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

Wu, Lijun; Xu, Feng; Zhu, Yimei; Brady, Alexander B.; Huang, Jianping; Durham, Jessica L.; Dooryhee, Eric; Marschilok, Amy C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.

doi:10.1021/acsnano.5b03274

Structural Defects of Silver Hollandite, Ag_xMn₈Oy, Nanorods: Dramatic Impact on Electrochemistry

Journal Article · Thu Jul 16 00:00:00 EDT 2015 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5b03274· OSTI ID:1370520

Wu, Lijun ^[1]; Xu, Feng ^[2]; Zhu, Yimei ^[1]; Brady, Alexander B. ^[3]; Huang, Jianping ^[3]; Durham, Jessica L. ^[3]; Dooryhee, Eric ^[1]; Marschilok, Amy C. ^[3]; Takeuchi, Esther S. ^[4]; Takeuchi, Kenneth J. ^[3]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Southeast Univ., Nanjing (China)
Stony Brook Univ., NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Hollandites (OMS-2) are an enticing 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 ~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. In this work, 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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 1370520

Alternate ID(s):: OSTI ID: 1229385

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 8 Vol. 9; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

25 ENERGY STORAGE
electron energy loss spectroscopy
lithium battery
octahedral molecular sieve
oxygen defects
silver hollandite
transmission electron microscopy