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

Wu, Xianyong; Markir, Aaron; Ma, Lu; Xu, Yunkai; Jiang, Heng; Leonard, Daniel P.; Shin, Woochul; Wu, Tianpin; Lu, Jun; Ji, Xiulei

doi:10.1002/anie.201905875

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

Journal Article · 13 July 2019 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201905875 · OSTI ID:1574296

Wu, Xianyong ^[1]; Markir, Aaron ^[1]; Ma, Lu ^[2]; Xu, Yunkai ^[1]; Jiang, Heng ^[1]; Leonard, Daniel P. ^[1]; Shin, Woochul ^[1]; Wu, Tianpin ^[2]; Lu, Jun ^[3];

^[1]

Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
Argonne National Laboratory, Lemont, IL (United States). X-ray Science Div., Advanced Photon Sources
Argonne National Laboratory, Lemont, IL (United States). Chemical Sciences and Engineering Div.

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 ₂ S. 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 ₂ S, 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 . 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 ₂ S/carbon composite cathode, and stable cycling over 110 cycles.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1574296

Alternate ID(s):: OSTI ID: 1545651

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 36; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 64 works

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References (70)

Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A. Angewandte Chemie International Edition, Vol. 51, Issue 40 https://doi.org/10.1002/anie.201201429	journal	September 2012
Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries Wan, Fang; Zhang, Yan; Zhang, Linlin Angewandte Chemie, Vol. 131, Issue 21 https://doi.org/10.1002/ange.201902679	journal	April 2019
An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode Guo, Zhaowei; Ma, Yuanyuan; Dong, Xiaoli Angewandte Chemie, Vol. 130, Issue 36 https://doi.org/10.1002/ange.201807121	journal	August 2018
An ultrafast rechargeable aluminium-ion battery Lin, Meng-Chang; Gong, Ming; Lu, Bingan Nature, Vol. 520, Issue 7547 https://doi.org/10.1038/nature14340	journal	April 2015
Dual-graphite cells based on the reversible intercalation of bis(trifluoromethanesulfonyl)imide anions from an ionic liquid electrolyte Rothermel, Sergej; Meister, Paul; Schmuelling, Guido Energy Environ. Sci., Vol. 7, Issue 10 https://doi.org/10.1039/C4EE01873G	journal	January 2014
Regulating Fast Anionic Redox for High-Voltage Aqueous Hydrogen-Ion-based Energy Storage Wang, Shengping; Zhao, Xiaoli; Yan, Xiaojun Angewandte Chemie, Vol. 131, Issue 1 https://doi.org/10.1002/ange.201811220	journal	December 2018
Lithium Bond Chemistry in Lithium-Sulfur Batteries Hou, Ting-Zheng; Xu, Wen-Tao; Chen, Xiang Angewandte Chemie, Vol. 129, Issue 28 https://doi.org/10.1002/ange.201704324	journal	June 2017
Lithium ion battery applications of molybdenum disulfide (MoS ₂ ) nanocomposites Stephenson, Tyler; Li, Zhi; Olsen, Brian Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE42591F	journal	January 2014
Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System Wu, Xianyong; Qi, Yitong; Hong, Jessica J. Angewandte Chemie, Vol. 129, Issue 42 https://doi.org/10.1002/ange.201707473	journal	September 2017
Natriumionenbatterien für die elektrochemische Energiespeicherung Kundu, Dipan; Talaie, Elahe; Duffort, Victor Angewandte Chemie, Vol. 127, Issue 11 https://doi.org/10.1002/ange.201410376	journal	February 2015
Hard and soft acids and bases, HSAB, part 1: Fundamental principles Pearson, Ralph G. Journal of Chemical Education, Vol. 45, Issue 9 https://doi.org/10.1021/ed045p581	journal	September 1968
Reversible S ⁰ /MgS _x Redox Chemistry in a MgTFSI ₂ /MgCl ₂ /DME Electrolyte for Rechargeable Mg/S Batteries Gao, Tao; Hou, Singyuk; Wang, Fei Angewandte Chemie, Vol. 129, Issue 43 https://doi.org/10.1002/ange.201708241	journal	September 2017
Reversible S ⁰ /MgS _x Redox Chemistry in a MgTFSI ₂ /MgCl ₂ /DME Electrolyte for Rechargeable Mg/S Batteries Gao, Tao; Hou, Singyuk; Wang, Fei Angewandte Chemie International Edition, Vol. 56, Issue 43 https://doi.org/10.1002/anie.201708241	journal	September 2017
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage Wang, Xianfu; Xie, Yiming; Tang, Kai Angewandte Chemie, Vol. 130, Issue 36 https://doi.org/10.1002/ange.201803664	journal	June 2018
Cyclohexanehexone with Ultrahigh Capacity as Cathode Materials for Lithium‐Ion Batteries Lu, Yong; Hou, Xuesen; Miao, Licheng Angewandte Chemie, Vol. 131, Issue 21 https://doi.org/10.1002/ange.201902185	journal	April 2019
A Rechargeable Battery with an Iron Metal Anode Wu, Xianyong; Markir, Aaron; Xu, Yunkai Advanced Functional Materials, Vol. 29, Issue 20 https://doi.org/10.1002/adfm.201900911	journal	March 2019
A High Capacity Calcium Primary Cell Based on the Ca-S System See, Kimberly A.; Gerbec, Jeffrey A.; Jun, Young-Si Advanced Energy Materials, Vol. 3, Issue 8 https://doi.org/10.1002/aenm.201300160	journal	April 2013
Textbook errors: Guest column. The solubility product constants of the metallic sulfides Waggoner, William H. Journal of Chemical Education, Vol. 35, Issue 7 https://doi.org/10.1021/ed035p339	journal	July 1958
Lithiumbatterien und elektrische Doppelschichtkondensatoren: aktuelle Herausforderungen Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A. Angewandte Chemie, Vol. 124, Issue 40 https://doi.org/10.1002/ange.201201429	journal	September 2012
Slope‐Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na‐Ion Batteries Qi, Yuruo; Lu, Yaxiang; Ding, Feixiang Angewandte Chemie, Vol. 131, Issue 13 https://doi.org/10.1002/ange.201900005	journal	February 2019
Smaller Sulfur Molecules Promise Better Lithium–Sulfur Batteries Xin, Sen; Gu, Lin; Zhao, Na-Hong Journal of the American Chemical Society, Vol. 134, Issue 45 https://doi.org/10.1021/ja308170k	journal	October 2012
Interaction of CuS and Sulfur in Li-S Battery System Sun, Ke; Su, Dong; Zhang, Qing Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.1021514jes	journal	January 2015
Metal sulfide nanostructures: synthesis, properties and applications in energy conversion and storage Lai, Chen-Ho; Lu, Ming-Yen; Chen, Lih-Juann J. Mater. Chem., Vol. 22, Issue 1 https://doi.org/10.1039/C1JM13879K	journal	January 2012
Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth Pan, Huilin; Chen, Junzheng; Cao, Ruiguo Nature Energy, Vol. 2, Issue 10 https://doi.org/10.1038/s41560-017-0005-z	journal	September 2017
Lithium Bond Chemistry in Lithium-Sulfur Batteries Hou, Ting-Zheng; Xu, Wen-Tao; Chen, Xiang Angewandte Chemie International Edition, Vol. 56, Issue 28 https://doi.org/10.1002/anie.201704324	journal	June 2017
An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode Guo, Zhaowei; Ma, Yuanyuan; Dong, Xiaoli Angewandte Chemie International Edition, Vol. 57, Issue 36 https://doi.org/10.1002/anie.201807121	journal	August 2018
Hard soft acids bases (HSAB) principle and organic chemistry Ho, Tse-Lok Chemical Reviews, Vol. 75, Issue 1 https://doi.org/10.1021/cr60293a001	journal	February 1975
Regulating Fast Anionic Redox for High-Voltage Aqueous Hydrogen-Ion-based Energy Storage Wang, Shengping; Zhao, Xiaoli; Yan, Xiaojun Angewandte Chemie International Edition, Vol. 58, Issue 1 https://doi.org/10.1002/anie.201811220	journal	December 2018
Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors Komaba, Shinichi; Hasegawa, Tatsuya; Dahbi, Mouad Electrochemistry Communications, Vol. 60 https://doi.org/10.1016/j.elecom.2015.09.002	journal	November 2015
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 Li, Yunming; Yang, Zhenzhong; Xu, Shuyin Advanced Science, Vol. 2, Issue 6 https://doi.org/10.1002/advs.201500031	journal	May 2015
Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System Wu, Xianyong; Qi, Yitong; Hong, Jessica J. Angewandte Chemie International Edition, Vol. 56, Issue 42 https://doi.org/10.1002/anie.201707473	journal	September 2017
Chemical Synthesis of K ₂ S ₂ and K ₂ S ₃ for Probing Electrochemical Mechanisms in K–S Batteries Gu, Sichen; Xiao, Neng; Wu, Feng ACS Energy Letters, Vol. 3, Issue 12 https://doi.org/10.1021/acsenergylett.8b01719	journal	October 2018
Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage Wang, Meng; Jiang, Chunlei; Zhang, Songquan Nature Chemistry, Vol. 10, Issue 6 https://doi.org/10.1038/s41557-018-0045-4	journal	April 2018
A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte Gao, Tao; Li, Xiaogang; Wang, Xiwen Angewandte Chemie International Edition, Vol. 55, Issue 34 https://doi.org/10.1002/anie.201603531	journal	July 2016
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage Kundu, Dipan; Talaie, Elahe; Duffort, Victor Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201410376	journal	February 2015
Highly Durable Na ₂ V ₆ O ₁₆ ·1.63H ₂ O Nanowire Cathode for Aqueous Zinc-Ion Battery Hu, Ping; Zhu, Ting; Wang, Xuanpeng Nano Letters, Vol. 18, Issue 3 https://doi.org/10.1021/acs.nanolett.7b04889	journal	February 2018
Slope-Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na-Ion Batteries Qi, Yuruo; Lu, Yaxiang; Ding, Feixiang Angewandte Chemie International Edition, Vol. 58, Issue 13 https://doi.org/10.1002/anie.201900005	journal	February 2019
On the origin of the extra capacity at low potential in materials for Li batteries reacting through conversion reaction Ponrouch, Alexandre; Taberna, Pierre-Louis; Simon, Patrice Electrochimica Acta, Vol. 61 https://doi.org/10.1016/j.electacta.2011.11.029	journal	February 2012
Understanding electrochemical potentials of cathode materials in rechargeable batteries Liu, Chaofeng; Neale, Zachary G.; Cao, Guozhong Materials Today, Vol. 19, Issue 2 https://doi.org/10.1016/j.mattod.2015.10.009	journal	March 2016
A Stable, Non‐Corrosive Perfluorinated Pinacolatoborate Mg Electrolyte for Rechargeable Mg Batteries Luo, Jian; Bi, Yujing; Zhang, Liping Angewandte Chemie, Vol. 131, Issue 21 https://doi.org/10.1002/ange.201902009	journal	March 2019
Electrocatalysis in Lithium Sulfur Batteries under Lean Electrolyte Conditions Yang, Yuxiang; Zhong, Yiren; Shi, Qiuwei Angewandte Chemie, Vol. 130, Issue 47 https://doi.org/10.1002/ange.201808311	journal	October 2018
Hard and soft acids and bases, HSAB, part II: Underlying theories Pearson, Ralph G. Journal of Chemical Education, Vol. 45, Issue 10 https://doi.org/10.1021/ed045p643	journal	October 1968
A Dual-Carbon Battery Based on Potassium-Ion Electrolyte Ji, Bifa; Zhang, Fan; Wu, Nanzhong Advanced Energy Materials, Vol. 7, Issue 20 https://doi.org/10.1002/aenm.201700920	journal	July 2017
Nature of extra capacity in MoS2 electrodes: Molybdenum atoms accommodate with lithium Wang, Longlu; Zhang, Qingfeng; Zhu, Jingyi Energy Storage Materials, Vol. 16 https://doi.org/10.1016/j.ensm.2018.04.025	journal	January 2019
Self-Established Rapid Magnesiation/De-Magnesiation Pathways in Binary Selenium-Copper Mixtures with Significantly Enhanced Mg-Ion Storage Reversibility Zhang, Zhonghua; Chen, Bingbing; Xu, Huimin Advanced Functional Materials, Vol. 28, Issue 1 https://doi.org/10.1002/adfm.201701718	journal	November 2017
Surface Chemistry in Cobalt Phosphide-Stabilized Lithium–Sulfur Batteries Zhong, Yiren; Yin, Lichang; He, Peng Journal of the American Chemical Society, Vol. 140, Issue 4 https://doi.org/10.1021/jacs.7b11434	journal	January 2018
Polysulfides Capture-Copper Additive for Long Cycle Life Lithium Sulfur Batteries Jia, Lei; Wu, Tianpin; Lu, Jun ACS Applied Materials & Interfaces, Vol. 8, Issue 44 https://doi.org/10.1021/acsami.6b10366	journal	October 2016
Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode Wang, Xingfeng; Bommier, Clement; Jian, Zelang Angewandte Chemie, Vol. 129, Issue 11 https://doi.org/10.1002/ange.201700148	journal	February 2017
A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte Gao, Tao; Li, Xiaogang; Wang, Xiwen Angewandte Chemie, Vol. 128, Issue 34 https://doi.org/10.1002/ange.201603531	journal	July 2016
Electrical Conduction and Phase Transition of Copper Sulfides Okamoto, Kimihiko; Kawai, Shichio Japanese Journal of Applied Physics, Vol. 12, Issue 8 https://doi.org/10.1143/JJAP.12.1130	journal	August 1973
A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode Kundu, Dipan; Adams, Brian D.; Duffort, Victor Nature Energy, Vol. 1, Issue 10 https://doi.org/10.1038/nenergy.2016.119	journal	August 2016
The Effect of Insertion Species on Nanostructured Open Framework Hexacyanoferrate Battery Electrodes Wessells, Colin D.; Peddada, Sandeep V.; McDowell, Matthew T. Journal of The Electrochemical Society, Vol. 159, Issue 2, p. A98-A103 https://doi.org/10.1149/2.060202jes	journal	January 2012
Catalytic oxidation of Li ₂ S on the surface of metal sulfides for Li−S batteries Zhou, Guangmin; Tian, Hongzhen; Jin, Yang Proceedings of the National Academy of Sciences, Vol. 114, Issue 5 https://doi.org/10.1073/pnas.1615837114	journal	January 2017
Carbon Electrodes for K-Ion Batteries Jian, Zelang; Luo, Wei; Ji, Xiulei Journal of the American Chemical Society, Vol. 137, Issue 36 https://doi.org/10.1021/jacs.5b06809	journal	September 2015
Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode Wang, Xingfeng; Bommier, Clement; Jian, Zelang Angewandte Chemie International Edition, Vol. 56, Issue 11 https://doi.org/10.1002/anie.201700148	journal	February 2017
Highly reversible zinc metal anode for aqueous batteries Wang, Fei; Borodin, Oleg; Gao, Tao Nature Materials, Vol. 17, Issue 6 https://doi.org/10.1038/s41563-018-0063-z	journal	April 2018
Toward a Reversible Calcium‐Sulfur Battery with a Lithium‐Ion Mediation Approach Yu, Xingwen; Boyer, Mathew J.; Hwang, Gyeong S. Advanced Energy Materials, Vol. 9, Issue 14 https://doi.org/10.1002/aenm.201803794	journal	February 2019
Electrocatalysis in Lithium Sulfur Batteries under Lean Electrolyte Conditions Yang, Yuxiang; Zhong, Yiren; Shi, Qiuwei Angewandte Chemie International Edition, Vol. 57, Issue 47 https://doi.org/10.1002/anie.201808311	journal	October 2018
Diffusion-free Grotthuss topochemistry for high-rate and long-life proton batteries Wu, Xianyong; Hong, Jessica J.; Shin, Woochul Nature Energy, Vol. 4, Issue 2 https://doi.org/10.1038/s41560-018-0309-7	journal	January 2019
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F. Nature Materials, Vol. 8, Issue 6, p. 500-506 https://doi.org/10.1038/nmat2460	journal	May 2009
Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage Wang, Xianfu; Xie, Yiming; Tang, Kai Angewandte Chemie International Edition, Vol. 57, Issue 36 https://doi.org/10.1002/anie.201803664	journal	June 2018
A High-Energy Room-Temperature Sodium-Sulfur Battery Xin, Sen; Yin, Ya-Xia; Guo, Yu-Guo Advanced Materials, Vol. 26, Issue 8 https://doi.org/10.1002/adma.201304126	journal	December 2013
High rate and stable cycling of lithium metal anode Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7362	journal	February 2015
Long-Life Room-Temperature Sodium-Sulfur Batteries by Virtue of Transition-Metal-Nanocluster-Sulfur Interactions Zhang, Bin-Wei; Sheng, Tian; Wang, Yun-Xiao Angewandte Chemie International Edition, Vol. 58, Issue 5 https://doi.org/10.1002/anie.201811080	journal	January 2019
Long‐Life Room‐Temperature Sodium–Sulfur Batteries by Virtue of Transition‐Metal‐Nanocluster–Sulfur Interactions Zhang, Bin‐Wei; Sheng, Tian; Wang, Yun‐Xiao Angewandte Chemie, Vol. 131, Issue 5 https://doi.org/10.1002/ange.201811080	journal	January 2019
A Stable, Non-Corrosive Perfluorinated Pinacolatoborate Mg Electrolyte for Rechargeable Mg Batteries Luo, Jian; Bi, Yujing; Zhang, Liping Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201902009	journal	March 2019
Cyclohexanehexone with Ultrahigh Capacity as Cathode Materials for Lithium‐Ion Batteries Lu, Yong; Hou, Xuesen; Miao, Licheng Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201902185	journal	May 2019
Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries Wan, Fang; Zhang, Yan; Zhang, Linlin Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201902679	journal	May 2019
High Rate and Stable Cycling of Lithium Metal Anode Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu ECS Meeting Abstracts, Vol. MA2015-01, Issue 15, p. 1155-1155 https://doi.org/10.1149/ma2015-01/15/1155	journal	April 2015

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