skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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/AgxMn8O16 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 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 tomore » 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.« less

Authors:
 [1];  [2];  [1];  [3];  [3];  [3];  [1];  [3];  [4];  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Southeast Univ., Nanjing (China)
  3. Stony Brook Univ., NY (United States)
  4. Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1370520
Grant/Contract Number:  
SC0012673; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 8; Related Information: m2M partners with Stony Brook University (lead); Brookhaven National Laboratory; Columbia University; Georgia Institute of Technology; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute; University of California, Berkeley; University of North Carolina at Chapel Hill; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; silver hollandite; octahedral molecular sieve; oxygen defects; transmission electron microscopy; electron energy loss spectroscopy; lithium battery

Citation Formats

Wu, Lijun, Xu, Feng, Zhu, Yimei, Brady, Alexander B., Huang, Jianping, Durham, Jessica L., Dooryhee, Eric, Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J.. Structural Defects of Silver Hollandite, AgxMn8Oy, Nanorods: Dramatic Impact on Electrochemistry. United States: N. p., 2015. Web. https://doi.org/10.1021/acsnano.5b03274.
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.. Structural Defects of Silver Hollandite, AgxMn8Oy, Nanorods: Dramatic Impact on Electrochemistry. United States. https://doi.org/10.1021/acsnano.5b03274
Wu, Lijun, Xu, Feng, Zhu, Yimei, Brady, Alexander B., Huang, Jianping, Durham, Jessica L., Dooryhee, Eric, Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J.. Thu . "Structural Defects of Silver Hollandite, AgxMn8Oy, Nanorods: Dramatic Impact on Electrochemistry". United States. https://doi.org/10.1021/acsnano.5b03274. https://www.osti.gov/servlets/purl/1370520.
@article{osti_1370520,
title = {Structural Defects of Silver Hollandite, AgxMn8Oy, Nanorods: Dramatic Impact on Electrochemistry},
author = {Wu, Lijun and Xu, Feng and Zhu, Yimei and Brady, Alexander B. and Huang, Jianping and Durham, Jessica L. and Dooryhee, Eric and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J.},
abstractNote = {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/AgxMn8O16 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 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.},
doi = {10.1021/acsnano.5b03274},
journal = {ACS Nano},
number = 8,
volume = 9,
place = {United States},
year = {2015},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 30 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Effects of Cu 2+ Ions on the Structure and Reactivity of Todorokite- and Cryptomelane-Type Manganese Oxide Octahedral Molecular Sieves
journal, July 1999

  • Nicolas-Tolentino, Elaine; Tian, Zheng-Rong; Zhou, Hua
  • Chemistry of Materials, Vol. 11, Issue 7
  • DOI: 10.1021/cm9811040

Selective exchange of divalent transition metal ions in cryptomelane-type manganic acid with tunnel structure
journal, March 1993

  • Tsuji, Masamichi; Komarneni, Sridhar
  • Journal of Materials Research, Vol. 8, Issue 3
  • DOI: 10.1557/JMR.1993.0611

Synthesis and Characterization of Silver Hollandite and Its Application in Emission Control
journal, August 2005

  • Li, Liyu; King, David L.
  • Chemistry of Materials, Vol. 17, Issue 17
  • DOI: 10.1021/cm0506508

Sorption Behavior of Radionuclides on Crystalline Synthetic Tunnel Manganese Oxides
journal, December 2000

  • Dyer, Alan; Pillinger, Martyn; Newton, Jon
  • Chemistry of Materials, Vol. 12, Issue 12
  • DOI: 10.1021/cm001142v

Direct Sonochemical Synthesis of Manganese Octahedral Molecular Sieve (OMS-2) Nanomaterials Using Cosolvent Systems, Their Characterization, and Catalytic Applications
journal, February 2012

  • Dharmarathna, Saminda; King’ondu, Cecil K.; Pedrick, Wyatt
  • Chemistry of Materials, Vol. 24, Issue 4
  • DOI: 10.1021/cm203366m

Microwave-Assisted Hydrothermal Synthesis of Cryptomelane-Type Octahedral Molecular Sieves (OMS-2) and Their Catalytic Studies
journal, June 2010

  • Huang, Hui; Sithambaram, Shanthakumar; Chen, Chun-Hu
  • Chemistry of Materials, Vol. 22, Issue 12
  • DOI: 10.1021/cm100220g

Synthetic Routes to Microporous Manganese Oxides
journal, October 1997


The structure of K 1.33 Mn 8 O 16 and cation ordering in hollandite-type structures
journal, April 1986

  • Vicat, J.; Fanchon, E.; Strobel, P.
  • Acta Crystallographica Section B Structural Science, Vol. 42, Issue 2
  • DOI: 10.1107/S0108768186098415

Structural, Magnetic and Electronic Transport Properties of Novel Hollandite-Type Molybdenum Oxide, Rb 1.5 Mo 8 O 16
journal, January 2006

  • Ozawa, Takashi; Suzuki, Isao; Sato, Hirohiko
  • Journal of the Physical Society of Japan, Vol. 75, Issue 1
  • DOI: 10.1143/JPSJ.75.014802

A Review of Porous Manganese Oxide Materials
journal, October 1998

  • Brock, Stephanie L.; Duan, Niangao; Tian, Zheng Rong
  • Chemistry of Materials, Vol. 10, Issue 10
  • DOI: 10.1021/cm980227h

Ag1.8Mn8O16: Square Planar Coordinated Ag⊕ Ions in the Channels of a Novel Hollandite Variant
journal, November 1984

  • Chang, Fung Ming; Jansen, Martin
  • Angewandte Chemie International Edition in English, Vol. 23, Issue 11
  • DOI: 10.1002/anie.198409061

Synthesis and Characterization of Ag−Hollandite Nanofibers and Its Catalytic Application in Ethanol Oxidation
journal, August 2007

  • Chen, Junli; Tang, Xingfu; Liu, Junlong
  • Chemistry of Materials, Vol. 19, Issue 17
  • DOI: 10.1021/cm070904k

Large-scale synthesis of Ag1.8Mn8O16 nanorods and their electrochemical lithium-storage properties
journal, January 2011

  • Sun, Yongming; Hu, Xianluo; Zhang, Wuxing
  • Journal of Nanoparticle Research, Vol. 13, Issue 8
  • DOI: 10.1007/s11051-010-0209-7

Synthesis and Electrochemistry of Silver Hollandite
journal, January 2010

  • Zhu, Shali; Marschilok, Amy C.; Lee, Chia-Ying
  • Electrochemical and Solid-State Letters, Vol. 13, Issue 8
  • DOI: 10.1149/1.3428747

Synthetic Control of Composition and Crystallite Size of Silver Hollandite, Ag x Mn 8 O 16 : Impact on Electrochemistry
journal, September 2012

  • Takeuchi, Kenneth J.; Yau, Shali Z.; Menard, Melissa C.
  • ACS Applied Materials & Interfaces, Vol. 4, Issue 10
  • DOI: 10.1021/am301443g

The Electrochemistry of Silver Hollandite Nanorods, Ag x Mn 8 O 16 : Enhancement of Electrochemical Battery Performance via Dimensional and Compositional Control
journal, January 2013

  • Takeuchi, Kenneth J.; Yau, Shali Z.; Subramanian, Aditya
  • Journal of The Electrochemical Society, Vol. 160, Issue 5
  • DOI: 10.1149/2.014305jes

Hollandites as a new class of multiferroics
journal, August 2014

  • Liu, Shuangyi; Akbashev, Andrew R.; Yang, Xiaohao
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06203

Electrochemical performance and ex situ analysis of ZnMn2O4 nanowires as anode materials for lithium rechargeable batteries
journal, February 2011


Microstructural Features of α-MnO[sub 2] Electrodes for Lithium Batteries
journal, January 1998

  • Shao-Horn, Y.
  • Journal of The Electrochemical Society, Vol. 145, Issue 2
  • DOI: 10.1149/1.1838307

Frame Stability of Tunnel-Structured Cryptomelane Nanofibers: The Role of Tunnel Cations
journal, July 2013


Extraction of EELS white-line intensities of manganese compounds: Methods, accuracy, and valence sensitivity
journal, March 2006


Alkali Metal Ions Insertion/Extraction Reactions with Hollandite-Type Manganese Oxide in the Aqueous Phase
journal, January 1995

  • Feng, Qi; Kanoh, Hirofumi; Miyai, Yoshitaka
  • Chemistry of Materials, Vol. 7, Issue 1
  • DOI: 10.1021/cm00049a023

ESCA and thermodynamic studies of alkali metal ion exchange reactions on an α-MnO2 phase with the tunnel structure
journal, January 2000

  • Tanaka, Y.; Tsuji, M.; Tamaura, Y.
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 7
  • DOI: 10.1039/a907614j

Large-Scale Synthesis of Silver Manganese Oxide Nanofibers and Their Oxygen Reduction Properties
journal, November 2013

  • Huang, Hui; Meng, Yongtao; Labonte, Alec
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp409507h

Structure, porosity, and redox in porous manganese oxide octahedral layer and molecular sieve materials
journal, January 2008

  • Suib, Steven L.
  • Journal of Materials Chemistry, Vol. 18, Issue 14
  • DOI: 10.1039/b714966m

White lines and d -electron occupancies for the 3 d and 4 d transition metals
journal, April 1993


Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


Unit-cell refinement from powder diffraction scans
journal, December 1981


R factors in Rietveld analysis: How good is good enough?
journal, March 2006


    Works referencing / citing this record:

    Suppressing Manganese Dissolution in Potassium Manganate with Rich Oxygen Defects Engaged High‐Energy‐Density and Durable Aqueous Zinc‐Ion Battery
    journal, February 2019

    • Fang, Guozhao; Zhu, Chuyu; Chen, Minghui
    • Advanced Functional Materials, Vol. 29, Issue 15
    • DOI: 10.1002/adfm.201808375

    Manganese-Oxide-Based Electrode Materials for Energy Storage Applications: How Close Are We to the Theoretical Capacitance?
    journal, August 2018


    Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries
    journal, July 2016

    • Qiu, Bao; Zhang, Minghao; Wu, Lijun
    • Nature Communications, Vol. 7, Issue 1
    • DOI: 10.1038/ncomms12108

    Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods
    journal, May 2017

    • Xu, Feng; Wu, Lijun; Meng, Qingping
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms15400

    Interlinked multiphase Fe-doped MnO 2 nanostructures: a novel design for enhanced pseudocapacitive performance
    journal, January 2016


    Synthesis of cryptomelane type α-MnO 2 (K x Mn 8 O 16 ) cathode materials with tunable K + content: the role of tunnel cation concentration on electrochemistry
    journal, January 2017

    • Poyraz, Altug S.; Huang, Jianping; Pelliccione, Christopher J.
    • Journal of Materials Chemistry A, Vol. 5, Issue 32
    • DOI: 10.1039/c7ta03476h

    Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches
    journal, December 2017


    Interface reconstruction with emerging charge ordering in hexagonal manganite
    journal, May 2018


    Capacity Retention for (De)lithiation of Silver Containing α-MnO 2 : Impact of Structural Distortion and Transition Metal Dissolution
    journal, January 2018

    • Huang, Jianping; Housel, Lisa M.; Quilty, Calvin D.
    • Journal of The Electrochemical Society, Vol. 165, Issue 11
    • DOI: 10.1149/2.0371811jes

    Synthesis and Characterization of 2 × 4 Tunnel Structured Manganese Dioxides as Cathodes in Rechargeable Li, Na, and Mg Batteries
    journal, January 2019

    • Poyraz, Altug S.; Quilty, Calvin D.; Housel, Lisa M.
    • Journal of The Electrochemical Society, Vol. 166, Issue 4
    • DOI: 10.1149/2.1341902jes