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

Title: Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

Abstract

Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg0.2MnO2·0.5H2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity of 158 mA h g-1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g-1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g-1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires inmore » Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na+ ion intercalation.« less

Authors:
 [1];  [1];  [2];  [2];  [1]
  1. Drexel Univ., Philadelphia, PA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1265902
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
RSC Advances
Additional Journal Information:
Journal Volume: 5; Journal Issue: 128; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Byles, B. W., West, P., Cullen, D. A., More, K. L., and Pomerantseva, E. Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries. United States: N. p., 2015. Web. doi:10.1039/C5RA20624C.
Byles, B. W., West, P., Cullen, D. A., More, K. L., & Pomerantseva, E. Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries. United States. https://doi.org/10.1039/C5RA20624C
Byles, B. W., West, P., Cullen, D. A., More, K. L., and Pomerantseva, E. Thu . "Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries". United States. https://doi.org/10.1039/C5RA20624C. https://www.osti.gov/servlets/purl/1265902.
@article{osti_1265902,
title = {Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries},
author = {Byles, B. W. and West, P. and Cullen, D. A. and More, K. L. and Pomerantseva, E.},
abstractNote = {Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg0.2MnO2·0.5H2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity of 158 mA h g-1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g-1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g-1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na+ ion intercalation.},
doi = {10.1039/C5RA20624C},
journal = {RSC Advances},
number = 128,
volume = 5,
place = {United States},
year = {Thu Dec 03 00:00:00 EST 2015},
month = {Thu Dec 03 00:00:00 EST 2015}
}

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

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries
journal, January 2015

  • Han, Man Huon; Gonzalo, Elena; Singh, Gurpreet
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE03192J

Magnesium Manganese Oxide Nanoribbons:  Synthesis, Characterization, and Catalytic Application
journal, September 2002

  • Liu, Jia; Cai, Jun; Son, Young-Chan
  • The Journal of Physical Chemistry B, Vol. 106, Issue 38
  • DOI: 10.1021/jp0208586

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

Manganese Oxide Octahedral Molecular Sieves: Preparation, Characterization, and Applications
journal, April 1993


Hydrated vanadium pentoxide with superior sodium storage capacity
journal, January 2015

  • Wei, Qiulong; Liu, Jin; Feng, Wei
  • Journal of Materials Chemistry A, Vol. 3, Issue 15
  • DOI: 10.1039/C5TA00502G

Manganese oxides for lithium batteries
journal, January 1997


Todorokite as a Li Insertion Cathode
journal, January 1998

  • Duncan, M. J.
  • Journal of The Electrochemical Society, Vol. 145, Issue 11
  • DOI: 10.1149/1.1838869

Investigations of lithium manganese oxide materials for lithium-ion batteries
journal, March 1997


Nanostructured manganese dioxides: Synthesis and properties as supercapacitor electrode materials
journal, January 2009


Critical Role of Crystal Water for a Layered Cathode Material in Sodium Ion Batteries
journal, May 2015


K 0.25 Mn 2 O 4 nanofiber microclusters as high power cathode materials for rechargeable lithium batteries
journal, January 2012

  • Zhang, Chaofeng; Feng, Chuanqi; Zhang, Peng
  • RSC Adv., Vol. 2, Issue 4
  • DOI: 10.1039/C1RA00510C

Todorokite-type MnO2 as a zinc-ion intercalating material
journal, December 2013


Synthesis of metal-doped todorokite-type MnO2 and its cathode characteristics for rechargeable lithium batteries
journal, August 2005


Structural and electrochemical studies of α-manganese dioxide (α-MnO2)
journal, October 1997


β-MnO2 nanorods with exposed tunnel structures as high-performance cathode materials for sodium-ion batteries
journal, November 2013

  • Su, Dawei; Ahn, Hyo-Jun; Wang, Guoxiu
  • NPG Asia Materials, Vol. 5, Issue 11
  • DOI: 10.1038/am.2013.56

Metal ion extraction/insertion reactions with todorokite-type manganese oxide in the aqueous phase
journal, September 1995

  • Feng, Qi; Kanoh, Hirofumi; Miyai, Yoshitaka
  • Chemistry of Materials, Vol. 7, Issue 9
  • DOI: 10.1021/cm00057a023

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

Activation of a MnO 2 cathode by water-stimulated Mg 2+ insertion for a magnesium ion battery
journal, January 2015

  • Song, Jaehee; Noked, Malakhi; Gillette, Eleanor
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 7
  • DOI: 10.1039/C4CP05591H

Preparation of todorokite-type manganese-based oxide and its application as lithium and magnesium rechargeable battery cathode
journal, July 2001


Synchrotron X-ray diffraction study of the structure and dehydration behavior of todorokite
journal, January 2003

  • Post, Jeffrey E.; Heaney, Peter J.; Hanson, Jonathan
  • American Mineralogist, Vol. 88, Issue 1
  • DOI: 10.2138/am-2003-0117

The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries
journal, May 2015


Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries
journal, May 2012

  • Kim, Sung-Wook; Seo, Dong-Hwa; Ma, Xiaohua
  • Advanced Energy Materials, Vol. 2, Issue 7, p. 710-721
  • DOI: 10.1002/aenm.201200026

Hydrothermal synthesis of α-MnO2 and β-MnO2 nanorods as high capacity cathode materials for sodium ion batteries
journal, January 2013

  • Su, Dawei; Ahn, Hyo-Jun; Wang, Guoxiu
  • Journal of Materials Chemistry A, Vol. 1, Issue 15
  • DOI: 10.1039/c3ta00031a

High power Na-ion rechargeable battery with single-crystalline Na0.44MnO2 nanowire electrode
journal, November 2012


Research Development on Sodium-Ion Batteries
journal, October 2014

  • Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500192f

Works referencing / citing this record:

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

The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries
journal, April 2016

  • Byles, B. W.; Palapati, N. K. R.; Subramanian, A.
  • APL Materials, Vol. 4, Issue 4
  • DOI: 10.1063/1.4948272

Brittle fracture to recoverable plasticity: Polytypism-dependent nanomechanics in todorokite-like nanobelts
text, January 2021

  • Shikder, MR Amin; Maksud, M.; Vasudevamurthy, G.
  • University of Illinois at Chicago
  • DOI: 10.25417/uic.14910282

Brittle fracture to recoverable plasticity: Polytypism-dependent nanomechanics in todorokite-like nanobelts
text, January 2021