DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach

Abstract

Alpha-MnO2 is an attractive cathode candidate for sodium-ion batteries attributed to its unique one-dimensional 2×2 tunnels for facile sodium-ion diffusion, in addition to its incomparable cost advantage. In particular, α-MnO2 shows superior rate capability with silver stabilizing ions at the center of tunnels that improve electrical conductivity. In this work, we directly compare structural transformation of silver-containing α-MnO2 nanorods (Ag1.22Mn8O16-x or L-Ag-HOL and Ag1.66Mn8O16-y or H–Ag-HOL), containing higher and lower concentrations of oxygen vacancies respectively, by transmission electron microscopy (TEM). The elaborate comparative and statistical TEM studies eliminate concerns regarding generalization errors and facilitate rational structural development of nanorods with improved functionality. It is found that sodium ions favorably diffuse through the area where oxygen vacancies are concentrated, and the samples with more silver ions and fewer oxygen vacancies (H–Ag-HOL) show more significant structural deformation with more inhomogeneous sodiation. The difference in functional electrochemistry coupled with the observed difference in inter- and intra-nanorod inhomogeneous structural evolution emphasizes the significance of the uniform electrical conductivity of the electrode. This work helps to improve the α-MnO2 electrode material for sodium-ion batteries as well as suggesting the importance of delicate statistical approaches for TEM investigations.

Authors:
 [1];  [2];  [2];  [3];  [4];  [5];  [3];  [6]; ORCiD logo [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Seoul National Univ., Seoul (Korea, Republic of)
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Stony Brook Univ., NY (United States). Dept. of Chemistry, and Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Stony Brook Univ., NY (United States). Dept. of Chemistry, and Dept. of Materials Science and Chemical Engineering
  6. Seoul National Univ., Seoul (Korea, Republic of)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566823
Alternate Identifier(s):
OSTI ID: 1778392
Report Number(s):
BNL-212113-2019-JAAM
Journal ID: ISSN 0378-7753
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 435; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 25 ENERGY STORAGE; Sodium ion battery; Manganese oxide; Transmission electron microscopy; Electrochemical reaction mechanism

Citation Formats

Lee, Seung-Yong, Housel, Lisa M., Huang, Jianping, Wu, Lijun, Takeuchi, Esther S., Marschilok, Amy C., Takeuchi, Kenneth J., Kim, Miyoung, and Zhu, Yimei. Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach. United States: N. p., 2019. Web. doi:10.1016/j.jpowsour.2019.226779.
Lee, Seung-Yong, Housel, Lisa M., Huang, Jianping, Wu, Lijun, Takeuchi, Esther S., Marschilok, Amy C., Takeuchi, Kenneth J., Kim, Miyoung, & Zhu, Yimei. Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach. United States. https://doi.org/10.1016/j.jpowsour.2019.226779
Lee, Seung-Yong, Housel, Lisa M., Huang, Jianping, Wu, Lijun, Takeuchi, Esther S., Marschilok, Amy C., Takeuchi, Kenneth J., Kim, Miyoung, and Zhu, Yimei. Thu . "Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach". United States. https://doi.org/10.1016/j.jpowsour.2019.226779. https://www.osti.gov/servlets/purl/1566823.
@article{osti_1566823,
title = {Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach},
author = {Lee, Seung-Yong and Housel, Lisa M. and Huang, Jianping and Wu, Lijun and Takeuchi, Esther S. and Marschilok, Amy C. and Takeuchi, Kenneth J. and Kim, Miyoung and Zhu, Yimei},
abstractNote = {Alpha-MnO2 is an attractive cathode candidate for sodium-ion batteries attributed to its unique one-dimensional 2×2 tunnels for facile sodium-ion diffusion, in addition to its incomparable cost advantage. In particular, α-MnO2 shows superior rate capability with silver stabilizing ions at the center of tunnels that improve electrical conductivity. In this work, we directly compare structural transformation of silver-containing α-MnO2 nanorods (Ag1.22Mn8O16-x or L-Ag-HOL and Ag1.66Mn8O16-y or H–Ag-HOL), containing higher and lower concentrations of oxygen vacancies respectively, by transmission electron microscopy (TEM). The elaborate comparative and statistical TEM studies eliminate concerns regarding generalization errors and facilitate rational structural development of nanorods with improved functionality. It is found that sodium ions favorably diffuse through the area where oxygen vacancies are concentrated, and the samples with more silver ions and fewer oxygen vacancies (H–Ag-HOL) show more significant structural deformation with more inhomogeneous sodiation. The difference in functional electrochemistry coupled with the observed difference in inter- and intra-nanorod inhomogeneous structural evolution emphasizes the significance of the uniform electrical conductivity of the electrode. This work helps to improve the α-MnO2 electrode material for sodium-ion batteries as well as suggesting the importance of delicate statistical approaches for TEM investigations.},
doi = {10.1016/j.jpowsour.2019.226779},
journal = {Journal of Power Sources},
number = C,
volume = 435,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Sodium-Ion Batteries
journal, May 2012

  • Slater, Michael D.; Kim, Donghan; Lee, Eungje
  • Advanced Functional Materials, Vol. 23, Issue 8, p. 947-958
  • DOI: 10.1002/adfm.201200691

Review—Practical Issues and Future Perspective for Na-Ion Batteries
journal, January 2015

  • Kubota, Kei; Komaba, Shinichi
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0151514jes

A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries
journal, September 2015


The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015

  • Kundu, Dipan; Talaie, Elahe; Duffort, Victor
  • Angewandte Chemie International Edition, Vol. 54, Issue 11
  • DOI: 10.1002/anie.201410376

Carbon Quantum Dots and Their Derivative 3D Porous Carbon Frameworks for Sodium-Ion Batteries with Ultralong Cycle Life
journal, October 2015

  • Hou, Hongshuai; Banks, Craig E.; Jing, Mingjun
  • Advanced Materials, Vol. 27, Issue 47
  • DOI: 10.1002/adma.201503816

Hierarchical Hollow-Microsphere Metal-Selenide@Carbon Composites with Rational Surface Engineering for Advanced Sodium Storage
journal, November 2018


Electrochemistry of Hollandite α-MnO 2 : Li-Ion and Na-Ion Insertion and Li 2 O Incorporation
journal, June 2013

  • Tompsett, David A.; Islam, M. Saiful
  • Chemistry of Materials, Vol. 25, Issue 12
  • DOI: 10.1021/cm400864n

Silver-Containing α-MnO 2 Nanorods: Electrochemistry in Na-Based Battery Systems
journal, September 2016

  • Huang, Jianping; Poyraz, Altug S.; Lee, Seung-Yong
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 5
  • DOI: 10.1021/acsami.6b08549

α-MnO2 as a cathode material for rechargeable Mg batteries
journal, September 2012


Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery
journal, December 2011

  • Xu, Chengjun; Li, Baohua; Du, Hongda
  • Angewandte Chemie International Edition, Vol. 51, Issue 4
  • DOI: 10.1002/anie.201106307

Unveiling the Structural Evolution of Ag 1.2 Mn 8 O 16 under Coulombically Controlled (De)Lithiation
journal, January 2018


Investigation of α-MnO 2 Tunneled Structures as Model Cation Hosts for Energy Storage
journal, February 2018


Probing the Release and Uptake of Water in α-MnO 2 · x H 2 O
journal, February 2017


Development and utility of manganese oxides as cathodes in lithium batteries
journal, March 2007


Asynchronous Crystal Cell Expansion during Lithiation of K + -Stabilized α-MnO 2
journal, April 2015

  • Yuan, Yifei; Nie, Anmin; Odegard, Gregory M.
  • Nano Letters, Vol. 15, Issue 5
  • DOI: 10.1021/nl5048913

Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry
journal, January 2017

  • Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.0911709jes

The Effect of Silver Ion Occupancy on Hollandite Lattice Structure
journal, January 2018

  • Brady, Alexander B.; Huang, Jianping; Durham, Jessica L.
  • MRS Advances, Vol. 3, Issue 10
  • DOI: 10.1557/adv.2018.238

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

Deliberately Designed Atomic-Level Silver-Containing Interface Results in Improved Rate Capability and Utilization of Silver Hollandite for Lithium-Ion Storage
journal, December 2017

  • Smith, Paul F.; Brady, Alexander B.; Lee, Seung-Yong
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 1
  • DOI: 10.1021/acsami.7b12307

Structural Defects of Silver Hollandite, Ag x Mn 8 O y , Nanorods: Dramatic Impact on Electrochemistry
journal, July 2015


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

Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry
journal, January 2017

  • Durham, Jessica L.; Huang, Jianping; Zhang, Bingjie
  • Journal of The Electrochemical Society, Vol. 164, Issue 14
  • DOI: 10.1149/2.1371714jes

Tracking inhomogeneity in high-capacity lithium iron phosphate batteries
journal, February 2015


Understanding Inhomogeneous Reactions in Li-Ion Batteries: Operando Synchrotron X-Ray Diffraction on Two-Layer Electrodes
journal, May 2015

  • Sasaki, Tsuyoshi; Villevieille, Claire; Takeuchi, Yoji
  • Advanced Science, Vol. 2, Issue 7
  • DOI: 10.1002/advs.201500083

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

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

Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy
journal, October 2017

  • Lee, Seung-Yong; Wu, Lijun; Poyraz, Altug S.
  • Advanced Materials, Vol. 29, Issue 43
  • DOI: 10.1002/adma.201703186

Determination of manganese oxidation states in solids by electron energy-loss spectroscopy
journal, January 1987


Electron-energy-loss core-edge structures in manganese oxides
journal, July 1993


High-resolution parallel electron energy-loss spectroscopy of Mn L2,3-edges in inorganic manganese compounds
journal, August 1994

  • Garvie, L. A. J.; Craven, A. J.
  • Physics and Chemistry of Minerals, Vol. 21, Issue 4
  • DOI: 10.1007/BF00202132

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