Potassium-Containing α-MnO2 Nanotubes: The Impact of Hollow Regions on Electrochemistry
Abstract
α-MnO2 type materials have been studied as electrode materials in rechargeable batteries and electrocatalysts due to their 2 × 2 tunneled crystal structures capable of accommodating cations and their tunable physiochemical properties. In this study, we deliberately synthesized K+ containing α-MnO2 (K0.9Mn8O16) hollow nanotubes varying the dimensions of the hollow regions and level of surface defects. The K0.9Mn8O16 nanotube material samples have similar crystallinity, thermal stability, and average Mn oxidation state. Oxygen surface defects in the hollow regions were revealed through detailed studies using electron energy loss spectroscopy. The impact of the hollow regions and associated surface defects on the electrochemistry of KxMn8O16 were investigated using cyclic voltammetry, galvanostatic intermittent titration technique, and galvanostatic cycling. The K0.9Mn8O16 nanotubes with a large hollow region (~30 nm) and higher level of surface defects show higher apparent lithium ion diffusion coefficients and lower polarization compared to the nanotubes with a small hollow region (~10 nm). In-situ lithiation demonstrated that the dimensions of the nanotube walls expanded, but the hollow region did not change in size as result of lithiation. Furthermore, this research demonstrates that tuning particle architecture and surface defects can positively impact functional behavior of electrochemical storage materials.
- Authors:
-
[2];
[2];
[4];
[4];
[4]
- Stony Brook Univ., NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1825734
- Report Number(s):
- BNL-222255-2021-JAAM
Journal ID: ISSN 0013-4651
- Grant/Contract Number:
- SC0012704; AC02-06CH11357; AC02-98CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 168; Journal Issue: 9; Journal ID: ISSN 0013-4651
- Publisher:
- IOP Publishing
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Huang, Jianping, Yan, Shan, Wu, Daren, Housel, Lisa, Hu, Xiaobing, Hwang, Sooyeon, Wang, Lei, Tong, Xiao, Wu, Lijun, Zhu, Yimei, Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J. Potassium-Containing α-MnO2 Nanotubes: The Impact of Hollow Regions on Electrochemistry. United States: N. p., 2021.
Web. doi:10.1149/1945-7111/ac275e.
Huang, Jianping, Yan, Shan, Wu, Daren, Housel, Lisa, Hu, Xiaobing, Hwang, Sooyeon, Wang, Lei, Tong, Xiao, Wu, Lijun, Zhu, Yimei, Marschilok, Amy C., Takeuchi, Esther S., & Takeuchi, Kenneth J. Potassium-Containing α-MnO2 Nanotubes: The Impact of Hollow Regions on Electrochemistry. United States. https://doi.org/10.1149/1945-7111/ac275e
Huang, Jianping, Yan, Shan, Wu, Daren, Housel, Lisa, Hu, Xiaobing, Hwang, Sooyeon, Wang, Lei, Tong, Xiao, Wu, Lijun, Zhu, Yimei, Marschilok, Amy C., Takeuchi, Esther S., and Takeuchi, Kenneth J. Mon .
"Potassium-Containing α-MnO2 Nanotubes: The Impact of Hollow Regions on Electrochemistry". United States. https://doi.org/10.1149/1945-7111/ac275e. https://www.osti.gov/servlets/purl/1825734.
@article{osti_1825734,
title = {Potassium-Containing α-MnO2 Nanotubes: The Impact of Hollow Regions on Electrochemistry},
author = {Huang, Jianping and Yan, Shan and Wu, Daren and Housel, Lisa and Hu, Xiaobing and Hwang, Sooyeon and Wang, Lei and Tong, Xiao and Wu, Lijun and Zhu, Yimei and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J.},
abstractNote = {α-MnO2 type materials have been studied as electrode materials in rechargeable batteries and electrocatalysts due to their 2 × 2 tunneled crystal structures capable of accommodating cations and their tunable physiochemical properties. In this study, we deliberately synthesized K+ containing α-MnO2 (K0.9Mn8O16) hollow nanotubes varying the dimensions of the hollow regions and level of surface defects. The K0.9Mn8O16 nanotube material samples have similar crystallinity, thermal stability, and average Mn oxidation state. Oxygen surface defects in the hollow regions were revealed through detailed studies using electron energy loss spectroscopy. The impact of the hollow regions and associated surface defects on the electrochemistry of KxMn8O16 were investigated using cyclic voltammetry, galvanostatic intermittent titration technique, and galvanostatic cycling. The K0.9Mn8O16 nanotubes with a large hollow region (~30 nm) and higher level of surface defects show higher apparent lithium ion diffusion coefficients and lower polarization compared to the nanotubes with a small hollow region (~10 nm). In-situ lithiation demonstrated that the dimensions of the nanotube walls expanded, but the hollow region did not change in size as result of lithiation. Furthermore, this research demonstrates that tuning particle architecture and surface defects can positively impact functional behavior of electrochemical storage materials.},
doi = {10.1149/1945-7111/ac275e},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 168,
place = {United States},
year = {Mon Sep 27 00:00:00 EDT 2021},
month = {Mon Sep 27 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
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
Potassium-Based α-Manganese Dioxide Nanofiber Binder-Free Self-Supporting Electrodes: A Design Strategy for High Energy Density Batteries
journal, May 2016
- Poyraz, Altug S.; Huang, Jianping; Wu, Lijun
- Energy Technology, Vol. 4, Issue 11
Co 3 O 4 Polyhedron@MnO 2 Nanotube Composite as Anode for High‐Performance Lithium‐Ion Batteries
journal, March 2021
- Cao, Zhiguang; Yang, Yuebei; Qin, Junling
- Small, Vol. 17, Issue 19
Superior-Performance Aqueous Zinc-Ion Batteries Based on the In Situ Growth of MnO 2 Nanosheets on V 2 CT X MXene
journal, January 2021
- Zhu, Xiaodong; Cao, Ziyi; Wang, Wenjie
- ACS Nano, Vol. 15, Issue 2
ATHENA and ARTEMIS Interactive Graphical Data Analysisusing IFEFFIT
journal, January 2005
- Ravel, B.; Newville, M.
- Physica Scripta
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
Synthesis of Single-Crystal Tetragonal α-MnO 2 Nanotubes
journal, August 2008
- Luo, J.; Zhu, H. T.; Fan, H. M.
- The Journal of Physical Chemistry C, Vol. 112, Issue 33
Structural Defects of Silver Hollandite, Ag x Mn 8 O y , Nanorods: Dramatic Impact on Electrochemistry
journal, July 2015
- Wu, Lijun; Xu, Feng; Zhu, Yimei
- ACS Nano, Vol. 9, Issue 8
MnO 2 ‐Based Materials for Environmental Applications
journal, January 2021
- Yang, Ruijie; Fan, Yingying; Ye, Ruquan
- Advanced Materials, Vol. 33, Issue 9
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
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
Manganese dioxides as rechargeable magnesium battery cathode; synthetic approach to understand magnesiation process
journal, May 2015
- Zhang, Ruigang; Arthur, Timothy S.; Ling, Chen
- Journal of Power Sources, Vol. 282
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
Low-Temperature Synthesis of α-MnO 2 Hollow Urchins and Their Application in Rechargeable Li + Batteries
journal, August 2006
- Li, Benxia; Rong, Guoxin; Xie, Yi
- Inorganic Chemistry, Vol. 45, Issue 16
Reversible aqueous zinc/manganese oxide energy storage from conversion reactions
journal, April 2016
- Pan, Huilin; Shao, Yuyan; Yan, Pengfei
- Nature Energy, Vol. 1, Issue 5
Hollow MnO2 spheres/porous reduced graphene oxide as a cathode host for high-performance lithium-sulfur batteries
journal, June 2020
- Yang, Yali; Ma, Guozheng; Huang, Jiaxing
- Journal of Solid State Chemistry, Vol. 286
A core-shell porous MnO2/Carbon nanosphere composite as the anode of lithium-ion batteries
journal, April 2021
- Cao, Zhiguang; Yang, Yuebei; Qin, Junling
- Journal of Power Sources, Vol. 491
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
Atomic-level tunnel engineering of todorokite MnO2 for precise evaluation of lithium storage mechanisms by in situ transmission electron microscopy
journal, September 2019
- Cai, Ran; Guo, Shiying; Meng, Qingping
- Nano Energy, Vol. 63
Potassium-Intercalated Manganese Dioxide as Lithium-Ion Battery Cathodes: a Density Functional Theory Study
journal, January 2019
- Ismail, Agus; Prabowo, Herry Agung; Alfaruqi, Muhammad Hilmy
- SINERGI, Vol. 23, Issue 1
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
Capture Lithium in αMnO 2 : Insights from First Principles
journal, October 2012
- Ling, Chen; Mizuno, Fuminori
- Chemistry of Materials, Vol. 24, Issue 20
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
Surface properties of α-MnO 2 : relevance to catalytic and supercapacitor behaviour
journal, January 2014
- Tompsett, David A.; Parker, Stephen C.; Islam, M. Saiful
- J. Mater. Chem. A, Vol. 2, Issue 37
Manganese oxides for lithium batteries
journal, January 1997
- Thackeray, Michael M.
- Progress in Solid State Chemistry, Vol. 25, Issue 1-2
Towards a universal curve for electron attenuation: Elastic scattering data for 45 elements
journal, March 1992
- Werner, W. S. M.
- Surface and Interface Analysis, Vol. 18, Issue 3
Hollow urchin-like Al-doped α-MnO2−x as advanced sulfur host for high-performance lithium-sulfur batteries
journal, February 2021
- Zhang, Dan; Li, Zhihao; Li, Yongfang
- Materials Letters, Vol. 285
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
Preparation and Characterization of Open Tunnel Oxide α-MnO2 Precipitated by Ozone Oxidation
journal, June 2001
- Kijima, Norihito; Yasuda, Hiroyuki; Sato, Toshio
- Journal of Solid State Chemistry, Vol. 159, Issue 1
Mesoporous Manganese Oxide Nanowires for High-Capacity, High-Rate, Hybrid Electrical Energy Storage
journal, September 2011
- Yan, Wenbo; Ayvazian, Talin; Kim, Jungyun
- ACS Nano, Vol. 5, Issue 10
Inhomogeneous structural evolution of silver-containing Alpha-MnO2 nanorods in sodium-ion batteries investigated by comparative transmission electron microscopy approach
journal, September 2019
- Lee, Seung-Yong; Housel, Lisa M.; Huang, Jianping
- Journal of Power Sources, Vol. 435
Hollow nitrogen-doped carbon/sulfur@MnO2 nanocomposite with structural and chemical dual-encapsulation for lithium-sulfur battery
journal, February 2020
- Chen, Hao; Dong, Wen-Da; Xia, Fan-Jie
- Chemical Engineering Journal, Vol. 381
α-MnO2 as a cathode material for rechargeable Mg batteries
journal, September 2012
- Zhang, Ruigang; Yu, Xiqian; Nam, Kyung-Wan
- Electrochemistry Communications, Vol. 23
Effect of Different Electrolytes on MnO 2 Anodes in Lithium-Ion Batteries
journal, January 2021
- Tsai, Yun-Chen; Kuo, Chia-Tung; Liu, Shih-Fu
- The Journal of Physical Chemistry C, Vol. 125, Issue 2
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
Reduced graphene oxide thin layer induced lattice distortion in high crystalline MnO2 nanowires for high-performance sodium- and potassium-ion batteries and capacitors
journal, April 2021
- Wang, Zhongmin; Yan, Xiangdong; Wang, Feng
- Carbon, Vol. 174
Investigation of α-MnO 2 Tunneled Structures as Model Cation Hosts for Energy Storage
journal, February 2018
- Housel, Lisa M.; Wang, Lei; Abraham, Alyson
- Accounts of Chemical Research, Vol. 51, Issue 3
Revealing and Rationalizing the Rich Polytypism of Todorokite MnO 2
journal, April 2018
- Hu, Xiaobing; Kitchaev, Daniil A.; Wu, Lijun
- Journal of the American Chemical Society, Vol. 140, Issue 22
Atomic Scale Account of the Surface Effect on Ionic Transport in Silver Hollandite
journal, August 2018
- Hu, Xiaobing; Huang, Jianping; Wu, Lijun
- Chemistry of Materials, Vol. 30, Issue 17
A Hollow-Structured Manganese Oxide Cathode for Stable Zn-MnO2 Batteries
journal, May 2018
- Guo, Xiaotong; Li, Jianming; Jin, Xu
- Nanomaterials, Vol. 8, Issue 5
Charge Storage Mechanism of MnO 2 Electrode Used in Aqueous Electrochemical Capacitor
journal, August 2004
- Toupin, Mathieu; Brousse, Thierry; Bélanger, Daniel
- Chemistry of Materials, Vol. 16, Issue 16
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
Porous Manganese Oxide Octahedral Molecular Sieves and Octahedral Layered Materials
journal, April 2008
- Suib, Steven L.
- Accounts of Chemical Research, Vol. 41, Issue 4
Quantitative temporally and spatially resolved X-ray fluorescence microprobe characterization of the manganese dissolution-deposition mechanism in aqueous Zn/α-MnO 2 batteries
journal, January 2020
- Wu, Daren; Housel, Lisa M.; Kim, Sung Joo
- Energy & Environmental Science, Vol. 13, Issue 11
M x Mn 8 O 16 (M = Ag or K) as promising cathode materials for secondary Mg based batteries: the role of the cation M
journal, January 2016
- Huang, Jianping; Poyraz, Altug S.; Takeuchi, Kenneth J.
- Chemical Communications, Vol. 52, Issue 21
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
Unraveling the Dissolution‐Mediated Reaction Mechanism of α‐MnO 2 Cathodes for Aqueous Zn‐Ion Batteries
journal, November 2020
- Kim, Sung Joo; Wu, Daren; Sadique, Nahian
- Small, Vol. 16, Issue 48
3D Hollow α‐MnO 2 Framework as an Efficient Electrocatalyst for Lithium–Oxygen Batteries
journal, February 2019
- Bi, Ran; Liu, Guoxue; Zeng, Cheng
- Small, Vol. 15, Issue 10