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

This content will become publicly available on July 13, 2020

Title: A Four-Electron Sulfur Electrode Hosting a Cu 2+/Cu + Redox Charge Carrier

Abstract

The elemental sulfur electrode with Cu 2+ as the charge carrier gives a four–electron sulfur electrode reaction through the sequential conversion of S↔CuS↔Cu 2S. The Cu–S redox–ion electrode delivers a high specific capacity of 3044 mAh g –1 based on the sulfur mass or 609 mAh g –1 based on the mass of Cu 2S, the completely discharged product, and displays an unprecedently high potential of sulfur/metal sulfide reduction at 0.5 V vs. SHE. The Cu–S electrode also exhibits an extremely low extent of polarization of 0.05 V and an outstanding cycle number of 1200 cycles retaining 72 % of the initial capacity at 12.5 A g –1. Here, the remarkable utility of this Cu–S cathode is further demonstrated in a hybrid cell that employs an Zn metal anode and an anion–exchange membrane as the separator, which yields an average cell discharge voltage of 1.15 V, the half–cell specific energy of 547 Wh kg –1 based on the mass of the Cu 2S/carbon composite cathode, and stable cycling over 110 cycles.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [1]
  1. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
  2. Argonne National Laboratory, Lemont, IL (United States). X-ray Science Div., Advanced Photon Sources
  3. Argonne National Laboratory, Lemont, IL (United States). Chemical Sciences and Engineering Div.
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF)
OSTI Identifier:
1574296
Alternate Identifier(s):
OSTI ID: 1545651
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 36; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; aqueous electrolytes; copper-sulfur chemistry; four-electron reaction; redox charge carriers; zinc battery

Citation Formats

Wu, Xianyong, Markir, Aaron, Ma, Lu, Xu, Yunkai, Jiang, Heng, Leonard, Daniel P., Shin, Woochul, Wu, Tianpin, Lu, Jun, and Ji, Xiulei. A Four-Electron Sulfur Electrode Hosting a Cu2+/Cu+ Redox Charge Carrier. United States: N. p., 2019. Web. doi:10.1002/anie.201905875.
Wu, Xianyong, Markir, Aaron, Ma, Lu, Xu, Yunkai, Jiang, Heng, Leonard, Daniel P., Shin, Woochul, Wu, Tianpin, Lu, Jun, & Ji, Xiulei. A Four-Electron Sulfur Electrode Hosting a Cu2+/Cu+ Redox Charge Carrier. United States. doi:10.1002/anie.201905875.
Wu, Xianyong, Markir, Aaron, Ma, Lu, Xu, Yunkai, Jiang, Heng, Leonard, Daniel P., Shin, Woochul, Wu, Tianpin, Lu, Jun, and Ji, Xiulei. Sat . "A Four-Electron Sulfur Electrode Hosting a Cu2+/Cu+ Redox Charge Carrier". United States. doi:10.1002/anie.201905875.
@article{osti_1574296,
title = {A Four-Electron Sulfur Electrode Hosting a Cu2+/Cu+ Redox Charge Carrier},
author = {Wu, Xianyong and Markir, Aaron and Ma, Lu and Xu, Yunkai and Jiang, Heng and Leonard, Daniel P. and Shin, Woochul and Wu, Tianpin and Lu, Jun and Ji, Xiulei},
abstractNote = {The elemental sulfur electrode with Cu2+ as the charge carrier gives a four–electron sulfur electrode reaction through the sequential conversion of S↔CuS↔Cu2S. The Cu–S redox–ion electrode delivers a high specific capacity of 3044 mAh g–1 based on the sulfur mass or 609 mAh g–1 based on the mass of Cu2S, the completely discharged product, and displays an unprecedently high potential of sulfur/metal sulfide reduction at 0.5 V vs. SHE. The Cu–S electrode also exhibits an extremely low extent of polarization of 0.05 V and an outstanding cycle number of 1200 cycles retaining 72 % of the initial capacity at 12.5 A g–1. Here, the remarkable utility of this Cu–S cathode is further demonstrated in a hybrid cell that employs an Zn metal anode and an anion–exchange membrane as the separator, which yields an average cell discharge voltage of 1.15 V, the half–cell specific energy of 547 Wh kg–1 based on the mass of the Cu2S/carbon composite cathode, and stable cycling over 110 cycles.},
doi = {10.1002/anie.201905875},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 58,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 13, 2020
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors
journal, September 2012

  • Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201201429

Lithiumbatterien und elektrische Doppelschichtkondensatoren: aktuelle Herausforderungen
journal, September 2012

  • Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A.
  • Angewandte Chemie, Vol. 124, Issue 40
  • DOI: 10.1002/ange.201201429

The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015

  • Kundu, Dipan; Talaie, Elahe; Duffort, Victor
  • Angewandte Chemie International Edition, Vol. 54, Issue 11
  • DOI: 10.1002/anie.201410376

Natriumionenbatterien für die elektrochemische Energiespeicherung
journal, February 2015

  • Kundu, Dipan; Talaie, Elahe; Duffort, Victor
  • Angewandte Chemie, Vol. 127, Issue 11
  • DOI: 10.1002/ange.201410376

Slope-Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na-Ion Batteries
journal, February 2019

  • Qi, Yuruo; Lu, Yaxiang; Ding, Feixiang
  • Angewandte Chemie International Edition, Vol. 58, Issue 13
  • DOI: 10.1002/anie.201900005

Slope‐Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na‐Ion Batteries
journal, February 2019


A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries
journal, May 2009

  • Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F.
  • Nature Materials, Vol. 8, Issue 6, p. 500-506
  • DOI: 10.1038/nmat2460

Cyclohexanehexone with Ultrahigh Capacity as Cathode Materials for Lithium‐Ion Batteries
journal, April 2019


Air-Stable Copper-Based P2-Na 7/9 Cu 2/9 Fe 1/9 Mn 2/3 O 2 as a New Positive Electrode Material for Sodium-Ion Batteries
journal, May 2015


Carbon Electrodes for K-Ion Batteries
journal, September 2015

  • Jian, Zelang; Luo, Wei; Ji, Xiulei
  • Journal of the American Chemical Society, Vol. 137, Issue 36
  • DOI: 10.1021/jacs.5b06809

Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors
journal, November 2015


Prototype systems for rechargeable magnesium batteries
journal, October 2000

  • Aurbach, D.; Lu, Z.; Schechter, A.
  • Nature, Vol. 407, Issue 6805, p. 724-727
  • DOI: 10.1038/35037553

A Stable, Non‐Corrosive Perfluorinated Pinacolatoborate Mg Electrolyte for Rechargeable Mg Batteries
journal, March 2019


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


A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode
journal, August 2016


An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode
journal, August 2018

  • Guo, Zhaowei; Ma, Yuanyuan; Dong, Xiaoli
  • Angewandte Chemie International Edition, Vol. 57, Issue 36
  • DOI: 10.1002/anie.201807121

An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode
journal, August 2018


Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries
journal, April 2019


Highly Durable Na 2 V 6 O 16 ·1.63H 2 O Nanowire Cathode for Aqueous Zinc-Ion Battery
journal, February 2018


An ultrafast rechargeable aluminium-ion battery
journal, April 2015

  • Lin, Meng-Chang; Gong, Ming; Lu, Bingan
  • Nature, Vol. 520, Issue 7547
  • DOI: 10.1038/nature14340

Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage
journal, June 2018

  • Wang, Xianfu; Xie, Yiming; Tang, Kai
  • Angewandte Chemie International Edition, Vol. 57, Issue 36
  • DOI: 10.1002/anie.201803664

Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage
journal, June 2018


Regulating Fast Anionic Redox for High-Voltage Aqueous Hydrogen-Ion-based Energy Storage
journal, December 2018

  • Wang, Shengping; Zhao, Xiaoli; Yan, Xiaojun
  • Angewandte Chemie International Edition, Vol. 58, Issue 1
  • DOI: 10.1002/anie.201811220

Regulating Fast Anionic Redox for High-Voltage Aqueous Hydrogen-Ion-based Energy Storage
journal, December 2018

  • Wang, Shengping; Zhao, Xiaoli; Yan, Xiaojun
  • Angewandte Chemie, Vol. 131, Issue 1
  • DOI: 10.1002/ange.201811220

Diffusion-free Grotthuss topochemistry for high-rate and long-life proton batteries
journal, January 2019


Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode
journal, February 2017

  • Wang, Xingfeng; Bommier, Clement; Jian, Zelang
  • Angewandte Chemie International Edition, Vol. 56, Issue 11
  • DOI: 10.1002/anie.201700148

Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode
journal, February 2017

  • Wang, Xingfeng; Bommier, Clement; Jian, Zelang
  • Angewandte Chemie, Vol. 129, Issue 11
  • DOI: 10.1002/ange.201700148

The Effect of Insertion Species on Nanostructured Open Framework Hexacyanoferrate Battery Electrodes
journal, January 2012

  • Wessells, Colin D.; Peddada, Sandeep V.; McDowell, Matthew T.
  • Journal of The Electrochemical Society, Vol. 159, Issue 2, p. A98-A103
  • DOI: 10.1149/2.060202jes

Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System
journal, September 2017

  • Wu, Xianyong; Qi, Yitong; Hong, Jessica J.
  • Angewandte Chemie International Edition, Vol. 56, Issue 42
  • DOI: 10.1002/anie.201707473

Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System
journal, September 2017

  • Wu, Xianyong; Qi, Yitong; Hong, Jessica J.
  • Angewandte Chemie, Vol. 129, Issue 42
  • DOI: 10.1002/ange.201707473

Dual-graphite cells based on the reversible intercalation of bis(trifluoromethanesulfonyl)imide anions from an ionic liquid electrolyte
journal, January 2014

  • Rothermel, Sergej; Meister, Paul; Schmuelling, Guido
  • Energy Environ. Sci., Vol. 7, Issue 10
  • DOI: 10.1039/C4EE01873G

A Dual-Carbon Battery Based on Potassium-Ion Electrolyte
journal, July 2017


High rate and stable cycling of lithium metal anode
journal, February 2015

  • Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7362

Highly reversible zinc metal anode for aqueous batteries
journal, April 2018


A Rechargeable Battery with an Iron Metal Anode
journal, March 2019

  • Wu, Xianyong; Markir, Aaron; Xu, Yunkai
  • Advanced Functional Materials, Vol. 29, Issue 20
  • DOI: 10.1002/adfm.201900911

Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth
journal, September 2017


Lithium Bond Chemistry in Lithium-Sulfur Batteries
journal, June 2017

  • Hou, Ting-Zheng; Xu, Wen-Tao; Chen, Xiang
  • Angewandte Chemie International Edition, Vol. 56, Issue 28
  • DOI: 10.1002/anie.201704324

Lithium Bond Chemistry in Lithium-Sulfur Batteries
journal, June 2017


Smaller Sulfur Molecules Promise Better Lithium–Sulfur Batteries
journal, October 2012

  • Xin, Sen; Gu, Lin; Zhao, Na-Hong
  • Journal of the American Chemical Society, Vol. 134, Issue 45
  • DOI: 10.1021/ja308170k

Surface Chemistry in Cobalt Phosphide-Stabilized Lithium–Sulfur Batteries
journal, January 2018

  • Zhong, Yiren; Yin, Lichang; He, Peng
  • Journal of the American Chemical Society, Vol. 140, Issue 4
  • DOI: 10.1021/jacs.7b11434

A High-Energy Room-Temperature Sodium-Sulfur Battery
journal, December 2013


Chemical Synthesis of K 2 S 2 and K 2 S 3 for Probing Electrochemical Mechanisms in K–S Batteries
journal, October 2018


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

Toward a Reversible Calcium‐Sulfur Battery with a Lithium‐Ion Mediation Approach
journal, February 2019

  • Yu, Xingwen; Boyer, Mathew J.; Hwang, Gyeong S.
  • Advanced Energy Materials, Vol. 9, Issue 14
  • DOI: 10.1002/aenm.201803794

Self-Established Rapid Magnesiation/De-Magnesiation Pathways in Binary Selenium-Copper Mixtures with Significantly Enhanced Mg-Ion Storage Reversibility
journal, November 2017

  • Zhang, Zhonghua; Chen, Bingbing; Xu, Huimin
  • Advanced Functional Materials, Vol. 28, Issue 1
  • DOI: 10.1002/adfm.201701718

Reversible S 0 /MgS x Redox Chemistry in a MgTFSI 2 /MgCl 2 /DME Electrolyte for Rechargeable Mg/S Batteries
journal, September 2017

  • Gao, Tao; Hou, Singyuk; Wang, Fei
  • Angewandte Chemie International Edition, Vol. 56, Issue 43
  • DOI: 10.1002/anie.201708241

Reversible S 0 /MgS x Redox Chemistry in a MgTFSI 2 /MgCl 2 /DME Electrolyte for Rechargeable Mg/S Batteries
journal, September 2017


Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries
journal, January 2017

  • Zhou, Guangmin; Tian, Hongzhen; Jin, Yang
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 5
  • DOI: 10.1073/pnas.1615837114

Polysulfides Capture-Copper Additive for Long Cycle Life Lithium Sulfur Batteries
journal, October 2016

  • Jia, Lei; Wu, Tianpin; Lu, Jun
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 44
  • DOI: 10.1021/acsami.6b10366

Long-Life Room-Temperature Sodium-Sulfur Batteries by Virtue of Transition-Metal-Nanocluster-Sulfur Interactions
journal, January 2019

  • Zhang, Bin-Wei; Sheng, Tian; Wang, Yun-Xiao
  • Angewandte Chemie International Edition, Vol. 58, Issue 5
  • DOI: 10.1002/anie.201811080

Interaction of CuS and Sulfur in Li-S Battery System
journal, January 2015

  • Sun, Ke; Su, Dong; Zhang, Qing
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.1021514jes

Electrocatalysis in Lithium Sulfur Batteries under Lean Electrolyte Conditions
journal, October 2018

  • Yang, Yuxiang; Zhong, Yiren; Shi, Qiuwei
  • Angewandte Chemie International Edition, Vol. 57, Issue 47
  • DOI: 10.1002/anie.201808311

Electrocatalysis in Lithium Sulfur Batteries under Lean Electrolyte Conditions
journal, October 2018


Understanding electrochemical potentials of cathode materials in rechargeable batteries
journal, March 2016


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

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


Electrical Conduction and Phase Transition of Copper Sulfides
journal, August 1973

  • Okamoto, Kimihiko; Kawai, Shichio
  • Japanese Journal of Applied Physics, Vol. 12, Issue 8
  • DOI: 10.1143/JJAP.12.1130

Metal sulfide nanostructures: synthesis, properties and applications in energy conversion and storage
journal, January 2012

  • Lai, Chen-Ho; Lu, Ming-Yen; Chen, Lih-Juann
  • J. Mater. Chem., Vol. 22, Issue 1
  • DOI: 10.1039/C1JM13879K

Textbook errors: Guest column. The solubility product constants of the metallic sulfides
journal, July 1958

  • Waggoner, William H.
  • Journal of Chemical Education, Vol. 35, Issue 7
  • DOI: 10.1021/ed035p339

Lithium ion battery applications of molybdenum disulfide (MoS 2 ) nanocomposites
journal, January 2014

  • Stephenson, Tyler; Li, Zhi; Olsen, Brian
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE42591F

On the origin of the extra capacity at low potential in materials for Li batteries reacting through conversion reaction
journal, February 2012


Nature of extra capacity in MoS2 electrodes: Molybdenum atoms accommodate with lithium
journal, January 2019


Hard and soft acids and bases, HSAB, part 1: Fundamental principles
journal, September 1968

  • Pearson, Ralph G.
  • Journal of Chemical Education, Vol. 45, Issue 9
  • DOI: 10.1021/ed045p581

Hard and soft acids and bases, HSAB, part II: Underlying theories
journal, October 1968

  • Pearson, Ralph G.
  • Journal of Chemical Education, Vol. 45, Issue 10
  • DOI: 10.1021/ed045p643

Hard soft acids bases (HSAB) principle and organic chemistry
journal, February 1975