skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1];  [2];  [1];  [1];  [1];  [1];  [3];  [2]; ORCiD logo [2];  [1]
  1. Alveo Energy, Palo Alto, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. New York Univ., New York, NY (United States). Dept. of Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); 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:
Journal Article: 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. 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, and Wessells, Colin D. Wed . "Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries". United States. doi: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},
issn = {2041-1723},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

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

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share:

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
  • DOI: 10.1139/v86-377

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
  • DOI: 10.1021/ja510347s

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
  • DOI: 10.1021/jz100708b

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
journal, May 2013


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
  • DOI: 10.1002/cber.19280610541

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
  • DOI: 10.1021/nl403669a

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
  • DOI: 10.1021/ja209799y

Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015


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
  • DOI: 10.1021/cr100290v

Full open-framework batteries for stationary energy storage
journal, January 2014

  • Pasta, Mauro; Wessells, Colin D.; Liu, Nian
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4007

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
  • DOI: 10.1103/RevModPhys.83.705

Resonant inelastic x-ray scattering of MnO : L 2 , 3 edge measurements and assessment of their interpretation
journal, January 2006


Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries
journal, September 2015


Electron delocalization in cyanide-bridged coordination polymer electrodes for Li-ion batteries studied by soft x-ray absorption spectroscopy
journal, July 2011


2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field
journal, September 1990


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
  • DOI: 10.1063/1.4974356

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
  • DOI: 10.1039/c2cc31777j

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
  • DOI: 10.1039/C5TA10571D

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Cost comparison of producing high-performance Li-ion batteries in the U.S. and in China
journal, June 2013


Cyanide complexes of the early transition metals (groups IVa-VIIa)
journal, November 1975


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
  • DOI: 10.1021/jp411782y

Recent Progress in Aqueous Lithium-Ion Batteries
journal, June 2012

  • Wang, Yonggang; Yi, Jin; Xia, Yongyao
  • Advanced Energy Materials, Vol. 2, Issue 7
  • DOI: 10.1002/aenm.201200065

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
  • DOI: 10.1021/ja061802i

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
  • DOI: 10.1063/1.4977592

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
  • DOI: 10.1038/ncomms1563

Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016


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
  • DOI: 10.1016/j.elspec.2013.03.008

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
  • DOI: 10.1021/jp2118949

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
  • DOI: 10.1038/ncomms7401

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
  • DOI: 10.1038/ncomms6280

    Works referencing / citing this record:

    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
    • DOI: 10.1002/batt.201900054

    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
    • DOI: 10.1002/batt.201900054