systems. Figure. Schematic illustration of the source for additional capacities seen in RuO 2 electrodes for LIBs. References 1 Idota, Y., Kubota, T., Matsufuji, A., Maekawa, Y. & Miyasaka, T. Tin-based amorphous oxide: A high-capacity lithium-ion-storage material. Science 276, 1395-1397 (1997). 2 Beaulieu, L. Y., Larcher, D., Dunlap, R. A. & Dahn, J. R. Reaction of Li with grain-boundary atoms in nanostructured compounds. Journal of the Electrochemical Society 147, 3206-3212 (2000). 3 Laruelle, S. et al. On the origin of the extra electrochemical capacity displayed by MO/Li cells at low potential. Journal of the Electrochemical Society 149, A627-A634 (2002). 4 Balaya, P., Li, H., Kienle, L. & Maier, J. Fully reversible homogeneous and heterogeneous Li storage in RuO2 with high capacity. Advanced Functional Materials 13, 621-625 (2003). 5 Maier, J. Mass storage in space charge regions of nano-sized systems (Nano-ionics. Part V). Faraday Discussions 134, 51-66 (2007). 6 Zhukovskii, Y. F., Balaya, P., Kotomin, E. A. & Maier, J. Evidence for interfacial-storage anomaly in nanocomposites for lithium batteries from first-principles simulations. Physical Review Letters 96, 058302 (2006). 7 Hu, Y. Y. et al. Origin of additional capacities in metal oxide lithium-ion battery electrodes. Nature Materials 12, 1130-1136 (2013).
Type of Medium:
Online Resource
ISSN:
2151-2043
DOI:
10.1149/MA2014-04/4/662
Language:
Unknown
Publisher:
The Electrochemical Society
Publication Date:
2014
detail.hit.zdb_id:
2438749-6
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