期刊
ACS NANO
卷 9, 期 8, 页码 8430-8439出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.5b03274
关键词
silver hollandite; octahedral molecular sieve; oxygen defects; transmission electron microscopy; electron energy loss spectroscopy; lithium battery
类别
资金
- Center for Mesoscale Transport Properties, an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012673]
- U.S. Department of Energy, Office of Basic Energy Science, Division of Materials Science and Engineering [DE-SC0012704]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0012704]
Hollandites (OMS-2) are an intriguing class of sorbents, catalysts, and energy storage materials with a tunnel structure permitting one-dimensional insertion and deinsertion of ions and small molecules along the c direction. A 7-fold increase in delivered capacity for Li/AgxMn8O16 electrochemical cells (160 versus 23 mAh/g) observed upon a seemingly small change in silver content (x similar to 1.1 (L-Ag-OMS-2) and 1.6 (H-Ag-OMS-2)) led us to characterize the structure and defects of the silver hollandite material. Herein, Ag hollandite nanorods are studied through the combined use of local (atomic imaging, electron diffraction, electron energy-loss spectroscopy) and bulk (synchrotron based X-ray diffraction, thermogravimetric analysis) techniques. Selected area diffraction and high resolution transmission electron microscopy show a structure consistent with that refined by XRD; however, the Ag occupancy varies significantly even within neighboring channels. Both local and bulk measurements indicate a greater quantity of oxygen vacancies in L-Ag-OMS-2, resulting in lower average Mn valence relative to H-Ag-OMS-2. Electron energy loss spectroscopy shows a lower Mn oxidation state on the surface relative to the interior of the nanorods, where the average Mn valence is approximately Mn3.7+ for H-Ag-OMS-2 and Mn3.5+ for L-Ag-OMS-2 nanorods, respectively. The higher delivered capacity of L-Ag-OMS-2 may be related to more oxygen vacancies compared to H-Ag-OMS-2. Thus, the oxygen vacancies and MnO6 octahedra distortion are assumed to open the MnO6 octahedra walls, facilitating Li diffusion in the ab plane. These results indicate crystallite size and surface defects are significant factors affecting battery performance.
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