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Title: A Four-Electron Sulfur Electrode Hosting a Cu2+/Cu+ Redox Charge Carrier

Abstract

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.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [1]
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  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); USDOE
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.
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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. https://doi.org/10.1002/anie.201905875
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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. https://doi.org/10.1002/anie.201905875. https://www.osti.gov/servlets/purl/1574296.
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@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}
}
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https://doi.org/10.1002/anie.201905875
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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Electrochemical performance and characterization on the Cu-S RIC electrode. (a) GCD profiles of the S/AC electrode (50 wt.% sulfur) in a threeelectrode cell at a current rate of 100 mA g-1. The specific capacity and current rate are based on the sulfur mass in the S/AC nanocomposite; (b)more » Normalized XANES of the Cu-K edge spectra; (c) GCD profiles of the S/C electrode with large sulfur crystals at 10 mA g-1; (d) Ex situ XRD patterns at different SOC; (e) Schematics of the unit cells of S8, CuS, and Cu2S, showing the conversion pathways of the Cu-S RIC electrode; (f) Gibbs free energy changes and reaction potentials between Cu metal, S, CuS, and Cu2S. The redox couples of S/CuS, S/Cu2S, and CuS/Cu2S exhibit electron transfer numbers of 2, 4, and 2, which gives rise to the electromotive force (voltage) of 0.28 V (E1), 0.22 V (E2), and 0.17 V (E3), respectively, according to the equation of -ΔG = nEF.« less
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