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; Ma, Zhaohui; Li, Xiaogang; Xu, Kang; Wang, Chunsheng

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 Article · Fri Sep 22 00:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201708241· OSTI ID:1393995

Gao, Tao ^[1]; Hou, Singyuk ^[1]; Wang, Fei ^[1]; Ma, Zhaohui ^[1]; Li, Xiaogang ^[1]; Xu, Kang ^[2]; Wang, Chunsheng ^[1]

Department of Chemical and Bimolecular Engineering University of Maryland College Park MD 20740 USA
Electrochemistry Branch, Power and Energy Division Sensor and Electron Devices Directorate U.S. Army Research Laboratory Adelphi MD 20783 USA

Abstract

The redox chemistry of magnesium and its application in rechargeable Mg batteries has received increasing attention owing to the unique benefits of Mg metal electrodes, namely high reversibility without dendrite formation, low reduction potentials, and high specific capacities. The Mg/S couple is of particular interest owing to its high energy density and low cost. Previous reports have confirmed the feasibility of a rechargeable Mg/S battery; however, only limited cycling stability was achieved, and the complicated procedure for the preparation of the electrolytes has significantly compromised the benefits of Mg/S chemistry and hindered the development of Mg/S batteries. Herein, we report the development of the first rechargeable Mg/S battery with a MgTFSI ₂ /MgCl ₂ /DME electrolyte (DME=1,2‐dimethoxyethane, TFSI=bis(trifluoromethanesulfonyl)imide) and realize the best cycling stability among all reported Mg/S batteries by suppressing polysulfide dissolution. Mechanistic studies show that the battery works via S ⁰ /MgS _x redox processes and that the large voltage hysteresis is mainly due to the Mg anode overpotential.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001160

OSTI ID:: 1393995

Alternate ID(s):: OSTI ID: 1537455

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 43 Vol. 56; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (48)

Sulfur-Impregnated Activated Carbon Fiber Cloth as a Binder-Free Cathode for Rechargeable Li-S Batteries Elazari, Ran; Salitra, Gregory; Garsuch, Arnd Advanced Materials, Vol. 23, Issue 47, p. 5641-5644 https://doi.org/10.1002/adma.201103274	journal	November 2011
Performance Improvement of Magnesium Sulfur Batteries with Modified Non-Nucleophilic Electrolytes Zhao-Karger, Zhirong; Zhao, Xiangyu; Wang, Di Advanced Energy Materials, Vol. 5, Issue 3 https://doi.org/10.1002/aenm.201401155	journal	October 2014
Hybrid Mg ²⁺ /Li ⁺ Battery with Long Cycle Life and High Rate Capability Gao, Tao; Han, Fudong; Zhu, Yujie Advanced Energy Materials, Vol. 5, Issue 5 https://doi.org/10.1002/aenm.201401507	journal	November 2014
Novel Design Concepts of Efficient Mg-Ion Electrolytes toward High-Performance Magnesium-Selenium and Magnesium-Sulfur Batteries Zhang, Zhonghua; Cui, Zili; Qiao, Lixin Advanced Energy Materials, Vol. 7, Issue 11 https://doi.org/10.1002/aenm.201602055	journal	January 2017
Boron Clusters as Highly Stable Magnesium-Battery Electrolytes Carter, Tyler J.; Mohtadi, Rana; Arthur, Timothy S. Angewandte Chemie, Vol. 126, Issue 12 https://doi.org/10.1002/ange.201310317	journal	February 2014
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S. Angewandte Chemie, Vol. 127, Issue 27 https://doi.org/10.1002/ange.201412202	journal	May 2015
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
Radical-Mediated 1,2-Formyl/Carbonyl Functionalization of Alkenes and Application to the Construction of Medium-Sized Rings Li, Zhong-Liang; Li, Xiao-Hua; Wang, Na Angewandte Chemie, Vol. 128, Issue 48 https://doi.org/10.1002/ange.201608198	journal	October 2016
Boron Clusters as Highly Stable Magnesium-Battery Electrolytes Carter, Tyler J.; Mohtadi, Rana; Arthur, Timothy S. Angewandte Chemie International Edition, Vol. 53, Issue 12 https://doi.org/10.1002/anie.201310317	journal	February 2014
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S. Angewandte Chemie International Edition, Vol. 54, Issue 27 https://doi.org/10.1002/anie.201412202	journal	May 2015
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
Radical-Mediated 1,2-Formyl/Carbonyl Functionalization of Alkenes and Application to the Construction of Medium-Sized Rings Li, Zhong-Liang; Li, Xiao-Hua; Wang, Na Angewandte Chemie International Edition, Vol. 55, Issue 48 https://doi.org/10.1002/anie.201608198	journal	October 2016
Interlayer-Expanded Vanadium Oxychloride as an Electrode Material for Magnesium-Based Batteries Minella, Christian Bonatto; Gao, Ping; Zhao-Karger, Zhirong ChemElectroChem, Vol. 4, Issue 3 https://doi.org/10.1002/celc.201700034	journal	February 2017
A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions Aurbach, D. Solid State Ionics, Vol. 148, Issue 3-4 https://doi.org/10.1016/S0167-2738(02)00080-2	journal	June 2002
α-MnO2 as a cathode material for rechargeable Mg batteries Zhang, Ruigang; Yu, Xiqian; Nam, Kyung-Wan Electrochemistry Communications, Vol. 23 https://doi.org/10.1016/j.elecom.2012.07.021	journal	September 2012
Copper Selenide as a New Cathode Material based on Displacement Reaction for Rechargeable Magnesium Batteries Tashiro, Yuta; Taniguchi, Kouji; Miyasaka, Hitoshi Electrochimica Acta, Vol. 210 https://doi.org/10.1016/j.electacta.2016.05.202	journal	August 2016
Discharge reaction mechanism of room-temperature sodium–sulfur battery with tetra ethylene glycol dimethyl ether liquid electrolyte Ryu, Hosuk; Kim, Taebum; Kim, Kiwon Journal of Power Sources, Vol. 196, Issue 11, p. 5186-5190 https://doi.org/10.1016/j.jpowsour.2011.01.109	journal	June 2011
Thermodynamics and cell chemistry of room temperature sodium/sulfur cells with liquid and liquid/solid electrolyte Wenzel, Sebastian; Metelmann, Hauke; Raiß, Christine Journal of Power Sources, Vol. 243 https://doi.org/10.1016/j.jpowsour.2013.05.194	journal	December 2013
A novel non-aqueous aluminum sulfur battery Cohn, Gil; Ma, Lin; Archer, Lynden A. Journal of Power Sources, Vol. 283 https://doi.org/10.1016/j.jpowsour.2015.02.131	journal	June 2015
Is alpha-V2O5 a cathode material for Mg insertion batteries? Sa, Niya; Wang, Hao; Proffit, Danielle L. Journal of Power Sources, Vol. 323 https://doi.org/10.1016/j.jpowsour.2016.05.028	journal	August 2016
Nickel hexacyanoferrate, a versatile intercalation host for divalent ions from nonaqueous electrolytes Lipson, Albert L.; Han, Sang-Don; Kim, Soojeong Journal of Power Sources, Vol. 325 https://doi.org/10.1016/j.jpowsour.2016.06.019	journal	September 2016
Synthesis and electrochemical behavior of hollandite MnO2/acetylene black composite cathode for secondary Mg-ion batteries Rasul, Shahid; Suzuki, Shinya; Yamaguchi, Shu Solid State Ionics, Vol. 225 https://doi.org/10.1016/j.ssi.2012.01.019	journal	October 2012
Reversible Magnesium Intercalation into a Layered Oxyfluoride Cathode Incorvati, Jared T.; Wan, Liwen F.; Key, Baris Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b02746	journal	December 2015
Identifying the Discharge Product and Reaction Pathway for a Secondary Mg/O ₂ Battery Vardar, Gulin; Nelson, Emily G.; Smith, Jeffrey G. Chemistry of Materials, Vol. 27, Issue 22 https://doi.org/10.1021/acs.chemmater.5b03608	journal	November 2015
Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V ₂ O ₅ · n H ₂ O Xerogel Material Sa, Niya; Kinnibrugh, Tiffany L.; Wang, Hao Chemistry of Materials, Vol. 28, Issue 9 https://doi.org/10.1021/acs.chemmater.6b00026	journal	April 2016
High Capacity Rechargeable Magnesium-Ion Batteries Based on a Microporous Molybdenum–Vanadium Oxide Cathode Kaveevivitchai, Watchareeya; Jacobson, Allan J. Chemistry of Materials, Vol. 28, Issue 13 https://doi.org/10.1021/acs.chemmater.6b01245	journal	June 2016
Tuning the Reversibility of Mg Anodes via Controlled Surface Passivation by H ₂ O/Cl ^– in Organic Electrolytes Connell, Justin G.; Genorio, Bostjan; Lopes, Pietro Papa Chemistry of Materials, Vol. 28, Issue 22 https://doi.org/10.1021/acs.chemmater.6b03227	journal	October 2016
Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) ₂ in Diglyme: Implications for Multivalent Electrolytes Baskin, Artem; Prendergast, David The Journal of Physical Chemistry C, Vol. 120, Issue 7 https://doi.org/10.1021/acs.jpcc.5b08999	journal	February 2016
Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF ₃ SO ₂ ) ₂ N ^– at High Current Densities Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L. Langmuir, Vol. 33, Issue 37 https://doi.org/10.1021/acs.langmuir.7b01051	journal	July 2017
Fluorinated Alkoxide-Based Magnesium-Ion Battery Electrolytes that Demonstrate Li-Ion-Battery-Like High Anodic Stability and Solution Conductivity Crowe, Adam J.; Stringham, Kyle K.; Bartlett, Bart M. ACS Applied Materials & Interfaces, Vol. 8, Issue 35 https://doi.org/10.1021/acsami.6b07262	journal	August 2016
Layered TiS ₂ Positive Electrode for Mg Batteries Sun, Xiaoqi; Bonnick, Patrick; Nazar, Linda F. ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00145	journal	June 2016
A Fluorinated Alkoxyaluminate Electrolyte for Magnesium-Ion Batteries Herb, Jake T.; Nist-Lund, Carl A.; Arnold, Craig B. ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00356	journal	November 2016
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420 https://doi.org/10.1021/jacs.5b01004	journal	February 2015
Enhancing the Reversibility of Mg/S Battery Chemistry through Li ⁺ Mediation Gao, Tao; Noked, Malachi; Pearse, Alex J. Journal of the American Chemical Society, Vol. 137, Issue 38 https://doi.org/10.1021/jacs.5b07820	journal	September 2015
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
High power rechargeable magnesium/iodine battery chemistry Tian, Huajun; Gao, Tao; Li, Xiaogang Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14083	journal	January 2017
Structure and compatibility of a magnesium electrolyte with a sulphur cathode Kim, Hee Soo; Arthur, Timothy S.; Allred, Gary D. Nature Communications, Vol. 2, Article No. 427 https://doi.org/10.1038/ncomms1435	journal	August 2011
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
High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements Orikasa, Yuki; Masese, Titus; Koyama, Yukinori Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep05622	journal	July 2014
Performance study of magnesium–sulfur battery using a graphene based sulfur composite cathode electrode and a non-nucleophilic Mg electrolyte Vinayan, B. P.; Zhao-Karger, Zhirong; Diemant, Thomas Nanoscale, Vol. 8, Issue 6 https://doi.org/10.1039/C5NR04383B	journal	January 2016
Toward the design of high voltage magnesium–lithium hybrid batteries using dual-salt electrolytes Cheng, Yingwen; Choi, Daiwon; Han, Kee Sung Chemical Communications, Vol. 52, Issue 31 https://doi.org/10.1039/C6CC00986G	journal	January 2016
A high capacity thiospinel cathode for Mg batteries Sun, Xiaoqi; Bonnick, Patrick; Duffort, Victor Energy & Environmental Science, Vol. 9, Issue 7 https://doi.org/10.1039/C6EE00724D	journal	January 2016
Concentration dependent electrochemical properties and structural analysis of a simple magnesium electrolyte: magnesium bis(trifluoromethane sulfonyl)imide in diglyme Sa, Niya; Rajput, Nav Nidhi; Wang, Hao RSC Advances, Vol. 6, Issue 114 https://doi.org/10.1039/C6RA22816J	journal	January 2016
A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries Zhao-Karger, Zhirong; Gil Bardaji, Maria Elisa; Fuhr, Olaf Journal of Materials Chemistry A, Vol. 5, Issue 22 https://doi.org/10.1039/C7TA02237A	journal	January 2017
Electrolyte roadblocks to a magnesium rechargeable battery Muldoon, John; Bucur, Claudiu B.; Oliver, Allen G. Energy & Environmental Science, Vol. 5, Issue 3, p. 5941-5950 https://doi.org/10.1039/c2ee03029b	journal	January 2012
Mg rechargeable batteries: an on-going challenge Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279 https://doi.org/10.1039/c3ee40871j	journal	January 2013
Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable Magnesium Batteries Mizrahi, Oren; Amir, Nir; Pollak, Elad Journal of The Electrochemical Society, Vol. 155, Issue 2, p. A103-A109 https://doi.org/10.1149/1.2806175	journal	January 2008
Evaluation of (CF ₃ SO ₂ ) ₂ N ⁻ (TFSI) Based Electrolyte Solutions for Mg Batteries Shterenberg, Ivgeni; Salama, Michael; Yoo, Hyun Deog Journal of The Electrochemical Society, Vol. 162, Issue 13 https://doi.org/10.1149/2.0161513jes	journal	January 2015

Similar Records

Reversible S⁰/MgS_x Redox Chemistry in a MgTFSI₂/MgCl₂ /DME Electrolyte for Rechargeable Mg/S Batteries

Journal Article · Sun Aug 27 20:00:00 EDT 2017 · Angewandte Chemie · OSTI ID:1469863

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

Citation Formats

References (48)

Similar Records

Related Subjects

Reversible S ⁰ /MgS _x Redox Chemistry in a MgTFSI ₂ /MgCl ₂ /DME Electrolyte for Rechargeable Mg/S Batteries