Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries
Abstract
The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here in this paperwe report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese-3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic-aqueous cosolvent electrolyte to solve the long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 9 5% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.
- Authors:
-
[2];
- Alveo Energy, Palo Alto, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- New York Univ., New York, NY (United States). Dept. of Physics
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1433131
- Grant/Contract Number:
- AC02-05CH11231; AR00000300; DMR-1420073
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Firouzi, Ali, Qiao, Ruimin, Motallebi, Shahrokh, Valencia, Christian W., Israel, Hannah S., Fujimoto, Mai, Wray, L. Andrew, Chuang, Yi-De, Yang, Wanli, and Wessells, Colin D. Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries. United States: N. p., 2018.
Web. doi:10.1038/s41467-018-03257-1.
Firouzi, Ali, Qiao, Ruimin, Motallebi, Shahrokh, Valencia, Christian W., Israel, Hannah S., Fujimoto, Mai, Wray, L. Andrew, Chuang, Yi-De, Yang, Wanli, & Wessells, Colin D. Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries. United States. https://doi.org/10.1038/s41467-018-03257-1
Firouzi, Ali, Qiao, Ruimin, Motallebi, Shahrokh, Valencia, Christian W., Israel, Hannah S., Fujimoto, Mai, Wray, L. Andrew, Chuang, Yi-De, Yang, Wanli, and Wessells, Colin D. Wed .
"Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries". United States. https://doi.org/10.1038/s41467-018-03257-1. https://www.osti.gov/servlets/purl/1433131.
@article{osti_1433131,
title = {Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries},
author = {Firouzi, Ali and Qiao, Ruimin and Motallebi, Shahrokh and Valencia, Christian W. and Israel, Hannah S. and Fujimoto, Mai and Wray, L. Andrew and Chuang, Yi-De and Yang, Wanli and Wessells, Colin D.},
abstractNote = {The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here in this paperwe report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese-3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic-aqueous cosolvent electrolyte to solve the long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 9 5% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.},
doi = {10.1038/s41467-018-03257-1},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {Wed Feb 28 00:00:00 EST 2018},
month = {Wed Feb 28 00:00:00 EST 2018}
}
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Works referenced in this record:
Fast disproportionation of hexacyanomanganate(III) in acidic solution. Formation of hexacyanomanganate(IV) and kinetics of its decomposition
journal, December 1986
- López-Cueto, Guillermo; Ubide, Carlos
- Canadian Journal of Chemistry, Vol. 64, Issue 12, p. 2301-2304
Rhombohedral Prussian White as Cathode for Rechargeable Sodium-Ion Batteries
journal, February 2015
- Wang, Long; Song, Jie; Qiao, Ruimin
- Journal of the American Chemical Society, Vol. 137, Issue 7
Switching Redox-Active Sites by Valence Tautomerism in Prussian Blue Analogues AxMny[Fe(CN)6]·nH2O (A: K, Rb): Robust Frameworks for Reversible Li Storage
journal, June 2010
- Okubo, M.; Asakura, D.; Mizuno, Y.
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 14, p. 2063-2071
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
journal, May 2013
- Qiao, Ruimin; Chin, Timothy; Harris, Stephen J.
- Current Applied Physics, Vol. 13, Issue 3
Über einwertiges Mangan (II. Mitteil.)
journal, May 1928
- Manchot, W.; Gall, H.
- Berichte der deutschen chemischen Gesellschaft (A and B Series), Vol. 61, Issue 5
Highly Reversible Open Framework Nanoscale Electrodes for Divalent Ion Batteries
journal, October 2013
- Wang, Richard Y.; Wessells, Colin D.; Huggins, Robert A.
- Nano Letters, Vol. 13, Issue 11
Non-Prussian Blue Structures and Magnetic Ordering of Na 2 Mn II [Mn II (CN) 6 ] and Na 2 Mn II [Mn II (CN) 6 ]·2H 2 O
journal, January 2012
- Kareis, Christopher M.; Lapidus, Saul H.; Her, Jae-Hyuk
- Journal of the American Chemical Society, Vol. 134, Issue 4
Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015
- Qiao, Ruimin; Wang, Yuesheng; Olalde-Velasco, Paul
- Journal of Power Sources, Vol. 273
Electrochemical Energy Storage for Green Grid
journal, May 2011
- Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W.
- Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613
Full open-framework batteries for stationary energy storage
journal, January 2014
- Pasta, Mauro; Wessells, Colin D.; Liu, Nian
- Nature Communications, Vol. 5, Issue 1
Resonant inelastic x-ray scattering studies of elementary excitations
journal, June 2011
- Ament, Luuk J. P.; van Veenendaal, Michel; Devereaux, Thomas P.
- Reviews of Modern Physics, Vol. 83, Issue 2
Resonant inelastic x-ray scattering of : edge measurements and assessment of their interpretation
journal, January 2006
- Ghiringhelli, G.; Matsubara, M.; Dallera, C.
- Physical Review B, Vol. 73, Issue 3
Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries
journal, September 2015
- Qiao, Ruimin; Dai, Kehua; Mao, Jing
- Nano Energy, Vol. 16
Electron delocalization in cyanide-bridged coordination polymer electrodes for Li-ion batteries studied by soft x-ray absorption spectroscopy
journal, July 2011
- Asakura, Daisuke; Okubo, Masashi; Mizuno, Yoshifumi
- Physical Review B, Vol. 84, Issue 4
2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field
journal, September 1990
- de Groot, F. M. F.; Fuggle, J. C.; Thole, B. T.
- Physical Review B, Vol. 42, Issue 9
Modular soft x-ray spectrometer for applications in energy sciences and quantum materials
journal, January 2017
- Chuang, Yi-De; Shao, Yu-Cheng; Cruz, Alejandro
- Review of Scientific Instruments, Vol. 88, Issue 1
Prussian blue: a new framework of electrode materials for sodium batteries
journal, January 2012
- Lu, Yuhao; Wang, Long; Cheng, Jinguang
- Chemical Communications, Vol. 48, Issue 52, p. 6544-6546
Manganese–cobalt hexacyanoferrate cathodes for sodium-ion batteries
journal, January 2016
- Pasta, Mauro; Wang, Richard Y.; Ruffo, Riccardo
- Journal of Materials Chemistry A, Vol. 4, Issue 11
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Cost comparison of producing high-performance Li-ion batteries in the U.S. and in China
journal, June 2013
- Brodd, Ralph J.; Helou, Carlos
- Journal of Power Sources, Vol. 231
Cyanide complexes of the early transition metals (groups IVa-VIIa)
journal, November 1975
- Griffith, W. P.
- Coordination Chemistry Reviews, Vol. 17, Issue 2-3, p. 177-247
Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study
journal, January 2014
- Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira
- The Journal of Physical Chemistry B, Vol. 118, Issue 6
Recent Progress in Aqueous Lithium-Ion Batteries
journal, June 2012
- Wang, Yonggang; Yi, Jin; Xia, Yongyao
- Advanced Energy Materials, Vol. 2, Issue 7
Fe L-Edge XAS Studies of K 4 [Fe(CN) 6 ] and K 3 [Fe(CN) 6 ]: A Direct Probe of Back-Bonding
journal, August 2006
- Hocking, Rosalie K.; Wasinger, Erik C.; de Groot, Frank M. F.
- Journal of the American Chemical Society, Vol. 128, Issue 32
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017
- Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing
- Review of Scientific Instruments, Vol. 88, Issue 3
Copper hexacyanoferrate battery electrodes with long cycle life and high power
journal, November 2011
- Wessells, Colin D.; Huggins, Robert A.; Cui, Yi
- Nature Communications, Vol. 2, Article No. 550
A Polyionic, Large-Format Energy Storage Device Using an Aqueous Electrolyte and Thick-Format Composite NaTi 2 (PO 4 ) 3 /Activated Carbon Negative Electrodes
journal, November 2014
- Whitacre, J. F.; Shanbhag, S.; Mohamed, A.
- Energy Technology, Vol. 3, Issue 1
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016
- Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew
- Journal of Physics D: Applied Physics, Vol. 49, Issue 41
Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013
- Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
Fabrication of a Cyanide-Bridged Coordination Polymer Electrode for Enhanced Electrochemical Ion Storage Ability
journal, April 2012
- Asakura, Daisuke; Okubo, Masashi; Mizuno, Yoshifumi
- The Journal of Physical Chemistry C, Vol. 116, Issue 15, p. 8364-8369
Ti-substituted tunnel-type Na0.44MnO2 oxide as a negative electrode for aqueous sodium-ion batteries
journal, March 2015
- Wang, Yuesheng; Liu, Jue; Lee, Byungju
- Nature Communications, Vol. 6, Issue 1
Manganese hexacyanomanganate open framework as a high-capacity positive electrode material for sodium-ion batteries
journal, October 2014
- Lee, Hyun-Wook; Wang, Richard Y.; Pasta, Mauro
- Nature Communications, Vol. 5, Issue 1
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
text, January 2012
- Qiao, Ruimin; Chin, Timothy; Harris, Stephen J.
- arXiv
Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study
preprint, January 2013
- Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira
- arXiv
Über einwertiges Mangan (II. Mitteil.)
journal, May 1928
- Manchot, W.; Gall, H.
- Berichte der deutschen chemischen Gesellschaft (A and B Series), Vol. 61, Issue 5
Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013
- Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
Cost comparison of producing high-performance Li-ion batteries in the U.S. and in China
journal, June 2013
- Brodd, Ralph J.; Helou, Carlos
- Journal of Power Sources, Vol. 231
Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015
- Qiao, Ruimin; Wang, Yuesheng; Olalde-Velasco, Paul
- Journal of Power Sources, Vol. 273
Fe L-Edge XAS Studies of K 4 [Fe(CN) 6 ] and K 3 [Fe(CN) 6 ]: A Direct Probe of Back-Bonding
journal, August 2006
- Hocking, Rosalie K.; Wasinger, Erik C.; de Groot, Frank M. F.
- Journal of the American Chemical Society, Vol. 128, Issue 32
Non-Prussian Blue Structures and Magnetic Ordering of Na 2 Mn II [Mn II (CN) 6 ] and Na 2 Mn II [Mn II (CN) 6 ]·2H 2 O
journal, January 2012
- Kareis, Christopher M.; Lapidus, Saul H.; Her, Jae-Hyuk
- Journal of the American Chemical Society, Vol. 134, Issue 4
Rhombohedral Prussian White as Cathode for Rechargeable Sodium-Ion Batteries
journal, February 2015
- Wang, Long; Song, Jie; Qiao, Ruimin
- Journal of the American Chemical Society, Vol. 137, Issue 7
Highly Reversible Open Framework Nanoscale Electrodes for Divalent Ion Batteries
journal, October 2013
- Wang, Richard Y.; Wessells, Colin D.; Huggins, Robert A.
- Nano Letters, Vol. 13, Issue 11
Full open-framework batteries for stationary energy storage
journal, January 2014
- Pasta, Mauro; Wessells, Colin D.; Liu, Nian
- Nature Communications, Vol. 5, Issue 1
Manganese hexacyanomanganate open framework as a high-capacity positive electrode material for sodium-ion batteries
journal, October 2014
- Lee, Hyun-Wook; Wang, Richard Y.; Pasta, Mauro
- Nature Communications, Vol. 5, Issue 1
Prussian blue: a new framework of electrode materials for sodium batteries
journal, January 2012
- Lu, Yuhao; Wang, Long; Cheng, Jinguang
- Chemical Communications, Vol. 48, Issue 52, p. 6544-6546
Modular soft x-ray spectrometer for applications in energy sciences and quantum materials
journal, January 2017
- Chuang, Yi-De; Shao, Yu-Cheng; Cruz, Alejandro
- Review of Scientific Instruments, Vol. 88, Issue 1
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017
- Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing
- Review of Scientific Instruments, Vol. 88, Issue 3
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016
- Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew
- Journal of Physics D: Applied Physics, Vol. 49, Issue 41
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
text, January 2012
- Qiao, Ruimin; Chin, Timothy; Harris, Stephen J.
- arXiv
Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study
preprint, January 2013
- Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira
- arXiv
Works referencing / citing this record:
Prussian White Hierarchical Nanotubes with Surface‐Controlled Charge Storage for Sodium‐Ion Batteries
journal, February 2019
- Ren, Wenhao; Zhu, Zixuan; Qin, Mingsheng
- Advanced Functional Materials, Vol. 29, Issue 15
Few‐Layer Bismuthene with Anisotropic Expansion for High‐Areal‐Capacity Sodium‐Ion Batteries
journal, January 2019
- Zhou, Jing; Chen, Jiangchun; Chen, Mengxue
- Advanced Materials, Vol. 31, Issue 12
Electrolytes and Electrolyte/Electrode Interfaces in Sodium‐Ion Batteries: From Scientific Research to Practical Application
journal, March 2019
- Huang, Yongxin; Zhao, Luzi; Li, Li
- Advanced Materials, Vol. 31, Issue 21
Understanding Challenges of Cathode Materials for Sodium‐Ion Batteries using Synchrotron‐Based X‐Ray Absorption Spectroscopy
journal, July 2019
- Chen, Mingzhe; Chou, Shu‐Lei; Dou, Shi‐Xue
- Batteries & Supercaps, Vol. 2, Issue 10
Recent research progresses in ether‐ and ester‐based electrolytes for sodium‐ion batteries
journal, July 2019
- Lin, Zeheng; Xia, Qingbing; Wang, Wanlin
- InfoMat, Vol. 1, Issue 3
Ball-milling synthesis of ultrafine NayFexMn1-x[Fe(CN)6] as high-performance cathode in sodium-ion batteries
journal, December 2019
- Gong, Wenzhe; Zeng, Rui; Su, Shang
- Journal of Nanoparticle Research, Vol. 21, Issue 12
Ni 1.5 CoSe 5 nanocubes embedded in 3D dual N-doped carbon network as advanced anode material in sodium-ion full cells with superior low-temperature and high-power properties
journal, January 2018
- Wang, Ying-Ying; Fan, Haosen; Hou, Bao-Hua
- Journal of Materials Chemistry A, Vol. 6, Issue 45
A room temperature multivalent rechargeable iron ion battery with an ether based electrolyte: a new type of post-lithium ion battery
journal, January 2019
- Vijaya Kumar Saroja, Ajay Piriya; Samantaray, Sai Smruti; Sundara, Ramaprabhu
- Chemical Communications, Vol. 55, Issue 70
X-ray spectroscopy with variable line spacing based on reflection zone plate optics
journal, January 2018
- Yin, Zhong; Löchel, Heike; Rehanek, Jens
- Optics Letters, Vol. 43, Issue 18
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering
journal, January 2019
- Wu, Jinpeng; Li, Qinghao; Sallis, Shawn
- Condensed Matter, Vol. 4, Issue 1
X-ray spectroscopy with variable line spacing based on reflection zone plate optics
text, January 2018
- Yin, Zhong; Löchel, Heike; Rehanek, Jens
- Deutsches Elektronen-Synchrotron, DESY, Hamburg