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 »
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M); Brookhaven National Laboratory (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. doi: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}
}
Web of Science
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
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
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
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
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
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
Synthetic Routes to Microporous Manganese Oxides
journal, October 1997
- Ching, Stanton; Suib, Steven L.
- Comments on Inorganic Chemistry, Vol. 19, Issue 5
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
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
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
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
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
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
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
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
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
Hollandites as a new class of multiferroics
journal, August 2014
- Liu, Shuangyi; Akbashev, Andrew R.; Yang, Xiaohao
- Scientific Reports, Vol. 4, Issue 1
Electrochemical performance and ex situ analysis of ZnMn2O4 nanowires as anode materials for lithium rechargeable batteries
journal, February 2011
- Kim, Sung-Wook; Lee, Hyun-Wook; Muralidharan, Pandurangan
- Nano Research, Vol. 4, Issue 5
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
Frame Stability of Tunnel-Structured Cryptomelane Nanofibers: The Role of Tunnel Cations
journal, July 2013
- Gao, Tao; Norby, Poul
- European Journal of Inorganic Chemistry
Extraction of EELS white-line intensities of manganese compounds: Methods, accuracy, and valence sensitivity
journal, March 2006
- Riedl, T.; Gemming, T.; Wetzig, K.
- Ultramicroscopy, Vol. 106, Issue 4-5
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
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
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
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
White lines and d -electron occupancies for the 3 d and 4 d transition metals
journal, April 1993
- Pearson, D. H.; Ahn, C. C.; Fultz, B.
- Physical Review B, Vol. 47, Issue 14
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
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
Unit-cell refinement from powder diffraction scans
journal, December 1981
- Pawley, G. S.
- Journal of Applied Crystallography, Vol. 14, Issue 6
R factors in Rietveld analysis: How good is good enough?
journal, March 2006
- Toby, Brian H.
- Powder Diffraction, Vol. 21, Issue 1
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
Manganese-Oxide-Based Electrode Materials for Energy Storage Applications: How Close Are We to the Theoretical Capacitance?
journal, August 2018
- Hu, Yating; Wu, Yue; Wang, John
- Advanced Materials, Vol. 30, Issue 47
Synthesis of Silver Hollandite Nanorectangular Cuboids as Negative Electrode Material for High-Performance Asymmetric Supercapacitors and Lithium-Ion Capacitors
journal, October 2018
- Nagamuthu, Sadayappan; Ryu, Kwang-Sun
- Batteries & Supercaps, Vol. 2, Issue 1
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
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
A-site compositional effects in Ga-doped hollandite materials of the form BaxCsyGa2x+yTi8−2x−yO16: implications for Cs immobilization in crystalline ceramic waste forms
journal, June 2016
- Xu, Yun; Wen, Yi; Grote, Rob
- Scientific Reports, Vol. 6, Issue 1
Interlinked multiphase Fe-doped MnO 2 nanostructures: a novel design for enhanced pseudocapacitive performance
journal, January 2016
- Wang, Ziya; Wang, Fengping; Li, Yan
- Nanoscale, Vol. 8, Issue 13
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
Charge localization and ordering in hollandite group oxides: Impact of density functional theory approaches
journal, December 2017
- Kaltak, Merzuk; Fernández-Serra, Marivi; Hybertsen, Mark S.
- Physical Review Materials, Vol. 1, Issue 7
Interface reconstruction with emerging charge ordering in hexagonal manganite
journal, May 2018
- Cheng, Shaobo; Xu, Changsong; Deng, Shiqing
- Science Advances, Vol. 4, Issue 5
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
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
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
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
A-site compositional effects in Ga-doped hollandite materials of the form BaxCsyGa2x+yTi8−2x−yO16: implications for Cs immobilization in crystalline ceramic waste forms
journal, June 2016
- Xu, Yun; Wen, Yi; Grote, Rob
- Scientific Reports, Vol. 6, Issue 1
Interface reconstruction with emerging charge ordering in hexagonal manganite
journal, May 2018
- Cheng, Shaobo; Xu, Changsong; Deng, Shiqing
- Science Advances, Vol. 4, Issue 5