Structural Defects of Silver Hollandite, AgxMn8Oy, Nanorods: Dramatic Impact on Electrochemistry

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• 作者：Lijun Wu ; Feng Xu ; Yimei Zhu ; Alexander B. Brady ; Jianping Huang ; Jessica L. Durham ; Eric Dooryhee ; Amy C. Marschilok ; Esther S. Takeuchi ; Kenneth J. Takeuchi
• 刊名：ACS Nano
• 出版年：2015
• 出版时间：August 25, 2015
• 年：2015
• 卷：9
• 期：8
• 页码：8430-8439
• 全文大小：732K
• ISSN：1936-086X

文摘

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/Ag_xMn₈O₁₆ electrochemical cells (160 versus 23 mAh/g) observed upon a seemingly small change in silver content (x 鈭?.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 Mn^3.7+ for H-Ag-OMS-2 and Mn^3.5+ 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.