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
Abstract
α-MnO2 type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn8O16·0.81H2O, K0.81Mn8O16·0.78H2O and Ag1.33Mn8O16·0.95H2O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO2 type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn8O16·0.81H2O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K0.81Mn8O16·0.78H2O and Ag1.33Mn8O16·0.95H2O. After 100 cycles, Mn8O16·0.81H2O delivered ~200% more capacity than Ag1.33Mn8O16·0.95H2O (64 vs. 129 mAh/g) and ~35% more capacity than K0.81Mn8O16·0.78H2O (85 vs. 129 mAh/g).more »
- Authors:
-
[2];
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Energy Sciences Directorate
- Stony Brook Univ., NY (United States). Dept. of Chemistry
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Energy Sciences Directorate; Tsinghua Univ., Beijing (China). Dept. of Materials Science and Engineering
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Energy Sciences Directorate; Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1426450
- Report Number(s):
- BNL-203332-2018-JAAM
Journal ID: ISSN 0013-4651
- Grant/Contract Number:
- SC0012704; SC0012673; AC02-98CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 164; Journal Issue: 9; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Rechargeable; Li Battery; Cryptomelane; Hollandite; Manganese Dioxide; tunnel; cation; battery; energy storage; hollandite
Citation Formats
Poyraz, Altug S., Huang, Jianping, Cheng, Shaobo, Wu, Lijun, Tong, Xiao, Zhu, Yimei, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. 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. United States: N. p., 2017.
Web. doi:10.1149/2.0911709jes.
Poyraz, Altug S., Huang, Jianping, Cheng, Shaobo, Wu, Lijun, Tong, Xiao, Zhu, Yimei, Marschilok, Amy C., Takeuchi, Kenneth J., & Takeuchi, Esther S. 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. United States. https://doi.org/10.1149/2.0911709jes
Poyraz, Altug S., Huang, Jianping, Cheng, Shaobo, Wu, Lijun, Tong, Xiao, Zhu, Yimei, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Wed .
"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". United States. https://doi.org/10.1149/2.0911709jes. https://www.osti.gov/servlets/purl/1426450.
@article{osti_1426450,
title = {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},
author = {Poyraz, Altug S. and Huang, Jianping and Cheng, Shaobo and Wu, Lijun and Tong, Xiao and Zhu, Yimei and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S.},
abstractNote = {α-MnO2 type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn8O16·0.81H2O, K0.81Mn8O16·0.78H2O and Ag1.33Mn8O16·0.95H2O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO2 type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn8O16·0.81H2O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K0.81Mn8O16·0.78H2O and Ag1.33Mn8O16·0.95H2O. After 100 cycles, Mn8O16·0.81H2O delivered ~200% more capacity than Ag1.33Mn8O16·0.95H2O (64 vs. 129 mAh/g) and ~35% more capacity than K0.81Mn8O16·0.78H2O (85 vs. 129 mAh/g). Mn8O16·0.81H2O also showed higher effective lithium diffusion coefficients (DLi+) and higher rate capability compared to K0.81Mn8O16·0.78H2O and Ag1.33Mn8O16·0.95H2O suggesting faster Li+ ion diffusion in the absence of large metal tunnel cations.},
doi = {10.1149/2.0911709jes},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 164,
place = {United States},
year = {Wed Jul 12 00:00:00 EDT 2017},
month = {Wed Jul 12 00:00:00 EDT 2017}
}
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Works referenced in this record:
Galvanostatic Intermittent Titration Technique for Phase-Transformation Electrodes
journal, January 2010
- Zhu, Yujie; Wang, Chunsheng
- The Journal of Physical Chemistry C, Vol. 114, Issue 6
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
Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor
journal, March 2009
- Ragupathy, P.; Park, Dae Hoon; Campet, Guy
- The Journal of Physical Chemistry C, Vol. 113, Issue 15
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Nanostructured Mn-based oxides for electrochemical energy storage and conversion
journal, January 2015
- Zhang, Kai; Han, Xiaopeng; Hu, Zhe
- Chemical Society Reviews, Vol. 44, Issue 3
Cyclohexane oxidation catalyzed by manganese oxide octahedral molecular sieves—Effect of acidity of the catalyst
journal, March 2009
- Kumar, Ranjit; Sithambaram, Shanthakumar; Suib, Steven L.
- Journal of Catalysis, Vol. 262, Issue 2
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
Lithium ion insertion and extraction reactions with Hollandite-type manganese dioxide free from any stabilizing cations in its tunnel cavity
journal, September 2005
- Kijima, Norihito; Takahashi, Yasuhiko; Akimoto, Junji
- Journal of Solid State Chemistry, Vol. 178, 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
Nanosized silver-coated and doped manganese dioxide for rechargeable lithium batteries
journal, February 2011
- Abuzeid, Hanaa M.; Hashem, Ahmed M.; Narayanan, N.
- Solid State Ionics, Vol. 182, Issue 1
Synthesis, characterization and rate capability performance of the micro-porous MnO2 nanowires as cathode material in lithium batteries
journal, October 2015
- R., Ranjusha; S., Sonia T.; S., Roshny
- Materials Research Bulletin, Vol. 70
Rapid synthesis of cryptomelane-type manganese oxide under ultrasonic process
journal, October 2011
- Sun, Ming; Yu, Lin; Ye, Fei
- Materials Letters, Vol. 65, Issue 19-20
Effective recycling of manganese oxide cathodes for lithium based batteries
journal, January 2016
- Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo
- Green Chemistry, Vol. 18, Issue 11
R factors in Rietveld analysis: How good is good enough?
journal, March 2006
- Toby, Brian H.
- Powder Diffraction, Vol. 21, Issue 1
Effect of Phase Structure of MnO 2 Nanorod Catalyst on the Activity for CO Oxidation
journal, March 2008
- Liang, Shuhui; Teng, Fei; Bulgan, G.
- The Journal of Physical Chemistry C, Vol. 112, Issue 14
Microstructures and Spectroscopic Properties of Cryptomelane-type Manganese Dioxide Nanofibers
journal, July 2008
- Gao, Tao; Glerup, Marianne; Krumeich, Frank
- The Journal of Physical Chemistry C, Vol. 112, Issue 34
Tuning the K + Concentration in the Tunnel of OMS-2 Nanorods Leads to a Significant Enhancement of the Catalytic Activity for Benzene Oxidation
journal, November 2013
- Hou, Jingtao; Liu, Liangliang; Li, Yuanzhi
- Environmental Science & Technology, Vol. 47, Issue 23
Li-ion battery materials: present and future
journal, June 2015
- Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae
- Materials Today, Vol. 18, Issue 5
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
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
The role of vacancies and defects in Na0.44MnO2 nanowire catalysts for lithium–oxygen batteries
journal, January 2012
- Lee, Jin-Hyon; Black, Robert; Popov, Guerman
- Energy & Environmental Science, Vol. 5, Issue 11
Improvement of the electrochemical performance of nanosized α-MnO2 used as cathode material for Li-batteries by Sn-doping
journal, October 2011
- Hashem, A. M.; Abdel-Latif, A. M.; Abuzeid, H. M.
- Journal of Alloys and Compounds, Vol. 509, Issue 40
A review of conduction phenomena in Li-ion batteries
journal, December 2010
- Park, Myounggu; Zhang, Xiangchun; Chung, Myoungdo
- Journal of Power Sources, Vol. 195, Issue 24
Manganese Oxide Thin Film Preparation by Potentiostatic Electrolyses and Electrochromism
journal, January 2000
- Chigane, Masaya; Ishikawa, Masami
- Journal of The Electrochemical Society, Vol. 147, Issue 6
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
Influence of silver on the catalytic properties of the cryptomelane and Ag-hollandite types manganese oxides OMS-2 in the low-temperature CO oxidation
journal, July 2013
- Özacar, Mahmut; Poyraz, Altuğ S.; Genuino, Homer C.
- Applied Catalysis A: General, Vol. 462-463
Development and utility of manganese oxides as cathodes in lithium batteries
journal, March 2007
- Johnson, Christopher S.
- Journal of Power Sources, Vol. 165, Issue 2
Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries
journal, January 2015
- Byles, B. W.; West, P.; Cullen, D. A.
- RSC Advances, Vol. 5, Issue 128
Facile One-Step Template-Free Synthesis of Uniform Hollow Microstructures of Cryptomelane-Type Manganese Oxide K-OMS-2
journal, August 2010
- Galindo, Hugo M.; Carvajal, Yadira; Njagi, Eric
- Langmuir, Vol. 26, Issue 16
Capture Lithium in αMnO 2 : Insights from First Principles
journal, October 2012
- Ling, Chen; Mizuno, Fuminori
- Chemistry of Materials, Vol. 24, Issue 20
Tunnel structure effect of manganese oxides in complete oxidation of formaldehyde
journal, June 2009
- Chen, Tan; Dou, Hongying; Li, Xiaoling
- Microporous and Mesoporous Materials, Vol. 122, Issue 1-3, p. 270-274
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
Structural and chemical disorder of cryptomelane promoted by alkali doping: Influence on catalytic properties
journal, September 2012
- Santos, V. P.; Soares, O. S. G. P.; Bakker, J. J. W.
- Journal of Catalysis, Vol. 293
Evolution of Strategies for Modern Rechargeable Batteries
journal, June 2012
- Goodenough, John B.
- Accounts of Chemical Research, Vol. 46, Issue 5
Microstructural Effects on Charge-Storage Properties in MnO 2 -Based Electrochemical Supercapacitors
journal, April 2009
- Ghodbane, Ouassim; Pascal, Jean-Louis; Favier, Frédéric
- ACS Applied Materials & Interfaces, Vol. 1, Issue 5
Secondary batteries with multivalent ions for energy storage
journal, September 2015
- Xu, Chengjun; Chen, Yanyi; Shi, Shan
- Scientific Reports, Vol. 5, Issue 1
Effects of Alkali Metal and Ammonium Cation Templates on Nanofibrous Cryptomelane-type Manganese Oxide Octahedral Molecular Sieves (OMS-2)
journal, September 2003
- Liu, Jia; Makwana, Vinit; Cai, Jun
- The Journal of Physical Chemistry B, Vol. 107, Issue 35
Understanding electrochemical potentials of cathode materials in rechargeable batteries
journal, March 2016
- Liu, Chaofeng; Neale, Zachary G.; Cao, Guozhong
- Materials Today, Vol. 19, Issue 2
Developments in Nanostructured Cathode Materials for High-Performance Lithium-Ion Batteries
journal, June 2008
- Wang, Ying; Cao, Guozhong
- Advanced Materials, Vol. 20, Issue 12
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
Romanechite-structured Na 0.31 MnO 1.9 nanofibers as high-performance cathode material for a sodium-ion battery
journal, January 2015
- Li, Jin-Yue; Wu, Xing-Long; Zhang, Xiao-Hua
- Chemical Communications, Vol. 51, Issue 80
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
Ammonia- and lithia-doped manganese dioxide for 3 V lithium batteries
journal, July 2001
- Johnson, C. S.; Thackeray, M. M.
- Journal of Power Sources, Vol. 97-98
Todorokite-type MnO2 as a zinc-ion intercalating material
journal, December 2013
- Lee, Jonghyuk; Ju, Jeh Beck; Cho, Won Il
- Electrochimica Acta, Vol. 112
Evidence of Solid-Solution Reaction upon Lithium Insertion into Cryptomelane K 0.25 Mn 2 O 4 Material
journal, February 2014
- Pang, Wei Kong; Peterson, Vanessa K.; Sharma, Neeraj
- The Journal of Physical Chemistry C, Vol. 118, Issue 8
Electrochemical characterization of manganese oxide cathode materials based on Na0.4MnO2
journal, April 2004
- Hu, Felix; Doeff, Marca M.
- Journal of Power Sources, Vol. 129, 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
Structural and electrochemical studies of α-manganese dioxide (α-MnO2)
journal, October 1997
- Johnson, C. S.; Dees, D. W.; Mansuetto, M. F.
- Journal of Power Sources, Vol. 68, Issue 2
Synthesis and electrochemical properties of KMn8O16 nanorods for Lithium ion batteries
journal, January 2013
- Zheng, Hao; Feng, Chuanqi; Kim, Seung-Joo
- Electrochimica Acta, Vol. 88
Mn exchange splitting in mixed-valence manganites
journal, February 2002
- Galakhov, V. R.; Demeter, M.; Bartkowski, S.
- Physical Review B, Vol. 65, Issue 11
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
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
Porous Manganese Oxide Octahedral Molecular Sieves and Octahedral Layered Materials
journal, April 2008
- Suib, Steven L.
- Accounts of Chemical Research, Vol. 41, Issue 4
Selective oxidation of alcohols using octahedral molecular sieves: influence of synthesis method and property–activity relations
journal, October 2003
- Makwana, Vinit D.; Garces, L. Javier; Liu, Jia
- Catalysis Today, Vol. 85, Issue 2-4
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 Manganese Oxide Nanomaterials and Their Catalytic and Electrochemical Properties
journal, September 2011
- Qiu, Guohong; Huang, Hui; Dharmarathna, Saminda
- Chemistry of Materials, Vol. 23, Issue 17
Ce 3d XPS study of composite CexMn1−xO2−y wet oxidation catalysts
journal, July 2002
- Larachi, Faı̈çal; Pierre, Jérôme; Adnot, Alain
- Applied Surface Science, Vol. 195, Issue 1-4
Analysis of the Galvanostatic Intermittent Titration Technique (GITT) as applied to a lithium-ion porous electrode
journal, April 2009
- Dees, Dennis W.; Kawauchi, Shigehiro; Abraham, Daniel P.
- Journal of Power Sources, Vol. 189, Issue 1
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
In situ high-energy synchrotron X-ray diffraction studies and first principles modeling of α-MnO 2 electrodes in Li–O 2 and Li-ion coin cells
journal, January 2015
- Yang, Zhenzhen; Trahey, Lynn; Ren, Yang
- Journal of Materials Chemistry A, Vol. 3, Issue 14
Topotactic Reduction of Alpha-Manganese (Di)Oxide in Nonaqueous Lithium Cells
journal, January 1991
- Ohzuku, Tsutomu
- Journal of The Electrochemical Society, Vol. 138, Issue 2
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
Analysis of the chemical diffusion coefficient of lithium ions in Li3V2(PO4)3 cathode material
journal, February 2010
- Rui, X. H.; Ding, N.; Liu, J.
- Electrochimica Acta, Vol. 55, Issue 7
Works referencing / citing this record:
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