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

Title: Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach

Abstract

Calcium represents a promising anode for the development of high-energy-density, low-cost batteries. Yet, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calcium-sulfur (Ca-S) battery has not yet been reported. Herein, a basic study of a reversible nonaqueous room-temperature Ca-S battery is presented. The reversibility of the Ca-S chemistry and high utilization of the sulfur cathode are enabled by employing a Li+-ion-mediated calcium-based electrolyte. Mechanistic insights pursued by spectroscopic, electrochemical, microscopic, and theoretical simulation (density functional theory) investigations imply that the Li+-ions in the Ca-electrolyte stimulate the reactivation of polysulfide/sulfide species. The coordination of lithium to sulfur reduces the formation of sturdy Ca-S ionic bonds, thus boosting the reversibility of the Ca-S chemistry. Furthermore, the presence of Li+-ions facilitates the ionic charge transfer both in the electrolyte and across the solid electrolyte interphase layer, consequently reducing the interfacial and bulk impedance of Ca-S batteries. As a result, both the utilization of active sulfur in the cathode and the discharge voltage of Ca-S batteries are significantly improved.

Authors:
 [1];  [2];  [2]; ORCiD logo [1]
  1. Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program; Univ. of Texas, Austin, TX (United States). Texas Materials Inst. (TMI)
  2. Univ. of Texas, Austin, TX (United States). McKetta Dept. of Chemical Engineering
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Robert A. Welch Foundation
OSTI Identifier:
1598280
Alternate Identifier(s):
OSTI ID: 1494846
Grant/Contract Number:  
SC0005397
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 9; Journal Issue: 14; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; calcium‐sulfur chemistry; electrochemical mechanism; electrochemical performance; lithium‐ion mediation; rechargeable batteries

Citation Formats

Yu, Xingwen, Boyer, Mathew J., Hwang, Gyeong S., and Manthiram, Arumugam. Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach. United States: N. p., 2019. Web. doi:10.1002/aenm.201803794.
Yu, Xingwen, Boyer, Mathew J., Hwang, Gyeong S., & Manthiram, Arumugam. Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach. United States. https://doi.org/10.1002/aenm.201803794
Yu, Xingwen, Boyer, Mathew J., Hwang, Gyeong S., and Manthiram, Arumugam. Fri . "Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach". United States. https://doi.org/10.1002/aenm.201803794. https://www.osti.gov/servlets/purl/1598280.
@article{osti_1598280,
title = {Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach},
author = {Yu, Xingwen and Boyer, Mathew J. and Hwang, Gyeong S. and Manthiram, Arumugam},
abstractNote = {Calcium represents a promising anode for the development of high-energy-density, low-cost batteries. Yet, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calcium-sulfur (Ca-S) battery has not yet been reported. Herein, a basic study of a reversible nonaqueous room-temperature Ca-S battery is presented. The reversibility of the Ca-S chemistry and high utilization of the sulfur cathode are enabled by employing a Li+-ion-mediated calcium-based electrolyte. Mechanistic insights pursued by spectroscopic, electrochemical, microscopic, and theoretical simulation (density functional theory) investigations imply that the Li+-ions in the Ca-electrolyte stimulate the reactivation of polysulfide/sulfide species. The coordination of lithium to sulfur reduces the formation of sturdy Ca-S ionic bonds, thus boosting the reversibility of the Ca-S chemistry. Furthermore, the presence of Li+-ions facilitates the ionic charge transfer both in the electrolyte and across the solid electrolyte interphase layer, consequently reducing the interfacial and bulk impedance of Ca-S batteries. As a result, both the utilization of active sulfur in the cathode and the discharge voltage of Ca-S batteries are significantly improved.},
doi = {10.1002/aenm.201803794},
journal = {Advanced Energy Materials},
number = 14,
volume = 9,
place = {United States},
year = {2019},
month = {2}
}

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

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Electrochemistry of Sulfur and Polysulfides in Ionic Liquids
journal, December 2011

  • Manan, Ninie S. A.; Aldous, Leigh; Alias, Yatimah
  • The Journal of Physical Chemistry B, Vol. 115, Issue 47
  • DOI: 10.1021/jp208159v

Rechargeable Ca-Ion Batteries: A New Energy Storage System
journal, December 2015


Na 2 S-Carbon Nanotube Fabric Electrodes for Room-Temperature Sodium-Sulfur Batteries
journal, January 2015

  • Yu, Xingwen; Manthiram, Arumugam
  • Chemistry - A European Journal, Vol. 21, Issue 11
  • DOI: 10.1002/chem.201405344

Projector augmented-wave method
journal, December 1994


Room-Temperature Aluminum-Sulfur Batteries with a Lithium-Ion-Mediated Ionic Liquid Electrolyte
journal, March 2018


Room-Temperature Sodium–Sulfur Batteries with Liquid-Phase Sodium Polysulfide Catholytes and Binder-Free Multiwall Carbon Nanotube Fabric Electrodes
journal, September 2014

  • Yu, Xingwen; Manthiram, Arumugam
  • The Journal of Physical Chemistry C, Vol. 118, Issue 40
  • DOI: 10.1021/jp507655u

Improved Electrolyte Solutions for Rechargeable Magnesium Batteries
journal, January 2006

  • Gofer, Yosef; Chusid, Orit; Gizbar, Haim
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 5
  • DOI: 10.1149/1.2186003

Activated Li 2 S as a High-Performance Cathode for Rechargeable Lithium–Sulfur Batteries
journal, November 2014

  • Zu, Chenxi; Klein, Michael; Manthiram, Arumugam
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 22
  • DOI: 10.1021/jz5021108

Rational Design of Lithium–Sulfur Battery Cathodes Based on Experimentally Determined Maximum Active Material Thickness
journal, June 2017

  • Klein, Michael J.; Veith, Gabriel M.; Manthiram, Arumugam
  • Journal of the American Chemical Society, Vol. 139, Issue 27
  • DOI: 10.1021/jacs.7b03380

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Current Collector Corrosion in Ca-Ion Batteries
journal, January 2015

  • Lipson, Albert L.; Proffit, Danielle L.; Pan, Baofei
  • Journal of The Electrochemical Society, Vol. 162, Issue 8
  • DOI: 10.1149/2.0811508jes

Performance of calcium/thionyl chloride cells containing Sr(AlCl4)2 electrolyte
journal, January 1989


Polymer lithium–sulfur batteries with a Nafion membrane and an advanced sulfur electrode
journal, January 2015

  • Yu, Xingwen; Joseph, Jorphin; Manthiram, Arumugam
  • Journal of Materials Chemistry A, Vol. 3, Issue 30
  • DOI: 10.1039/C5TA04289E

A High Capacity Calcium Primary Cell Based on the Ca-S System
journal, April 2013

  • See, Kimberly A.; Gerbec, Jeffrey A.; Jun, Young-Si
  • Advanced Energy Materials, Vol. 3, Issue 8
  • DOI: 10.1002/aenm.201300160

Rechargeable Lithium–Sulfur Batteries
journal, July 2014

  • Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500062v

Chemistry of Sputter-Deposited Lithium Sulfide Films
journal, July 2017

  • Klein, Michael J.; Veith, Gabriel M.; Manthiram, Arumugam
  • Journal of the American Chemical Society, Vol. 139, Issue 31
  • DOI: 10.1021/jacs.7b03379

Sulfur Copolymer: A New Cathode Structure for Room-Temperature Sodium–Sulfur Batteries
journal, September 2017


Performance Enhancement and Mechanistic Studies of Magnesium–Sulfur Cells with an Advanced Cathode Structure
journal, July 2016


Advancing towards a veritable calcium-ion battery: CaCo2O4 positive electrode material
journal, June 2016


Towards a calcium-based rechargeable battery
journal, October 2015

  • Ponrouch, A.; Frontera, C.; Bardé, F.
  • Nature Materials, Vol. 15, Issue 2
  • DOI: 10.1038/nmat4462

Ambient-Temperature Energy Storage with Polyvalent Metal-Sulfur Chemistry
journal, October 2017


A reversible nonaqueous room-temperature potassium-sulfur chemistry for electrochemical energy storage
journal, November 2018


Experimental and Theoretical Analysis of Products and Reaction Intermediates of Lithium–Sulfur Batteries
journal, May 2014

  • Cañas, Natalia A.; Fronczek, David N.; Wagner, Norbert
  • The Journal of Physical Chemistry C, Vol. 118, Issue 23
  • DOI: 10.1021/jp5013208

Electrochemical characteristics of calcium in organic electrolyte solutions and vanadium oxides as calcium hosts
journal, June 2003


Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage
journal, April 2018


In Situ -Formed Li 2 S in Lithiated Graphite Electrodes for Lithium–Sulfur Batteries
journal, November 2013

  • Fu, Yongzhu; Zu, Chenxi; Manthiram, Arumugam
  • Journal of the American Chemical Society, Vol. 135, Issue 48
  • DOI: 10.1021/ja409705u

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte
journal, July 2016

  • Gao, Tao; Li, Xiaogang; Wang, Xiwen
  • Angewandte Chemie International Edition, Vol. 55, Issue 34
  • DOI: 10.1002/anie.201603531

Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures
journal, August 2015


Performance Improvement of Magnesium Sulfur Batteries with Modified Non-Nucleophilic Electrolytes
journal, October 2014

  • Zhao-Karger, Zhirong; Zhao, Xiangyu; Wang, Di
  • Advanced Energy Materials, Vol. 5, Issue 3
  • DOI: 10.1002/aenm.201401155

Secondary Calcium Solid Electrolyte High Temperature Battery
journal, January 1986

  • Sammells, Anthony F.
  • Journal of The Electrochemical Society, Vol. 133, Issue 1
  • DOI: 10.1149/1.2108533

Potassium–Sulfur Batteries: A New Member of Room-Temperature Rechargeable Metal–Sulfur Batteries
journal, August 2014

  • Zhao, Qing; Hu, Yuxiang; Zhang, Kai
  • Inorganic Chemistry, Vol. 53, Issue 17
  • DOI: 10.1021/ic500919e

Electrode–Electrolyte Interfaces in Lithium–Sulfur Batteries with Liquid or Inorganic Solid Electrolytes
journal, October 2017


Recent Advances in Lithium Sulfide Cathode Materials and Their Use in Lithium Sulfur Batteries
journal, April 2015

  • Son, Yoonkook; Lee, Jung-Soo; Son, Yeonguk
  • Advanced Energy Materials, Vol. 5, Issue 16
  • DOI: 10.1002/aenm.201500110

Hybrid Mg 2+ /Li + Battery with Long Cycle Life and High Rate Capability
journal, November 2014


Reversible Calcium Ion Batteries Using a Dehydrated Prussian Blue Analogue Cathode
journal, July 2016


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Achieving High-Performance Room-Temperature Sodium–Sulfur Batteries With S@Interconnected Mesoporous Carbon Hollow Nanospheres
journal, December 2016

  • Wang, Yun-Xiao; Yang, Jianping; Lai, Weihong
  • Journal of the American Chemical Society, Vol. 138, Issue 51
  • DOI: 10.1021/jacs.6b08685

Toward Reversible Room-Temperature Calcium-Ion Batteries
journal, June 2018


Electrochemical Energy Storage with a Reversible Nonaqueous Room-Temperature Aluminum-Sulfur Chemistry
journal, May 2017


A Novel Calcium-Ion Battery Based on Dual-Carbon Configuration with High Working Voltage and Long Cycling Life
journal, April 2018


Enhancing the Reversibility of Mg/S Battery Chemistry through Li + Mediation
journal, September 2015

  • Gao, Tao; Noked, Malachi; Pearse, Alex J.
  • Journal of the American Chemical Society, Vol. 137, Issue 38
  • DOI: 10.1021/jacs.5b07820

The Electrochemical Behavior of Calcium Electrodes in a Few Organic Electrolytes
journal, January 1991

  • Aurbach, D.
  • Journal of The Electrochemical Society, Vol. 138, Issue 12
  • DOI: 10.1149/1.2085455

Suppression of the polysulfide-shuttle behavior in Li–S batteries through the development of a facile functional group on the polypropylene separator
journal, January 2016

  • Yu, Xingwen; Joseph, Jorphin; Manthiram, Arumugam
  • Materials Horizons, Vol. 3, Issue 4
  • DOI: 10.1039/C6MH00043F

Comparison of the behavior of the Li/SOCl2 and Ca/SOCl2 systems at elevated temperatures
journal, December 1989


Electrochemical reduction of sulfur in aprotic solvents
journal, August 1973

  • Martin, Robert P.; Doub, William H.; Roberts, Julian L.
  • Inorganic Chemistry, Vol. 12, Issue 8
  • DOI: 10.1021/ic50126a047

Thermodynamic aspects of shape memory alloys
journal, December 2001


Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond
journal, October 2014

  • Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500049y

ReaxFF molecular dynamics simulations on lithiated sulfur cathode materials
journal, January 2015

  • Islam, Md Mahbubul; Ostadhossein, Alireza; Borodin, Oleg
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 5
  • DOI: 10.1039/C4CP04532G

Calcium Cobalt Hexacyanoferrate Cathodes for Rechargeable Divalent Ion Batteries
journal, April 2016

  • Padigi, Prasanna; Kuperman, Neal; Thiebes, Joseph James
  • Journal of New Materials for Electrochemical Systems, Vol. 19, Issue 2
  • DOI: 10.14447/jnmes.v19i2.231

A class of polysulfide catholytes for lithium–sulfur batteries: energy density, cyclability, and voltage enhancement
journal, January 2015

  • Yu, Xingwen; Manthiram, Arumugam
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 3
  • DOI: 10.1039/C4CP04895D

Ambient Temperature Sodium-Sulfur Batteries
journal, January 2015


Insertion of Calcium Ion into Prussian Blue Analogue in Nonaqueous Solutions and Its Application to a Rechargeable Battery with Dual Carriers
journal, December 2015

  • Shiga, Tohru; Kondo, Hiroki; Kato, Yuichi
  • The Journal of Physical Chemistry C, Vol. 119, Issue 50
  • DOI: 10.1021/acs.jpcc.5b10245

Calcium Thionyl Chloride High-Rate Reserve Cell
journal, January 1981

  • Peled, E.
  • Journal of The Electrochemical Society, Vol. 128, Issue 9
  • DOI: 10.1149/1.2127768

Correlation hole of the spin-polarized electron gas, with exact small-wave-vector and high-density scaling
journal, December 1991


Potassium barium hexacyanoferrate – A potential cathode material for rechargeable calcium ion batteries
journal, January 2015


XPS of sulphide mineral surfaces: metal-deficient, polysulphides, defects and elemental sulphur
journal, August 1999


Die Gitterkonstanten von CaO, CaS, CaSe, CaTe
journal, July 1927


A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte
journal, July 2016


Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021


Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020


Works referencing / citing this record:

A Four‐Electron Sulfur Electrode Hosting a Cu 2+ /Cu + Redox Charge Carrier
journal, July 2019


Current Status and Future Prospects of Metal–Sulfur Batteries
journal, May 2019


Design of a composite cathode and a graphene coated separator for a stable room-temperature aluminum–sulfur battery
journal, January 2020

  • Zheng, Xiao; Tang, Ruixian; Zhang, Yu
  • Sustainable Energy & Fuels, Vol. 4, Issue 4
  • DOI: 10.1039/c9se00762h

A Four‐Electron Sulfur Electrode Hosting a Cu 2+ /Cu + Redox Charge Carrier
journal, September 2019

  • Wu, Xianyong; Markir, Aaron; Ma, Lu
  • Angewandte Chemie International Edition, Vol. 58, Issue 36
  • DOI: 10.1002/anie.201905875