Cross-Linked Ionomer Gel Separators for Polysulfide Shuttle Mitigation in Magnesium–Sulfur Batteries: Elucidation of Structure–Property Relationships

Ford, Hunter O.; Merrill, Laura C.; He, Peng; Upadhyay, Sunil P.; Schaefer, Jennifer L.

doi:10.1021/acs.macromol.8b01717

Title: Cross-Linked Ionomer Gel Separators for Polysulfide Shuttle Mitigation in Magnesium–Sulfur Batteries: Elucidation of Structure–Property Relationships

Journal Article · 21 October 2018 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.8b01717 · OSTI ID:1504959

Ford, Hunter O. ^[1]; Merrill, Laura C. ^[1]; He, Peng ^[1]; Upadhyay, Sunil P. ^[1];

^[1]

Univ. of Notre Dame, IN (United States)

Cross-linked ionomer networks of varying poly- (ethylene glycol) diacrylate cross-linker chain length, ionic comonomer chemistry, and comonomer ratio have been studied for their use as polysulfide shuttle inhibiting separators in magnesium–sulfur (Mg–S) batteries. Through the use of X-ray scattering, polysulfide diffusion experiments, conductivity measurements, and Mg–S cell cycling, it was determined in this work that inclusion of tethered anions in polymer networks mitigates the polysulfide shuttle effect. Polysulfide crossover through networks into a bulk electrolyte can be reduced by absorption into the polymer gel, steric rejection, and electrostatic rejection, with the predominance of these mechanisms dictated by polymer composition and structure. The best network composition allowed an initial Mg–S cell discharge capacity of 522 mAh/g compared to a discharge capacity of 365 mAh/g using a literature standard glass fiber separator. The ionomer cell saw 67% capacity retention after three cycles, whereas the glass fiber separator could not complete the first charging cycle due to the polysulfide shuttle.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); The Society of Arthur J. Schmitt Fellows; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1504959

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 51; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (31)

High Rate Magnesium-Sulfur Battery with Improved Cyclability Based on Metal-Organic Framework Derivative Carbon Host Zhou, Xuejun; Tian, Jing; Hu, Jiulin Advanced Materials, Vol. 30, Issue 7 https://doi.org/10.1002/adma.201704166	journal	January 2018
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
Tungsten Disulfide Catalysts Supported on a Carbon Cloth Interlayer for High Performance Li-S Battery Park, Jungjin; Yu, Byeong-Chul; Park, Joong Sun Advanced Energy Materials, Vol. 7, Issue 11 https://doi.org/10.1002/aenm.201602567	journal	January 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
A Delicately Designed Sulfide Graphdiyne Compatible Cathode for High-Performance Lithium/Magnesium-Sulfur Batteries Du, Huiping; Zhang, Zhonghua; He, Jianjiang Small, Vol. 13, Issue 44 https://doi.org/10.1002/smll.201702277	journal	September 2017
Single-ion polymer electrolytes based on a delocalized polyanion for lithium batteries Meziane, Rachid; Bonnet, Jean-Pierre; Courty, Matthieu Electrochimica Acta, Vol. 57 https://doi.org/10.1016/j.electacta.2011.03.074	journal	December 2011
Advanced chemical strategies for lithium–sulfur batteries: A review Fan, Xiaojing; Sun, Wenwei; Meng, Fancheng Green Energy & Environment, Vol. 3, Issue 1 https://doi.org/10.1016/j.gee.2017.08.002	journal	January 2018
Application of lithiated Nafion ionomer film as functional separator for lithium sulfur cells Jin, Zhaoqing; Xie, Kai; Hong, Xiaobin Journal of Power Sources, Vol. 218 https://doi.org/10.1016/j.jpowsour.2012.06.100	journal	November 2012
Highly Conductive, Sulfonated, UV-Cross-Linked Separators for Li–S Batteries Ma, Lin; Nath, Pooja; Tu, Zhengyuan Chemistry of Materials, Vol. 28, Issue 14 https://doi.org/10.1021/acs.chemmater.6b02190	journal	July 2016
Heterogeneity and its Influence on the Properties of Difunctional Poly(ethylene glycol) Hydrogels: Structure and Mechanics Malo de Molina, Paula; Lad, Sahger; Helgeson, Matthew E. Macromolecules, Vol. 48, Issue 15 https://doi.org/10.1021/acs.macromol.5b01115	journal	July 2015
Ion States and Transport in Styrenesulfonate Methacrylic PEO ₉ Random Copolymer Ionomers Wang, Jing-Han Helen; Yang, Cathy Han-Chang; Masser, Hanqing Macromolecules, Vol. 48, Issue 19 https://doi.org/10.1021/acs.macromol.5b01524	journal	September 2015
Performance Enhancement and Mechanistic Studies of Magnesium–Sulfur Cells with an Advanced Cathode Structure Yu, Xingwen; Manthiram, Arumugam ACS Energy Letters, Vol. 1, Issue 2 https://doi.org/10.1021/acsenergylett.6b00213	journal	July 2016
Nucleation under Soft Confinement: Role of Polymer–Solute Interactions Diao, Ying; Helgeson, Matthew E.; Siam, Zeina A. Crystal Growth & Design, Vol. 12, Issue 1 https://doi.org/10.1021/cg201434r	journal	December 2011
Rechargeable Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500062v	journal	July 2014
Nanoscale Morphology in Precisely Sequenced Poly(ethylene- co -acrylic acid) Zinc Ionomers Seitz, Michelle E.; Chan, Christopher D.; Opper, Kathleen L. Journal of the American Chemical Society, Vol. 132, Issue 23 https://doi.org/10.1021/ja101991d	journal	June 2010
Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak Hall, Lisa M.; Seitz, Michelle E.; Winey, Karen I. Journal of the American Chemical Society, Vol. 134, Issue 1 https://doi.org/10.1021/ja209142b	journal	December 2011
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
Morphology of Photopolymerized End-Linked Poly(ethylene glycol) Hydrogels by Small-Angle X-ray Scattering Waters, Dale J.; Engberg, Kristin; Parke-Houben, Rachel Macromolecules, Vol. 43, Issue 16 https://doi.org/10.1021/ma101070s	journal	August 2010
Understanding the Role of Different Conductive Polymers in Improving the Nanostructured Sulfur Cathode Performance Li, Weiyang; Zhang, Qianfan; Zheng, Guangyuan Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl403130h	journal	October 2013
Strong Sulfur Binding with Conducting Magnéli-Phase Ti _n O _{2 n –1} Nanomaterials for Improving Lithium–Sulfur Batteries Tao, Xinyong; Wang, Jianguo; Ying, Zhuogao Nano Letters, Vol. 14, Issue 9 https://doi.org/10.1021/nl502331f	journal	August 2014
Permselective Graphene Oxide Membrane for Highly Stable and Anti-Self-Discharge Lithium–Sulfur Batteries Huang, Jia-Qi; Zhuang, Ting-Zhou; Zhang, Qiang ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/nn507178a	journal	February 2015
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
Order causes secondary Bragg peaks in soft materials Förster, Stephan; Timmann, Andreas; Schellbach, Carsten Nature Materials, Vol. 6, Issue 11 https://doi.org/10.1038/nmat1995	journal	August 2007
Ionic shield for polysulfides towards highly-stable lithium–sulfur batteries Huang, Jia-Qi; Zhang, Qiang; Peng, Hong-Jie Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE42223B	journal	January 2014
Hollow polyaniline sphere@sulfur composites for prolonged cycling stability of lithium–sulfur batteries Ma, Guoqiang; Wen, Zhaoyin; Jin, Jun J. Mater. Chem. A, Vol. 2, Issue 27 https://doi.org/10.1039/C4TA00483C	journal	January 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
The unexpected discovery of the Mg(HMDS) ₂ /MgCl ₂ complex as a magnesium electrolyte for rechargeable magnesium batteries Liao, Chen; Sa, Niya; Key, Baris Journal of Materials Chemistry A, Vol. 3, Issue 11 https://doi.org/10.1039/C5TA00118H	journal	January 2015
Electrochemical performance of lithium/sulfur batteries using perfluorinated ionomer electrolyte with lithium sulfonyl dicyanomethide functional groups as functional separator Jin, Zhaoqing; Xie, Kai; Hong, Xiaobin RSC Advances, Vol. 3, Issue 23 https://doi.org/10.1039/c3ra41517a	journal	January 2013
Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries Zhao-Karger, Zhirong; Zhao, Xiangyu; Fuhr, Olaf RSC Advances, Vol. 3, Issue 37 https://doi.org/10.1039/c3ra43206h	journal	January 2013
Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries Elmore, Clay; Seidler, Morgan; Ford, Hunter Batteries, Vol. 4, Issue 2 https://doi.org/10.3390/batteries4020028	journal	June 2018
A Simple Preparation of Polyaniline-coated Sulfur Composites for use as Cathodes in Li–S Batteries Hyun, Jungeun; Lee, Pyoung-Chan; Jung, Myoung-Jo Electrochemistry, Vol. 84, Issue 11 https://doi.org/10.5796/electrochemistry.84.836	journal	January 2016

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